CN112840242B - Polarizing film with adhesive layer and image display device - Google Patents

Polarizing film with adhesive layer and image display device Download PDF

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Publication number
CN112840242B
CN112840242B CN201980067253.1A CN201980067253A CN112840242B CN 112840242 B CN112840242 B CN 112840242B CN 201980067253 A CN201980067253 A CN 201980067253A CN 112840242 B CN112840242 B CN 112840242B
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Prior art keywords
adhesive layer
polarizing film
meth
layer
transparent
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CN112840242A (en
Inventor
木村智之
石原康隆
宝田翔
藤田昌邦
外山雄祐
三田聪司
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Nitto Denko Corp
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Nitto Denko Corp
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Priority claimed from PCT/JP2019/046788 external-priority patent/WO2020111232A1/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • 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
    • G02F1/133528—Polarisers
    • 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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • Theoretical Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Human Computer Interaction (AREA)
  • Nanotechnology (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention relates to a polarizing film with an adhesive layer, which has: an iodine-based polarizer, a transparent protective film provided only on one surface of the polarizer, and a transparent layer provided on the other surface of the polarizer, wherein an adhesive layer is provided through the transparent layer, and wherein the adhesive layer is used by bonding to the transparent conductive layer of a transparent conductive substrate having a transparent substrate and a transparent conductive layer, and wherein the polarizing film with an adhesive layer has a predetermined ratio of change in resistance to the transparent conductive layer. When the adhesive layer is bonded to the transparent conductive layer and placed in a humidified environment, a stable surface resistance value of the transparent conductive layer can be maintained.

Description

Polarizing film with adhesive layer and image display device
Technical Field
The present invention relates to a polarizing film with an adhesive layer. The present invention also relates to a laminate comprising a transparent conductive substrate to which the polarizing film with an adhesive layer is applied. The present invention also relates to an image display device using the laminate. The present invention also relates to an image display panel and an image display device using the polarizing film with an adhesive layer.
Background
In the image display panel of the present invention, for example, a liquid crystal panel used in a liquid crystal display device or the like, a polarizing film is generally laminated on both sides of a liquid crystal cell formed of a pair of transparent substrates and a liquid crystal layer disposed therebetween via an adhesive layer. Such an adhesive layer is required to have high durability, and for example, in a durability test using heating, humidification, or the like, which is generally performed as an environmental acceleration test, it is required that defects such as peeling and lifting of the adhesive layer do not occur.
Various studies have been made on such an adhesive composition for optical use, and for example, an adhesive composition has been proposed which does not cause peeling or foaming even when placed under high humidity and heat conditions after an optical film is attached (for example, refer to patent document 1).
There are members in which a transparent conductive layer such as an Indium Tin Oxide (ITO) thin film or an organic conductive film using a conductive polymer is formed on one transparent substrate constituting a liquid crystal cell of a liquid crystal panel. The transparent conductive layer plays a role of preventing light leakage (charging unevenness) caused by alignment disorder of the liquid crystal layer due to charging by static electricity. In the case of using the liquid crystal display device for a touch panel, the transparent conductive layer functions as a shielding electrode for separating a driving electric field in the liquid crystal cell from the touch panel. In view of the above, a polarizing film with an adhesive layer has been proposed which can maintain a stable surface resistance value in a humidified environment even when the polarizing film is bonded to the transparent conductive layer (patent document 2).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2009-242767
Patent document 2: japanese patent application laid-open No. 2015-145491
Disclosure of Invention
Problems to be solved by the invention
As the polarizing film with an adhesive layer, there is a case where an adhesive layer is provided on a single-sided protective polarizing film having a transparent protective film provided only on one side of a polarizer and no transparent protective film provided on the other side. Since the single-sided protective polarizing film with an adhesive layer has a transparent protective film on only one side, the polarizing film can be thinned and the cost of one transparent protective film can be reduced as compared with the case where transparent protective films are provided on both sides. On the other hand, it is known that when the single-sided protective polarizing film with an adhesive layer is applied to a transparent conductive layer, one surface of the polarizer is not covered with the transparent protective film, and therefore, in the system using an iodine-based polarizer as the polarizer, iodine and/or iodide ions generated by the iodine-based polarizer may pass through the adhesive layer and corrode the transparent conductive layer. Further, if the transparent conductive layer is corroded, the surface resistance increases, and display unevenness due to electrification is likely to occur. In addition, it is known that when a liquid crystal display device is used for a touch panel, a shielding function is lowered, and thus there is a concern that malfunction of the touch panel may occur.
The purpose of the present invention is to provide a polarizing film with an adhesive layer, which is a polarizing film with an adhesive layer provided on a single-sided protective polarizing film having a transparent protective film on only one side of an iodine-based polarizing film, and which can maintain a stable surface resistance value of a transparent conductive layer even when the adhesive layer is bonded to the transparent conductive layer and placed in a humidified environment.
Another object of the present invention is to provide a laminate comprising the transparent conductive substrate to which the polarizing film with an adhesive layer is applied. The present invention also provides an image display panel and an image display device using the polarizing film with an adhesive layer or the laminate.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a polarizing film with an adhesive layer described below, and have completed the present invention.
That is, the present invention relates to a polarizing film with an adhesive layer, which has: a polarizer, a transparent protective film provided on only one surface of the polarizer, and a transparent layer provided on the other surface of the polarizer, wherein an adhesive layer is provided through the transparent layer,
The polarizer is an iodine-based polarizer containing iodine and/or iodide ions,
the pressure-sensitive adhesive layer-containing polarizing film satisfies a change ratio of a surface resistance value represented by the general formula (1), the general formula (1): r is R 250 /R i ≤1.5
(wherein R is as defined above i The surface resistance value (Ω/≡) of the transparent conductive layer obtained by bonding the adhesive layer of the polarizing film with an adhesive layer to the metallic transparent conductive layer on the transparent conductive substrate having the transparent substrate and the transparent conductive layer, after autoclave treatment at 50 ℃ under 5 atm for 15 minutes,
r is as described above 250 The surface resistance value (Ω/≡) of the transparent conductive layer after the autoclave treatment was further subjected to high temperature and high humidity treatment at 65 ℃ and 95% rh for 250 hours.
The pressure-sensitive adhesive layer-attached polarizing film preferably satisfies a change ratio of a surface resistance value represented by the general formula (2), the general formula (2): r is R 500 /R 250 ≤1.8
(wherein R is as defined above 250 The surface resistance value (Ω/≡) of the transparent conductive layer obtained by bonding the adhesive layer of the polarizing film with an adhesive layer to the transparent conductive layer on the transparent conductive substrate having the transparent substrate and the transparent conductive layer after the autoclave treatment at 50℃and 5 atm for 15 minutes and further the high-temperature and high-humidity treatment at 65℃and 95% RH for 500 hours,
R is as described above 500 The surface resistance value (Ω/≡) of the transparent conductive layer after the autoclave treatment was further subjected to high temperature and high humidity treatment at 65 ℃ and 95% rh for 500 hours.
In the polarizing film with an adhesive layer, the transparent layer is preferably formed directly on the polarizer.
In the polarizing film with an adhesive layer, the thickness of the transparent layer is preferably 10 μm or less.
As the transparent layer, a cured product of a material for forming a urethane prepolymer, which is a reaction product of an isocyanate compound and a polyol, can be used for the polarizing film with an adhesive layer. As the isocyanate compound, at least 1 selected from toluene diisocyanate and diphenylmethane diisocyanate is preferably used.
The pressure-sensitive adhesive layer-attached polarizing film may contain an epoxy resin as the transparent layer.
The pressure-sensitive adhesive layer-attached polarizing film may be formed by using a resin composition containing the following polymer (a) and epoxy resin (b),
the polymer (a) is a polymer 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 a monomer represented by the following general formula (1),
[ chemical formula 1]
(wherein X represents a functional group containing at least 1 reactive group selected from the group consisting of vinyl, (meth) acryl, styryl, (meth) acrylamide, vinyl ether, epoxy, oxetane, hydroxyl, amino, aldehyde, and carboxyl, R 1 R is R 2 Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, R 1 R is R 2 Optionally linked to each other to form a ring),
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.
Preferably, the functional group represented by X in the above general formula (1) is a functional group represented by the following general formula (2),
general formula (2): Z-Y-
(wherein Z represents a functional group containing at least 1 reactive group selected from the group consisting of a vinyl group, a (meth) acryloyl group, a styryl group, a (meth) acrylamido group, a vinyl ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group, and Y represents an organic group).
As the polarizing film with an adhesive layer, an adhesive layer formed from an adhesive composition containing a (meth) acrylic polymer (a) can be used for the adhesive layer.
As the polarizing film with an adhesive layer, an adhesive layer formed from an adhesive composition containing a (meth) acrylic polymer (a) and an ionic compound (B) can be used as the adhesive layer.
In the polarizing film with an adhesive layer, the (meth) acrylic polymer (a) preferably contains an alkyl (meth) acrylate (a 1) and an amide group-containing monomer (a 2) as monomer units.
In the polarizing film with an adhesive layer, the amide group-containing monomer (a 2) is preferably an N-vinyl lactam-containing monomer.
In the polarizing film with an adhesive layer, the (meth) acrylic polymer (a) preferably contains 0.1 wt% or more of the amide group-containing monomer (a 2) as a monomer unit.
In the polarizing film with an adhesive layer, the ionic compound (B) is preferably an alkali metal salt. The ionic compound (B) is preferably contained in an amount of 0.01 part by weight or more based on 100 parts by weight of the (meth) acrylic polymer (A).
In the polarizing film with an adhesive layer, the transparent conductive layer is preferably formed of indium tin oxide.
The present invention also relates to a laminate comprising: the polarizing film with an adhesive layer, and a transparent conductive substrate having a transparent substrate and a transparent conductive layer,
The adhesive layer of the polarizing film with an adhesive layer is bonded to the transparent conductive layer of the transparent conductive substrate.
The present invention also relates to an image display device in which the adhesive layer of the polarizing film with an adhesive layer and a liquid crystal panel having a transparent conductive layer are bonded to each other so that the adhesive layer of the polarizing film with an adhesive layer contacts the transparent conductive layer of the liquid crystal panel.
The present invention also relates to an image display device using the laminate as a touch panel.
The present invention also relates to an image display panel having the above-described polarizing film with an adhesive layer. The image display panel preferably includes a transparent conductive substrate having a transparent conductive layer, and the adhesive layer of the polarizing film with an adhesive layer is bonded to the transparent conductive layer of the image display panel.
The present invention also relates to an image display device having the above image display panel.
ADVANTAGEOUS EFFECTS OF INVENTION
The polarizing film used in the polarizing film with an adhesive layer of the present invention is a single-sided protective polarizing film having a transparent protective film on only one surface of a polarizer, and is advantageous from the viewpoints of thickness reduction and cost reduction. On the other hand, in the polarizing film with an adhesive layer in which an adhesive layer is applied to a one-sided protective polarizing film, when an iodine-based polarizer is used as a polarizer and the adhesive layer is bonded to a transparent conductive layer, there is no concern that iodine and/or iodide ions generated by the iodine-based polarizer pass through the adhesive layer and corrode the transparent conductive layer. In the present invention, a transparent layer is provided between the polarizer and the adhesive layer in the polarizing film with an adhesive layer, and therefore, movement of iodine and/or iodide ions in the polarizer to the adhesive layer can be suppressed by the transparent layer. Therefore, it is considered that corrosion of the transparent conductive layer due to iodine and/or iodide ions can be suppressed even in a humidified environment, and the surface resistance value of the transparent conductive layer can be maintained within a desired value range for a long period of time, so that stable optical characteristics can be satisfied. In addition, it is considered that display unevenness due to electrification can be suppressed, and occurrence of malfunction can be suppressed.
As described above, the pressure-sensitive adhesive layer-attached polarizing film of the present invention has excellent durability to the transparent conductive layer even in a humidified environment, and according to the present invention, a laminate including a transparent conductive substrate to which the pressure-sensitive adhesive layer-attached polarizing film is applied, and an image display panel and an image display device using the laminate can be provided.
Drawings
Fig. 1 is a cross-sectional view showing an example of a polarizing film with an adhesive layer according to the present invention.
Fig. 2 is a cross-sectional view showing an example of the polarizing film with an adhesive layer according to the present invention.
Fig. 3 is a cross-sectional view showing an example of the laminate of the present invention.
Fig. 4 is a cross-sectional view showing an example of a touch-sensitive liquid crystal panel using the polarizing film with an adhesive layer of the present invention.
Fig. 5 is a cross-sectional view showing an example of a touch-sensitive liquid crystal panel using the polarizing film with an adhesive layer of the present invention.
Fig. 6 is a cross-sectional view showing an example of a touch-sensitive liquid crystal panel using the polarizing film with an adhesive layer of the present invention.
Symbol description
1. Polarizing film with adhesive layer
11. Single-sided protective polarizing film
a polarizer
b transparent protective film
c transparent layer
d conductive layer
21. Adhesive layer
F transparent conductive substrate
F1 Transparent conductive layer
F2 Transparent substrate
L-shaped laminate
11. 12 first polarizing film, second polarizing film
21. 22 first and second adhesive layers
3. Liquid crystal layer
41. 42 first transparent substrate, second transparent substrate
5. Touch sensor unit
6. Drive electrode and sensor unit
7. Driving electrode
C liquid crystal cell
Detailed Description
The adhesive layer-attached polarizing film of the present invention is shown in fig. 1, for example. As shown in fig. 1, a single-sided protective polarizing film 11 is used in the adhesive layer-attached polarizing film 1, the single-sided protective polarizing film 11 having: a polarizer a, a transparent protective film b provided on only one surface of the polarizer a, and a transparent layer c provided on the other surface of the polarizer a. The adhesive layer 21 is provided on the one-sided protective polarizing film 11 through the transparent layer c. In order to suppress an increase in the moisture content of the polarizer in a high-temperature and high-humidity environment, the transparent layer c is preferably directly provided on the polarizer a. The transparent layer c is described later. As shown in fig. 2, the polarizing film 1 with an adhesive layer may have a conductive layer d between the transparent layer c and the adhesive layer 21. The conductive layer d is described later. The antistatic property can be improved by the conductive layer d. The conductive layer d is provided through the transparent layer c, and therefore, the problem of discoloration of the polarizer end portion in a humidified environment due to the conductive layer c being directly provided on the polarizer a can be suppressed.
The polarizing film with an adhesive layer of the present invention is used as a laminate L shown in fig. 3, for example, to be applied to a transparent conductive substrate. In the laminate L shown in fig. 3, an example is given of a case where the adhesive layer 21 of the polarizing film 1 with an adhesive layer shown in fig. 1 is bonded to the transparent conductive layer F1 of the transparent conductive substrate F having the transparent conductive layer F1 on the transparent substrate F2.
In the polarizing film with an adhesive layer of the present invention, the surface resistance value (Ω/≡), that is, R, of the transparent conductive layer measured under the following conditions for the laminate i 、R 250 The ratio of change in the surface resistance value represented by the following general formula (1) is satisfied.
General formula (1): r is R 250 /R i ≤1.5
The variation ratio is preferably 1.3 or less, more preferably 1.2 or less.
In addition, it is preferable that the surface resistance value (Ω/≡), that is, R, of the transparent conductive layer measured under the following conditions for the laminate 250 、R 500 The ratio of change in the surface resistance value represented by the following general formula (2) is satisfied.
General formula (2): r is R 500 /R 250 ≤1.8
The variation ratio is preferably 1.5 or less, more preferably 1.2 or less.
R i The laminate obtained by bonding the adhesive layer of the polarizing film with an adhesive layer to the transparent conductive layer on the transparent conductive substrate having the transparent substrate and the transparent conductive layer has a surface resistance value (Ω/≡) of the transparent conductive layer after autoclave treatment at 50 ℃ under 5 atm for 15 minutes.
R 250 The surface resistance value (Ω/≡) of the transparent conductive layer after the autoclave treatment was further subjected to high temperature and high humidity treatment at 65 ℃ and 95% rh for 250 hours.
R 500 The surface resistance value (Ω/≡) of the transparent conductive layer after the autoclave treatment was further subjected to high temperature and high humidity treatment at 65 ℃ and 95% rh for 500 hours.
< polarizing film with adhesive layer >
First, each member constituting the polarizing film with an adhesive layer of the present invention will be described.
The polarizer is not particularly limited, and various polarizers may be used. Examples of the polarizer include: a polarizer obtained by unidirectionally stretching a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene-vinyl acetate copolymer partially saponified film, which is adsorbed with a dichroic material such as iodine or a dichroic dye; and a polyene oriented film such as a dehydrated polyvinyl alcohol product or a desalted polyvinyl chloride product. Among them, a polarizer containing a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.
As the polarizer, a thin polarizer having a thickness of 10 μm or less may be used. From the viewpoint of thickness reduction, the thickness is preferably 1 to 7. Mu.m. Such a thin polarizer is preferable in that it has little unevenness in thickness, excellent visibility, and little dimensional change, and therefore, it has excellent durability, and further, it can be thinned as a polarizing film thickness.
As a material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like can be used. Specific examples of such thermoplastic resins include: cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic polyolefin resins (for example, norbornene resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, mixtures thereof, and the like. A transparent protective film may be bonded to one side of the polarizer through an adhesive layer, and a thermosetting resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, or silicone or an ultraviolet curable resin may be used as the transparent protective film on the other side.
As a material of the transparent protective film, a cellulose resin and a (meth) acrylic resin are preferable because the above-mentioned change ratio of the surface resistance value of the transparent conductive layer to which the adhesive layer is attached can be controlled to a small level. As the (meth) acrylic resin, a (meth) acrylic resin having a lactam ring structure is preferably used. Examples of the (meth) acrylic resin having a lactam ring structure include (meth) acrylic resins having a lactam ring structure described in JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, JP-A-2002-254544, JP-A-2005-146084, and the like. In particular, cellulose resin is preferable to (meth) acrylic resin in terms of effectively suppressing cracks of the polarizer, which is a problem in the one-side protective polarizing film.
The transparent protective film may be provided with a functional layer such as a hard coat layer, an antireflection layer, an anti-sticking layer, a diffusion layer, an antiglare layer, etc. on one surface to which the polarizer is not bonded.
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 adhesives such as aqueous, solvent-based, hot-melt-based, radical-curable, and cationic-curable adhesives can be used, and aqueous adhesives or radical-curable adhesives are preferable.
Transparent layer >, transparent layer
Hereinafter, the transparent layer will be described in detail.
The thickness of the transparent layer is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, still more preferably 1.5 μm or less, still more preferably 1 μm or less, from the viewpoints of reduction in thickness and optical reliability. If the transparent layer is too thick, the thickness of the polarizing film becomes thick, and there is a concern that the optical reliability of the polarizer may be lowered. On the other hand, from the viewpoint of suppressing the fluctuation ratio of the surface resistance value of the pressure-sensitive adhesive layer to a small level, the thickness of the transparent layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.
As a material for forming the transparent layer, a material having transparency and having a predetermined ratio of change in surface resistance of the transparent conductive layer to which the adhesive layer is attached can be used. Examples of such a material include a urethane prepolymer (a) containing a reaction product of an isocyanate compound and a polyol.
The isocyanate compound is preferably a polyfunctional isocyanate compound, and specifically, a polyfunctional aromatic isocyanate compound, an alicyclic isocyanate compound, an aliphatic isocyanate compound, a dimer thereof, or the like is exemplified.
Examples of the polyfunctional aromatic isocyanate compound include: benzene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, methylenebis 4-phenyl isocyanate, p-phenylene diisocyanate, and the like.
Examples of the polyfunctional alicyclic isocyanate compound include: 1, 3-cyclopentene diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-diisocyanate methylcyclohexane, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, and the like.
Examples of the polyfunctional aliphatic isocyanate compound include: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and the like.
Examples of the polyfunctional isocyanate compound include polyfunctional isocyanate compounds having 3 or more isocyanate groups such as tris (6-isocyanatohexyl) isocyanurate.
Examples of the polyol 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-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerol, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, and the like.
In the present invention, as the urethane prepolymer (a), a material having a rigid structure in which a cyclic structure (benzene ring, cyanurate ring, isocyanurate ring, etc.) occupies a large proportion of the structure is preferably used. For example, the polyfunctional isocyanate compound may be used singly or in combination of 1 or 2 or more, but from the viewpoint of suppressing the mixing of moisture into the polarizer, an aromatic isocyanate compound is preferable. Other polyfunctional isocyanate compounds may be used in combination with the aromatic isocyanate compounds. In particular, among the aromatic isocyanate compounds, at least 1 selected from toluene diisocyanate and diphenylmethane diisocyanate is preferably used as the isocyanate compound.
As the urethane prepolymer (a), trimethylolpropane-trimethylbenzene isocyanate, trimethylolpropane-tris (diphenylmethane diisocyanate) are preferably used. The urethane prepolymer (a) is a compound having a terminal isocyanate group, and can be obtained by, for example, mixing an isocyanate compound with a polyol, stirring the mixture, and reacting the mixture. It is generally preferable to mix the isocyanate compound with the polyol in such a manner that the isocyanate groups are in excess relative to the hydroxyl groups of the polyol.
The urethane prepolymer (a) may be a urethane prepolymer having a terminal isocyanate group to which a protecting group is added. Examples of the protecting group include oximes and lactams. The urethane prepolymer in which the isocyanate groups are protected is heated to dissociate the protecting groups from the isocyanate groups, thereby reacting the isocyanate groups.
The material for forming the transparent layer may contain, in addition to the urethane prepolymer (a), a compound (b) having at least 2 functional groups having active hydrogen reactive with isocyanate groups. Examples of the functional group having an active hydrogen reactive with an isocyanate group include a hydroxyl group and an amino group. The more the number of functional groups having active hydrogen in the compound (b), the more the reaction sites with the isocyanate groups of the urethane prepolymer (a) are, the more easily a cured product is formed, and therefore the number of functional groups is preferably 3 or more.
The molecular weight of the compound (b) divided by the number of functional groups is preferably 350 or less. By defining the relationship between the molecular weight and the number of functional groups, the reactivity of the compound (b) with the isocyanate group of the urethane prepolymer (a) can be ensured.
The molecular weight of the compound (b) is preferably 1000 or less. In view of compatibility in preparing a forming material in the form of a solution together with the urethane prepolymer (a), the molecular weight of the compound (b) is preferably set to a range of 1000 or less.
As the above compound (b), for example, there can be exemplified: polyols, polyamines, compounds having hydroxyl groups and amino groups in the molecule, and the like.
Examples of the polyol include: 2-functional alcohols such as 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-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, and polypropylene glycol; 3-functional alcohols such as glycerol and trimethylolpropane; 4-functional alcohols such as pentaerythritol, hexanetriol, sorbitol, and the like; and alkylene oxide (e.g., propylene oxide) adducts of polyoxypropylene glycerol ether, polyoxypropylene trimethylolpropane ether, polyoxypropylene sorbitol ether, and the like to the above-mentioned polyols.
Examples of the polyamine include: ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4, 4' -diamine, dimer diamine, etc.
Examples of the compound having a hydroxyl group and an amino group in the molecule include: diamines having a hydroxyl group in the molecule, such as 2-hydroxyethyl ethylenediamine, 2-hydroxyethyl propylenediamine, di (2-hydroxyethyl) ethylenediamine, di (2-hydroxyethyl) propylenediamine, 2-hydroxypropyl ethylenediamine, and di (2-hydroxypropyl) ethylenediamine;
alkanolamines such as ethanolamine, diethanolamine and triethanolamine.
In view of preventing deterioration of optical reliability of the polarizer, it is preferable to use a polyol as the above-mentioned compound (b), and in view of reactivity with the urethane prepolymer (a), trimethylol propane is particularly preferable.
The above-mentioned forming material contains the above-mentioned 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 blending ratio of the compound (b) to the urethane prepolymer (a) is preferably 5% by weight or more based on 100% by weight (solid content ratio) of the total of the urethane prepolymer (a) and the compound (b). The blending ratio of the compound (b) is preferably 10% by weight or more from the viewpoint of improving the film strength. On the other hand, when the blending ratio of the compound (b) is large, deterioration of the optical reliability of the polarizer may occur, and therefore, the blending ratio of the compound (b) is preferably 80% by weight or less, more preferably 50% by weight or less.
In addition, in order to improve the reactivity of isocyanate groups, a reaction catalyst may be used as the above-mentioned forming material. The reaction catalyst is not particularly limited, and a tin-based catalyst or an amine-based catalyst is preferable. The reaction catalyst may be used in an amount of 1 or 2 or more. In general, the reaction catalyst is used in an amount of 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 speed becomes high, and foaming of the formed material is caused. Even if the foaming-finished material is used, sufficient adhesion cannot be obtained. In general, when a reaction catalyst is used, it is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.
In addition, in order to improve the reactivity of isocyanate groups, a reaction catalyst may be used. The reaction catalyst is not particularly limited, and tin-based catalysts or amine-based catalysts are suitable. The reaction catalyst may be used in an amount of 1 or 2 or more. The amount of the reaction catalyst used is usually 5 parts by weight or less relative to 100 parts by weight of the urethane prepolymer. When the amount of the reaction catalyst is large, the crosslinking reaction speed becomes high, and foaming of the formed material occurs. Even if the foaming-finished material is used, sufficient adhesion cannot be obtained. In general, when a reaction catalyst is used, it is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 4 parts by weight.
As the tin catalyst, any of inorganic and organic catalysts can be used, but organic catalysts are preferred. Examples of the inorganic tin catalyst include: stannous chloride, stannic chloride, and the like. The organotin-based catalyst is preferably a material having a skeleton such as a methyl group, an ethyl group, an ether group, or an ester group and having at least 1 organic group such as an aliphatic group or an alicyclic group. Examples include: tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate, and the like.
In addition, the amine catalyst is not particularly limited. For example, catalysts having at least 1 organic group such as alicyclic group, such as quinacridine, amidine, diazabicycloundecene, etc. are preferable. Further, triethylamine and the like are exemplified as the amine catalyst. In addition, cobalt naphthenate, benzyltrimethylammonium hydroxide, and the like can be exemplified as the reaction catalyst other than the above.
The above-mentioned forming material is usually used in the form of a solution containing the above-mentioned urethane prepolymer (a) and the above-mentioned compound (b). The solution may be solvent-based or aqueous such as emulsion, colloidal dispersion or aqueous solution.
The organic solvent is not particularly limited as long as it does not have a functional group containing active hydrogen reactive with an isocyanate group and the urethane prepolymer (a) and the compound (b) constituting the formation material are uniformly dissolved. The organic solvent may be used in an amount of 1 or 2 or more in combination. The organic solvent may be different solvents for the urethane prepolymer (a) and the compound (b). In this case, after each solution is prepared, each solution may be mixed, thereby preparing a formation material. In addition, an organic solvent may be further added to the prepared formation material, thereby adjusting the viscosity of the formation material. In the case of a solvent-based solution dissolved in an organic solvent, alcohols, water, and the like, which are exemplified below, may be contained as the solvent.
The 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; halogenated alkanes such as 1, 2-dichloroethane; ethers such as t-butyl methyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and acetylacetone.
In the case of being aqueous, for example, alcohols such as n-butanol and isopropyl alcohol, and ketones such as acetone may be blended. In the case of forming the urethane prepolymer into an aqueous form, the urethane prepolymer may be formed by using a dispersant, or by introducing a functional group having low reactivity with an isocyanate group, such as a carboxylate, sulfonate, or quaternary ammonium salt, or a water-dispersible component, such as polyethylene glycol.
< epoxy resin >)
Further, as a material for forming the transparent layer, an epoxy resin is exemplified.
As the epoxy resin, any suitable epoxy resin may be used. As the epoxy resin, an epoxy resin having an aromatic ring is preferably used. By using the epoxy resin, the change with time of the surface resistance value of the pressure-sensitive adhesive layer can be suppressed, the adhesion to the polarizer is more excellent, and discoloration from the end of the polarizer can be prevented. In addition, when the adhesive layer is formed on the transparent layer, the anchoring force of the adhesive layer can be improved. Examples of the epoxy resin having an aromatic ring include: bisphenol-type epoxy resins such as bisphenol-a-type epoxy resins, bisphenol-F-type epoxy resins, and bisphenol-S-type epoxy resins; novolac type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin and the like; glycidyl ethers of tetrahydroxyphenyl methane, glycidyl ethers of tetrahydroxybenzophenone, epoxy resins of epoxy type such as epoxidized polyvinyl phenol, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and the like. Bisphenol A type epoxy resin, biphenyl type epoxy resin, bisphenol F type epoxy resin are preferably used. By using these epoxy resins, discoloration from the end of the polarizer can be further prevented. The epoxy resin may be used in an amount of 1 or 2 or more.
The weight average molecular weight (Mw) of the epoxy resin is preferably 20000 or more, more preferably 30000 or more, and further preferably 37000 or more. By setting the weight average molecular weight of the epoxy resin to the above range, discoloration from the end of the polarizer can be further prevented. The weight average molecular weight can be measured by GPC, for example.
As the material for forming the transparent layer, for example, a composition containing a polymer (a) (hereinafter also referred to as a polymer (a)) 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 a monomer represented by the following general formula (1) and an epoxy resin (b) can be used. The content ratio of the polymer (a) to the epoxy resin (b) is preferably 95:5 to 60:40 or 40:60 to 1:99 in terms of weight ratio.
[ chemical formula 2]
(wherein X represents a functional group containing at least 1 reactive group selected from the group consisting of vinyl, (meth) acryl, styryl, (meth) acrylamide, vinyl ether, epoxy, oxetane, hydroxyl, amino, aldehyde, and carboxyl, R 1 R is R 2 Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, R 1 R is R 2 May be linked to each other to form a ring).
The content ratio of the polymer (a) to the epoxy resin (b) in the composition is 95:5 to 60:40 or 40:60 to 1:99 by weight. By setting the content ratio of the polymer (a) to the epoxy resin (b) to the above range, a resin composition for a transparent layer can be obtained which can suppress the change in the surface resistance value of the adhesive layer with time, has excellent adhesion to a polarizer, and can prevent discoloration from the end of the polarizer. In addition, when the adhesive layer is formed on the transparent layer by setting the content ratio of the polymer (a) to the epoxy resin (b) to the above range, the anchoring force of the adhesive layer can be improved. As a result, a polarizing plate (one-side protective polarizing film with a transparent layer) can be obtained that combines adhesion between the polarizer and the transparent layer and anchoring force of the adhesive layer formed on the transparent layer. The content ratio of the polymer (a) to the epoxy resin (b) is preferably 95:5 to 80:20 or 20:80 to 5:95, more preferably 90:10 to 70:30 or 30:70 to 10:90 in terms of weight ratio. The closer the content ratio of the polymer (a) to the epoxy resin (b) is to the equivalent amount (50:50), the more the protective layer may be whitened.
< Polymer (a) >)
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 a monomer represented by the general formula (1).
The polymer (a) typically has a structure represented by the following formula. The polymer (a) has a boron-containing substituent (for example, a repeating unit of k in the following formula) in a side chain by polymerizing a monomer represented by the above general formula (1) with an acrylic monomer component. This improves adhesion between the polarizer and the layer (transparent layer) formed using the resin composition. The boron-containing substituent may be contained continuously or randomly in the polymer.
The polymer (a) may be used in an amount of 1 or 2 or more.
[ chemical formula 3]
(wherein R is 6 Represents an arbitrary functional group, j and k represent integers of 1 or more).
The weight average molecular weight of the polymer (a) is preferably 10000 or more, more preferably 20000 or more, further preferably 35000 or more, particularly preferably 50000 or more. The weight average molecular weight of the polymer (a) is preferably 250000 or less, more preferably 200000 or less, and further preferably 150000 or less. When the weight average molecular weight of the polymer (a) is in the above range, the crack resistance of a layer (transparent layer) formed using the resin composition can be improved. The weight average molecular weight can be measured by GPC (solvent: dimethylformamide (DMF)).
The glass transition temperature of the polymer (a) is preferably 50℃or higher, more preferably 60℃or higher, and still more preferably 80℃or higher. The glass transition temperature of the polymer (a) is preferably 300℃or lower. When the glass transition temperature is in the above range, the crack resistance of a layer (transparent layer) formed using the resin composition can be improved.
The polymer (a) is obtained by polymerizing a monomer composition containing more than 50 parts by weight of an acrylic monomer, more than 0 parts by weight and less than 50 parts by weight of a monomer represented by the formula (1), a polymerization initiator, and any other monomer by any suitable polymerization method. As the polymerization method, solution polymerization is preferably used. By polymerizing the polymer (a) by solution polymerization, a polymer having a higher molecular weight can be obtained.
Acrylic monomer
As the acrylic monomer, any suitable acrylic monomer may be used. Examples include: (meth) acrylate monomers having a linear or branched structure and (meth) acrylate monomers having a cyclic structure. In the present specification, (meth) acrylic refers to acrylic acid and/or methacrylic acid.
Examples of the (meth) acrylic acid ester monomer having a linear or branched structure include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and the like. Methyl (meth) acrylate is preferably used. The (meth) acrylic acid ester monomer may be used in an amount of 1 or 2 or more.
Examples of the (meth) acrylic acid ester monomer having a cyclic structure include: biphenyl group-containing monomers such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, biphenyl (meth) acrylate, o-biphenoxyethyl (meth) acrylate, o-biphenoxyethoxyethyl (meth) acrylate, m-biphenoxyethyl (meth) acrylate, p-biphenoxyethyl (meth) acrylate, o-biphenoxy-2-hydroxypropyl (meth) acrylate, p-biphenoxy-2-hydroxypropyl (meth) acrylate, m-biphenoxy-2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl=carbamate, N- (meth) acryloyloxyethyl-m-biphenyl=carbamate, o-phenylphenol glycidyl ether acrylate, terphenyl (meth) acrylate, and the like. Preferably, 1-adamantyl (meth) acrylate and dicyclopentanyl (meth) acrylate are used. By using these monomers, a polymer having a high glass transition temperature can be obtained. These monomers may be used alone in 1 kind, or may be used in combination of 2 or more kinds. In the present specification, (meth) acryl means acryl and/or methacryl.
In addition, a silsesquioxane compound having a (meth) acryloyl group may be used instead of the (meth) acrylic acid ester monomer. By using a silsesquioxane compound, an acrylic polymer having a high glass transition temperature can be obtained. Silsesquioxane compounds having various skeleton structures, for example, skeletons of cage structures, ladder structures, random structures, and the like are known. The silsesquioxane compound may have only 1 kind of these structures, or may have 2 or more kinds thereof. The silsesquioxane compound may be used in an amount of 1 or 2 or more.
As the silsesquioxane compound having a (meth) acryloyl group, for example, may be used: MAC grade, AC grade of the SQ series of east asia synthesis corporation. The MAC level 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. The AC grade is an acryl-containing silsesquioxane compound, and specific examples thereof include: AC-SQ TA-100, AC-SQ SI-20, etc.
More than 50 parts by weight of acrylic monomer is used. The acrylic monomer may be used so that the total amount of the monomer represented by the above general formula (1) is 100 parts by weight.
Monomers represented by the general formula (1)
The side chain of the polymer (a) is introduced with a boron-containing substituent by using a monomer represented by the general formula (1). Therefore, it is typically possible to improve adhesion between a polarizer made of a PVA-based resin and a layer (transparent layer) formed using the resin composition. In addition, the water resistance of the layer (transparent layer) itself formed using the resin composition can be improved, and discoloration from the end of the polarizer can be prevented. The monomer may be used in an amount of 1 or 2 or more.
[ chemical formula 4]
(wherein X represents a functional group containing at least 1 reactive group selected from the group consisting of vinyl, (meth) acryl, styryl, (meth) acrylamide, vinyl ether, epoxy, oxetane, hydroxyl, amino, aldehyde, and carboxyl, R 1 R is R 2 Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, R 1 R is R 2 May be linked to each other to form a ring).
Examples of the aliphatic hydrocarbon group include a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, a cyclic alkyl group having 3 to 20 carbon atoms which may be substituted, and an alkenyl group having 2 to 20 carbon atoms. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms which may be substituted, and a naphthyl group having 10 to 20 carbon atoms which may be substituted. As the heterocyclic group, a 5-membered ring group or a 6-membered ring group containing at least 1 hetero atom which may be substituted is exemplified. R is as follows 1 R is R 2 Can be connected to each other to form a ring. R is R 1 R is R 2 Preferably a hydrogen atom, or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
The reactive group contained in the functional group represented by X is at least 1 selected from the group consisting of a vinyl group, a (meth) acryl group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an aldehyde group, and a carboxyl group. The reactive groups are preferably (meth) acryl groups and/or (meth) acrylamides. By having these reactive groups, adhesion between the polarizer and a layer (transparent layer) formed using the resin composition can be improved.
In one embodiment, the functional group represented by X is preferably represented by general formula (2): Z-Y- (wherein Z represents a functional group containing at least 1 reactive group selected from the group consisting of vinyl, (meth) acryl, styryl, (meth) acrylamide, vinyl ether, epoxy, oxetanyl, hydroxyl, amino, aldehyde, and carboxyl, and Y represents an organic group). The organic group mentioned above specifically means an organic group having 1 to 20 carbon atoms which may have a substituent, and more specifically, examples thereof include: a linear or branched alkylene group optionally having a substituent of 1 to 20 carbon atoms, a cyclic alkylene group optionally having a substituent of 3 to 20 carbon atoms, a phenylene group optionally having a substituent of 6 to 20 carbon atoms, a naphthylene group optionally having a substituent of 10 to 20 carbon atoms, and the like.
The monomer represented by the above general formula (1) may be specifically the following compound.
[ chemical formula 5]
Examples of the monomer represented by the general formula (1) include, in addition to the above-mentioned compounds, esters of hydroxyethylacrylamide and boric acid, esters of methylolacrylamide and boric acid, esters of hydroxyethyl acrylate and boric acid, esters of hydroxybutyl acrylate and boric acid, and esters of (meth) acrylic acid esters and boric acid.
The monomer represented by the above general formula (1) may be used in an amount of more than 0 parts by weight and less than 50 parts by weight. Preferably, the amount is 0.01 to less than 50 parts by weight, more preferably 0.05 to 20 parts by weight, and still more preferably 0.1 to 10 parts by weight. When the content of the monomer is more than 50 parts by weight, discoloration from the end portion becomes easy to occur.
Polymerization initiator
As the polymerization initiator, any suitable polymerization initiator may be used. Examples include: peroxides such as benzoyl peroxide, lauroyl peroxide, sodium peroxide, and the like; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile and the like. The polymerization initiator may be used in an amount of 1 or 2 or more.
The content of the polymerization initiator may be any suitable amount. The content of the polymerization initiator is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 2 parts by weight.
Polymerization methods
As described above, the polymer (a) is preferably obtained by solution polymerization of the monomer components such as the acrylic monomer and the monomer represented by the general formula (1). As the solvent used in the solution polymerization, any suitable solvent may be used. Examples include: water; alcohols such as methanol, ethanol, and isopropanol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone; tetrahydrofuran, twoCyclic ether compounds such as alkanes. These solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds. In addition, an organic solvent may be used in combination with water.
The polymerization reaction may be carried out at any suitable temperature and time. For example, the polymerization reaction may be carried out at 50℃to 100℃and preferably at 60℃to 80 ℃. The reaction time is, for example, 1 to 8 hours, preferably 3 to 5 hours.
Epoxy resin (b) >, and
as the epoxy resin (b), any suitable epoxy resin may be used. As the epoxy resin (b), an epoxy resin having an aromatic ring is preferably used. By using an epoxy resin having an aromatic ring as the epoxy resin (b), a resin composition for a transparent layer which has more excellent adhesion to a polarizer and can prevent discoloration from the end of the polarizer can be obtained. In addition, when the adhesive layer is formed on the transparent layer, the anchoring force of the adhesive layer can be improved. Examples of the epoxy resin having an aromatic ring include: bisphenol-type epoxy resins such as bisphenol-a-type epoxy resins, bisphenol-F-type epoxy resins, and bisphenol-S-type epoxy resins; novolac type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin and the like; glycidyl ethers of tetrahydroxyphenyl methane, glycidyl ethers of tetrahydroxybenzophenone, epoxy resins of epoxy type such as epoxidized polyvinyl phenol, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and the like. Bisphenol A type epoxy resin, biphenyl type epoxy resin, bisphenol F type epoxy resin are preferably used. By using these epoxy resins, discoloration from the end of the polarizer can be further prevented. The epoxy resin may be used in an amount of 1 or 2 or more.
The weight average molecular weight (Mw) of the epoxy resin (b) is preferably 20000 or more, more preferably 30000 or more, and further preferably 37000 or more. By setting the weight average molecular weight of the epoxy resin (b) to the above range, discoloration from the end of the polarizer can be further prevented. The weight average molecular weight can be measured by GPC, for example.
< other Components >)
The resin composition for transparent layer may contain any appropriate other components in addition to the epoxy resin, the polymer (a) and the epoxy resin (b). Examples of the other components include: solvents, and additives. As the solvent, a solvent which can be used in the solution polymerization of the polymer (a) may be used, or other solvents may be used. As other solvents, ethyl acetate, toluene, methyl ethyl ketone, cyclopentanone are preferably used. These solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
As the additive, any suitable additive may be used. Examples include: surfactant, ultraviolet absorber, antioxidant, tackifier, etc. The additive may be used in an amount of 1 or 2 or more. These additives may be used in any suitable amount.
Preparation method of resin composition for transparent layer
The resin composition for transparent layer may be prepared by any suitable method. For example, the polymer (a), the epoxy resin (b), and any appropriate additive used as needed may be mixed in any appropriate solvent. In the case of polymerizing the polymer (a) by solution polymerization, the polymer (a) can be prepared by adding and mixing the epoxy resin (b) and any appropriate additives to a polymerization solution of the polymer (a).
Examples of the transparent layer-forming material other than the urethane prepolymer (a) -containing forming material, the epoxy resin-containing forming material, and the composition containing the polymer (a) and the epoxy resin (b) include: cyanoacrylate-forming materials, epoxy-forming materials, urethane acrylate-forming materials, and the like.
The formation of the transparent layer may be appropriately selected depending on the kind of the formation material, and for example, the formation material may be applied to a polarizer or the like and then cured, and the transparent layer may be obtained as a coating layer. This is generally done by the following method: after the application, the cured layer is formed by drying at about 30 to 100 ℃, preferably about 50 to 80 ℃ for about 0.5 to 15 minutes. In the case where the above-mentioned forming material contains an isocyanate component, the annealing treatment may be performed at about 30 to 100 ℃, preferably about 50 to 80 ℃ for about 0.5 to 24 hours in order to promote the reaction.
< adhesive layer >)
The adhesive layer is formed of an adhesive. As the binder, various binders can be used, and examples thereof include: rubber-based adhesives, acrylic adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl pyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, and the like. The adhesive base polymer is selected according to the kind of the above adhesive. Among the above adhesives, acrylic adhesives are preferably used in view of excellent optical transparency, excellent adhesion characteristics such as suitable wettability, cohesiveness and adhesiveness, and excellent weather resistance and heat resistance.
The acrylic adhesive is prepared from an adhesive composition containing a (meth) acrylic polymer (A). Hereinafter, the adhesive composition will be described.
The (meth) acrylic polymer (a) contains an alkyl (meth) acrylate (a 1) as a monomer unit as a main component. The term "meth" acrylate means an acrylate and/or a methacrylate, and the meaning of the term "meth" is the same as that of the present invention.
As the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer (a), there may be exemplified a linear or branched alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, dodecyl, isotetradecyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl. They may be used alone or in combination. The average number of carbon atoms of these alkyl groups is preferably 3 to 9.
The weight ratio of the alkyl (meth) acrylate (a 1) in the weight ratio of all the constituent monomers (100% by weight) constituting the (meth) acrylic polymer (a) is preferably 70% by weight or more in terms of the monomer units. The weight ratio of the alkyl (meth) acrylate (a 1) may be considered to be the remainder of the other comonomer. The weight ratio of the alkyl (meth) acrylate (a 1) is preferably set to the above range in order to ensure adhesion.
For the purpose of improving the adhesion and heat resistance, 1 or more kinds of comonomers having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or vinyl group may be copolymerized in the (meth) acrylic polymer (a) in addition to the monomer unit of the alkyl (meth) acrylate (a 1).
As the above comonomer, for example, there can be exemplified: amide group-containing monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, and the like. Among these, the amide group-containing monomer (a 2) is preferable when the ionic compound (B) described later is blended.
When an amide group introduced into a side chain of the (meth) acrylic polymer (a) as a base polymer is present in the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer, the presence of the amide group is preferable in that the pressure-sensitive adhesive layer can be prevented from increasing in terms of fluctuation in surface resistance value of the pressure-sensitive adhesive layer adjusted by blending the ionic compound (B) even in a humidified environment, and is kept within a desired value range. The presence of the amide group introduced into the side chain of the (meth) acrylic polymer (a) as a functional group of the comonomer is considered to improve the compatibility of the (meth) acrylic polymer (a) with the ionic compound (B).
In addition, when the adhesive layer has an amide group introduced into a side chain of the (meth) acrylic polymer (a) as a base polymer, durability against both glass and a transparent conductive layer (ITO layer or the like) is good, and peeling, tilting or the like can be suppressed in a state of being attached to a liquid crystal panel. In addition, durability can be satisfied even in a humidified environment (after a humidification reliability test).
The amide group-containing monomer (a 2) is a compound having an amide group in its structure and having a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Specific examples of the amide group-containing monomer (a 2) include acrylamide-based monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-isopropyl acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-hydroxymethyl-N-propyl (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl (meth) acrylamide, mercaptoethyl (meth) acrylamide, and the like; n-acryl heterocyclic monomers such as N- (meth) acryl morpholine, N- (meth) acryl piperidine, and N- (meth) acryl pyrrolidine; n-vinyl lactam-containing monomers such as N-vinylpyrrolidone and N-vinyl-epsilon-caprolactam. The amide group-containing monomer (a 2) is preferable in terms of suppressing an increase in the surface resistance value with time (particularly in a humidified environment) and satisfying durability. In particular, among the amide group-containing monomers (a 2), the N-vinyl lactam-containing monomers are preferable in terms of suppressing an increase in the surface resistance value and satisfying durability against the transparent conductive layer (touch sensor layer) in the case of time (in particular, in a humidified environment). Although not illustrated in the above, the amide group-containing monomer having a hydroxyl group tends to improve conductivity when combined with the ionic compound (B), and when the proportion of the amide group-containing monomer having a hydroxyl group to be used increases, there are problems in anchoring force with a polarizing film (optical film) and reworkability with a transparent conductive layer (touch sensor layer), and therefore, it is preferable not to use the compound.
The weight ratio of the amide group-containing monomer (a 2) is preferably 0.1% by weight or more from the viewpoint of suppressing an increase in the surface resistance value with time (particularly in a humidified environment). The weight ratio is preferably 0.3% by weight or more, more preferably 0.5% by weight or more. On the other hand, if the weight ratio becomes too large, the anchoring property to a base film such as a polarizing film tends to be lowered, and therefore, the weight ratio is preferably 35% by weight or less, more preferably 30% by weight or less, and further preferably 25% by weight or less.
The carboxyl group-containing monomer is a compound having a carbonyl group in its structure and having a polymerizable unsaturated double bond such as a (meth) acryloyl group or vinyl group. Specific examples of the carboxyl group-containing monomer include, for example: carboxylic ethyl (meth) acrylate, carboxylic pentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. Among the carboxyl group-containing monomers, acrylic acid is preferred from the viewpoints of copolymerizability, price and adhesive properties.
The hydroxyl group-containing monomer is a compound having a hydroxyl group in its structure and containing a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group. Specific examples of the hydroxyl group-containing monomer include, for example: 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, hydroxyalkyl (meth) acrylates such as 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl acrylate. Among the above hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate are preferred, and 4-hydroxybutyl (meth) acrylate is particularly preferred from the viewpoint of durability.
When the adhesive composition contains a crosslinking agent, the carboxyl group-containing monomer and the hydroxyl group-containing monomer form reaction sites with the crosslinking agent. Since the carboxyl group-containing monomer, the hydroxyl group-containing monomer and the intermolecular crosslinking agent have high reactivity, the carboxyl group-containing monomer and the intermolecular crosslinking agent are preferably used in order to improve the cohesiveness and heat resistance of the obtained adhesive layer. The carboxyl group-containing monomer is preferable in terms of durability and reworkability, and the hydroxyl group-containing monomer is preferable in terms of reworkability.
The weight ratio of the carboxyl group-containing monomer is preferably 2% by weight or less, more preferably 0.01 to 2% by weight, still more preferably 0.05 to 1.5% by weight, still more preferably 0.1 to 1% by weight, and most preferably 0.1 to 0.5% by weight. The weight ratio of the carboxyl group-containing monomer is preferably 0.01% by weight or more in terms of durability. On the other hand, if it exceeds 2 wt%, it is not preferable in view of re-operability. The carboxyl group-containing monomer may not be particularly used in terms of suppressing corrosion of the transparent conductive layer.
The above weight ratio of the hydroxyl group-containing monomer is preferably 3% by weight or less, more preferably 0.01 to 3% by weight, still more preferably 0.1 to 2% by weight, still more preferably 0.2 to 2% by weight. From the viewpoint of crosslinking the pressure-sensitive adhesive layer, durability, and adhesive properties, the weight ratio of the hydroxyl group-containing monomer is preferably 0.01% by weight or more. On the other hand, if it exceeds 3 wt%, it is not preferable in terms of durability.
In addition, as the comonomer, for example, can be used: aromatic ring-containing (meth) acrylates. The aromatic ring-containing (meth) acrylate is a compound having an aromatic ring structure in its structure and containing a (meth) acryloyl group. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring.
Specific examples of the aromatic ring-containing (meth) acrylate include: benzyl (meth) acrylate, phenyl (meth) acrylate, o-phenylphenol (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, ethylene oxide modified cresol (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, toluene (meth) acrylate, styrene (meth) acrylate and other (meth) acrylates having a benzene ring; (meth) acrylates having a naphthalene ring, such as hydroxyethylated β -naphthol acrylate, 2-naphthylethyl (meth) acrylate, 2-naphthyloxyethyl acrylate, 2- (4-methoxy-1-naphthyloxyethyl (meth) acrylate, and the like; aromatic ring-containing (meth) acrylates having a biphenyl ring, such as biphenyl (meth) acrylate.
The aromatic ring-containing (meth) acrylate is preferably benzyl (meth) acrylate or phenoxyethyl (meth) acrylate, and particularly preferably phenoxyethyl (meth) acrylate, in view of the 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, still more preferably 10 to 22% by weight, and still more preferably 14 to 20% by weight. When the weight ratio of the aromatic ring-containing (meth) acrylate is 3% by weight or more, it is preferable to suppress the occurrence of the irregular square. On the other hand, when the content is more than 25% by weight, the suppression of unevenness is insufficient, and durability tends to be lowered.
Specific examples of the other comonomers other than the above include anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; sulfonic acid group-containing monomers such as allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidopropane sulfonic acid, and sulfopropyl (meth) acrylate; and phosphate group-containing monomers such as 2-hydroxyethyl acryloyl phosphate.
Examples of the monomer for modification include: alkylaminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate and the like; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; succinimide-based monomers such as N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, and N- (meth) acryloyl-8-oxyoctamethylene succinimide; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-dodecylmaleimide and N-phenylmaleimide; and (3) a itaconimide monomer such as N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide and N-dodecyl itaconimide.
Further, as the modifying monomer, vinyl monomers such as vinyl acetate and vinyl propionate may be used; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; glycol (meth) acrylates such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, fluorine-containing (meth) acrylate, silicone (meth) acrylate, 2-methoxyethyl acrylate, and other acrylic monomers. Further, isoprene, butadiene, isobutylene, vinyl ether and the like are exemplified.
Further, as the copolymerizable monomer other than the above, a silane-based monomer containing a silicon atom and the like can be mentioned. Examples of the silane monomer include: 3-acryloxypropyl triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyl trimethoxysilane, 4-vinylbutyl triethoxysilane, 8-vinyloctyl trimethoxysilane, 8-vinyloctyl triethoxysilane, 10-methacryloxydecyl trimethoxysilane, 10-acryloxydecyl trimethoxysilane, 10-methacryloxydecyl triethoxysilane, 10-acryloxydecyl triethoxysilane, and the like.
In addition, as the comonomer, it is possible to use: and (3) a multifunctional monomer having 2 or more unsaturated double bonds such as (meth) acryloyl groups and vinyl groups, such as an esterified product of (meth) acrylic acid and a polyhydric alcohol, such as tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol a diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like, a polyester (meth) acrylate, an epoxy (meth) acrylate, a urethane (meth) acrylate, and the like, wherein 2 or more unsaturated double bonds such as (meth) acryloyl groups and vinyl groups are added to a skeleton such as a polyester, an epoxy, a urethane or the like, as the same functional group as the monomer component.
The proportion of the other comonomer in the (meth) acrylic polymer (a) is preferably about 0 to 10%, more preferably about 0 to 7%, and even more preferably about 0 to 5% by weight of the total constituent monomers (100% by weight) of the (meth) acrylic polymer (a).
The weight average molecular weight of the (meth) acrylic polymer (A) of the present invention is usually preferably 100 to 250 tens of thousands. In view of durability, particularly heat resistance, the weight average molecular weight is preferably 120 to 200 ten thousand. When the weight average molecular weight is 100 ten thousand or more, it is preferable in terms of heat resistance. In addition, when the weight average molecular weight is more than 250 ten thousand, the adhesive tends to be easily hardened, and peeling easily occurs. The weight average molecular weight (Mw)/number average molecular weight (Mn) representing the molecular weight distribution is preferably 1.8 or more and 10 or less, more preferably 1.8 to 7, and still more preferably 1.8 to 5. When the molecular weight distribution (Mw/Mn) is more than 10, it is not preferable in terms of durability. The weight average molecular weight and molecular weight distribution (Mw/Mn) were obtained from values measured by GPC (gel permeation chromatography) and calculated by conversion to polystyrene.
The production of the (meth) acrylic polymer (a) can be carried out by appropriately selecting known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerization. The (meth) acrylic polymer (a) may be any copolymer such as a random copolymer, a block copolymer, or a graft copolymer.
In the solution polymerization, for example, ethyl acetate, toluene, or the like is used as a polymerization solvent. As a specific example of the solution polymerization, the reaction is carried out under a reaction condition in which a polymerization initiator is added under a flow of an inert gas such as nitrogen, usually at about 50 to 70℃for about 5 to 30 hours.
The polymerization initiator, chain transfer agent, emulsifier, etc. used in the radical polymerization are not particularly limited, and may be appropriately selected and used. The weight average molecular weight of the (meth) acrylic polymer (a) can be controlled according to the amount of the polymerization initiator, the amount of the chain transfer agent, and the reaction conditions, and the amount thereof can be appropriately adjusted according to the type thereof.
The adhesive composition of the present invention contains an ionic compound (B). As ionic compound (B), alkali metal salts and/or organic cation-anion salts can be preferably used. The alkali metal salt may be an organic salt or an inorganic salt of an alkali metal. In the present invention, the term "organic cation-anion salt" refers to an organic salt having a cation portion composed of an organic substance, and an anion portion may be an organic substance or an inorganic substance. "organic cation-anion salts" are also referred to as ionic liquids, ionic solids. By containing the ionic compound (B) in the pressure-sensitive adhesive layer, the surface resistance value of the pressure-sensitive adhesive layer can be reduced, generation of static electricity can be suppressed, and light leakage (charging unevenness) caused by disturbance of alignment of the liquid crystal layer due to charging can be suppressed more efficiently.
< alkali Metal salt >
Examples of the alkali metal ion constituting the cation portion of the alkali metal salt include ions of lithium, sodium, potassium, and the like. Among these alkali metal ions, lithium ions are preferred.
The anion part of the alkali metal salt may be formed of an organic material or an inorganic material. Examples of the anion unit constituting the organic salt include: CH (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- Anions represented by the following general formulae (A) to (D), and the like.
(A)：(C n F 2n+1 SO 2 ) 2 N - (wherein n is an integer of 10 to 10),
(B)：CF 2 (C m F 2m SO 2 ) 2 N - (wherein m is an integer of 1 to 10),
(C)： - O 3 S(CF 2 ) l SO 3 - (wherein l is an integer of 1 to 10),
(D)：(C p F 2p+1 SO 2 )N - (C q F 2q+1 SO 2 ) (wherein, p and q are integers of 1 to 10).
In particular, an ionic compound having good ionization can be obtained in the anion portion containing a fluorine atom, and thus is preferably used. As the anion part constituting the inorganic salt, cl can be used - 、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. As the anion part, (CF) is preferable 3 SO 2 ) 2 N - 、(C 2 F 5 SO 2 ) 2 N - (perfluoroalkylsulfonyl) imides of the above-mentioned general formula (A) are, in particular, (CF) is preferred 3 SO 2 ) 2 N - The trifluoromethanesulfonyl imide shown.
Specific examples of the organic salt of an alkali metal include: sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, liCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、Li(CF 3 SO 2 ) 2 N、Li(C 2 F 5 SO 2 ) 2 N、Li(C 4 F 9 SO 2 ) 2 N、Li(CF 3 SO 2 ) 3 C、KO 3 S(CF 2 ) 3 SO 3 K、LiO 3 S(CF 2 ) 3 SO 3 K, etc., among these, liCF is preferred 3 SO 3 、Li(CF 3 SO 2 ) 2 N、Li(C 2 F 5 SO 2 ) 2 N、Li(C 4 F 9 SO 2 ) 2 N、Li(CF 3 SO 2 ) 3 C, etc., more preferably Li (CF) 3 SO 2 ) 2 N、Li(C 2 F 5 SO 2 ) 2 N、Li(C 4 F 9 SO 2 ) 2 Lithium salts of fluorine-containing imides in the form of lithium bis (fluorosulfonyl) imide salts such as N are particularly preferred. Further, 4, 5-tetrafluoro-1, 3, 2-dithiazolidine-1, 3-lithium tetraoxide salts and the like are exemplified.
Examples of the inorganic salt of an alkali metal include lithium perchlorate and lithium iodide.
< organic cation-anion salt >
The organic cation-anion salt used in the present invention is composed of a cation component and an anion component,the cation component is composed of an organic substance. Specific examples of the cationic component include: pyridine compoundCation, piperidine->Cation, pyrrolidine->Cations, cations having a pyrroline skeleton, imidazole +.>Cationic, tetrahydropyrimidine->Cationic, dihydropyrimidine->Cation, pyrazole->Cationic, pyrazoline->Cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl +.>Cations, and the like.
Examples of the anionic component include: cl - 、Br - 、I - 、AlCl 4 - 、Al 2 Cl 7 - 、BF 4 - 、PF 6 - 、ClO 4 - 、NO 3 - 、CH 3 COO - 、CF 3 COO - 、CH 3 SO 3 - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 3 C - 、AsF 6 - 、SbF 6 - 、NbF 6 - 、TaF 6 - 、(CN) 2 N - 、C 4 F 9 SO 3 - 、C 3 F 7 COO - 、(CF 3 SO 2 )(CF 3 CO)N - 、 - O 3 S(CF 2 ) 3 SO 3 - Anions represented by the following general formulae (A) to (D), and the like.
(A)：(C n F 2n+1 SO 2 ) 2 N - (wherein n is an integer of 0 to 10),
(B)：CF 2 (C m F 2m SO 2 ) 2 N - (wherein m is an integer of 1 to 10),
(C)： - O 3 S(CF 2 ) l SO 3 - (wherein l is an integer of 1 to 10),
(D)：(C p F 2p+1 SO 2 )N - (C q F 2q+1 SO 2 ) (wherein, p and q are integers of 1 to 10).
Among them, particularly, an anionic component containing a fluorine atom is preferably used because an ionic compound having good ionization can be obtained.
The organic cation-anion salt is suitably selected from compounds comprising a combination of the above-mentioned cation component and anion component. Preferable specific examples of the organic cation-anion salt include, for example: methyl trioctylammonium bis (trifluoromethylsulfonyl) imide, 1-methyl-1-propylpyrrolidine Bis (trifluoromethanesulfonyl) imide, ethylmethylimidazole +.>Bis (fluorosulfonyl imide). Of these, 1-methyl-1-propylpyrrolidine is more preferable>Bis (trifluoromethanesulfonyl) imide, ethylmethylimidazole +.>Bis (fluorosulfonyl imide).
The ionic compound (B) may be an inorganic salt such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, or ammonium sulfate, in addition to the alkali metal salt and the organic cation-anion salt.
The ionic compound (B) may be used alone or in combination of plural kinds in order to obtain a desired resistance value. In particular, to control the surface resistance value of the adhesive layer to be 1×10 10 ～1×10 12 When the range of Ω/≡is in the range, the alkali metal salt is preferable as the ionic compound (B) in terms of improving antistatic performance, and even if the amount of the alkali metal salt to be blended is small, an adhesive having high antistatic performance can be obtained. On the other hand, to control the surface resistance value of the adhesive layer to 1X 10 8 ～1×10 10 In the case where Ω/≡is in the range, the ionic compound (B) is preferably an organic cation-anion salt from the viewpoint of improving antistatic performance, and even if the amount of the organic cation-anion salt to be blended is small, an adhesive having high antistatic performance can be obtained.
The proportion of the ionic compound (B) in the adhesive composition of the present invention may be appropriately adjusted so that the antistatic property of the adhesive layer and the sensitivity of the touch panel are satisfied. For example, it is preferable to consider the weight ratio of the amide group-containing monomer (a 2) introduced into the (meth) acrylic polymer (a), the kind of transparent protective film of the polarizing film, and the like, and to adjust the ratio of the ionic compound (B) so that the surface resistance value of the adhesive layer becomes 1.0×10 according to the kind of liquid crystal panel incorporating the touch sensing function 8 ～1.0×10 12 Omega/≡. For example, in the liquid crystal panel with built-in touch sensing function shown in fig. 4, it is preferable to use an adhesive layerIs controlled to be 1 x 10 8 ～1×10 10 Omega/≡. In the liquid crystal panel of the semi-embedded type shown in fig. 5 or the embedded type built-in touch sensor function shown in fig. 6, it is preferable that the initial surface resistance value of the adhesive layer is controlled to be 1×10 10 ～1×10 12 Omega/≡.
When the amount of the ionic compound (B) increases, the ionic compound (B) may precipitate, and further, humidification peeling may easily occur. The proportion of the ionic compound (B) is, for example, generally preferably 40 parts by weight or less, more preferably 30 parts by weight or less, further preferably 20 parts by weight or less, and most preferably 10 parts by weight or less, based on 100 parts by weight of the (meth) acrylic polymer (a). On the other hand, the use of the ionic compound (B) in an amount of 0.01 parts by weight or more is preferable in terms of improvement of antistatic properties. From this viewpoint, the ionic compound (B) is preferably 0.1 part by weight or more, more preferably 0.5 part by weight or more. On the other hand, if the ionic compound (B) increases, the surface resistance value becomes too low, and there is a possibility that the sensitivity of the touch panel may be lowered due to a baseline fluctuation (malfunction at the time of touch caused by the surface resistance value being too low).
The adhesive composition of the present invention may contain a crosslinking agent (C). As the crosslinking agent (C), an organic crosslinking agent or a polyfunctional metal chelate can be used. Examples of the organic crosslinking agent include: isocyanate-based crosslinking agents, peroxide-based crosslinking agents, epoxy-based crosslinking agents, imine-based crosslinking agents, and the like. The polyfunctional metal chelate is a chelate obtained by covalently or coordinately bonding a polyvalent metal and an organic compound. As the polyvalent metal atom, al, cr, zr, co, cu, fe, ni, V, zn, in, ca, mg, mn, Y, ce, sr, ba, mo, la, sn, ti can be exemplified. Examples of the atoms in the covalently or coordinately bonded organic compound include oxygen atoms, and examples of the organic compound include alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, and ketone compounds.
As the crosslinking agent (C), an isocyanate-based crosslinking agent and/or a peroxide-based crosslinking agent is preferable.
As the isocyanate-based crosslinking agent (C), a compound having at least 2 isocyanate groups can be used. For example, a known aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate and the like which are generally used in urethanization reaction can be used.
The peroxide may be used suitably as long as it is a peroxide that generates a radical active species by heating or light irradiation and crosslinks a base polymer of the adhesive composition, but in view of handleability and stability, it is preferable to use a peroxide having a 1-minute half-life temperature of 80 to 160 ℃, and more preferable to use a peroxide having a 1-minute half-life temperature of 90 to 140 ℃.
Examples of the peroxide that can be used include: di (2-ethylhexyl) peroxydicarbonate (1-min half-life temperature: 90.6 ℃), di (4-t-butylcyclohexyl) peroxydicarbonate (1-min half-life temperature: 92.1 ℃), di (sec-butyl) peroxydicarbonate (1-min half-life temperature: 92.4 ℃), t-butyl peroxyneodecanoate (1-min half-life temperature: 103.5 ℃), t-hexyl peroxypivalate (1-min half-life temperature: 109.1 ℃), t-butyl peroxypivalate (1-min half-life temperature: 110.3 ℃), dilauroyl peroxide (1-min half-life temperature: 116.4 ℃), di (1-min half-life temperature: 117.4 ℃), di (1, 3-tetramethylbutyl) peroxy2-ethylhexanoate (1-min half-life temperature: 124.3 ℃), di (4-methylbenzoyl) peroxide (1-min half-life temperature: 128.2 ℃), t-butyl peroxyisobutyrate (1-min half-life temperature: 109.1-min half-life temperature: 1-life temperature: 136; 1-cyclohexane (1-t-life temperature: 149 ℃)). Among them, bis (4-t-butylcyclohexyl) peroxydicarbonate (1-minute half-life temperature: 92.1 ℃ C.), dilauryl peroxide (1-minute half-life temperature: 116.4 ℃ C.), dibenzoyl peroxide (1-minute half-life temperature: 130.0 ℃ C.), and the like can be preferably used because of particularly excellent crosslinking reaction efficiency.
The amount of the crosslinking agent (C) is preferably 3 parts by weight or less, more preferably 0.01 to 3 parts by weight, still more preferably 0.02 to 2 parts by weight, and still more preferably 0.03 to 1 part by weight based on 100 parts by weight of the (meth) acrylic polymer (A). If the amount of the crosslinking agent (C) is less than 0.01 part by weight, the adhesive layer may be insufficiently crosslinked to fail to satisfy durability and adhesive properties, whereas if it is more than 3 parts by weight, the adhesive layer may be excessively hard and durability may be deteriorated.
The adhesive composition of the present invention may contain a silane coupling agent (D). By using the silane coupling agent (D), durability can be improved. Specific examples of the silane coupling agent include: epoxy-containing silane coupling agents such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, amino-containing silane coupling agents such as 3-aminopropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyldimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, N-phenyl-gamma-aminopropyl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, and isocyanate-containing silane coupling agents such as 3-isocyanatopropyl triethoxysilane. As the silane coupling exemplified above, an epoxy group-containing silane coupling agent is preferable.
As the silane coupling agent (D), a silane coupling agent having a plurality of alkoxysilyl groups in the molecule may be used. Specific examples include: x-41-1053, X-41-1059, A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, etc. manufactured by Xinyue chemical Co. These silane coupling agents having a plurality of alkoxysilyl groups in the molecule are not easily volatilized, and are preferable because having a plurality of alkoxysilyl groups is effective for improving durability. In particular, when the adherend of the optical film with the pressure-sensitive adhesive layer is a transparent conductive layer (for example, ITO or the like) which is less susceptible to alkoxysilyl groups than glass, durability is also suitable. The silane coupling agent having a plurality of alkoxysilyl groups in the molecule is preferably one having an epoxy group in the molecule, and more preferably one having a plurality of epoxy groups in the molecule. Silane coupling agents having a plurality of alkoxysilyl groups in the molecule and epoxy groups tend to have good durability even when the adherend is a transparent conductive layer (for example, ITO or the like). Specific examples of the silane coupling agent having a plurality of alkoxysilyl groups and epoxy groups in the molecule include X-41-1053 and X-41-1059-A, X-41-1056 manufactured by Xinshi chemical Co., ltd, and X-41-1056 manufactured by Xinshi chemical Co., ltd. Having a large epoxy group content is particularly preferable.
The silane coupling agent (D) may be used alone or in combination of 2 or more kinds, and the total content thereof is preferably 5 parts by weight or less, more preferably 0.001 to 5 parts by weight, still more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 1 part by weight, still more preferably 0.05 to 0.6 part by weight, based on 100 parts by weight of the (meth) acrylic polymer (a), to improve the durability.
The adhesive composition of the present invention may contain a polyether compound (E) having a reactive silyl group. The polyether compound (E) is preferable in that the re-operability can be improved. The polyether compound (E) may be a polyether compound disclosed in, for example, japanese patent application laid-open No. 2010-275522.
The proportion of the polyether compound (E) in the adhesive composition of the present invention is preferably 10 parts by weight or less, and preferably 0.001 to 10 parts by weight, relative to 100 parts by weight of the (meth) acrylic polymer (a). When the polyether compound (E) is less than 0.001 parts by weight, the effect of improving the reworkability may be insufficient. The polyether compound (E) is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more. On the other hand, when the polyether compound (E) is more than 10 parts by weight, it is not preferable in terms of durability. The polyether compound (E) is preferably 5 parts by weight or less, more preferably 2 parts by weight or less. The proportion of the polyether compound (E) may be set to a preferable range by using the upper limit or the lower limit.
The pressure-sensitive adhesive composition of the present invention may contain other known additives, for example, a polyether compound such as polyalkylene glycol, a colorant, a pigment or the like, a powder, a dye, a surfactant, a plasticizer, a thickener, a surface lubricant, a leveling agent, a softener, an antioxidant, an anti-aging agent, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, an inorganic or organic filler, a metal powder, a granule, a foil or the like, as appropriate depending on the application. In addition, redox compounds added with a reducing agent may be used within a controllable range. These additives are used preferably in a range of 5 parts by weight or less, more preferably 3 parts by weight or less, still more preferably 1 part by weight or less, relative to 100 parts by weight of the (meth) acrylic polymer (a).
As a method for forming the adhesive layer, for example, a method in which the adhesive composition is applied to a separator or the like subjected to a peeling treatment, and after drying to remove a polymerization solvent or the like, the adhesive layer is formed and then transferred to an optical film (polarizing film) can be used; or a method of forming an adhesive layer on an optical film by applying the adhesive composition to an optical film (polarizing film), and drying to remove a polymerization solvent or the like. In the case of applying the adhesive, one or more solvents other than the polymerization solvent may be newly added.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is, for example, about 1 to 100. Mu.m, preferably 2 to 50. Mu.m, more preferably 2 to 40. Mu.m, still more preferably 5 to 35. Mu.m.
< conductive layer >)
The thickness of the conductive layer d is preferably 1 μm or less, more preferably 0.01 to 0.5 μm, still more preferably 0.01 to 0.2 μm, and still more preferably 0.01 to 0.1 μm, from the viewpoint of stability of the surface resistance value and adhesion to the adhesive layer 21. In addition, from the viewpoint of antistatic function, the surface resistance value of the conductive layer d is preferably 1×10 8 ～1×10 12 Ω/≡, more preferably 1×10 8 ～1×10 11 Ω/≡, more preferably 1×10 8 ～1×10 10 Ω。
The conductive layer may be formed of various antistatic compositions. As the antistatic agent for forming the conductive layer, ionic surfactants, conductive polymers, conductive fine particles, carbon nanotubes, and the like can be used.
Among these antistatic agents, conductive polymers and carbon nanotubes are preferably used from the viewpoints of optical characteristics, appearance, antistatic effects, and stability of antistatic effects when heated and humidified. Particularly, a conductive polymer such as polyaniline or polythiophene is preferably used. The conductive polymer may be an organic solvent-soluble, water-soluble or water-dispersible polymer, and preferably a water-soluble conductive polymer or a water-dispersible conductive polymer. This is because the water-soluble conductive polymer and the water-dispersible conductive polymer can be prepared as an aqueous solution or an aqueous dispersion to form a coating liquid for forming an antistatic layer, and the coating liquid does not require a nonaqueous organic solvent, and can suppress the denaturation of the optical film substrate due to the organic solvent. The aqueous solution or dispersion may contain an aqueous solvent other than water. Examples may include: alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, isopentyl alcohol, sec-pentanol, t-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, and cyclohexanol.
The water-soluble conductive polymer such as polyaniline and polythiophene and the water-dispersible conductive polymer preferably have a hydrophilic functional group in the molecule. Examples of the hydrophilic functional group include: a sulfonic acid group, an amino group, an amide group, an imide group, a quaternary ammonium salt group, a hydroxyl group, a mercapto group, a hydrazine group, a carboxyl group, a sulfate group, a phosphate group, or a salt thereof, or the like. The water-soluble conductive polymer or the water-dispersible conductive polymer can be easily prepared by having a hydrophilic functional group in a molecule, which is easily dissolved in water and easily dispersed in water in a particulate form.
Examples of the commercially available water-soluble conductive polymer include polyaniline sulfonic acid (150000 in terms of weight average molecular weight converted to polystyrene, manufactured by Mitsubishi Yang Zhushi Co., ltd.). Examples of the commercial products of the water-dispersible conductive polymer include polythiophene-based conductive polymers (trade name Denatron series, manufactured by Nagase Chemtex).
In addition, as a material for forming the conductive layer, a binder component may be added together with the antistatic agent in order to improve film formability of the antistatic agent, adhesiveness to an optical film, and the like. In the case where the antistatic agent is a water-soluble conductive polymer or an aqueous material of a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. As examples of the binder, there may be mentioned: containing Oxazoline-based polymers, polyurethane-based resins, polyester-based resins, acrylic resins, polyether-based resins, cellulose-based resins, polyvinyl alcohol-based resins, epoxy resins, polyvinylpyrrolidone, polystyrene-based resins, polyethylene glycol, pentaerythritol, and the like. Particularly preferred are polyurethane resins, polyester resins, and acrylic resins. These binders may be used in an amount of 1 or 2 or more in combination as appropriate for the purpose.
The amount of antistatic agent and binder may vary depending on the kind thereof, but is preferably such that the surface resistance value of the resulting conductive layer becomes 1X 10 8 ～1×10 12 Ω/≡is controlled.
< laminate >
Hereinafter, a description will be given of the laminate shown in fig. 3, which is the transparent conductive layer formed by bonding the adhesive layer of the polarizing film with an adhesive layer to the transparent conductive substrate having the transparent conductive layer on the transparent substrate.
The material constituting the transparent conductive layer of the transparent conductive substrate is not particularly limited, and a metal oxide of at least one metal selected from indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten can be used. The metal oxide may further contain the metal atoms as shown above, if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, or the like is preferably used, and ITO is particularly preferably used. The ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
The ITO may be crystalline ITO or amorphous ITO, and is preferably used.
Examples of the transparent conductive layer of the transparent conductive substrate include a metal mesh formed by forming fine metal wires in a lattice pattern and a transparent conductive layer formed by coating fine metal particles. Any suitable metal (including alloy materials) may be used as the constituent metal material as long as it is a metal having high conductivity. Specifically, for example, 1 or more metals selected from gold, platinum, silver, aluminum and copper are preferable, and aluminum, silver, copper or gold is preferable from the viewpoint of conductivity.
The thickness of the transparent conductive layer is not particularly limited, but is preferably 10nm to 1000nm, more preferably 50 to 400nm.
The method for forming the transparent conductive layer is not particularly limited, and conventionally known methods can be used. Specifically, for example, a vacuum vapor deposition method, a sputtering method, and an ion plating method can be exemplified. In the case of applying the coating liquid, examples thereof include: micro gravure coating, roll coating, dip coating, flow coating, spin coating, die coating, cast transfer, spray coating, and the like. In addition, in the case of a metal mesh, it can be obtained by, for example, the following method: a photosensitive composition (composition for forming a transparent conductive layer) containing a silver salt is applied to an adherend such as a release film, and then subjected to exposure treatment and development treatment to form fine metal wires into a predetermined pattern. The transparent conductive layer may be obtained by printing a paste (composition for forming a transparent conductive layer) containing fine metal particles into a predetermined pattern. In addition, a suitable method may be employed 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 transparent resin film base materials. The transparent resin film substrate may be the substrate described above.
If necessary, an undercoat layer, an anti-oligomer layer, or the like may be provided between the transparent conductive layer and the transparent substrate.
For example, the laminate of the present invention can be suitably used for the production of a substrate (member) constituting a device such as an image display device (liquid crystal display device, organic EL (electroluminescence) display device, PDP (plasma display panel), electronic paper, etc.), an input device (touch panel, etc.) or a substrate (member) used for such a device, and can be particularly suitably used for the production of an optical substrate for a touch panel. Further, a touch panel such as a resistive film type or a capacitive type may be used.
Image display panel and image display device
The polarizing film with an adhesive layer of the present invention can be applied to various image display portions to form an image display panel. The pressure-sensitive adhesive layer-equipped polarizing film of the present invention has a small fluctuation ratio of the surface resistance value, and can be suitably applied to a liquid crystal panel having a built-in touch sensing function. In particular, the adhesive layer of the polarizing film with an adhesive layer of the present invention and the image display panel having a transparent conductive substrate having a transparent conductive layer are suitably applied to the adhesive layer of the polarizing film with an adhesive layer to be bonded to the transparent conductive layer of the image display panel.
The polarizing film with the adhesive layer and the transparent conductive substrate were as described above. The image display panel is preferably provided with the transparent conductive substrate, and forms a part of the image display device together with the adhesive-equipped polarizing film.
A liquid crystal panel of a representative embodiment of an image display panel to which the polarizing film with an adhesive layer of the present invention is applied will be described. A liquid crystal cell used in a liquid crystal panel includes a transparent conductive substrate having a transparent conductive layer on a transparent substrate, and the transparent conductive substrate is generally provided on a surface of the liquid crystal cell on a viewing side. The liquid crystal cell including the transparent conductive substrate used in the present invention is composed of a transparent conductive layer, a transparent substrate, a liquid crystal layer, and a transparent substrate.
In addition to the above-described configuration, an optical film such as a retardation film, a viewing angle compensation film, or a brightness enhancement film may be provided in the liquid crystal panel as appropriate.
The liquid crystal layer is not particularly limited, and for example, may be used: any type of liquid crystal layer such as TN type, STN type, pi type, VA type, and IPS 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, transparent resin film base material. The transparent resin film substrate may be the substrate described above.
The polarizing film with an adhesive layer conventionally used in the art may be used on the light source side of the liquid crystal layer, and the corresponding members described in the present specification may be preferably used.
Specific examples of the image display device to which the image display panel can be applied include a liquid crystal display device, an organic Electroluminescence (EL) display, a Plasma Display (PD), and a field emission display (FED: field Emission Display).
The polarizing film with an adhesive layer of the present invention can be applied to various image display panels that can be applied to existing image display devices. Other configurations of the image display apparatus are similar to those of the conventional image display apparatus. The polarizing film with an adhesive layer of the present invention has a feature of suppressing corrosion of a transparent conductive layer and not impairing a shielding function even after long-term use, and is therefore particularly suitable for use in an image display device having a touch panel.
Specific examples of the liquid crystal panel having the touch sensing function are shown in fig. 4 to 6. In fig. 4 to 6, a case where the adhesive layer-attached polarizing film 1 shown in fig. 1 is used as the adhesive layer-attached polarizing film of the present invention on the visible side of a liquid crystal cell is exemplified. That is, the one-sided protective polarizing film 11, the adhesive layer 21 of fig. 1 are shown in fig. 4 to 6 in the form of the first polarizing film 11, the first adhesive layer 21. The polarizing film 1 with the adhesive layer shown in fig. 2 is also applicable to the visible side of the liquid crystal cell of fig. 4 to 6.
Fig. 4 shows a so-called in-line touch-sensing-function-incorporated liquid crystal panel having, from the visible side, a first polarizing film 11, a first adhesive layer 21, a first transparent substrate 41, a touch sensor portion 5, a liquid crystal layer 3, a driving electrode/sensor portion 6, a second transparent substrate 42, a second adhesive layer 22, and a second polarizing film 12. In the liquid crystal panel with built-in touch sensing function of fig. 4, for example, the liquid crystal cell C has the touch sensor portion 5 and the driving electrode/sensor portion 6 in the first and second glass substrates 41 and 42 (in the liquid crystal cell) sandwiching the liquid crystal layer 3.
Fig. 5 is a modified example of a so-called in-line (semi-in-line) liquid crystal panel having a built-in touch sensing function, and has a configuration of first polarizing film 11, first adhesive layer 21, touch sensor portion 5, first transparent substrate 41, liquid crystal layer 3, drive electrode/sensor portion 6, second transparent substrate 42, second adhesive layer 22, and second polarizing film 12 from the visible side. In the liquid crystal panel with built-in touch sensing function of fig. 5, for example, the touch sensor portion 5 is directly in contact with the first pressure-sensitive adhesive layer 21 on the outer side of the first transparent substrate 41 in the liquid crystal cell C, and the drive electrode/sensor portion 6 is provided on the second transparent substrate 42 side in the first and second glass substrates 41 and 42 (in the liquid crystal cell) sandwiching the liquid crystal layer 3.
Fig. 6 shows a so-called built-in touch sensor function liquid crystal panel having, from the visible side, a first polarizing film 11, a first adhesive layer 21, a touch sensor section 5, a driving electrode/sensor section 6, a first transparent substrate 41, a liquid crystal layer 3, a driving electrode 7, a second transparent substrate 42, a second adhesive layer 22, and a second polarizing film 12. In the liquid crystal panel with built-in touch sensing function shown in fig. 6, for example, the liquid crystal cell C has a touch sensor portion 5 and a driving electrode/sensor portion 6 on the outer side of the first transparent substrate 41, the touch sensor portion 5 is directly in contact with the first adhesive layer 21, and the driving electrode 7 is provided on the side of the second transparent substrate 42 in the first glass substrate and the second glass substrate 41, 42 (in the liquid crystal cell) sandwiching the liquid crystal layer 3.
In the liquid crystal panel having the built-in touch sensing function, when the touch sensor portion 5 of the liquid crystal cell C is in direct contact with the first adhesive layer 21, the antistatic function of the first adhesive layer 21 (containing an ionic compound) tends to be lowered, and particularly in a humidified environment. Therefore, the touch-sensor-function-incorporated liquid crystal panel of the present invention can be suitably used in the in-line type (modification) shown in fig. 5 or the out-line type touch-sensor-incorporated liquid crystal panel shown in fig. 6 in the above-described examples.
The first polarizing film 11 of the liquid crystal cell C disposed on the viewing side and the second polarizing film 12 disposed on the opposite side of the viewing side may be used by laminating other optical films according to the adaptability of the respective disposed positions. Examples of the other optical film include: a reflection plate, a counter-transmission plate, a phase difference film (including a 1/2 wave plate, a 1/4 wave plate, and the like), a visual compensation film, a brightness enhancement film, and the like are optical films as optical layers used in the formation of liquid crystal display devices and the like in some cases. These other optical films may use 1 layer or more than 2 layers. In the case of using these other optical films, it is also preferable to use an adhesive layer closest to the liquid crystal layer 3 side as the first adhesive layer 21.
The liquid crystal layer 3 included in the liquid crystal cell C is a liquid crystal layer suitable for a liquid crystal panel having a built-in touch sensing function, and includes liquid crystal molecules that are uniformly aligned in the absence of an electric field. As the liquid crystal layer 3, for example, an IPS mode liquid crystal layer is preferably used. As the liquid crystal layer 3, any type of liquid crystal layer such as a TN type, an STN type, a pi type, a VA type, or the like can be used. The thickness of the liquid crystal layer is, for example, about 1.5 μm to 4 μm.
In the liquid crystal cell C, the first transparent substrate 41 and the second transparent substrate 42 can sandwich the liquid crystal layer 3 to form a liquid crystal cell. Depending on the form of the liquid crystal panel having the touch sensing function, the touch sensor section 5, the drive electrode/sensor section 6, the drive electrode 7, and the like are formed in or out of the liquid crystal cell. In addition, a color filter substrate may be provided on the liquid crystal cell (first transparent substrate 41).
Examples of the material forming the transparent substrate include glass and a polymer film. Examples of the polymer film include: polyethylene terephthalate, polycycloolefin, polycarbonate, and the like. When the transparent substrate is made of glass, the thickness thereof is, for example, about 0.3mm to 1 mm. When the transparent substrate is formed of a polymer film, the thickness thereof is, for example, about 10 μm to 200 μm. The transparent substrate may have an easy-to-adhere layer and a hard coat layer on the surface thereof.
The touch sensor portion 5 (capacitive sensor), the drive electrode/sensor portion 6, and the drive electrode 7 are formed as transparent conductive layers. 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, tungsten, and alloys of these metals. The transparent conductive layer may be formed of a metal oxide of indium, tin, zinc, potassium, antimony, zirconium, or cadmium, and specifically, indium oxide, tin oxide, titanium oxide, cadmium oxide, or a mixture thereof. Further, other metal compounds composed of copper iodide or the like are used. The metal oxide may further contain an oxide of a metal atom shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, or the like is preferably used, and ITO is particularly preferably used. The ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.
The position of the touch sensor layer 5 formed in the liquid crystal cell C is not limited, and the touch sensor layer 5 may be formed according to the form of a liquid crystal panel having a built-in touch sensing function. For example, in fig. 4 to 6, a case where the touch sensor layer 5 is disposed between the first polarizing film 11 and the liquid crystal layer 3 is illustrated. The touch sensor layer 5 may be formed in the form of a transparent electrode pattern on the first transparent substrate 41, for example. The drive electrode/sensor unit 6 and the drive electrode 7 may be patterned with transparent electrodes according to a conventional method depending on the form of the liquid crystal panel having the touch sensing function. The transparent electrode pattern is generally electrically connected to a lead line (not shown) formed at an end portion of the transparent substrate, and the lead line is connected to a controller IC (not shown). The transparent electrode pattern may have any shape other than a comb shape, such as a stripe shape or a diamond shape, depending on the application. The transparent electrode pattern has a height of, for example, 10nm to 100nm and a width of 0.1mm to 5mm.
In addition, the liquid crystal panel having a touch sensing function can be suitably used as a member for forming a liquid crystal display device, such as a member using a backlight or a reflective plate in an illumination system.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The parts and% in each example are based on weight. The room temperature conditions are 23℃and 65% RH.
Determination of weight average molecular weight of (meth) acrylic Polymer (A)
The weight average molecular weight (Mw) of the (meth) acrylic polymer (A) was measured by GPC (gel permeation chromatography), and Mw/Mn was measured in the same manner. The same applies to the measurement of the weight average molecular weight of the polymer (a) and the like (excluding the solvent).
Analysis device: manufactured by Tosoh Co., ltd., HLC-8120GPC
Column: manufactured by Tosoh corporation, G7000H XL +GMH XL +GMH XL
Column size: each 7.8mm phi multiplied by 30cm and totaling 90cm
Column temperature: 40 DEG C
Flow rate: 0.8mL/min
Injection amount: 100 mu L
Eluent: tetrahydrofuran (THF)
Detector: differential Refractometer (RI)
Standard sample: polystyrene
(production of thin polarizer A)
A laminate was produced by applying a corona treatment to one side of a substrate of an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 μm) having a water absorption of 0.75% and a Tg of 75℃and applying an aqueous solution containing polyvinyl 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, trade name "GOHSEFIMER Z200" manufactured by Nippon chemical industry Co., ltd.) in a ratio of 9:1 to the corona-treated surface at 25℃and drying the resultant solution.
The obtained laminate was subjected to free-end unidirectional stretching (auxiliary stretching treatment in a gas atmosphere) in an oven at 120 ℃ between rolls having different peripheral speeds, the stretching being performed to 2.0 times in the longitudinal direction (longitudinal direction).
Next, the laminate was immersed in an insolubilization bath (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 30 ℃ for 30 seconds (insolubilization treatment).
Next, the polarizer was immersed in a dyeing liquid at a liquid temperature of 30 ℃ while adjusting the iodine concentration and the immersion time so that the polarizer became a predetermined transmittance. In this example, an aqueous iodine solution obtained by adding 0.2 part by weight of iodine to 100 parts by weight of water and 1.0 part by weight of potassium iodide was immersed for 60 seconds (dyeing treatment).
Then, the resultant solution was immersed in a crosslinking bath (aqueous boric acid solution obtained by mixing 3 parts by weight of potassium iodide with 100 parts by weight of water and 3 parts by weight of boric acid) at a liquid temperature of 30℃for 30 seconds (crosslinking treatment).
Then, the laminate was immersed in an aqueous boric acid solution (aqueous solution obtained by mixing 4 parts by weight of boric acid with 5 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 70 ℃ and uniaxially stretched (stretched in aqueous solution) between rolls having different peripheral speeds along the longitudinal direction (longitudinal direction) so that the total stretching ratio became 5.5 times.
Then, the laminate was immersed in a washing bath (aqueous solution obtained by mixing 100 parts by weight of water with 4 parts by weight of potassium iodide) at a liquid temperature of 30 ℃ (washing treatment).
By the above operation, an optical film laminate including a polarizer having a thickness of 5 μm was obtained.
(transparent protective film)
A cellulose triacetate resin film having a thickness of 25 μm was used.
(preparation of adhesive for transparent protective film)
An ultraviolet curable adhesive was prepared by mixing 45 parts by weight of acryloylmorpholine, 45 parts by weight of 1, 9-nonanediol diacrylate, 10 parts by weight of an acrylic oligomer (ARUFON UP1190, manufactured by eastern synthesis Co., ltd.), 3 parts by weight of a photopolymerization initiator (IRGACURE 907, manufactured by basf Co., ltd.), and 1.5 parts by weight of a polymerization initiator (KAYACURE DETX-S, manufactured by japan chemical Co., ltd.).
< transparent layer Forming Material >
Forming material A: as the solution of the urethane prepolymer (a), a 75% ethyl acetate solution of a urethane prepolymer made of Toluene Diisocyanate (TDI) and Trimethylolpropane (TMP) (trade name "cornonate L" manufactured by eason corporation) was used.
On the other hand, trimethylolpropane was dissolved in cyclopentanone so that the solid content concentration became 10%, and a trimethylolpropane solution was prepared.
To 100 parts of the above 75% ethyl acetate solution of the urethane prepolymer (trade name "cornonate L" manufactured by eason corporation), the above trimethylolpropane solution was added so that the urethane prepolymer: the solid content ratio of trimethylolpropane was 90:10, and 0.1 part of dioctyltin dilaurate (trade name "EMBILIZER OL-1" manufactured by Tokyo refining Co., ltd.) was further added, and a solid content concentration was 10% by methyl isobutyl ketone as a solvent, whereby a forming material (coating liquid) was prepared.
Forming material B: to 100 parts of a 75% ethyl acetate solution (trade name "Coronate L" manufactured by Tosoh corporation) of a urethane prepolymer prepared from toluene diisocyanate and trimethylolpropane, 0.1 part (trade name "EMBILIZER OL-1" manufactured by Tokyo Seisakusho Co., ltd.) of a dioctyltin dilaurate was added, and a urethane prepolymer coating liquid having a solid content of 10% was prepared from methyl isobutyl ketone as a solvent.
Forming material C: 97.0 parts of methyl methacrylate, 3.0 parts of a monomer represented by the general formula (1) (a monomer of the general formula (1 e)) and 0.2 parts of a polymerization initiator (2, 2' -azobisisobutyronitrile) were dissolved in 200 parts of toluene. Next, the polymerization was carried out in a nitrogen atmosphere at 70℃for 5 hours to obtain a polymer (a) (solid content: 33% by weight). The weight average molecular weight of the obtained polymer (a) was 85000.
An acrylic-epoxy resin-forming material (coating liquid) was prepared by mixing 15 parts of the above polymer (a) with 85 parts of an epoxy resin (trade name: jER (registered trademark) YX7200B35, manufactured by mitsubishi chemical corporation).
Forming material D: an aqueous solution having a solid content of 4% by weight was prepared by dissolving a polyvinyl alcohol resin (manufactured by JAPAN VAM & POVAL Co., ltd., trade name: JC-25) having a polymerization degree of 2500 and a saponification degree of 99.0% in pure water.
Example 1
Preparation of acrylic Polymer (A)
A4-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, and a condenser was charged with a monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate. Further, 0.1 part of 2,2' -azobisisobutyronitrile as a polymerization initiator was added together with 100 parts of ethyl acetate to 100 parts of the above-mentioned monomer mixture (solid content), and after nitrogen substitution by introducing nitrogen gas while stirring slowly, the liquid temperature in the flask was kept at about 55℃for 8 hours to perform polymerization, whereby a solution of a (meth) acrylic polymer having a weight average molecular weight (Mw) of 160 ten thousand and Mw/Mn=3.7 was prepared.
(preparation of adhesive composition)
An acrylic pressure-sensitive adhesive composition was prepared by mixing 100 parts of the solid content of the acrylic polymer solution obtained above with 0.1 part of an isocyanate crosslinking agent (Takenate D160N, trimethylolpropane hexamethylene diisocyanate, manufactured by Sanyo chemical Co., ltd.) 0.3 part of benzoyl peroxide (Nyper BMT, manufactured by Japanese fat & oil Co., ltd.) and 0.3 part of an epoxy group-containing silane coupling agent (X-41-1056, manufactured by Xinyue chemical Co., ltd.).
(preparation of adhesive layer)
Next, a solution of the above-mentioned acrylic adhesive composition was applied to one side of a polyethylene terephthalate film (separator: manufactured by mitsubishi chemical polyester film, product of MRF 38) treated with a silicone-based release agent, and dried at 155 ℃ for 1 minute so that the thickness of the adhesive layer after drying was 20 μm, and an adhesive layer was formed on the surface of the separator.
< fabrication of Single-sided protective polarizing film >
The ultraviolet-curable adhesive a was applied to the surface of the polarizer a of the optical film laminate so that the thickness of the cured adhesive layer became 1 μm, and the transparent protective film (cellulose triacetate resin film) was attached thereto, and then ultraviolet rays were irradiated as active energy rays to cure the adhesive. The ultraviolet irradiation used was a metal halide lamp having gallium enclosed therein, and an irradiation device: light HAMMER10, valve manufactured by Fusion UV Systems company: v valve, maximum illuminance of 1600mW/cm 2 Cumulative exposure of 1000/mJ/cm 2 The illuminance of ultraviolet light (wavelength 380 to 440 nm) was measured by using the Sola-Check system manufactured by Solatell company. Next, the amorphous PET substrate was peeled off, and a single-sided protective polarizing film using a thin polarizer was produced. The optical characteristics of the resulting single-sided protective polarizing film were: the transmittance of the monomer is 42.8 percent and the polarization degree is 99.99 percent.
< production of Single-sided protective polarizing film with transparent layer >)
The transparent layer-forming material a was applied to one surface of the polarizer of the one-sided protective polarizing film (polarizer surface on which no transparent protective film was provided) by a wire bar coater, and then heat-treated at 60 ℃ for 12 hours to form a urethane resin layer having a thickness of 3 μm.
< production of Single-sided protective polarizing film with adhesive layer >
Next, the adhesive layer formed on the separator was transferred to the transparent layer formed on the one-sided protective polarizing film, and a polarizing film with the adhesive layer was produced.
Examples 2 to 17 and comparative examples 1 to 4
In example 1, a transparent layer-attached single-sided protective polarizing film and an adhesive layer-attached single-sided protective polarizing film were produced in the same manner as in example 1 except that the composition of the monomer mixture used in the production of the acrylic polymer (a), the type of the ionic compound (B) used in the production of the adhesive composition (EMI-FSI or Li-TFSI) or the blending ratio thereof, the thickness of the adhesive layer, the type of the transparent layer-forming material or the thickness thereof were changed as shown in table 1.
In addition, for the transparent layers of examples 14 to 17, the material C for forming the transparent layer was applied to one surface of the polarizer of the one-side protective polarizing film (the polarizer surface on which the transparent protective film was not provided) by a wire bar coater, and then heat-treated at 60℃for 2 minutes to form a transparent layer having a thickness of 0.5. Mu.m.
The transparent layer of comparative example 4 was formed as follows: the forming agent C was applied to one surface of the polarizer of the one-sided protective polarizing film (the polarizer surface on which the transparent protective film was not provided) by a wire bar coater, and then heated at 60 ℃ for 3 minutes to form a polyvinyl alcohol resin layer having a thickness of 1 μm.
In comparative examples 1 to 3, no transparent layer was formed.
The amount of the ionic compound (B) to be blended is a value of 100 parts by weight based on the solid content of the solution of the acrylic polymer.
The adhesive layer-attached single-sided protective polarizing films obtained in the above examples and comparative examples were evaluated as follows, and the evaluation results are shown in table 1.
< Corrosion resistance test >
As the transparent conductive substrate having the transparent substrate and the transparent conductive layer, ITO-coated glass obtained by sputtering amorphous ITO onto alkali-free glass (trade name "EG-XG" manufactured by Corning Co., ltd.) having a thickness of 0.7mm was used. ITO having an Sn ratio of 3 wt% was used as ITO. The Sn ratio of ITO was calculated from the weight of Sn atoms/(weight of Sn atoms+weight of In atoms). The glass with ITO was cut into pieces of 25mm by 25mm, the single-sided protective polarizing films with an adhesive layer obtained in examples and comparative examples were cut into pieces of 15mm by 15mm, and the films were bonded to the center of the glass with ITO on which the ITO film was formed, and then subjected to autoclave treatment at 50℃for 15 minutes at 5atm, to obtain samples as samples for evaluating the ITO corrosiveness.
To-be-bonded beltThe value obtained by measuring the surface resistance value of the amorphous ITO layer before the one-sided protective polarizing film of the adhesive layer was set to "R" i ”。
After the sample for measurement was put into an atmosphere at 60℃and 90% RH for 250 hours or 500 hours, the single-sided protective polarizing film with the adhesive layer was peeled off, and the surface resistance value of each amorphous ITO layer was measured to obtain a value "R" 250 "or" R 500 ”。
The surface resistance value was measured using HL5500PC manufactured by Accent Optical Technologies corporation.
From the measurement results of the surface resistance values, the change ratios were calculated: r is R 250 /R i Ratio of change: r is R 500 /R 250 The results are shown in Table 1.
R 250 /R i When the resistance is 1.5 or less, the resistance value is preferably increased by heat and humidity, because the resistance is small and the corrosion resistance is excellent.
In addition, R 500 /R 250 When the resistance is 1.8 or less, the resistance value is preferably increased by heat and humidity, because the resistance is small and the corrosion resistance is excellent.
< evaluation of end discoloration >
The polarizing films with the adhesive layers obtained in examples and comparative examples were cut into 50mm×50mm, and after separation of the separator, the films were bonded to each other with an adhesive layer interposed therebetween by alkali glass (glass microscope slide, manufactured by Songbo Nitro Co., ltd.) having a thickness of 1.2 to 1.5mm, to prepare samples. After this sample was kept at 60℃under a high-temperature and high-humidity atmosphere of 90% RH for 500 hours, the end discoloration amount was measured by a differential interference microscope (product name "MX-61L" manufactured by Olympus). The end discoloration amount was measured as follows: the straight line distance connecting the corners at the position closest to the center among the portions having a lighter color than the center on the diagonal lines of the 4 corners of the sample was set as the end discoloration amount (μm), and the average value of the 4 corners was set as the end discoloration amount of the sample.
The device comprises: manufactured by Olympus Co., ltd., MX-61L
Measurement conditions:
lens magnification: 5 times of
ISO：200
Shutter speed: 1/100
Reflected light amount: scale 0
White balance: automatic machine
A transmission light controller: LG-PS2
Transmitted light amount: scale 5
Transmitted light polarization direction: direction of crossed nicols relative to transmission axis of polarizing film
Surface resistance value (Ω/≡): conductivity >
The adhesive layer-attached single-sided protective polarizing films obtained in the above examples and comparative examples were evaluated as follows, and the evaluation results are shown in table 1. In each evaluation, "initial" was a value measured immediately after the production of the one-sided protective polarizing film or liquid crystal panel with an adhesive layer, and "after humidification" was a value measured after the obtained polarizing film or liquid crystal panel with an adhesive layer was put into a humidified atmosphere of 60 ℃/95% rh for 250 hours and further dried at 40 ℃ for 1 hour.
After the separator was peeled from the polarizing film with the adhesive layer, the surface resistance value of the adhesive layer surface was measured. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., ltd.
The fluctuation ratio (b/a) in table 1 is a value calculated from the "initial" surface resistance value (a) and the "humidified" surface resistance value (b) (rounded value of the second digit after the decimal point).
As an index of less potential for occurrence of "malfunction", a value having a smaller fluctuation ratio was evaluated according to the following criteria.
A: the variation ratio is 2 or less.
B: the variation ratio is greater than 2 and less than 10.
C: the variation ratio is 10 or more.
In the table 1, the contents of the components,
BA represents a butyl acrylate ester, and,
NVP represents N-vinyl-2-pyrrolidone,
HBA represents 4-hydroxybutyl acrylate,
AA represents an acrylic acid, and is preferably an acrylic acid,
EMI-FSI means ethyl methylimidazoleA bis (fluorosulfonyl) imide salt,
Li-TFSI represents lithium bis (trifluoromethanesulfonyl) imide.
As shown in table 1, when an adhesive layer of a polarizing film with an adhesive layer provided on a single-side protective polarizing film using an iodine-based polarizer was bonded to a transparent conductive layer, it was found that a stable surface resistance value of the transparent conductive layer was maintained even when the polarizing film was placed in a humidified environment, according to an example in which the adhesive layer was provided with a predetermined transparent layer.

Claims (17)

1. A polarizing film with an adhesive layer, comprising: a polarizer, a transparent protective film provided only on one surface of the polarizer, and a transparent layer directly formed on the other surface of the polarizer, and an adhesive layer is provided across the transparent layer,
The polarizer is an iodine type polarizer containing iodine and/or iodide ions,
the transparent layer is a cured product of a material for forming a urethane prepolymer (a) which is a reactant of an isocyanate compound and a polyol, and a compound (b) having at least 2 functional groups having active hydrogen which is reactive with an isocyanate group,
the polarizing film with an adhesive layer satisfies the change ratio of the surface resistance value represented by formula (1),
formula (1): r is R 250 /R i ≤1.5
Wherein the R is i An adhesive layer bonded to the polarizing film with an adhesive layer and having a transparent propertyA laminate obtained by laminating the transparent conductive layer on the transparent conductive substrate of the transparent conductive layer and the transparent substrate is subjected to autoclave treatment at 50 ℃ under 5 atm for 15 minutes to obtain a surface resistance value (Ω/≡),
the R is 250 The surface resistance value (Ω/≡) of the transparent conductive layer after the autoclave-treated laminate was further subjected to high-temperature and high-humidity treatment at 65 ℃ and 95% rh for 250 hours.
2. The polarizing film with an adhesive layer according to claim 1, wherein,
the isocyanate compound contains at least 1 selected from toluene diisocyanate and diphenylmethane diisocyanate.
3. The polarizing film with an adhesive layer according to claim 1 or 2, wherein,
the polarizing film with an adhesive layer satisfies the change ratio of the surface resistance value represented by formula (2),
formula (2): r is R 500 /R 250 ≤1.8
Wherein the R is 250 The laminate obtained by bonding the adhesive layer of the polarizing film with an adhesive layer to the transparent conductive layer on the transparent conductive substrate having the transparent substrate and the transparent conductive layer is subjected to autoclave treatment at 50℃under 5 atm for 15 minutes, and further subjected to high-temperature high-humidity treatment at 65℃under 95% RH for 250 hours,
the R is 500 The surface resistance value (Ω/≡) of the transparent conductive layer after the autoclave treatment was further subjected to high temperature and high humidity treatment at 65 ℃ and 95% rh for 500 hours.
4. The polarizing film with an adhesive layer according to claim 1 or 2, wherein,
the transparent layer has a thickness of 10 μm or less.
5. The polarizing film with an adhesive layer according to claim 1 or 2, wherein,
the adhesive layer is formed from an adhesive composition containing a (meth) acrylic polymer (a).
6. The polarizing film with an adhesive layer according to claim 1 or 2, wherein,
the adhesive layer is formed from an adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B).
7. The polarizing film with an adhesive layer according to claim 5, wherein,
the (meth) acrylic polymer (A) contains an alkyl (meth) acrylate (a 1) and an amide group-containing monomer (a 2) as monomer units.
8. The adhesive layer-carrying polarizing film according to claim 7, wherein,
the amide group-containing monomer (a 2) is an N-vinyl lactam-containing monomer.
9. The adhesive layer-carrying polarizing film according to claim 7, wherein,
the (meth) acrylic polymer (a) contains 0.1% by weight or more of the amide group-containing monomer (a 2) as a monomer unit.
10. The adhesive layer-carrying polarizing film according to claim 6, wherein,
the ionic compound (B) is an alkali metal salt.
11. The adhesive layer-carrying polarizing film according to claim 6, wherein,
the ionic compound (B) is contained in an amount of 0.01 parts by weight or more based on 100 parts by weight of the (meth) acrylic polymer (A).
12. The polarizing film with an adhesive layer according to claim 1 or 2, wherein,
The transparent conductive layer is formed of indium tin oxide.
13. A laminate, comprising:
the adhesive layer-attached polarizing film according to any one of claims 1 to 12
A transparent conductive substrate having a transparent substrate and a transparent conductive layer,
the adhesive layer of the polarizing film with an adhesive layer is bonded to the transparent conductive layer of the transparent conductive substrate.
14. An image display device using the laminate according to claim 13 as a touch panel.
15. An image display panel having the adhesive layer-attached polarizing film according to any one of claims 1 to 12.
16. The image display panel of claim 15, wherein,
the image display panel includes a transparent conductive substrate having a transparent conductive layer, and the adhesive layer of the polarizing film with an adhesive layer is bonded to the transparent conductive layer of the image display panel.
17. An image display device having the image display panel of claim 15 or 16.
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