CN112888994A - Liquid crystal panel with touch sensing function, liquid crystal display device, and polarizing film with adhesive layer - Google Patents

Liquid crystal panel with touch sensing function, liquid crystal display device, and polarizing film with adhesive layer Download PDF

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Publication number
CN112888994A
CN112888994A CN201980067298.9A CN201980067298A CN112888994A CN 112888994 A CN112888994 A CN 112888994A CN 201980067298 A CN201980067298 A CN 201980067298A CN 112888994 A CN112888994 A CN 112888994A
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group
adhesive layer
meth
liquid crystal
polarizing film
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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/JP2019/046798 external-priority patent/WO2020111236A1/en
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • G06F3/0412—Digitisers structurally integrated in a display
    • 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
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Nonlinear Science (AREA)
  • Human Computer Interaction (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

The present invention relates to a liquid crystal panel with a built-in touch sensing function, which comprises: a first polarizing film disposed on a viewing side of the liquid crystal cell having the touch sensor function built therein and a second polarizing film disposed on an opposite side to the viewing side; and a first pressure-sensitive adhesive layer disposed between the first polarizing film and the liquid crystal cell, wherein the first polarizing film has a transparent protective film only on one surface of the polarizer and a transparent layer on the other surface thereof, and is provided on the first pressure-sensitive adhesive layer via the transparent layer, the first pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (a) and an ionic compound (B), and the first pressure-sensitive adhesive layer has a small change in surface resistance value even in a humidified environment and can satisfy a stable antistatic function in a humidified environment.

Description

Liquid crystal panel with touch sensing function, liquid crystal display device, and polarizing film with adhesive layer
Technical Field
The present invention relates to a liquid crystal panel with a touch sensing function and a liquid crystal display device. The liquid crystal display device with a touch sensing function of the present invention can be used as various input display devices such as a mobile device. The present invention also relates to a polarizing film with an adhesive layer, and the polarizing film with an adhesive layer of the present invention can be applied to, for example, a liquid crystal panel with a touch sensor function and a liquid crystal display device.
Background
The liquid crystal display device is generally attached with a polarizing film from both sides of a liquid crystal cell via an adhesive layer according to its image forming method. Further, products in which a touch panel is mounted on a display screen of a liquid crystal display device have also been put to practical use. As the touch panel, there are various types such as a capacitive type, a resistive film type, an optical type, an ultrasonic type, and an electromagnetic induction type, but a capacitive type has been widely used. In recent years, a liquid crystal display device with a touch sensing function incorporating a capacitive sensor as a touch sensor portion has been used.
On the other hand, when the polarizing film with the pressure-sensitive adhesive layer is attached to a liquid crystal cell in the production of a liquid crystal display device, the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer is peeled off from the release film, and static electricity is generated by the peeling of the release film. The static electricity thus generated affects the alignment of the liquid crystal layer in the liquid crystal display device, resulting in a defect. The generation of static electricity can be suppressed by, for example, forming an antistatic layer on the outer surface of the polarizing film.
On the other hand, a capacitance sensor in a liquid crystal display device with a touch sensing function detects a weak capacitance formed between a transparent electrode pattern and a finger when the finger of a user approaches the surface of the liquid crystal display device. When a conductive layer such as an antistatic layer is provided between the transparent electrode pattern and the user's finger, an electric field between the drive electrode and the sensor electrode is disturbed, thereby making the sensor electrode capacity unstable, lowering the touch panel sensitivity, and causing malfunction. In a liquid crystal display device with a touch sensing function, it is required to suppress the generation of static electricity and also suppress the malfunction of a capacitance sensor. For example, in order to reduce the occurrence of display defects and erroneous operations in a liquid crystal display device with a touch sensing function, it has been proposed to dispose a liquid crystal layer having a surface resistance value of 1.0 × 10 on the visible side thereof9～1.0×1011Omega/□ (patent document 1).
In addition, for the purpose of preventing unevenness of a liquid crystal panel due to static electricity, adhesion of foreign substances, and the like, an adhesive for an optical film having an antistatic function has been proposed (patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-105154
Patent document 2: japanese patent laid-open publication No. 2017-067942
Disclosure of Invention
Problems to be solved by the invention
According to the polarizing film having an antistatic layer described in patent document 1, generation of static electricity can be suppressed to some extent. However, in patent document 1, since the arrangement position of the antistatic layer is shifted from the original position where static electricity is generated, it is not effective as compared with the case where an antistatic function is provided to the pressure-sensitive adhesive layer.
In addition, the pressure-sensitive adhesive layer containing an ionic compound is effective in suppressing generation of static electricity and preventing unevenness of static electricity, as compared with the antistatic layer provided on the polarizing film. However, it is known that the antistatic function of the adhesive layer containing an ionic compound deteriorates with time. In particular, it is known that under a humidified environment (after a humidified reliability test), ionic compounds in the pressure-sensitive adhesive layer segregate at the interface with the optical film (polarizing film) or migrate into the optical film (polarizing film), and the surface resistance value of the pressure-sensitive adhesive layer increases, resulting in a significant decrease in the antistatic function. It is known that such a reduction in the antistatic function of the pressure-sensitive adhesive layer causes the generation of static unevenness and malfunction of the liquid crystal display device with a touch sensing function.
In addition, as the polarizing film with an adhesive layer, a polarizing film with an adhesive layer may be used in which an adhesive layer is provided on a single-side protective polarizing film provided with a transparent protective film only on one side of a polarizer and not provided on the other side. Since the pressure-sensitive adhesive layer-attached single-sided protective polarizing film has the transparent protective film only on one side, the polarizing film can be made thinner and the cost of one transparent protective film can be reduced as compared with the case of having the transparent protective films on both sides. On the other hand, in the one-side protective polarizing film with a pressure-sensitive adhesive layer, when the pressure-sensitive adhesive layer contains an ionic compound to impart an antistatic function, the ionic compound in the pressure-sensitive adhesive layer has a particularly large influence on the polarizer, and there is a problem that the polarizer deteriorates with time and the optical properties after a humidification test are greatly reduced.
According to patent document 2, a stable antistatic function can be satisfied in a humidified environment, but in patent document 2, in the case of using the above one-side protective polarizing film with an adhesive layer, further improvement of the antistatic function of the adhesive layer in a humidified environment is also required.
An object of the present invention is to provide a touch-sensing liquid crystal panel in which a one-sided protective polarizing film having a transparent protective film only on one surface of a polarizer is bonded to a visible side of a touch-sensing liquid crystal cell using an adhesive layer containing an ionic compound, and which can satisfy a stable antistatic function in a humidified environment. Another object of the present invention is to provide a liquid crystal display device using the liquid crystal panel. Another object of the present invention is to provide a polarizing film with an adhesive layer, which can be applied to the liquid crystal panel with a touch sensor function.
Means for solving the problems
The present inventors have made extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a liquid crystal panel with a touch sensing function or the like described below, and have completed the present invention.
That is, the present invention relates to a liquid crystal panel with a built-in touch sensing function, including:
a liquid crystal cell having a liquid crystal layer and a touch sensor portion and having a touch sensing function built therein;
a first polarizing film disposed on a viewing side of the liquid crystal cell and a second polarizing film disposed on an opposite side to the viewing side; and
a first adhesive layer disposed between the first polarizing film and the liquid crystal cell,
wherein the first polarizing film has: a 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 the first polarizing film is provided on the first pressure-sensitive adhesive layer with the transparent layer interposed therebetween,
the first pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B),
the first adhesive layer satisfies: the variation ratio (b/a) of the surface resistance value is less than or equal to 10,
wherein a represents a surface resistance value of the first pressure-sensitive adhesive layer when the first polarizing film with the pressure-sensitive adhesive layer is peeled immediately after the first polarizing film with the first pressure-sensitive adhesive layer provided on the transparent layer of the first polarizing film and the separator provided on the first pressure-sensitive adhesive layer is produced, and b represents a surface resistance value of the first pressure-sensitive adhesive layer when the first polarizing film with the pressure-sensitive adhesive layer is put into a humidified atmosphere of 60 ℃/95% RH for 250 hours and further dried at 40 ℃ for 1 hour, and then the separator is peeled.
In the liquid crystal panel with a touch sensor function, the transparent layer is preferably formed directly on the polarizer.
In the liquid crystal panel with a built-in touch sensor function, the thickness of the transparent layer is preferably 10 μm or less.
In the liquid crystal panel with a built-in touch sensor function, a cured product of a material forming a urethane prepolymer which is a reaction product of an isocyanate compound and a polyol can be used as the transparent layer. As the isocyanate compound, at least 1 selected from the group consisting of toluene diisocyanate and diphenylmethane diisocyanate is preferably used.
The liquid crystal panel with a built-in touch sensor function may contain an epoxy resin as the transparent layer.
The liquid crystal panel with a built-in touch sensor function can be obtained by using, as the transparent layer, a resin composition containing the following polymer (A) and epoxy resin (b),
the polymer (A) is obtained by polymerizing more than 50 parts by weight of an acrylic monomer and more than 0 part by weight and less than 50 parts by weight of a monomer represented by the following general formula (1),
[ chemical formula 1]
Figure BDA0003016076730000041
(wherein X represents a functional group containing at least 1 reactive group selected from the group consisting of a vinyl group, (meth) acryloyl group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group, and carboxyl group, and R1And R2Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, R1And R2Optionally joined 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.
The functional group represented by X in the above general formula (1) is preferably 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 a vinyl group, (meth) acryloyl group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group, and carboxyl group, and Y represents an organic group).
In the liquid crystal panel having a touch sensor function, the (meth) acrylic polymer (a) preferably contains an alkyl (meth) acrylate (a1) and an amide group-containing monomer (a2) as monomer units.
In the liquid crystal panel with a built-in touch sensor function, the amide group-containing monomer (a2) is preferably an N-vinyl lactam group-containing monomer.
In the liquid crystal panel with a built-in touch sensor function, it is preferable that the amide group-containing monomer (a2) is contained as a monomer unit in the (meth) acrylic polymer (a) in an amount of 0.1 wt% or more.
In the liquid crystal panel with a touch sensor function, it is preferable that the ionic compound (B) is an alkali metal salt, and the surface resistance value of the first pressure-sensitive adhesive layer represented by a is 1 × 1010～1×1012Omega/□. In addition, the above separation is preferableThe sub-compound (B) is an organic cation-anion salt, and the surface resistance value of the first pressure-sensitive adhesive layer represented by the above-mentioned a is 1X 108～1×1010Ω/□。
The liquid crystal panel with a built-in touch sensor function preferably contains the ionic compound (B) in an amount of 0.01 parts by weight or more per 100 parts by weight of the (meth) acrylic polymer (a).
In the liquid crystal panel with a built-in touch sensor function, a conductive layer may be provided between the transparent layer and the first adhesive layer.
The liquid crystal panel with a built-in touch sensor function can be suitably applied to a case where the touch sensor portion is in direct contact with the first pressure-sensitive adhesive layer.
The present invention also relates to a liquid crystal display device having the liquid crystal panel with a built-in touch sensor function.
In addition, the present invention relates to a polarizing film with an adhesive layer, having: a 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,
and a pressure-sensitive adhesive layer is provided through the transparent layer,
the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B),
the first adhesive layer satisfies: the variation ratio (b/a) of the surface resistance value is less than or equal to 10,
wherein a represents the surface resistance value of the pressure-sensitive adhesive layer when the pressure-sensitive adhesive layer-attached polarizing film is peeled off immediately after the polarizing film is produced in a state in which a separator is provided on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film, and b represents the surface resistance value of the pressure-sensitive adhesive layer when the pressure-sensitive adhesive layer-attached polarizing film in a state in which the separator is provided is put into a humidified atmosphere of 60 ℃/95% RH for 250 hours and further dried at 40 ℃ for 1 hour, and then the separator is peeled off.
The polarizing film with an adhesive layer may be applied in the same preferred manner as the polarizing film with an adhesive layer used for the liquid crystal panel with a touch sensor function.
ADVANTAGEOUS EFFECTS OF INVENTION
The panel with a built-in touch sensing function of the present invention includes: the liquid crystal display device includes a liquid crystal cell including a touch sensor unit, and a first adhesive layer provided between the liquid crystal cell and a first polarizing film disposed on a viewing side of the liquid crystal cell. The first pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (a) and an ionic compound (B) as monomer units. The ionic compound (B) is contained in the first pressure-sensitive adhesive layer, and the surface resistance value of the first pressure-sensitive adhesive layer can be reduced, and the generation of static electricity can be suppressed, whereby the alignment disorder of the liquid crystal layer due to charging and the occurrence of light leakage (charging unevenness) can be suppressed.
On the other hand, from the viewpoint of reduction in thickness and cost, it is advantageous that the first polarizing film is a one-side protective polarizing film having a transparent protective film only on one surface of the polarizer. On the other hand, when the first pressure-sensitive adhesive layer is applied to a one-side protective polarizing film, in a humidified environment, the water is mixed into the first pressure-sensitive adhesive layer, so that the compatibility balance in the layer is broken, and an ionic compound enters the inside of the polarizer, thereby changing the surface resistance value of the first pressure-sensitive adhesive layer. Further, the ionic compound may be brought into contact with the polarizer to degrade optical characteristics such as a degree of polarization. However, in the present invention, since the transparent layer is provided between the polarizer of the first polarizing film and the first adhesive layer, the intrusion of the ionic compound in the first adhesive layer into the polarizer can be suppressed by the transparent layer. Therefore, it is considered that even in a humidified environment, the ionic compound (B) in the first pressure-sensitive adhesive layer can be prevented from segregating and migrating to the interface of the polarizing film or the like, the deterioration of the polarizer over time can be prevented, the surface resistance value of the first pressure-sensitive adhesive layer can be maintained within a desired value range for a long period of time, and stable antistatic function and optical properties can be satisfied. In addition, by disposing the conductive layer between the transparent layer and the first adhesive layer, antistatic performance can be improved. Since the conductive layer is provided through the transparent layer, the problem of discoloration from the end of the polarizer in a humidified environment due to the conductive layer being provided directly on the polarizer does not occur.
It is considered that the liquid crystal panel with a touch sensing function according to the present invention can suppress uneven charging due to static electricity generation, suppress occurrence of malfunction, and suppress sensitivity reduction of the touch panel. The liquid crystal panel with a touch sensing function of the present invention is particularly suitable when an In-Cell (In-Cell) type liquid crystal Cell or an out-Cell (On-Cell) type liquid crystal Cell is used as a liquid crystal Cell with a built-In touch sensing function.
Drawings
Fig. 1 is a cross-sectional view showing an example of a liquid crystal panel with a touch sensing function according to the present invention.
Fig. 2 is a cross-sectional view showing an example of a liquid crystal panel with a touch sensing function according to the present invention.
Fig. 3 is a cross-sectional view showing an example of a liquid crystal panel with a touch sensing function according to the present invention.
Fig. 4 is a cross-sectional view showing an example of the polarizing film with an adhesive layer of the present invention.
Fig. 5 is a cross-sectional view showing an example of the polarizing film with an adhesive layer of the present invention.
Description of the symbols
11. 12 first and second polarizing films
21. 22 first adhesive layer, second adhesive layer
3 liquid crystal layer
41. 42 first and second transparent substrates
5 touch sensor unit
6 Driving electrode and sensor part
7 drive electrode
C liquid crystal unit
a polarizer
b transparent protective film
c transparent layer
d conductive layer
Detailed Description
A touch sensor function built-in liquid crystal panel according to the present invention will be described with reference to the accompanying drawings. The liquid crystal panel with a built-in touch sensing function of the present invention includes: a liquid crystal cell C having a liquid crystal layer 3 and a touch sensor portion 5; a first polarizing film 11 disposed on the viewing side of the liquid crystal cell C and a second polarizing film 12 disposed on the opposite side to the viewing side; and a first pressure-sensitive adhesive layer 21 disposed between the first polarizing film 11 and the liquid crystal cell C. The above-described configurations of the touch sensor function-incorporating liquid crystal panel of the present invention can be simply expressed as first polarizing film 11/first pressure-sensitive adhesive layer 21/liquid crystal cell C/second polarizing film 12 from the viewing side. In the liquid crystal panel with a built-in touch sensor function, the order of the respective components is simply shown, but other components may be appropriately provided between the respective components.
The first polarizing film 11 may be a polarizing film with an adhesive layer. Fig. 4 shows an example of a polarizing film with an adhesive layer, which is a one-side protective polarizing film having a polarizer a and a transparent protective film b provided only on one surface of the polarizer a, and has a transparent layer c on the other surface of the polarizer a, as shown in fig. 4. The first polarizing film 11 is provided on the first pressure-sensitive adhesive layer 21 with the transparent layer c interposed therebetween. The transparent layer c is preferably provided directly on the polarizer a, from the viewpoint of suppressing an increase in the moisture content of the polarizer in a high-temperature and high-humidity environment. The transparent layer c will be described later. As shown in fig. 5, the polarizing film with an adhesive layer may have a conductive layer d between the transparent layer c and the first adhesive layer 21. The conductive layer d will be described later.
Specific examples of the liquid crystal panel with a touch sensor function according to the present invention are shown in fig. 1 to 3, for example.
Fig. 1 shows a so-called in-cell touch sensor function-equipped liquid crystal panel having a structure of, from the viewing side, a first polarizing film 11, a first pressure-sensitive adhesive layer 21, a first transparent substrate 41, a touch sensor unit 5, a liquid crystal layer 3, a driving electrode/sensor unit 6, a second transparent substrate 42, a second pressure-sensitive adhesive layer 22, and a second polarizing film 12. In the liquid crystal panel with built-in touch sensor function of the built-in type of fig. 1, for example, the liquid crystal cell C has a touch sensor portion 5 and a 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. 2 shows a modification of a so-called in-cell (semi-in-cell) touch sensor function-incorporating liquid crystal panel, which has a configuration of a first polarizing film 11, a first pressure-sensitive adhesive layer 21, a touch sensor unit 5, a first transparent substrate 41, a liquid crystal layer 3, a driving electrode/sensor unit 6, a second transparent substrate 42, a second pressure-sensitive adhesive layer 22, and a second polarizing film 12 from the viewing side. In the liquid crystal panel with built-in touch sensor function of the built-in type shown in fig. 2, for example, the touch sensor section 5 of the liquid crystal cell C is in direct contact with the first pressure-sensitive adhesive layer 21 on the outer side of the first transparent substrate 41, and the driving electrode/sensor section 6 is provided on one side of the second transparent substrate 42 in the first and second glass substrates 41 and 42 (in the liquid crystal cell) sandwiching the liquid crystal layer 3.
Fig. 3 shows a so-called external-mount type touch sensor function-incorporated liquid crystal panel, which has a configuration of a first polarizing film 11, a first pressure-sensitive adhesive layer 21, a touch sensor unit 5, a driving electrode/sensor unit 6, a first transparent substrate 41, a liquid crystal layer 3, a driving electrode 7, a second transparent substrate 42, a second pressure-sensitive adhesive layer 22, and a second polarizing film 12 from the viewing side. In the externally-embedded touch sensor function-incorporated liquid crystal panel of fig. 3, for example, the liquid crystal cell C has a touch sensor portion 5 and a drive electrode/sensor portion 6 on the outer side of the first transparent substrate 41, the touch sensor portion 5 is in direct contact with the first pressure-sensitive adhesive layer 21, and the drive electrode 7 is provided on one side of the second transparent substrate 42 in the first glass substrate and the second glass substrates 41 and 42 (in the liquid crystal cell) sandwiching the liquid crystal layer 3.
In the liquid crystal panel with a built-in touch sensor function, when the touch sensor portion 5 of the liquid crystal cell C is in direct contact with the first pressure-sensitive adhesive layer 21, the antistatic function of the first pressure-sensitive adhesive layer 21 (containing an ionic compound) is likely to be lowered, and particularly, is likely to be lowered in a humidified environment. Therefore, in the example of the above example, the liquid crystal panel with a built-in touch sensing function of the present invention is suitably applied to a liquid crystal panel with a built-in touch sensing function of an in-cell type (modification) shown in fig. 2 or an out-cell type shown in fig. 3.
The polarizing film having the above-described configuration can be used for the first polarizing film 11, and a polarizing film having a transparent protective film on one or both surfaces of a polarizer is generally used for the second polarizing film 12. The first polarizing film 11 and the second polarizing film 12 are disposed on both sides of the liquid crystal layer 3 so that the transmission axis (or the absorption axis) is orthogonal to each other.
The polarizer is not particularly limited, and various polarizers can be used. Examples of polarizers include: a polarizer obtained by uniaxially 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, while adsorbing a dichroic material such as iodine or a dichroic dye thereon; and polyene-based alignment films such as dehydrated polyvinyl alcohol and desalted polyvinyl chloride. Among them, a polarizer containing a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.
Further, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that it has less unevenness in thickness, is excellent in visibility, and has less dimensional change, so that it has excellent durability, and can be made thin even as the thickness of a polarizing film.
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 triacetylcellulose, 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, and mixtures thereof. A transparent protective film may be bonded to one side of the polarizer via an adhesive layer, and a thermosetting resin or an ultraviolet-curable resin such as a (meth) acrylic resin, a urethane resin, an acrylic urethane resin, an epoxy resin, or a silicone resin may be used as the transparent protective film on the other side.
As the material of the transparent protective film, a cellulose resin or a (meth) acrylic resin is preferable because the variation ratio (b/a) of the surface resistance value of the first pressure-sensitive adhesive layer can be controlled to be small. 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 Japanese patent application laid-open Nos. 2000-230016, 2001-151814, 2002-120326, 2002-254544 and 2005-146084. In particular, cellulose resins are preferable to (meth) acrylic resins in terms of effectively suppressing polarizer cracks, which are problematic in single-sided protective polarizing films.
The transparent protective film may have a functional layer such as a hard coat layer, an antireflection layer, an adhesion prevention layer, a diffusion layer, and an antiglare layer on the side 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 water-based, solvent-based, hot-melt, radical-curable, and cation-curable adhesives can be used, and a water-based adhesive or a radical-curable adhesive is preferred.
The first polarizing film 11 disposed on the viewing side and the second polarizing film 12 disposed on the opposite side to the viewing side of the liquid crystal cell C may be used by laminating other optical films according to the arrangement positions thereof. Examples of the other optical film include: optical films as optical layers used in the formation of liquid crystal display devices and the like in some cases, such as a reflective plate, a transflective plate, a retardation film (including 1/2 wave plates, 1/4 wave plates, and the like), a visual compensation film, and a brightness enhancement film. These other optical films may be used in 1 or more than 2 layers. In the case of using these other optical films, the pressure-sensitive adhesive layer closest to the liquid crystal layer 3 is also preferably used as the first pressure-sensitive adhesive layer 21.
The first pressure-sensitive adhesive layer 21 is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (a) and an ionic compound (B). The details of the adhesive composition will be described later.
The second adhesive layer 22 is formed of an adhesive. As the binder, various binders can be used, and examples thereof include: rubber-based adhesives, acrylic-based 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-mentioned pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit suitable wettability, cohesive property, adhesion properties such as adhesiveness, and weather resistance, heat resistance, and the like. The thickness of the second pressure-sensitive adhesive layer 22 is not particularly limited, and is, for example, about 1 to 100 μm, preferably 2 to 50 μm, more preferably 2 to 40 μm, and further preferably 5 to 35 μm.
As the liquid crystal layer 3 included in the liquid crystal cell C, a liquid crystal layer suitable for a liquid crystal panel incorporating a touch sensing function is used, and the liquid crystal layer includes liquid crystal molecules that are uniformly aligned in a state where no electric field is present. As the liquid crystal layer 3, for example, an IPS liquid crystal layer is preferably used. As the liquid crystal layer 3, any type of liquid crystal layer such as TN type, STN type, pi type, VA type, or the like can be used. The thickness of the liquid crystal layer is, for example, about 1.5 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. The touch sensor unit 5, the drive electrode/sensor unit 6, the drive electrode 7, and the like are formed in the liquid crystal cell or outside the liquid crystal cell according to the form of the liquid crystal panel incorporating the touch sensing function. In addition, a color filter substrate may be provided on the liquid crystal cell (first transparent substrate 41).
Examples of the material for forming the transparent substrate include glass and a polymer film. Examples of the polymer film include: polyethylene terephthalate, polycycloolefins, polycarbonates, and the like. When the transparent substrate is formed 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 to 200 μm. The transparent substrate may have an easy-adhesion layer and a hard coat layer on its surface.
The touch sensor section 5 (capacitive sensor), the drive electrode/sensor section 6, and the drive electrode 7 are formed as transparent conductive layers. The material constituting the transparent conductive layer is not particularly limited, and examples thereof include: metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, and tungsten, and alloys of these metals. As a material constituting the transparent conductive layer, metal oxides of indium, tin, zinc, potassium, antimony, zirconium, and cadmium, specifically, metal oxides of indium oxide, tin oxide, titanium oxide, cadmium oxide, and a mixture thereof can be cited. In addition, 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, as 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 wt% of indium oxide and 1 to 20 wt% of tin oxide.
The position of the liquid crystal cell C where the touch sensor layer 5 is formed is not particularly limited, and the touch sensor layer 5 may be formed according to the form of a liquid crystal panel incorporating a touch sensing function. For example, in fig. 1 to 3, 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 driving electrode/sensor section 6 and the driving electrode 7 may be formed with a transparent electrode pattern according to a conventional method depending on the form of a liquid crystal panel incorporating a touch sensing function. The transparent electrode pattern is usually 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 shape of the transparent electrode pattern may be any shape such as a stripe shape or a diamond shape, in addition to the comb shape, depending on the application. The transparent electrode pattern has a height of, for example, 10 to 100nm and a width of, for example, 0.1 to 5 mm.
The liquid crystal panel with a touch sensor function can be suitably used for a member forming a liquid crystal display device, such as a member using a backlight or a reflector in an illumination system.
The transparent layer will be described in detail below.
From the viewpoint of thinning and optical reliability, the thickness of the transparent layer is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, further preferably 1.5 μm or less, and further preferably 1 μm or less. When the transparent layer is too thick, the thickness of the polarizing film becomes thick, and the optical reliability of the polarizer may be lowered. On the other hand, the thickness of the transparent layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more, from the viewpoint of suppressing the variation ratio of the surface resistance value of the pressure-sensitive adhesive layer to a small level.
The transparent layer may be formed of a material having transparency and a predetermined variation ratio of the surface resistance value of the pressure-sensitive adhesive layer. As such a material, a material having a diameter of a free volume hole of the transparent layer smaller than a molecular size of a hydrate of the ionic compound (B) contained in the pressure-sensitive adhesive layer is effective, and examples thereof include a material containing a urethane prepolymer (a) which is 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, alicyclic isocyanate, aliphatic isocyanate compound, or a dimer thereof may be mentioned.
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-phenylisocyanate, 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 tolylene 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, 4-trimethylhexamethylene diisocyanate, and the like.
The polyfunctional isocyanate compound includes a polyfunctional isocyanate compound having 3 or more isocyanate groups such as tris (6-isocyanatohexyl) isocyanurate.
Examples of the polyhydric alcohol 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, it is preferable to use a rigid structure having a large proportion of a cyclic structure (benzene ring, cyanurate ring, isocyanurate ring, etc.) in the structure of the molecule as the urethane prepolymer (a). For example, the polyfunctional isocyanate compounds can be used singly or in combination of 1 or more, but from the viewpoint of suppressing the mixing of water into the polarizer, aromatic isocyanate compounds are preferable. Other polyfunctional isocyanate compounds may be used in combination with the aromatic isocyanate compound. In particular, among the aromatic isocyanate compounds, at least 1 selected from the group consisting of toluene diisocyanate and diphenylmethane diisocyanate is preferably used as the isocyanate compound.
As the urethane prepolymer (a), trimethylolpropane-trimethylbenzene isocyanate and 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 and stirring and reacting the mixture. It is generally preferred to mix the isocyanate compound with the polyol in such a manner that the isocyanate group is in excess with respect to the hydroxyl group of the polyol.
In addition, a urethane prepolymer having a protective group for a terminal isocyanate group may be used as the urethane prepolymer (a). As the protecting group, there are oxime, lactam and the like. The urethane prepolymer having an isocyanate group protected therein is heated to dissociate the protecting group from the isocyanate group, thereby reacting the isocyanate group.
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, which is reactive with an isocyanate group. Examples of the functional group having an active hydrogen reactive with an isocyanate group include a hydroxyl group and an amino group. The number of the functional groups having active hydrogen in the compound (b) is preferably 3 or more because the more the number of the functional groups is, the more the reaction points with the isocyanate groups of the urethane prepolymer (a) are, the more easily a cured product is formed.
Further, it is preferable that the value obtained by dividing the molecular weight of the compound (b) by the number of the functional groups is 350 or less. By defining the relationship between the molecular weight and the number of functional groups in this way, 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. From the viewpoint of compatibility when a forming material is prepared 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-mentioned compound (b), for example: polyols, polyamines, compounds having hydroxyl groups and amino groups in the molecule, and the like.
Examples of the polyhydric alcohol 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 glycerin and trimethylolpropane; 4-functional alcohols such as pentaerythritol, hexanetriol and sorbitol; 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 polyhydric alcohols.
Examples of polyamines include: ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4, 4' -diamine, and dimer diamine.
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-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, bis (2-hydroxyethyl) ethylenediamine, bis (2-hydroxyethyl) propylenediamine, 2-hydroxypropyl ethylenediamine, and bis (2-hydroxypropyl) ethylenediamine;
alkanolamines such as ethanolamine, diethanolamine, and triethanolamine.
In view of preventing deterioration of optical reliability of the polarizer, a polyol is preferably used as the compound (b), and trimethylolpropane is particularly preferable in view of reactivity with the urethane prepolymer (a).
The forming material contains the urethane prepolymer (a) as a main component. The urethane prepolymer (a) preferably contains 50% by weight or more of the solid content of the forming material.
The mixing 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 compounding 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 compounding ratio of the compound (b) is increased, deterioration of optical reliability of the polarizer may occur, and therefore, the compounding 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 the isocyanate group, a reaction catalyst may be used as the forming material. The reaction catalyst is not particularly limited, and a tin-based catalyst or an amine-based catalyst is preferred. The reaction catalyst may be used in 1 or 2 or more species. The amount of the reaction catalyst used is usually 5 parts by weight or less based on 100 parts by weight of the urethane prepolymer (a). When the amount of the reaction catalyst is large, the crosslinking reaction speed becomes fast, causing foaming of the formed material. Even when the foamed forming material is used, sufficient adhesiveness cannot be obtained. In general, when the reaction catalyst is used, it is preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 4 parts by weight.
In addition, a reaction catalyst may be used in order to increase the reactivity of the isocyanate group. The reaction catalyst is not particularly limited, and a tin-based catalyst or an amine-based catalyst is suitable. The reaction catalyst may be used in 1 or 2 or more species. 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 fast, and foaming of the formed material occurs. Even when the foamed forming material is used, sufficient adhesiveness cannot be obtained. In general, when a reaction catalyst is used, it is preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 4 parts by weight.
The tin catalyst may be either an inorganic one or an organic one, but is preferably an organic one. Examples of the inorganic tin-based catalyst include: stannous chloride, stannic chloride, and the like. The organic tin catalyst is preferably one having a skeleton such as a methyl group, an ethyl group, an ether group, or an ester group and having at least 1 kind of organic group such as an aliphatic group or an alicyclic group. Examples thereof include: tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate, and the like.
The amine catalyst is not particularly limited. For example, a catalyst having at least 1 organic group such as an alicyclic group is preferable, such as quinacridone, amidine, diazabicycloundecene, etc. Further, as the amine catalyst, triethylamine and the like can be mentioned. Examples of the reaction catalyst other than the above include cobalt naphthenate and benzyltrimethylammonium hydroxide.
The forming material is usually used in the form of a solution containing the urethane prepolymer (a) and the compound (b). The solution may be a solvent, or may be an aqueous solution such as an emulsion, a colloidal dispersion, or an aqueous solution.
The organic solvent is not particularly limited as long as it does not have a functional group containing an active hydrogen reactive with an isocyanate group and uniformly dissolves the urethane prepolymer (a) and the compound (b) constituting the forming material. The organic solvent may be used in 1 kind or in combination of 2 or more kinds. The organic solvent may be different solvents for the urethane prepolymer (a) and the compound (b). In this case, the respective solutions may be mixed after being prepared, thereby preparing the forming material. In addition, an organic solvent may be further added to the prepared forming material to adjust the viscosity of the forming material. In the case of a solvent-based solution dissolved in an organic solvent, alcohols, water, and the like exemplified below may be contained as the solvent.
As the organic solvent, there may be mentioned: 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.
When the aqueous dispersion is formed, alcohols such as n-butanol and isopropanol, and ketones such as acetone may be added. When the urethane prepolymer is formed into an aqueous solution, the urethane prepolymer may be formed into an aqueous solution by using a dispersant or introducing a functional group having low reactivity with an isocyanate group such as a carboxylate, a sulfonate or a 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 adhesive layer can be suppressed, the adhesiveness with the polarizer is more excellent, and the discoloration from the end of the polarizer can be prevented. Further, when the adhesive layer is formed on the transparent layer, the anchoring force of the adhesive layer can be increased. Examples of the epoxy resin having an aromatic ring include: bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; novolac type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin, and the like; and polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinylphenol, 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 1 kind alone, or 2 or more kinds may be used in combination.
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 making the weight average molecular weight of the epoxy resin in 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 part 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]
Figure BDA0003016076730000161
(wherein X represents a functional group containing at least 1 reactive group selected from the group consisting of a vinyl group, (meth) acryloyl group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group, and carboxyl group, and R1And R2Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, R1And R2May be connected 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 ratio. When the content ratio of the polymer (a) to the epoxy resin (b) is in the above range, a resin composition for a transparent layer which can suppress a change with time in the surface resistance value of the pressure-sensitive adhesive layer, has excellent adhesion to the polarizer, and can prevent discoloration from the end of the polarizer can be obtained. When the content ratio of the polymer (a) to the epoxy resin (b) is in the above range, the anchoring force of the adhesive layer can be increased when the adhesive layer is formed on the transparent layer. As a result, a polarizing plate (transparent-layer-attached one-side protective polarizing film) can be obtained which satisfies both of the adhesion between the polarizer and the transparent layer and the 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 same amount (50:50), the more likely the whitening of the protective layer may occur.
< Polymer (a) >
The polymer (a) is obtained by polymerizing more than 50 parts by weight of an acrylic monomer and more than 0 part 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 (e.g., a repeating unit of k in the following formula) in a side chain thereof by polymerizing the monomer represented by the above general formula (1) with an acrylic monomer component. This can improve the adhesion between the polarizer and the layer (transparent layer) formed using the resin composition. The substituent containing boron may be contained continuously or randomly in the polymer.
The polymer (a) may be used in 1 type alone, or may be used in combination of 2 or more types.
[ chemical formula 3]
Figure BDA0003016076730000171
(in the formula, R6Represents an arbitrary functional group, and j and k represent an integer of 1 or more).
The weight average molecular weight of the polymer (a) is preferably 10000 or more, more preferably 20000 or more, further preferably 35000 or more, and 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. By setting the weight average molecular weight of the polymer (a) to the above range, the crack resistance of the layer (transparent layer) formed using the above resin composition can be improved. The weight average molecular weight can be measured by GPC (solvent: Dimethylformamide (DMF)), for example.
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 part by weight and less than 50 parts by weight of a monomer represented by the formula (1), a polymerization initiator, and optionally other monomers, 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 can be used. Examples thereof include: (meth) acrylate monomers having a linear or branched structure, and (meth) acrylate monomers having a cyclic structure. In the present specification, (meth) acrylic acid means acrylic acid and/or methacrylic acid.
Examples of the (meth) acrylate 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) acrylate monomer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the (meth) acrylate monomer having a cyclic structure include: 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-diphenoxyethyl (meth) acrylate, o-diphenoxyethoxyethyl (meth) acrylate, m-diphenoxyethyl acrylate, p-diphenoxyethyl (meth) acrylate, o-diphenoxy-2-hydroxypropyl (meth) acrylate, p-diphenoxy-2-hydroxypropyl (meth) acrylate, m-diphenoxy-2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl-carbamate, and mixtures thereof, Biphenyl group-containing monomers such as N- (meth) acryloyloxyethyl-p-biphenyl-carbamate, N- (meth) acryloyloxyethyl-m-biphenyl-carbamate, and o-phenylphenol glycidyl ether acrylate, tribiphenyl (meth) acrylate, and o-terphenoxyethyl (meth) acrylate. 1-adamantyl (meth) acrylate and dicyclopentyl (meth) acrylate are preferably 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 in 2 or more kinds. In the present specification, a (meth) acryloyl group means an acryloyl group and/or a methacryloyl group.
In addition, a silsesquioxane compound having a (meth) acryloyl group may be used instead of the (meth) acrylate monomer. By using the silsesquioxane compound, an acrylic polymer having a high glass transition temperature can be obtained. Silsesquioxane compounds having various skeleton structures, for example, a cage structure, a ladder structure, a random structure, and the like are known as silsesquioxane compounds. The silsesquioxane compound may have only 1 of these structures, or may have 2 or more of them. The silsesquioxane compound may be used in 1 kind alone, or in combination of 2 or more kinds.
As the silsesquioxane compound having a (meth) acryloyl group, for example: MAC grade, and AC grade of the SQ series of east asia synthesis corporation. The MAC grade is a silsesquioxane compound containing a methacryloyl group, and specific examples thereof include: MAC-SQ TM-100, MAC-SQ SI-20, MAC-SQ HDM, etc. The AC grade is an acryloyl group-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 acrylic monomer and the monomer represented by the above general formula (1) is 100 parts by weight.
A monomer represented by the general formula (1)
A substituent containing boron is introduced into a side chain of the polymer (a) by using a monomer represented by the general formula (1). Therefore, the adhesion of the polarizer made of a PVA-based resin to the layer (transparent layer) formed using the resin composition can be typically improved. Further, 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 alone in 1 kind, or may be used in combination of 2 or more kinds.
[ chemical formula 4]
Figure BDA0003016076730000191
(wherein X represents a functional group containing at least 1 reactive group selected from the group consisting of a vinyl group, (meth) acryloyl group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group, and carboxyl group, and R1And R2Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, R1And R2May be connected to each other to form a ring).
The aliphatic hydrocarbon group includes a C1-20 linear or branched alkyl group optionally having a substituent, a C3-20 cyclic alkyl group optionally having a substituent, and a C2-20 alkenyl group. Examples of the aryl group include a phenyl group having 6 to 20 carbon atoms which may have a substituent, a naphthyl group having 10 to 20 carbon atoms which may have a substituent, and the like. 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. In addition, R is1And R2May be connected to each other to form a ring. R1And R2Preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably hydrogenAn 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) acryloyl 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 group is preferably a (meth) acryloyl group and/or a (meth) acrylamide group. By having these reactive groups, the adhesion between the polarizer and the 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 a vinyl group, (meth) acryloyl group, styryl group, (meth) acrylamide group, vinyl ether group, epoxy group, oxetanyl group, hydroxyl group, amino group, aldehyde group, and carboxyl group, and Y represents an organic group). The organic group 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 having 1 to 20 carbon atoms and optionally having a substituent, a cyclic alkylene group having 3 to 20 carbon atoms and optionally having a substituent, a phenylene group having 6 to 20 carbon atoms and optionally having a substituent, a naphthylene group having 10 to 20 carbon atoms and optionally having a substituent, and the like.
As the monomer represented by the above general formula (1), the following compounds can be specifically used.
[ chemical formula 5]
Figure BDA0003016076730000211
Examples of the monomer represented by the general formula (1) include, in addition to the compounds exemplified above, esters of hydroxyethyl acrylamide and boric acid, esters of hydroxymethyl acrylamide and boric acid, esters of hydroxyethyl acrylate and boric acid, and 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 a content of more than 0 part by weight and less than 50 parts by weight. Preferably 0.01 part by weight or more and less than 50 parts by weight, more preferably 0.05 part by weight to 20 parts by weight, and further preferably 0.1 part by weight 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 can be used. Examples thereof include: peroxides such as benzoyl peroxide, lauroyl peroxide, and sodium peroxide; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile and the like. The polymerization initiator may be used in 1 species alone or in 2 or more species.
The content of the polymerization initiator may be any appropriate 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 Process
As described above, the polymer (a) is preferably obtained by solution polymerization of monomer components such as an acrylic monomer and a monomer represented by the general formula (1). As the solvent used in the solution polymerization, any suitable solvent can be used. Examples thereof 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, di
Figure BDA0003016076730000221
Cyclic ether compounds such as alkanes. These solvents may be used alone in 1 kind, or may be used in combination in 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 can 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) >
As the epoxy resin (b), any appropriate epoxy resin can be used. As the epoxy resin (b), an epoxy resin having an aromatic ring is preferably used. 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. Further, when the adhesive layer is formed on the transparent layer, the anchoring force of the adhesive layer can be increased. Examples of the epoxy resin having an aromatic ring include: bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; novolac type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin, and the like; and polyfunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinylphenol, 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 1 kind alone, or 2 or more kinds may be used in combination.
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 making the weight average molecular weight of the epoxy resin (b) in 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 ingredients >
The resin composition for transparent layers may contain any appropriate other component in addition to the epoxy resin, the polymer (a) and the epoxy resin (b). Examples of other components include: a solvent, and an additive. As the solvent, a solvent that can be used when the polymer (a) is solution-polymerized may be used, and other solvents may be used. As the other solvent, ethyl acetate, toluene, methyl ethyl ketone, and cyclopentanone are preferably used. These solvents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
As the additive, any suitable additive may be used. Examples thereof include: surfactant, ultraviolet absorbent, antioxidant, tackifier, etc. The additive may be used in a single amount of 1 kind, or may be used in combination of 2 or more kinds. 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 epoxy resin composition can be prepared by mixing the polymer (a), the epoxy resin (b), and any appropriate additive used as needed in any appropriate solvent. In addition, when the polymer (a) is polymerized by solution polymerization, it can be prepared by adding and mixing the epoxy resin (b) and any appropriate additive to a polymerization solution of the polymer (a).
Examples of the material for forming the transparent layer other than the material for forming the urethane prepolymer (a), the material for forming the epoxy resin, and the material for forming 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 and then cured, and the transparent layer may be obtained as a coating layer. This is generally carried out by the following method: and drying the coating at about 30 to 100 ℃, preferably about 50 to 80 ℃ for about 0.5 to 15 minutes after the coating, thereby forming a cured layer. When the forming material contains an isocyanate component, the reaction may be accelerated by annealing at about 30 to 100 ℃, preferably at about 50 to 80 ℃ for about 0.5 to 24 hours.
The adhesive composition for forming the first adhesive layer 21 will be described below.
The pressure-sensitive adhesive composition contains a (meth) acrylic polymer (A) and an ionic compound (B).
The (meth) acrylic polymer (a) contains, as a main component, an alkyl (meth) acrylate (a1) as a monomer unit. The term (meth) acrylate refers to acrylate and/or methacrylate, and has the same meaning as (meth) acrylate in the present invention.
Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer (A) include linear or branched alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group, a decyl group, an isodecyl group, a dodecyl group, an isomyristyl group, a lauryl group, a tridecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. 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 (a1) is preferably 70% by weight or more of the weight ratio of all the constituent monomers (100% by weight) constituting the (meth) acrylic polymer (a) in terms of monomer units. The weight ratio of the alkyl (meth) acrylate (a1) may be considered as the remainder of the other comonomers. It is preferable to set the weight ratio of the alkyl (meth) acrylate (a1) within the above range in order to secure adhesiveness.
For the purpose of improving adhesiveness and heat resistance, in the (meth) acrylic polymer (a), in addition to the monomer unit of the alkyl (meth) acrylate (a1), 1 or more kinds of comonomers having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group may be introduced by copolymerization.
As the above-mentioned comonomer, for example: amide group-containing monomers, carboxyl group-containing monomers, hydroxyl group-containing monomers, and the like. Of these, the amide group-containing monomer (a2) is preferred.
In the case where the amide group introduced into the side chain of the (meth) acrylic polymer (a) as the base polymer is present in the pressure-sensitive adhesive composition used for forming the first pressure-sensitive adhesive layer, the presence of the amide group makes it possible to suppress the variation and increase in the surface resistance value of the first pressure-sensitive adhesive layer adjusted by blending the ionic compound (B) even in a humidified environment, and is preferable in that the variation and increase is maintained within a desired value range. It is considered that the compatibility between the (meth) acrylic polymer (a) and the ionic compound (B) is improved by the presence of an amide group introduced as a functional group of the comonomer into the side chain of the (meth) acrylic polymer (a).
In addition, when the amide group introduced into the side chain of the (meth) acrylic polymer (a) as the base polymer is present in the pressure-sensitive adhesive layer, the durability to both glass and a transparent conductive layer (ITO layer and the like) is good, and peeling, lifting and the like in a state of being attached to a liquid crystal panel can be suppressed. In addition, durability can be satisfied even in a humidified environment (after a humidification reliability test).
The amide group-containing monomer (a2) is a compound having an amide 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 amide group-containing monomer (a2) include acrylamide 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, and mercaptoethyl (meth) acrylamide; n-acryloyl heterocyclic monomers such as N- (meth) acryloyl morpholine, N- (meth) acryloyl piperidine, and N- (meth) acryloyl pyrrolidine; and N-vinyl lactam-containing monomers such as N-vinylpyrrolidone and N-vinyl-epsilon-caprolactam. The amide group-containing monomer (a2) is preferable in terms of suppressing an increase in surface resistance value with time (particularly in a humidified environment) and satisfying durability. In particular, among the amide group-containing monomers (a2), N-vinyl lactam group-containing monomers are particularly preferable in that the increase in surface resistance value is suppressed over time (particularly under a humidified environment) and the durability against the transparent conductive layer (touch sensor layer) is satisfied. Although not illustrated above, it is preferable that the amide group-containing monomer having a hydroxyl group is not used because the conductivity tends to be improved when combined with the ionic compound (B), and the anchor force with respect to the polarizing film (optical film) and reworking property with respect to the transparent conductive layer (touch sensor layer) are problematic when the use ratio of the amide group-containing monomer having a hydroxyl group is increased.
The weight ratio of the amide group-containing monomer (a2) is preferably 0.1% by weight or more, from the viewpoint of suppressing an increase in surface resistance value with time (particularly in a humidified environment). The above weight ratio is preferably 0.3 wt% or more, and more preferably 0.5 wt% or more. On the other hand, if the weight ratio is too large, the anchoring property to a base material film such as a polarizing film tends to be lowered, and therefore, the weight ratio is preferably 35% by weight or less, more preferably 20% by weight or less, still more preferably 10% by weight or less, and particularly preferably less than 5% by weight.
The carboxyl group-containing monomer is a compound having a carbonyl 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 carboxyl group-containing monomer include: (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. Among the above carboxyl group-containing monomers, acrylic acid is preferred from the viewpoint 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: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl acrylate. Among the above hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable from the viewpoint of durability, and 4-hydroxybutyl (meth) acrylate is particularly preferable.
When the binder composition contains a crosslinking agent, the carboxyl group-containing monomer and the hydroxyl group-containing monomer serve as 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, they are preferably used for improving the cohesive property and heat resistance of the pressure-sensitive adhesive layer to be obtained. The carboxyl group-containing monomer is preferable in terms of both durability and reworkability, and the hydroxyl group-containing monomer is preferable in terms of reworkability.
The weight ratio of the carboxyl group-containing monomer is preferably 2% by weight or less, more preferably 0.01 to 2% by weight, even more preferably 0.05 to 1.5% by weight, even more preferably 0.1 to 1% by weight, and most preferably 0.1 to 0.5% by weight. It is preferable to set the weight ratio of the carboxyl group-containing monomer to 0.01 wt% or more in terms of durability. On the other hand, when the amount is more than 2% by weight, it is not preferable from the viewpoint of the reworkability.
The weight ratio of the hydroxyl group-containing monomer is preferably 3% by weight or less, more preferably 0.01 to 3% by weight, even more preferably 0.1 to 2% by weight, and even 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 wt% or more. On the other hand, if the amount is more than 3% by weight, the amount is not preferable in view of durability.
In addition, as comonomers, for example: an aromatic ring-containing (meth) acrylate. The aromatic ring-containing (meth) acrylate is a compound having an aromatic ring structure in its structure and 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: (meth) acrylates having a benzene ring such as 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, methylphenyl (meth) acrylate, and styryl (meth) acrylate; (meth) acrylates having a naphthalene ring such as hydroxyethylated β -naphthol acrylate, 2-naphthylethyl (meth) acrylate, 2-naphthyloxyethyl acrylate, and 2- (4-methoxy-1-naphthyloxy) ethyl (meth) acrylate; 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, from the viewpoint of adhesion characteristics 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, even more preferably 10 to 22% by weight, and even 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 display unevenness. On the other hand, if the amount is more than 25% by weight, the suppression of the display unevenness is rather insufficient, and the durability tends to be lowered.
Specific examples of the other comonomers other than the above include acid 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) acrylamidopropanesulfonic acid, and sulfopropyl (meth) acrylate; phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate, and the like.
Further, as examples of the monomer for the purpose of modification, there may be mentioned: alkylaminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; succinimide 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 itaconimide monomers such as N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, and N-dodecylitaconimide.
As the modifying monomer, a vinyl monomer such as vinyl acetate or vinyl propionate; 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, methoxy ethylene glycol (meth) acrylate, and methoxy polypropylene glycol (meth) acrylate; acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine-containing (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate. Further, isoprene, butadiene, isobutylene, vinyl ether and the like are exemplified.
Examples of the copolymerizable monomer other than those described above include silane-based monomers containing a silicon atom. Examples of the silane monomer include: 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-acryloxydecyltriethoxysilane, and the like.
In addition, as comonomers, it is possible to use: a polyfunctional 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, for example, 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, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, a polyester (meth) acrylate obtained by adding 2 or more unsaturated double bonds such as (meth) acryloyl groups and vinyl groups to a polyester, epoxy, urethane, or other skeleton as functional groups similar to those of the monomer components, Epoxy (meth) acrylates, urethane (meth) acrylates, and the like.
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 still more preferably about 0 to 5% in the weight ratio 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 preferably from 100 to 250 ten thousand. In consideration 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. When the weight average molecular weight is more than 250 ten thousand, the adhesive tends to be easily hardened and easily peeled off. 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 view of durability. The weight average molecular weight and the molecular weight distribution (Mw/Mn) were determined from values measured by GPC (gel permeation chromatography) and calculated in terms of 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 polymerizations. The (meth) acrylic polymer (a) to be obtained 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 stream of an inert gas such as nitrogen, and a polymerization initiator is added thereto, usually under reaction conditions of about 50 to 70 ℃ and about 5 to 30 hours.
The polymerization initiator, chain transfer agent, emulsifier, and the like 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 by the amount of the polymerization initiator, the chain transfer agent and the reaction conditions, and the amount thereof can be appropriately adjusted depending on the kind thereof.
The adhesive composition of the present invention contains an ionic compound (B). As the ionic compound (B), an alkali metal salt and/or an organic cation-anion salt can be preferably used. The alkali metal salt may be an organic salt or an inorganic salt of an alkali metal. The term "organic cation-anion salt" as used herein means an organic salt in which the cation portion is composed of an organic substance, and the anion portion may be either an organic substance or an inorganic substance. The "organic cation-anion salt" is also referred to as an ionic liquid or an ionic solid.
< alkali Metal salt >
Examples of the alkali metal ion constituting the cation portion of the alkali metal salt include lithium, sodium, potassium and the like. Among these alkali metal ions, lithium ions are preferable.
The anion portion of the alkali metal salt may be composed of an organic substance or an inorganic substance. Examples of the anion portion constituting the organic salt include: CH (CH)3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)3C-、C4F9SO3 -、C3F7COO-、(CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -、PF6 -、CO3 2-And anions represented by the following general formulae (A) to (D).
(A)：(CnF2n+1SO2)2N-(wherein n is an integer of 10 to 10),
(B)：CF2(CmF2mSO2)2N-(wherein m is an integer of 1 to 10),
(C)：-O3S(CF2)lSO3 -(wherein l is an integer of 1 to 10),
(D)：(CpF2p+1SO2)N-(CqF2q+1SO2) And (wherein p and q are integers of 1 to 10).
In particular, an anionic moiety containing a fluorine atom is preferably used because an ionic compound having good ion dissociation properties can be obtained. As the anion portion constituting the inorganic salt, Cl may be used-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-And the like. As the anion portion, (CF) is preferable3SO2)2N-、(C2F5SO2)2N-The (perfluoroalkylsulfonyl) imide represented by the above general formula (A) is particularly preferably (CF)3SO2)2N-Bis (trifluoromethanesulfonyl) imide shown, and (FSO)2)2N-Bis (fluorosulfonyl) imide is shown.
Specific examples of the organic salt of an alkali metal include: sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF3SO3、Li(CF3SO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C、KO3S(CF2)3SO3K、LiO3S(CF2)3SO3K, etc., among these, LiCF is preferred3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C, etc., more preferably Li (CF)3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2A fluorine-containing imide lithium salt such as a bis (fluorosulfonyl) imide lithium salt, for example, N, and a (perfluoroalkylsulfonyl) imide lithium salt is particularly preferable. Further, lithium salt of 4,4,5, 5-tetrafluoro-1, 3, 2-dithiazolidine-1, 1,3, 3-tetraoxide 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, and the cation component is composed of an organic substance. Specific examples of the cationic component include: pyridine compound
Figure BDA0003016076730000301
Cation, piperidine
Figure BDA0003016076730000302
Cation, pyrrolidine
Figure BDA0003016076730000303
Cation, cation having pyrroline skeleton, imidazole
Figure BDA0003016076730000304
Positive ions,Tetrahydropyrimidines
Figure BDA0003016076730000305
Cationic dihydropyrimidines
Figure BDA0003016076730000306
Cationic, pyrazoles
Figure BDA0003016076730000307
Cationic pyrazolines
Figure BDA0003016076730000308
Cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl
Figure BDA0003016076730000309
Cations, and the like.
Examples of the anionic component include: cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-、C4F9SO3 -、C3F7COO-、(CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -And anions represented by the following general formulae (A) to (D).
(A)：(CnF2n+1SO2)2N-(wherein n is an integer of 0 to 10),
(B)：CF2(CmF2mSO2)2N-(wherein m is an integer of 1 to 10),
(C)：-O3S(CF2)lSO3 -(wherein l is an integer of 1 to 10),
(D)：(CpF2p+1SO2)N-(CqF2q+1SO2) And (wherein p and q are integers of 1 to 10).
Among these, an anionic component containing a fluorine atom is preferably used because an ionic compound having good ionization property can be obtained.
The organic cation-anion salt is suitably selected from compounds composed of a combination of the above-mentioned cation component and anion component. Preferred examples of the organic cation-anion salt include: methyltrioctylammonium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidine
Figure BDA00030160767300003010
Bis (trifluoromethanesulfonyl) imide and ethylmethylimidazole
Figure BDA00030160767300003011
Bis (fluorosulfonyl imide). Among them, 1-methyl-1-propylpyrrolidine is more preferable
Figure BDA00030160767300003012
Bis (trifluoromethanesulfonyl) imide and ethylmethylimidazole
Figure BDA00030160767300003013
Bis (fluorosulfonyl imide).
In addition, examples of the ionic compound (B) include inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate, in addition to the alkali metal salts and the organic cation-anion salts described above.
The ionic compound (B) may be used alone or in combination of two or more in order to obtain a desired resistance value. Particularly, the surface resistance of the adhesive layer is controlled to 1X 1010～1×1012In the case where the range of Ω/□ is intended, the ionic compound (B) is preferably an alkali metal salt in view of improving antistatic performance, and by using an alkali metal salt, a pressure-sensitive adhesive having high antistatic performance can be obtained even if the blending proportion is small. On the other hand, the surface resistance of the adhesive layer was controlled to 1X 108～1×1010In the case where the range of Ω/□ is intended, the ionic compound (B) is preferably an organic cation-anion salt in view of improving antistatic performance, and by using the organic cation-anion salt, even if the blending ratio 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 can be appropriately adjusted so as to satisfy the antistatic property of the adhesive layer and the sensitivity of the touch panel. For example, it is preferable to adjust the ratio of the ionic compound (B) so that the surface resistance value of the pressure-sensitive adhesive layer is 1.0 × 10 in consideration of the weight ratio of the amide group-containing monomer (a2) introduced into the (meth) acrylic polymer (a), the type of the transparent protective film of the polarizing film, and the like, and in accordance with the type of the liquid crystal panel having a touch sensor function incorporated therein8～1.0×1012Range of omega/□. For example, in the liquid crystal panel with built-in touch sensor function of the built-in type shown in fig. 1, it is preferable to control the initial surface resistance value of the first pressure-sensitive adhesive layer to 1 × 108～1×1010Range of omega/□. In the liquid crystal panel with a touch sensor function of the semi-embedded type shown in fig. 2 or the external embedded type shown in fig. 3, the initial surface resistance value of the first pressure-sensitive adhesive layer is preferably controlled to 1 × 1010～1×1012Range of omega/□.
The first pressure-sensitive adhesive layer is controlled so as to satisfy a variation ratio (b/a) of the surface resistance value of 10 or less. A first polarizing film with a pressure-sensitive adhesive layer was produced in a state in which the first pressure-sensitive adhesive layer was provided on the transparent layer of the first polarizing film and a separator was provided on the first pressure-sensitive adhesive layer, wherein a represents a surface resistance value of the first pressure-sensitive adhesive layer when the separator was peeled off immediately after the first polarizing film with the pressure-sensitive adhesive layer was produced, and b represents a surface resistance value of the first pressure-sensitive adhesive layer when the first polarizing film with the pressure-sensitive adhesive layer was put into a humidified atmosphere at 60 ℃/95% RH for 250 hours and further dried at 40 ℃ for 1 hour, and then the separator was peeled off. When the variation ratio (b/a) is more than 10, the antistatic function of the pressure-sensitive adhesive layer in a humidified environment is lowered. The variation ratio (b/a) is preferably 5 or less, more preferably 3.5 or less, further preferably 2.5 or less, further preferably 2 or less, and most preferably 1.5 or less.
The proportion of the ionic compound (B) is preferably, for example, 0.01 part by weight or more based on 100 parts by weight of the (meth) acrylic polymer (a). It is preferable to use 0.01 part by weight or more of the ionic compound (B) in order to improve the antistatic property. From this viewpoint, the ionic compound (B) is preferably 0.1 part by weight or more, and more preferably 0.5 part by weight or more. On the other hand, when the amount of the ionic compound (B) increases, the surface resistance value becomes too low, and there is a possibility that the sensitivity of the touch panel is lowered due to a baseline variation (malfunction at the time of touch caused by too low surface resistance value). When the amount of the ionic compound (B) is increased, the ionic compound (B) may be precipitated, and the wet peeling is likely to occur. From this viewpoint, the ionic compound (B) is usually 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.
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 compound can be used. Examples of the organic crosslinking agent include: isocyanate crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, imine crosslinking agents, and the like. The polyfunctional metal chelate compound is a chelate compound obtained by covalently bonding or coordinately bonding a polyvalent metal to an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn and Ti. Examples of the atom in the covalently or coordinately bonded organic compound include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.
The crosslinking agent (C) is preferably an isocyanate-based crosslinking agent and/or a peroxide-based crosslinking agent.
As the isocyanate-based crosslinking agent (C), a compound having at least 2 isocyanate groups can be used. For example, known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and the like, which are generally used in the urethanization reaction, can be used.
The peroxide may be suitably used as long as it is a peroxide which generates radical active species by heating or light irradiation and crosslinks the base polymer of the pressure-sensitive adhesive composition, but in view of handling and stability, a peroxide having a 1-minute half-life temperature of 80 to 160 ℃ is preferably used, and a peroxide having a 1-minute half-life temperature of 90 to 140 ℃ is more preferably used.
Examples of peroxides that can be used include: di (2-ethylhexyl) peroxydicarbonate (1-minute half-life temperature: 90.6 ℃ C.), di (4-tert-butylcyclohexyl) peroxydicarbonate (1-minute half-life temperature: 92.1 ℃ C.), di-sec-butyl peroxydicarbonate (1-minute half-life temperature: 92.4 ℃ C.), tert-butyl peroxyneodecanoate (1-minute half-life temperature: 103.5 ℃ C.), tert-hexyl peroxypivalate (1-minute half-life temperature: 109.1 ℃ C.), tert-butyl peroxypivalate (1-minute half-life temperature: 110.3 ℃ C.), dilauroyl peroxide (1-minute half-life temperature: 116.4 ℃ C.), di-n-octanoyl peroxide (1-minute half-life temperature: 117.4 ℃ C.), 1,3, 3-tetramethylbutyl peroxy2-ethylhexanoate (1-minute half-life temperature: 124.3 ℃ C.), di (4-methylbenzoyl) peroxide (1-minute half-life temperature: 128.2 ℃ C.), and, Dibenzoyl peroxide (1 minute half-life temperature: 130.0 ℃ C.), tert-butyl peroxyisobutyrate (1 minute half-life temperature: 136.1 ℃ C.), 1-bis (tert-hexyl peroxide) cyclohexane (1 minute half-life temperature: 149.2 ℃ C.). Among them, bis (4-t-butylcyclohexyl) peroxydicarbonate (1-minute half-life temperature: 92.1 ℃ C.), dilauroyl 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 its 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). When the amount of the crosslinking agent (C) is less than 0.01 parts by weight, the crosslinking of the pressure-sensitive adhesive layer may be insufficient, and the durability and the adhesive properties may not be satisfied, whereas when the amount is more than 3 parts by weight, the pressure-sensitive adhesive layer tends to be too hard and the durability tends to be lowered.
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: an epoxy-containing silane coupling agent such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, an amino-containing silane coupling agent such as 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine and N-phenyl-gamma-aminopropyltrimethoxysilane, a (meth) acryloyl silane coupling agent such as 3-acryloxypropyltrimethoxysilane or 3-methacryloxypropyltriethoxysilane, a (meth) acryloyl silane coupling agent such as a silane coupling agent, a silane coupling agent, Isocyanate-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane, and the like. As the silane coupling exemplified above, an epoxy group-containing silane coupling agent is preferable.
Further, as the silane coupling agent (D), a silane coupling agent having a plurality of alkoxysilyl groups in the molecule may be used. Specific examples thereof include: x-41-1053, X-41-1059, 1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, and X-40-2651 manufactured by shin-Etsu chemical Co. These silane coupling agents having a plurality of alkoxysilyl groups in the molecule are less volatile, and are preferable because they have a plurality of alkoxysilyl groups and are effective for improving durability. In particular, when the adherend of the optical film with an adhesive layer is a transparent conductive layer (for example, ITO or the like) in which alkoxysilyl groups are less reactive than glass, the 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. Even when the adherend is a transparent conductive layer (for example, ITO), the silane coupling agent having a plurality of alkoxysilyl groups in the molecule and an epoxy group tends to have good durability. Specific examples of the silane coupling agent having a plurality of alkoxysilyl groups in the molecule and an epoxy group include X-41-1053 and X-41-1059A, X-41-1056 manufactured by shin-Etsu chemical Co., Ltd, and X-41-1056 manufactured by shin-Etsu 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, and the total content thereof is preferably 5 parts by weight or less, more preferably 0.001 to 5 parts by weight, even more preferably 0.01 to 1 part by weight, even more preferably 0.02 to 1 part by weight, and even more preferably 0.05 to 0.6 part by weight, based on 100 parts by weight of the (meth) acrylic polymer (a), and is an amount for improving 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 reworkability can be improved. The polyether compound (E) may be, for example, a polyether compound disclosed in 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, based on 100 parts by weight of the (meth) acrylic polymer (a). When the amount of 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 part by weight or more, more preferably 0.1 part by weight or more. On the other hand, when the amount of the polyether compound (E) is more than 10 parts by weight, it is not preferable in view of durability. The polyether compound (E) is preferably 5 parts by weight or less, more preferably 2 parts by weight or less. The ratio of the polyether compound (E) may be set in a preferable range by using the upper limit value or the lower limit value.
The pressure-sensitive adhesive composition of the present invention may contain other known additives, and for example, a polyether compound such as a polyalkylene glycol such as polypropylene glycol, a colorant, a powder such as a pigment, a dye, a surfactant, a plasticizer, a thickener, a surface lubricant, a leveling agent, a softening agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, an inorganic or organic filler, a metal powder, granules, a foil, and the like may be added as appropriate depending on the application. Further, redox species to which a reducing agent is added 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, and still more preferably 1 part by weight or less, based on 100 parts by weight of the (meth) acrylic polymer (a).
The pressure-sensitive adhesive layer can be formed, for example, by a method in which the pressure-sensitive adhesive composition is applied to a separator or the like subjected to a peeling treatment, and the pressure-sensitive adhesive layer is formed by drying and removing a polymerization solvent or the like, and then transferred onto an optical film (polarizing film); or a method in which the pressure-sensitive adhesive composition is applied to an optical film (polarizing film), and the polymerization solvent or the like is dried to remove the polymerization solvent and form a pressure-sensitive adhesive layer on the optical film. In the case of applying the adhesive, one or more solvents other than the polymerization solvent may be newly added.
The thickness of the first pressure-sensitive adhesive layer 21 is not particularly limited, and is, for example, about 1 to 100 μm, preferably 2 to 50 μm, more preferably 2 to 40 μm, and further preferably 5 to 35 μm.
< conductive layer >
The thickness of the conductive layer d is preferably 1 μm or less, more preferably 0.01 to 0.5 μm, even more preferably 0.01 to 0.2 μm, and even more preferably 0.01 to 0.1 μm, from the viewpoint of stability of surface resistance value and adhesion to the first pressure-sensitive adhesive layer 21. In addition, from the viewpoint of antistatic function, the surface resistance value of the conductive layer d is preferably 1 × 108～1×1012Omega/□, more preferably 1X 108～1×1011Omega/□, more preferably 1X 108～1×1010Ω。
The conductive layer can be formed from various antistatic agent 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 viewpoint of optical properties, appearance, antistatic effect, and stability of antistatic effect in hot and humid conditions. In particular, a conductive polymer such as polyaniline or polythiophene is preferably used. As the conductive polymer, an organic solvent-soluble, water-soluble or water-dispersible polymer can be suitably used, and a water-soluble conductive polymer or a water-dispersible conductive polymer is preferably used. This is because the water-soluble conductive polymer or the water-dispersible conductive polymer can be used as an aqueous solution or an aqueous dispersion to prepare a coating solution for forming an antistatic layer, and the coating solution does not require the use of a nonaqueous organic solvent and can suppress the denaturation of the optical film substrate by the organic solvent. The aqueous solution or aqueous dispersion may contain an aqueous solvent other than water. Examples thereof include: alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol, tert-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, and cyclohexanol.
The water-soluble conductive polymer or water-dispersible conductive polymer such as polyaniline or polythiophene preferably has a hydrophilic functional group in the molecule. Examples of the hydrophilic functional group include: sulfonic acid groups, amino groups, amide groups, imine groups, quaternary ammonium salt groups, hydroxyl groups, mercapto groups, hydrazine groups, carboxyl groups, sulfate groups, phosphate groups, or salts thereof. The water-soluble conductive polymer or water-dispersible conductive polymer can be easily produced by having a hydrophilic functional group in the molecule, and thereby easily dissolving in water and dispersing in water in the form of fine particles.
Examples of commercially available products of water-soluble conductive polymers include polyaniline sulfonic acid (weight average molecular weight of 150000 in terms of polystyrene, manufactured by mitsubishi positive corporation) and the like. Examples of commercially available products of water dispersible conductive polymers include polythiophene-based conductive polymers (trade name Denatron series, manufactured by Nagase ChemteX corporation), and the like.
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-forming properties of the antistatic agent, adhesion to the optical film, and the like. In the case where the antistatic agent is an aqueous material of a water-soluble conductive polymer or a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. Examples of binders include: comprises
Figure BDA0003016076730000351
Oxazoline-based polymers, polyurethane-based resins, polyester-based resins, acrylic-based resins, polyether-based resins, cellulose-based resins, polyvinyl alcohol-based resins, epoxy resins, polyvinyl pyrrolidone, 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 combination of 1 or more than 2 as appropriate for their use.
The amount of the antistatic agent or the binder to be used varies depending on the kind thereof, but is preferably such that the surface resistance of the conductive layer to be obtained becomes 1X 108～1×1012The mode of omega/□ is controlled.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In each example, parts and% are on a weight basis. The following conditions of standing at room temperature are not particularly limited, and are 23 ℃ and 65% RH.
< (meth) acrylic Polymer (A) determination of weight-average molecular weight
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).
An analysis device: HLC-8120GPC, manufactured by Tosoh corporation
Column: G7000H, manufactured by Tosoh corporationXL+GMHXL+GMHXL
Column size: each 7.8mm phi x 30cm totals 90cm
Column temperature: 40 deg.C
Flow rate: 0.8mL/min
Injection amount: 100 μ L
Eluent: tetrahydrofuran (THF)
The detector: differential Refractometer (RI)
Standard sample: polystyrene
(production of thin polarizer A)
One surface of a substrate of an amorphous isophthalic acid-copolymerized polyethylene terephthalate (IPA-copolymerized PET) film (thickness: 100 μm) having a water absorption rate of 0.75% and a Tg of 75 ℃ was subjected to corona treatment, and an aqueous solution containing polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl-modification rate 4.6%, saponification degree 99.0 mol% or more, manufactured by japan synthetic chemical industries, ltd., trade name "gohseferz 200") in a ratio of 9:1 was applied to the corona-treated surface at 25 ℃ and dried to form a PVA-based resin layer having a thickness of 11 μm, thereby producing a laminate.
The resultant laminate was subjected to free-end uniaxial stretching (auxiliary stretching treatment in a gas atmosphere) of 2.0 times in the longitudinal direction (longitudinal direction) in an oven at 120 ℃ between rolls having different peripheral speeds.
Next, the laminate was immersed in an insolubilization bath (an aqueous boric acid solution prepared 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 polarizing plate was immersed in a dyeing solution at a liquid temperature of 30 ℃ while adjusting the iodine concentration and the immersion time so as to achieve a predetermined transmittance. In this example, an aqueous iodine solution prepared by adding 0.2 parts by weight of iodine and 1.0 part by weight of potassium iodide to 100 parts by weight of water was immersed for 60 seconds (dyeing treatment).
Subsequently, the substrate was immersed in a crosslinking bath (aqueous boric acid solution prepared by mixing 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 30 ℃ for 30 seconds (crosslinking treatment).
Then, the laminate was immersed in an aqueous boric acid solution (aqueous solution prepared by mixing 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ℃, and uniaxially stretched in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds so that the total stretching ratio became 5.5 times (stretching treatment in the aqueous solution).
Then, the laminate was immersed in a cleaning bath (aqueous solution containing 4 parts by weight of potassium iodide per 100 parts by weight of water) at a liquid temperature of 30 ℃ (cleaning 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 obtained by polymerizing a (meth) acrylic monomer (ARUFON UP1190, manufactured by Toyo 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 Kayaku chemical Co., Ltd.).
(Material for Forming transparent layer)
Forming a material A: as the solution of the urethane prepolymer (a), a 75% ethyl acetate solution of a urethane prepolymer prepared from Tolylene Diisocyanate (TDI) and Trimethylolpropane (TMP) (trade name "Coronate L" available from Tosoh Corp.).
On the other hand, a trimethylolpropane solution was prepared by dissolving trimethylolpropane in cyclopentanone so that the solid content concentration became 10%.
To 100 parts of a 75% ethyl acetate solution of the urethane prepolymer (product of Tosoh corporation, trade name "Coronate L") was added the above trimethylolpropane solution so that the ratio of urethane prepolymer: the solid content ratio of trimethylolpropane was 90:10, 0.1 part of dioctyltin dilaurate catalyst (product name "EMBILIZER OL-1" available from Tokyo Seiki Kaisha) was further added, and a solid content concentration of methyl isobutyl ketone as a solvent was adjusted to 10%, thereby preparing a forming material (coating liquid).
Forming a material B: a urethane prepolymer coating solution was prepared by adding 0.1 part of dioctyltin dilaurate catalyst (trade name "EMBILIZER OL-1" manufactured by Tokyo Seisaku Co., Ltd.) to 100 parts of a 75% ethyl acetate solution of a urethane prepolymer prepared from tolylene diisocyanate and trimethylolpropane (trade name "Coronate L") and then adding methyl isobutyl ketone as a solvent to the mixture to give a solid content concentration of 10%.
Forming a material C: to 80 parts of a urethane acrylate resin (product name "violet UV-1700" manufactured by japan synthetic company) were added 20 parts of N-hydroxyethyl acrylamide (product name "HEAA" manufactured by nippon corporation) and 3 parts of a photopolymerization initiator (IRGACURE 907 manufactured by BASF corporation), and a urethane acrylate coating liquid was prepared so that a solid content concentration was 10% by using methyl isobutyl ketone as a solvent.
Forming a material D: 97.0 parts of methyl methacrylate, 3.0 parts of a monomer represented by general formula (1) (a monomer of general formula (1 e)), and 0.2 part of a polymerization initiator (2, 2' -azobisisobutyronitrile) were dissolved in 200 parts of toluene. Then, the polymerization reaction was carried out for 5 hours while heating to 70 ℃ in a nitrogen atmosphere, to obtain a polymer (a) (solid content concentration: 33% by weight). The weight average molecular weight of the resulting polymer (a) was 85000.
An acrylic-epoxy resin-forming material (coating liquid) was prepared by mixing 15 parts of the polymer (a) and 85 parts of an epoxy resin (product name: jER (registered trademark) YX7200B35, manufactured by mitsubishi chemical corporation).
Forming a material E: a polyvinyl alcohol resin (product name: JC-25, manufactured by JAPAN VAM & POVAL Co., Ltd.) having a polymerization degree of 2500 and a saponification degree of 99.0% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight.
(preparation of Material for Forming conductive layer)
8.6 parts by weight of a solution (trade name: Denatron P-580W, tradename of tradename, trade
Figure BDA0003016076730000381
A coating liquid for forming a conductive layer having a solid content of 0.5% by weight was prepared by mixing 1 part of a solution of an oxazoline-based acrylic polymer (trade name: EPOCROS WS-700, manufactured by Nippon catalyst Co., Ltd.) and 90.4 parts of water. The obtained coating liquid for forming a conductive layer contained 0.04% by weight of a polythiophene polymer and contained
Figure BDA0003016076730000382
Oxazoline-based acrylic acid polymer 0.25 wt%.
Example 1
< preparation of acrylic Polymer (A) >
A4-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a condenser was charged with a monomer mixture containing 96.2 parts of butyl acrylate, 3 parts of N-vinyl-2-pyrrolidone, 0.5 part of 4-hydroxybutyl acrylate, and 0.3 part of acrylic acid. Further, 0.1 part of 2, 2' -azobisisobutyronitrile as a polymerization initiator was added to 100 parts of the monomer mixture (solid content) together with 100 parts of ethyl acetate, nitrogen gas was introduced while slowly stirring the mixture for nitrogen substitution, and then the liquid temperature in the flask was kept near 55 ℃ to carry out polymerization for 8 hours, thereby preparing a solution of a (meth) acrylic polymer having a weight average molecular weight (Mw) of 160 ten thousand and a Mw/Mn of 3.7.
(preparation of adhesive composition)
Ethylmethylimidazole as the ionic compound (B) was blended in 100 parts by weight of the solid content of the acrylic polymer solution obtained above
Figure BDA0003016076730000391
A solution of an acrylic pressure-sensitive adhesive composition was prepared from 7 parts of bis (fluorosulfonyl imide), 0.1 part of an isocyanate crosslinking agent (Takenate D160N manufactured by Mitsui chemical Co., Ltd., trimethylolpropane hexamethylene diisocyanate), 0.3 part of benzoyl peroxide (Nyper BMT manufactured by Nippon oil & fat Co., Ltd.), and 0.3 part of an epoxy group-containing silane coupling agent (X-41-1056 manufactured by shin-Etsu chemical Co., Ltd.).
(preparation of adhesive layer)
Then, the solution of the acrylic pressure-sensitive adhesive composition was applied to a silicone-based release agent-treated surface of a polyethylene terephthalate film (separator: MRF38, manufactured by Mitsubishi chemical polyester film Co., Ltd.), and dried at 155 ℃ for 1 minute so that the thickness of the pressure-sensitive adhesive layer after drying became 20 μm, and a pressure-sensitive adhesive layer was formed on the surface of the separator.
< production 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, the transparent protective film (acrylic) was bonded thereto, and then ultraviolet rays were irradiated as active energy rays to cure the adhesive. The ultraviolet irradiation uses a gallium-sealed metal halide lamp and an irradiation device: light HAMMER10 manufactured by Fusion UV Systems, valve: v valve, maximum illumination 1600mW/cm2Cumulative dose of radiation 1000/mJ/cm2(wavelength 380 to 440nm) and the illuminance of ultraviolet light were measured by using Sola-Check system manufactured by Solatell corporation. Next, the amorphous PET substrate was peeled off, and a single-sided protective polarizing film using a thin polarizer was produced. The optical properties of the resulting single-sided protective polarizing film were: the monomer transmittance is 42.8 percent, and the polarization degree is 99.99 percent.
< preparation of Single-sided protective polarizing film with transparent layer >
The material a for forming the transparent layer was applied to one surface of the polarizer of the single-sided protective polarizing film (polarizer surface not provided with a transparent protective film) by a wire bar coater, and then heat-treated at 60 ℃ for 5 minutes to form a urethane resin layer having a thickness of 3 μm.
< production of one-sided protective polarizing film with adhesive layer >
Next, the pressure-sensitive adhesive layer formed on the separator was transferred to the transparent layer formed on the one-side protective polarizing film, and the one-side protective polarizing film with the pressure-sensitive adhesive layer was produced.
Examples 2 to 18 and comparative examples 1 to 3
In example 1, a one-side protective polarizing film with a transparent layer and a one-side protective polarizing film with an adhesive layer were produced in the same manner as in example 1 except that the composition of the monomer mixture used for producing the acrylic polymer (a), the kind (EMI-FSI or Li-TFSI) of the ionic compound (B) used for producing the adhesive composition, the blending ratio thereof, the thickness of the adhesive layer, the kind of the material for forming the transparent layer, the thickness thereof, and the presence or absence of the conductive layer were changed as shown in table 1.
In the transparent layer of example 5, the material B for forming the transparent layer was applied to one surface of the polarizer of the single-sided protective polarizing film (polarizer surface not provided with a transparent protective film) 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. In addition, the formation of the transparent layer of example 6 was performed as follows: the material C was applied to one surface of the polarizer of the single-sided protective polarizing film (polarizer surface not provided with a transparent protective film) by a wire bar coater, and then heated at 90 ℃ for 1 minute. After heating, the coating layer was irradiated with a cumulative light amount of 300mJ/cm by a high-pressure mercury lamp2The urethane acrylate resin layer was formed to a thickness of 1 μm.
The transparent layers of examples 16 to 18 were formed as follows: the material D for forming the transparent layer was applied to one surface of the polarizer of the single-sided protective polarizing film (polarizer surface not provided with a transparent protective film) 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 formation of the transparent layer of comparative example 2 was performed as follows: the above-mentioned forming material E was applied to one surface of the polarizer of the single-sided protective polarizing film (polarizer surface having no transparent protective film) by a wire bar coater, and then heated at 60 ℃ for 3 minutes to form a polyvinyl alcohol resin layer having a thickness of 1.5. mu.m.
In comparative examples 1 and 3, no transparent layer was formed.
In example 15, the conductive layer forming coating liquid was applied to the transparent layer of the one-side protective polarizing film with a transparent layer so that the thickness after drying became 0.06 μm, and dried at 80 ℃ for 2 minutes to form a conductive layer. The resulting conductive layers each contained 8 wt% of a thiophene polymer
Figure BDA0003016076730000411
Oxazoline-based acrylic polymer 50 wt%.
The surface resistance of the conductive layer was measured on the conductive layer before the adhesive layer was formed and the conductive layer-side surface of the polarizing film with the transparent layer. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
The pressure-sensitive adhesive layer-attached one-side protective polarizing films obtained in the above examples and comparative examples were subjected to the following evaluations, and the evaluation results are shown in table 1. In each evaluation, "initial" is a value measured immediately after the production of the pressure-sensitive adhesive layer-attached one-side protective polarizing film or liquid crystal panel, and "after humidification" is a value measured after the obtained pressure-sensitive adhesive layer-attached polarizing film or liquid crystal panel is put into a humidified atmosphere at 60 ℃/95% RH for 250 hours and further dried at 40 ℃ for 1 hour.
< sheet resistance value (Ω/□): conductivity >
After the separator was peeled from the polarizing film with the pressure-sensitive adhesive layer, the surface resistance value of the pressure-sensitive adhesive layer surface was measured. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd. The surface resistance value of the pressure-sensitive adhesive layer surface in example 15 is a value measured from the surface of the conductive pressure-sensitive adhesive layer in a state where both the conductive layer and the conductive pressure-sensitive adhesive layer are present.
The variation ratio (b/a) in table 1 is a value (rounded value of the second decimal place) calculated from the "initial" surface resistance value (a) and the "post-humidification" surface resistance value (b).
As an index for reducing the risk of occurrence of "malfunction", a value with a small variation ratio is evaluated according to the following criteria.
A: a variation ratio of 2 or less
B: variation ratio of more than 2 and less than 10
C: variation ratio of 10 or more
< ESD test >
After the separator was peeled off from the one-side protective polarizing film with an adhesive layer, the resultant was bonded to the visible side of the in-cell liquid crystal cell or the out-cell liquid crystal cell as shown in table 1, thereby producing a liquid crystal panel with a built-in touch sensor function. That is, the polarizing films with adhesive layers obtained in examples 1 to 10 and 15 and comparative examples 1 to 2 were bonded to the first transparent substrate of the embedded liquid crystal cell shown in fig. 1 to form a first adhesive layer and a first polarizing film. The polarizing films with adhesive layers obtained in examples 11 to 14 and comparative example 3 were bonded to the sensor layer (touch sensor unit) of the externally-embedded liquid crystal cell shown in fig. 3, and a first adhesive layer and a first polarizing film were formed. An ESD (electrostatic discharge) gun (10kV) was applied to the polarizing film surface of the liquid crystal panel, and the time until the white spot portion was disappeared by the electricity was measured and judged according to the following criteria.
(evaluation criteria)
A: within 1 second
B: more than 1 second to within 3 seconds
C: more than 3 seconds to less than 10 seconds
D: more than 10 seconds
Figure BDA0003016076730000431
In the context of table 1, the following,
BA represents a butyl acrylate and is a butyl acrylate,
NVP represents N-vinyl-2-pyrrolidone,
HBA represents 4-hydroxybutyl acrylate,
AA represents an acrylic acid, and AA represents an acrylic acid,
EMI-FSI for ethylmethylimidazole
Figure BDA0003016076730000441
A bis (fluorosulfonyl) imide salt,
Li-TFSI represents lithium bis (trifluoromethanesulfonyl) imide.
As shown in table 1, it is understood from the descriptions of the examples and comparative examples that, in the case of using the one-side protective polarizing film, even when the initial surface resistance value of the pressure-sensitive adhesive layer is set to be low by blending the ionic compound with the acrylic polymer, in the example in which the one-side protective polarizing film has a predetermined transparent layer, the fluctuation ratio of the surface resistance value after humidification of the pressure-sensitive adhesive layer can be controlled to 10 or less, and the increase of the surface resistance value can be suppressed. That is, in the embodiment, since the variation ratio of the surface resistance value of the pressure-sensitive adhesive layer is small, the surface resistance value can be maintained within a desired range even after humidification, the touch panel sensitivity can be favorably maintained, the ESD test is favorable, and the static electricity unevenness can be suppressed.

Claims (32)

1. A liquid crystal panel with a built-in touch sensing function, comprising:
a liquid crystal cell having a liquid crystal layer and a touch sensor portion and having a touch sensing function built therein;
a first polarizing film disposed on a viewing side of the liquid crystal cell and a second polarizing film disposed on an opposite side to the viewing side; and
a first adhesive layer disposed between the first polarizing film and the liquid crystal cell,
wherein the first polarizing film has: a 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 the first polarizing film is provided on the first adhesive layer with the transparent layer interposed therebetween,
the first pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B),
the first adhesive layer satisfies: the variation ratio (b/a) of the surface resistance value is less than or equal to 10,
wherein a represents a surface resistance value of the first pressure-sensitive adhesive layer when the first polarizing film with the pressure-sensitive adhesive layer is peeled off immediately after the first polarizing film with the pressure-sensitive adhesive layer is produced in a state in which the first pressure-sensitive adhesive layer is provided on the transparent layer of the first polarizing film and a separator is provided on the first pressure-sensitive adhesive layer, and b represents a surface resistance value of the first pressure-sensitive adhesive layer when the first polarizing film with the pressure-sensitive adhesive layer is put into a humidified atmosphere of 60 ℃/95% RH for 250 hours and further dried at 40 ℃ for 1 hour, and then the separator is peeled off.
2. The touch sensor function built-in liquid crystal panel according to claim 1,
the transparent layer is formed directly on the polarizer.
3. The liquid crystal panel with built-in touch sensing function according to claim 1 or 2,
the thickness of the transparent layer is 10 μm or less.
4. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 3,
the transparent layer is a cured product of a forming material containing a urethane prepolymer which is a reaction product of an isocyanate compound and a polyol.
5. The liquid crystal panel with built-in touch sensing function according to claim 4,
the isocyanate compound contains at least 1 selected from the group consisting of toluene diisocyanate and diphenylmethane diisocyanate.
6. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 3,
the transparent layer contains an epoxy resin.
7. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 3,
the transparent layer is a resin composition containing a polymer (a) and an epoxy resin (b),
the polymer (a) is obtained by polymerizing more than 50 parts by weight of an acrylic monomer and more than 0 part by weight and less than 50 parts by weight of a monomer represented by the following general formula (1),
Figure FDA0003016076720000021
wherein X represents a functional group containing at least 1 reactive group selected from a vinyl group, a (meth) acryloyl 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, and R1And R2Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, R1And R2Optionally linked to each other to form a ring,
the content ratio of the polymer (a) to the epoxy resin (b) is 95: 5-60: 40 or 40: 60-1: 99 by weight ratio.
8. The liquid crystal panel with built-in touch sensing function according to claim 7,
the functional group represented by X in the general formula (1) is a functional group represented by a general formula (2),
general formula (2): Z-Y-
Wherein Z represents a functional group containing at least 1 reactive group selected from a vinyl group, a (meth) acryloyl 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, and Y represents an organic group.
9. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 8,
the (meth) acrylic polymer (A) contains, as monomer units, an alkyl (meth) acrylate (a1) and an amide group-containing monomer (a 2).
10. The touch sensor function built-in liquid crystal panel according to claim 9,
the amide group-containing monomer (a2) is an N-vinyl lactam-containing monomer.
11. The liquid crystal panel with built-in touch sensing function according to claim 9 or 10,
the (meth) acrylic polymer (A) contains 0.1% by weight or more of the amide group-containing monomer (a2) as a monomer unit.
12. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 11,
the ionic compound (B) is an alkali metal salt, and the surface resistance value of the first pressure-sensitive adhesive layer represented by a is 1X 1010～1×1012Ω/□。
13. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 12,
the ionic compound (B) is an organic cation-anion salt, and the surface resistance value of the first adhesive layer represented by a is 1X 108～1×1010Ω/□。
14. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 13,
the ionic compound (B) is contained in an amount of 0.01 part by weight or more based on 100 parts by weight of the (meth) acrylic polymer (A).
15. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 14,
a conductive layer is between the transparent layer and the first adhesive layer.
16. The touch sensor function built-in liquid crystal panel according to any one of claims 1 to 15,
the touch sensor portion is directly connected to the first adhesive layer.
17. A liquid crystal display device having the touch sensor function built-in liquid crystal panel according to any one of claims 1 to 16.
18. An adhesive layer-equipped polarizing film having: a polarizer, a transparent protective film disposed only on one surface of the polarizer, and a transparent layer disposed on the other surface of the polarizer,
and an adhesive layer is provided through the transparent layer,
wherein the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer (A) and an ionic compound (B),
the first adhesive layer satisfies: the variation ratio (b/a) of the surface resistance value is less than or equal to 10,
wherein a represents a surface resistance value of the pressure-sensitive adhesive layer when the polarizing film with the pressure-sensitive adhesive layer is peeled off immediately after the polarizing film with the pressure-sensitive adhesive layer is produced in a state in which a separator is provided on the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer, and b represents a surface resistance value of the pressure-sensitive adhesive layer when the polarizing film with the pressure-sensitive adhesive layer is put into a humidified atmosphere of 60 ℃/95% RH for 250 hours and further dried at 40 ℃ for 1 hour, and then the separator is peeled off.
19. The adhesive layer-equipped polarizing film according to claim 18,
the transparent layer is formed directly on the polarizer.
20. The adhesive layer-equipped polarizing film according to claim 18 or 19,
the thickness of the transparent layer is 10 μm or less.
21. The adhesive layer-equipped polarizing film according to any one of claims 18 to 20,
the transparent layer is a cured product of a forming material containing a urethane prepolymer which is a reaction product of an isocyanate compound and a polyol.
22. The adhesive layer-equipped polarizing film according to claim 21,
the isocyanate compound contains at least 1 selected from the group consisting of toluene diisocyanate and diphenylmethane diisocyanate.
23. The adhesive layer-equipped polarizing film according to any one of claims 18 to 20,
the transparent layer contains an epoxy resin.
24. The adhesive layer-equipped polarizing film according to any one of claims 18 to 20,
the transparent layer is a resin composition containing a polymer (a) and an epoxy resin (b),
the polymer (a) is obtained by polymerizing more than 50 parts by weight of an acrylic monomer and more than 0 part by weight and less than 50 parts by weight of a monomer represented by the following general formula (1),
Figure FDA0003016076720000041
wherein X represents a compound containing a group selected from a vinyl group, a (meth) acryloyl group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group and an oxetane groupFunctional group of at least 1 reactive group selected from the group consisting of a hydroxyl group, an amino group, an aldehyde group and a carboxyl group, R1And R2Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, R1And R2Optionally linked to each other to form a ring,
the content ratio of the polymer (a) to the epoxy resin (b) is 95: 5-60: 40 or 40: 60-1: 99 by weight ratio.
25. The adhesive layer-equipped polarizing film according to claim 24,
the functional group represented by X in the general formula (1) is a functional group represented by a general formula (2),
general formula (2): Z-Y-
Wherein Z represents a functional group containing at least 1 reactive group selected from a vinyl group, a (meth) acryloyl 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, and Y represents an organic group.
26. The adhesive layer-equipped polarizing film according to any one of claims 18 to 25,
the (meth) acrylic polymer (A) contains, as monomer units, an alkyl (meth) acrylate (a1) and an amide group-containing monomer (a 2).
27. The adhesive layer-equipped polarizing film according to claim 26,
the amide group-containing monomer (a2) is an N-vinyl lactam-containing monomer.
28. The adhesive layer-equipped polarizing film according to claim 26 or 27,
the (meth) acrylic polymer (A) contains 0.1% by weight or more of the amide group-containing monomer (a2) as a monomer unit.
29. The adhesive layer-equipped polarizing film according to any one of claims 18 to 28,
the ionic compound (B) is an alkali metal salt, and the surface resistance value of the first pressure-sensitive adhesive layer represented by a is 1X 1010～1×1012Ω/□。
30. The adhesive layer-equipped polarizing film according to any one of claims 18 to 30,
the ionic compound (B) is an organic cation-anion salt, and the surface resistance value of the first adhesive layer represented by a is 1X 108～1×1010Ω/□。
31. The adhesive layer-equipped polarizing film according to any one of claims 18 to 30,
the ionic compound (B) is contained in an amount of 0.01 part by weight or more based on 100 parts by weight of the (meth) acrylic polymer (A).
32. The adhesive layer-equipped polarizing film according to any one of claims 18 to 31,
a conductive layer is between the transparent layer and the first adhesive layer.
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