CN112433287B - Polarizing film with adhesive layer and image display device - Google Patents

Polarizing film with adhesive layer and image display device Download PDF

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Publication number
CN112433287B
CN112433287B CN202011114600.2A CN202011114600A CN112433287B CN 112433287 B CN112433287 B CN 112433287B CN 202011114600 A CN202011114600 A CN 202011114600A CN 112433287 B CN112433287 B CN 112433287B
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adhesive layer
polarizing film
film
image display
meth
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CN112433287A (en
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山本真也
形见普史
柳沼宽教
保井淳
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Nitto Denko Corp
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Nitto Denko Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention relates to a polarizing film with an adhesive layer and an image display device. The polarizing film with an adhesive layer of the present invention is used in an image display device at a position closer to the viewing side than an image display portion, and has a polarizing film and adhesive layers on both sides of the polarizing film, wherein the polarizing film has a polarizer and transparent protective films on both sides of the polarizer, the transparent protective film on the viewing side of the polarizer has a transmittance of less than 6% at 380nm, and the adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function. According to the present invention, it is possible to provide a polarizing film with an adhesive layer which can solve the problem of reduction in yield, can provide a sufficient ultraviolet blocking function even when the polarizing film is thin, and can suppress the occurrence of curling.

Description

Polarizing film with adhesive layer and image display device
The present application is a divisional application of chinese patent application with application number 2016877555. X, of which the application date is 2016, 11 and 18.
Technical Field
The present invention relates to a polarizing film with an adhesive layer used in an image display device. The present invention also relates to an image display device using the polarizing film with an adhesive layer. Examples of the image display device include a liquid crystal display device, an organic EL (electro luminescence) display device, a PDP (plasma display panel), and electronic paper.
Background
In a liquid crystal display device, an organic EL display device, and the like, it is necessary to dispose polarizing elements on both sides of a liquid crystal cell in the liquid crystal display device, for example, due to the image forming method, and a polarizing film is generally attached thereto. In addition, various optical elements have been used for display panels such as liquid crystal panels and organic EL panels, in addition to polarizing films, in order to improve the display quality of the display.
Polarizing films used in these image display devices generally have a structure in which a polarizer is sandwiched between two protective films, and triacetyl cellulose (TAC) is widely used as a protective film.
In recent years, along with the trend of weight reduction and thinning of image display devices, thinning of each member used in the image display devices has been demanded, and thinning of protective films of polarizing films has been demanded. When the thickness of the protective film is reduced, ultraviolet rays incident on the image display device cannot be sufficiently blocked, and the following problems occur: not only polarizers but also various optical members including liquid crystal panels, organic EL elements, and the like used in image display devices are degraded by ultraviolet rays.
In order to solve such a problem, for example, the following adhesive sheet is known: a transparent double-sided adhesive sheet for an image display device, which is provided between a surface protection panel and a viewing side of a liquid crystal module in the image display device, for integrating both members, wherein the adhesive sheet has at least one ultraviolet absorbing layer, a light transmittance at a wavelength of 380nm of 30% or less, and a visible light transmittance at a longer wavelength side than a wavelength of 430nm of 80% or more (for example, see patent document 1); an adhesive sheet having an adhesive layer containing an acrylic polymer and a triazine-based ultraviolet light absorber (for example, see patent document 2). In addition, it is known that an adhesive optical film having an adhesive layer provided on one side or both sides of the optical film can impart an ultraviolet absorbing function to the adhesive layer (for example, see patent document 3).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-211305
Patent document 2: japanese patent laid-open publication No. 2013-75978
Patent document 3: japanese patent No. 4208187
Disclosure of Invention
Problems to be solved by the invention
In recent years, as described in patent documents 1 to 3, it is known to attach various members used in an image display device using a transparent adhesive having an ultraviolet absorbing function, but in this case, there is a problem in that uneven thickness or deterioration in yield occurs, from the viewpoint of workability.
In addition, depending on the use of the polarizing film, the polarizing film is sometimes required to have a higher ultraviolet absorbing function. Specifically, there is a demand for a polarizing film which does not change in optical characteristics even when exposed to ultraviolet rays for a long period of time (specifically, about 300 hours) or when exposed to ultraviolet rays having a wide wavelength range, and which satisfies a higher ultraviolet absorption function.
In addition, there is a problem that the resulting polarizing film is curled due to the polarizer of the polarizing film and the thinning of the protective film.
Accordingly, an object of the present invention is to provide a polarizing film with an adhesive layer, which can solve the problem of reduced yield, can provide a higher ultraviolet blocking function even when the polarizing film is thin, and can suppress the occurrence of curling. The present invention also provides an image display device using the polarizing film with an adhesive layer.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found the following polarizing film with an adhesive layer, and have completed the present invention.
That is, the present invention relates to a polarizing film with an adhesive layer used in an image display device at a position closer to the viewing side than an image display portion, characterized in that,
the polarizing film with an adhesive layer has a polarizing film and adhesive layers on both sides of the polarizing film,
the polarizing film has a polarizer and transparent protective films on both sides of the polarizer,
the transparent protective film on the visual side of the polarizer has a transmittance of less than 6% at 380nm, and
the pressure-sensitive adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function.
Preferably, the transparent protective film on the viewing side of the polarizer is at least one film selected from the group consisting of a triacetyl cellulose film, an acrylic film, a polyethylene terephthalate film, and a polyolefin film having a cyclic or norbornene structure, and the transparent protective film on the viewing side of the polarizer has a thickness of 40 μm or less.
The thickness of the adhesive layer on the viewing side of the polarizing film is preferably 2 times or more the thickness of the adhesive layer on the image display portion side of the polarizing film.
Preferably, the adhesive layer on the viewing side of the polarizing film has a transmittance of 9% or less at a wavelength of 380nm and a transmittance of 60% or more at a wavelength of 400 nm.
The b-value of the adhesive layer on the viewing side of the polarizing film is preferably 3.0 or less.
Preferably, the adhesive layer on the viewing side of the polarizing film has a transmittance of 9% or less at a wavelength of 380nm and a transmittance of 75% or less at a wavelength of 420 nm.
The pressure-sensitive adhesive layer on the viewing side of the polarizing film preferably contains an acrylic polymer as a base polymer.
The polarizing film with an adhesive layer of the present invention is preferably used for a liquid crystal display device or an organic EL display device.
The present invention also relates to an image display device, wherein the polarizing film with an adhesive layer of the present invention is used at a position closer to the viewing side than the image display portion.
Effects of the invention
The polarizing film with an adhesive layer of the present invention has a structure in which an adhesive layer having an ultraviolet absorbing function is laminated in advance on the viewing side of the polarizing film, and therefore, the problems of process removal and yield reduction can be solved, and even when the polarizing film is thin, a higher ultraviolet blocking function can be imparted, and curling can be suppressed. Further, since the image display device of the present invention uses the polarizing film with an adhesive layer, deterioration of various optical members including a liquid crystal panel and an organic EL element used in the image display device due to ultraviolet rays can be suppressed.
Drawings
Fig. 1 is a cross-sectional view schematically showing one embodiment of the adhesive layer-attached polarizing film of the present invention.
Fig. 2 is a cross-sectional view schematically showing an embodiment of the image display device of the present invention.
Fig. 3 is a cross-sectional view schematically showing an embodiment of the image display apparatus of the present invention.
Fig. 4 is a cross-sectional view schematically showing an embodiment of the image display apparatus of the present invention.
Detailed Description
1. Polarizing film with adhesive layer
The adhesive layer-equipped polarizing film of the present invention is characterized in that,
in the image display device, the image display device is used at a position closer to the visual recognition side than the image display part,
the polarizing film with an adhesive layer has a polarizing film and adhesive layers on both sides of the polarizing film,
the polarizing film has a polarizer and transparent protective films on both sides of the polarizer,
the transparent protective film on the visual side of the polarizer has a transmittance of less than 6% at 380nm, and
the pressure-sensitive adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function.
As shown in fig. 1, the polarizing film 1 with an adhesive layer of the present invention may be configured to include a viewing side adhesive layer 2a, a viewing side transparent protective film 3a, a polarizer 4, a image display side transparent protective film 3b, and an image display side adhesive layer 2b, or may be configured to further include a retardation film or the like. Specifically, the configuration of the viewing side adhesive layer 2a, the viewing side transparent protective film 3a, the polarizer 4, the image display side transparent protective film 3b, the image display side adhesive layer 2b, the retardation film (not shown), the image display side adhesive layer (not shown), and the like may be adopted. The polarizing film 5 is constituted by a viewing-side transparent protective film 3a, a polarizer 4, and an image display-side transparent protective film 3 b. The respective layers are described in detail below.
(1) Visual recognition side adhesive layer
In the present invention, the pressure-sensitive adhesive layer on the visual inspection side (visual inspection side pressure-sensitive adhesive layer) of the polarizing film is characterized by having an ultraviolet absorbing function. The composition of the visual recognition side adhesive layer is not particularly limited as long as it has an ultraviolet absorbing function.
The visual recognition side adhesive layer may be formed using an appropriate adhesive, and the kind thereof is not particularly limited. Examples of the adhesive include rubber adhesives, acrylic adhesives, silicone adhesives, polyurethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, and cellulose adhesives. Among these adhesives, acrylic adhesives are preferably used in view of excellent optical transparency, excellent adhesion properties such as proper adhesiveness, cohesiveness and tackiness, and excellent weather resistance and heat resistance. The acrylic adhesive (composition) contains an acrylic polymer as a base polymer.
The acrylic pressure-sensitive adhesive composition preferably contains, for example, a partial polymer containing a monomer component of an alkyl (meth) acrylate and/or a (meth) acrylic polymer obtained from the monomer component, and an ultraviolet absorber.
(1-1) partial Polymer of monomer component and (meth) acrylic Polymer
The acrylic pressure-sensitive adhesive composition contains a partial polymer containing a monomer component of an alkyl (meth) acrylate and/or a (meth) acrylic polymer obtained from the monomer component.
Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having a linear or branched alkyl group having 1 to 24 carbon atoms at the ester end. The alkyl (meth) acrylate may be used singly or in combination of two or more. The term "alkyl (meth) acrylate" means alkyl acrylate and/or alkyl methacrylate, and the term "methyl" as used herein means the same.
The alkyl (meth) acrylate may be exemplified by, for example, the branched alkyl (meth) acrylate having 1 to 9 carbon atoms. The alkyl (meth) acrylate is preferable in terms of easily obtaining a balance of adhesive properties. Specifically, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and the like may be cited, and one or a combination of two or more of them may be used.
In the present invention, the alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms at the ester end is preferably 40% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, based on the total amount of the monofunctional monomer components forming the (meth) acrylic polymer.
The monomer component may contain a comonomer other than the alkyl (meth) acrylate as a monofunctional monomer component. The comonomer may be used as the remainder of the above alkyl (meth) acrylate in the monomer component.
As the comonomer, for example, a cyclic nitrogen-containing monomer may be contained. The cyclic nitrogen-containing monomer may be a monomer having a cyclic nitrogen structure, which contains a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, without particular limitation. The cyclic nitrogen structure preferably has a nitrogen atom within the cyclic structure. Examples of the cyclic nitrogen-containing monomer include lactam-type vinyl monomers such as N-vinylpyrrolidone, N-vinyl-. Epsilon. -caprolactam, and methyl vinylpyrrolidone; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl
Figure BDA0002728475330000071
And vinyl monomers having nitrogen-containing heterocyclic rings such as oxazole and vinyl morpholine. Further, a (meth) acrylic monomer containing a heterocyclic ring such as a morpholine ring, a piperidine ring, a pyrrolidine ring, or a piperazine ring can be exemplified. Specifically, N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like can be cited. Among the above-mentioned cyclic nitrogen-containing monomers, lactam-based vinyl monomers are preferable.
In the present invention, the cyclic nitrogen-containing monomer is preferably 0.5 to 50% by weight, more preferably 0.5 to 40% by weight, and still more preferably 0.5 to 30% by weight, relative to the total amount of the monofunctional monomer components forming the (meth) acrylic polymer.
The monomer component used in the present invention may contain a hydroxyl group-containing monomer as a monofunctional monomer component. As the hydroxyl group-containing monomer, a monomer having a hydroxyl group and containing a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate; hydroxyalkyl naphthenates of (meth) acrylic acid such as (4-hydroxymethyl cyclohexyl) methyl (meth) acrylate. Examples of the solvent include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. These hydroxyl group-containing monomers may be used alone or in combination. Among them, hydroxyalkyl (meth) acrylates are preferable.
In the present invention, the hydroxyl group-containing monomer is preferably 1% by weight or more, more preferably 2% by weight or more, and still more preferably 3% by weight or more, based on the total amount of the monofunctional monomer components forming the (meth) acrylic polymer, in terms of improving the adhesive strength and cohesive force. On the other hand, when the hydroxyl group-containing monomer is too much, the pressure-sensitive adhesive layer may be hardened and the adhesive strength may be lowered, and the viscosity of the pressure-sensitive adhesive may be too high or gelation may occur, so that the hydroxyl group-containing monomer is preferably 30% by weight or less, more preferably 27% by weight or less, and still more preferably 25% by weight or less, relative to the total amount of the monofunctional monomer components forming the (meth) acrylic polymer.
The monomer component forming the (meth) acrylic polymer may contain other functional group-containing monomers as monofunctional monomers, and examples thereof include carboxyl group-containing monomers and monomers having a cyclic ether group.
As the carboxyl group-containing monomer, a monomer having a carboxyl group and having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group can be used without particular limitation. 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 isocrotonic acid, and these carboxyl group-containing monomers may be used alone or in combination. For itaconic acid, maleic acid, their anhydrides may be used. Among them, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable. The carboxyl group-containing monomer may be optionally used as the monomer component used in the production of the (meth) acrylic polymer of the present invention, but may not be used.
The monomer having a cyclic ether group may be a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and a cyclic ether group such as an epoxy group or an oxetanyl group. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and 4-hydroxybutyl glycidyl (meth) acrylate. Examples of the oxetanyl group-containing monomer include 3-oxetanyl methyl (meth) acrylate, 3-methyl oxetanyl methyl (meth) acrylate, 3-ethyl oxetanyl methyl (meth) acrylate, 3-butyl oxetanyl methyl (meth) acrylate, and 3-hexyl oxetanyl methyl (meth) acrylate. These monomers having a cyclic ether group may be used alone or in combination.
In the present invention, the carboxyl group-containing monomer and the monomer having a cyclic ether group are preferably 30% by weight or less, more preferably 27% by weight or less, and still more preferably 25% by weight or less, based on the total amount of the monofunctional monomer components forming the (meth) acrylic polymer.
Among the monomer components forming the (meth) acrylic polymer of the present invention, examples of the comonomer include a monomer derived from CH 2 ＝C(R 1 )COOR 2 (R is as described above) 1 Represents hydrogen or methyl, R 2 Represents a substituted alkane having 1 to 3 carbon atomsA group, a cyclic cycloalkyl group).
Here, R is as R 2 The substituent of the substituted alkyl group having 1 to 3 carbon atoms is preferably an aryl group having 3 to 8 carbon atoms or an aryloxy group having 3 to 8 carbon atoms. The aryl group is not limited, but a phenyl group is preferable.
As such a group consisting of CH 2 ＝C(R 1 )COOR 2 Examples of the monomer include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 3, 5-trimethylcyclohexyl (meth) acrylate, and isobornyl (meth) acrylate. These monomers may be used alone or in combination.
In the present invention, the above-mentioned monomer component represented by CH is used in relation to the total amount of monofunctional monomer components forming the (meth) acrylic polymer 2 ＝C(R 1 )COOR 2 The (meth) acrylate represented may be used at 50 wt% or less, preferably 45 wt% or less, more preferably 40 wt% or less, and still more preferably 35 wt% or less.
As other comonomers it is also possible to use vinyl acetate, vinyl propionate, styrene, alpha-methylstyrene; glycol acrylate monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; acrylic monomers such as tetrahydrofurfuryl (meth) acrylate, fluoro (meth) acrylate, polysiloxane (meth) acrylate, and 2-methoxyethyl acrylate; amide group-containing monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers, and the like. Further, as the comonomer, a monomer having a cyclic structure such as terpene (meth) acrylate or tetrahydrodicyclopentadiene (meth) acrylate can be used.
Further, a silane monomer containing a silicon atom and the like can be exemplified. Examples of the silane monomer include: 3-acryloxypropyl triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyl trimethoxysilane, 4-vinylbutyl triethoxysilane, 8-vinyloctyl trimethoxysilane, 8-vinyloctyl triethoxysilane, 10-methacryloxydecyl trimethoxysilane, 10-acryloxydecyl trimethoxysilane, 10-methacryloxydecyl triethoxysilane, 10-acryloxydecyl triethoxysilane, and the like.
The monomer component forming the (meth) acrylic polymer of the present invention may contain a polyfunctional monomer as needed in order to adjust the cohesive force of the adhesive, in addition to the monofunctional monomer exemplified above.
The polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and examples thereof include: ester compounds of a polyhydric alcohol such as (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 2-ethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetramethylolmethane tri (meth) acrylate with (meth) acrylic acid; allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and the like. Among them, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate can be preferably used. The polyfunctional monomer may be used singly or in combination of two or more.
The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, and the like, and is preferably 3 parts by weight or less, more preferably 2 parts by weight or less, and still more preferably 1 part by weight or less, based on 100 parts by weight of the total of the monofunctional monomers. The lower limit is not particularly limited, but is preferably 0 parts by weight or more, more preferably 0.001 parts by weight or more. The adhesive strength can be improved by using the polyfunctional monomer in an amount within the above range.
The production of the (meth) acrylic polymer may be carried out by appropriately selecting known production methods such as solution polymerization, radiation polymerization such as Ultraviolet (UV) polymerization, bulk polymerization, and various radical polymerization such as emulsion polymerization. The obtained (meth) acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
In the present invention, a partial polymer of the above monomer component may be suitably used.
In the case of producing the (meth) acrylic polymer by radical polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, and the like used in radical polymerization may be appropriately added to the monomer component to perform polymerization. The polymerization initiator, chain transfer agent, emulsifier, etc. used in the radical polymerization are not particularly limited, and may be appropriately selected and used. The weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of the polymerization initiator, the amount of the chain transfer agent, and the reaction conditions, and the amount thereof can be appropriately adjusted according to the kind of the polymerization initiator, the chain transfer agent, and the reaction conditions.
For example, in solution polymerization or the like, for example, ethyl acetate, toluene or the like is used as a polymerization solvent. As a specific example of the solution polymerization, a polymerization initiator is added under an inert gas flow such as nitrogen, and the reaction is usually carried out under a reaction condition of about 50 to about 70℃for about 5 to about 30 hours.
Examples of the thermal polymerization initiator used for solution polymerization and the like include: 2,2 '-azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), dimethyl 2,2 '-azobis (2-methylpropionate), 4' -azobis (4-cyanovaleric acid), azobisisovaleronitrile 2,2 '-azobis (2-amidinopropane) dihydrochloride, 2' -azobis [2- (5-methyl-2-imidazolin-2-yl) propane ] dihydrochloride, 2 '-azobis (2-methylpropionamidine) disulfate, 2' -azobis (N, azo initiators such as N '-dimethylene isobutyl amidine) and 2,2' -azobis [ N- (2-carboxyethyl) -2-methylpropionamidine ] hydrate (VA-057, manufactured by Wako pure chemical industries, ltd.); examples of the peroxide initiator include, but are not limited to, a peroxide initiator such as potassium persulfate, persulfate such as ammonium persulfate, bis (2-ethylhexyl) peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 3-tetramethylbutyl peroxy2-ethylhexanoate, bis (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butyl peroxyisobutyrate, 1-bis (t-hexylperoxy) cyclohexane, t-butylhydroperoxide, hydrogen peroxide, and a redox initiator obtained by combining a peroxide with a reducing agent such as a combination of persulfate and sodium hydrogen sulfite, and a combination of peroxide and sodium ascorbate.
The polymerization initiator may be used alone or in combination of two or more, and the amount of the polymerization initiator is preferably about 1 part by weight or less, more preferably about 0.005 part by weight to about 1 part by weight, and still more preferably about 0.02 part by weight to about 0.5 part by weight, based on 100 parts by weight of the total amount of the monomer components.
In the case of using 2,2' -azobisisobutyronitrile as the polymerization initiator, the amount of the polymerization initiator to be used is preferably about 0.2 parts by weight or less, more preferably about 0.06 parts by weight to about 0.2 parts by weight, based on 100 parts by weight of the total amount of the monomer components.
Examples of the chain transfer agent include: lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2, 3-dimercapto-1-propanol, and the like. The chain transfer agent may be used alone or in combination of two or more, and the total content thereof is about 0.3 parts by weight or less based on 100 parts by weight of the total monomer components.
Examples of the emulsifier used in the case of performing emulsion polymerization include: anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, and the like; nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, and the like. These emulsifiers may be used either singly or as a combination of two or more.
As the reactive emulsifier, there may be mentioned, for example, aqualon HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (all of which are manufactured by the first Industrial pharmaceutical Co., ltd.), ADEKA REASAP SE10N (manufactured by the company Ai Dike (ADEKA)), and the like as specific examples of the emulsifier having introduced a radical polymerizable functional group such as an allyl ether group. The amount of the emulsifier used is preferably 5 parts by weight or less relative to 100 parts by weight of the total amount of the monomer components.
In the case of producing the (meth) acrylic polymer by radiation polymerization, the (meth) acrylic polymer can be produced by polymerizing the monomer component by irradiation with radiation such as electron beam or Ultraviolet (UV) radiation. Among them, ultraviolet polymerization is preferable. Hereinafter, ultraviolet polymerization, which is a preferred embodiment in radiation polymerization, will be described.
In the case of ultraviolet polymerization, it is preferable to contain a photopolymerization initiator in the monomer component because of the advantage of shortening the polymerization time. Therefore, in the case of performing ultraviolet polymerization, it is preferable that the ultraviolet curable acrylic pressure-sensitive adhesive composition is formed by ultraviolet polymerization of, for example, the above-mentioned monomer component containing alkyl (meth) acrylate and/or a partial polymer of the above-mentioned monomer component, an ultraviolet absorber and a photopolymerization initiator. The pressure-sensitive adhesive layer formed by ultraviolet polymerization of the ultraviolet-curable acrylic pressure-sensitive adhesive composition is preferably a pressure-sensitive adhesive layer having a thickness of 150 μm or more, since a pressure-sensitive adhesive layer having a wide thickness range can be formed.
The photopolymerization initiator (A) preferably has an absorption band at a wavelength of 400nm or more. When the ultraviolet absorber is contained in the adhesive composition, ultraviolet light is absorbed by the ultraviolet absorber during ultraviolet polymerization, and thus sufficient polymerization is not possible. However, if the photopolymerization initiator (A) has an absorption band at a wavelength of 400nm or more, it is preferable because it can be sufficiently polymerized even if it contains an ultraviolet absorber.
Examples of the photopolymerization initiator (A) having an absorption band at a wavelength of 400nm or more include bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819, manufactured by Basf), 2,4, 6-trimethylbenzoyl diphenylphosphine oxide (LUCIRIN TPO, manufactured by BASF), and the like.
The photopolymerization initiator (A) having an absorption band at a wavelength of 400nm or more may be used alone or in combination of two or more.
The amount of the photopolymerization initiator (A) having an absorption band at a wavelength of 400nm or more is not particularly limited, but is preferably smaller than the amount of the ultraviolet absorber to be described later, and is preferably about 0.005 to about 1 part by weight, more preferably about 0.02 to about 0.5 part by weight, based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer. The addition amount of the photopolymerization initiator (a) is preferably in the above range, since ultraviolet polymerization can be sufficiently performed.
The photopolymerization initiator (B) may be contained to have an absorption band at a wavelength of less than 400 nm. The photopolymerization initiator (B) preferably has no absorption band at a wavelength of 400nm or more. The photopolymerization initiator (B) is not particularly limited as long as it generates radicals by ultraviolet rays to initiate photopolymerization and has an absorption band at a wavelength of less than 400nm, and any of conventionally used photopolymerization initiators can be suitably used. For example, benzoin ether type photopolymerization initiators, acetophenone type photopolymerization initiators, α -ketol type photopolymerization initiators, photoactive oxime type photopolymerization initiators, benzoin type photopolymerization initiators, benzil type photopolymerization initiators, benzophenone type photopolymerization initiators, ketal type photopolymerization initiators, thioxanthone type photopolymerization initiators, acylphosphine oxide type photopolymerization initiators, and the like can be used.
Specifically, examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-dimethoxy-1, 2-diphenylethane-1-one, anisoin methyl ether, and the like.
Examples of the acetophenone photopolymerization initiator include 2, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4-t-butyldichloroacetophenone.
Examples of the α -ketol photopolymerization initiator include 2-methyl-2-hydroxyphenylacetone and 1- [4- (2-hydroxyethyl) phenyl ] -2-hydroxy-2-methylpropan-1-one.
Examples of the photo-active oxime-type photopolymerization initiator include 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime.
Examples of the benzoin photopolymerization initiator include benzoin.
Examples of the benzil photopolymerization initiator include benzil.
Examples of the benzophenone photopolymerization initiator include benzophenone, benzoyl benzoic acid, 3' -dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α -hydroxycyclohexyl phenyl ketone.
The ketal photopolymerization initiator comprises benzil dimethyl ketal and the like.
Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
Examples of the photopolymerization initiator include 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide.
The photopolymerization initiator (B) having an absorption band at a wavelength of less than 400nm may be used singly or in combination of two or more. The photopolymerization initiator (B) having an absorption band at a wavelength of less than 400nm may be added in an amount of preferably about 0.005 to about 0.5 parts by weight, more preferably about 0.02 to about 0.1 parts by weight, based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer, within a range that does not impair the effects of the present invention.
In the present invention, when the above monomer component is subjected to ultraviolet polymerization, it is preferable that: a partial polymer (prepolymer composition) of a monomer component obtained by adding a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400nm to the monomer component and irradiating a part of the polymer with ultraviolet rays is polymerized, and ultraviolet polymerization is carried out by adding the photopolymerization initiator (A) having an absorption band at a wavelength of 400nm or more and an ultraviolet absorber to the prepolymer composition. When the photopolymerization initiator (A) having an absorption band at a wavelength of 400nm or more is added to a partial polymer (prepolymer composition) of a monomer component obtained by partial polymerization by irradiation with ultraviolet rays, it is preferable to add the photopolymerization initiator after dissolving the photopolymerization initiator in a monomer.
(1-2) ultraviolet absorber
The ultraviolet absorber contained in the acrylic pressure-sensitive adhesive composition is not particularly limited, and examples thereof include triazine ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, hydroxybenzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, and the like, and these ultraviolet absorbers may be used singly or in combination of two or more. Among them, the triazine-based ultraviolet light absorber and the benzotriazole-based ultraviolet light absorber are preferable, and at least one ultraviolet light absorber selected from the group consisting of a triazine-based ultraviolet light absorber having two or less hydroxyl groups in one molecule and a benzotriazole-based ultraviolet light absorber having one benzotriazole skeleton in one molecule is preferable because of its good solubility in a monomer used in the formation of the acrylic adhesive composition and high ultraviolet light absorbing ability in the vicinity of 380 nm.
Triazine ultraviolet as a compound having two or more hydroxyl groups in one moleculeSpecific examples of the line absorber include: 2, 4-bis [ {4- (4-ethylhexyl oxy) -4-hydroxy } phenyl } ]-6- (4-methoxyphenyl) -1,3, 5-triazine (Tinosorb S, manufactured by Basf); 2, 4-bis [ 2-hydroxy-4-butoxyphenyl group]-6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine (manufactured by TINUVIN 460, basf); 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-hydroxyphenyl group [ (C) 10 -C 16 (mainly C 12 -C 13 ) Alkyl oxy) methyl]Reaction products of ethylene oxide (manufactured by TINUVIN400, BASF); 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl]-5- [3- (dodecyloxy) -2-hydroxypropoxy group]Phenol), the reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine with 2-ethylhexyl glycidate (manufactured by TINUVIN405, BASF); 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy]Phenol (manufactured by TINUVIN1577, BASF); 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy]Phenol (ADK STAB LA46, ai Dike (ADEKA) manufactured); 2- (2-hydroxy-4- [ 1-octyloxy-carbonylethoxy)]Phenyl) -4, 6-bis (4-phenylphenyl) -1,3, 5-triazine (TINUVIN 479, manufactured by BASF corporation), and the like.
As the benzotriazole-based ultraviolet absorber having one benzotriazole skeleton in one molecule, there can be mentioned: 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1, 3-tetramethylbutyl) phenol (manufactured by TINUVIN928, BASF), 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole (manufactured by TINUVIN PS, BASF), an ester compound of phenylpropionic acid with 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl group) (manufactured by TINUVIN384-2, BASF); 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN 900, manufactured by BASF); 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1, 3-tetramethylbutyl) phenol (TINUVIN 928, manufactured by BASF); methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate/polyethylene glycol 300 (manufactured by TINUVIN1130, BASF); 2- (2H-benzotriazol-2-yl) P-cresol (manufactured by TINUVIN P, BASF); 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN 234, manufactured by BASF); 2- [ 5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6-tert-butylphenol (manufactured by TINUVIN326, BASF); 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-pentylphenol (TINUVIN 328, manufactured by BASF); 2- (2H-benzotriazol-2-yl) -4- (1, 3-tetramethylbutyl) phenol (manufactured by TINUVIN329, BASF); reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol 300 (manufactured by TINUVIN213, BASF); 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-cresol (TINUVIN 571, manufactured by BASF); 2- [ 2-hydroxy-3- (3, 4,5, 6-tetrahydrophthalimidomethyl) -5-methylphenyl ] benzotriazole (Sumisorb 250, manufactured by Sumitomo chemical Co., ltd.) and the like.
Examples of the benzophenone-based ultraviolet absorber (benzophenone-based compound) and the hydroxybenzophenone-based ultraviolet absorber (hydroxybenzophenone-based compound) include: 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2' -dihydroxy-4, 4-dimethoxybenzophenone, and the like.
Examples of the salicylate-based ultraviolet absorber (salicylate-based compound) include: phenyl 2-acryloyloxy benzoate, phenyl 2-acryloyloxy-3-methylbenzoate, phenyl 2-acryloyloxy-4-methylbenzoate, phenyl 2-acryloyloxy-5-methylbenzoate, phenyl 2-acryloyloxy-3-methoxybenzoate, phenyl 2-hydroxybenzoate, phenyl 2-hydroxy-3-methylbenzoate, phenyl 2-hydroxy-4-methylbenzoate, phenyl 2-hydroxy-5-methylbenzoate, phenyl 2-hydroxy-3-methoxybenzoate, 2, 4-di-t-butylphenyl 3, 5-di-t-butyl-4-hydroxybenzoate (manufactured by TINUVIN120, BASF), and the like.
Examples of the cyanoacrylate ultraviolet absorber (cyanoacrylate compound) include: alkyl 2-cyanoacrylates, cycloalkyl 2-cyanoacrylates, alkoxyalkyl 2-cyanoacrylates, alkenyl 2-cyanoacrylates, alkynyl 2-cyanoacrylates, and the like.
Examples of the ultraviolet absorber include dyes such as "FDB-001" (manufactured by mountain chemical Co., ltd.), "SMP-122" (manufactured by Linne chemical Co., ltd.), azomethine compound (manufactured by BONASORB UA-3911, orient chemical Co., ltd.), indole compound (manufactured by BONASORB UA-3701, orient chemical Co., ltd.), disperse YELLOW 54 (manufactured by KAYASET YELLOW AG, japanese chemical Co., ltd.), quinophthalone compound (manufactured by MS YELLOW HD-137, manufactured by mountain chemical Co., ltd.), solvent YELLOW 93 (manufactured by PLASTILLOW 8000, manufactured by chemical Co., ltd.), and solvent YELLOW 163 (manufactured by KP Plast Yellow MK, ji and chemical Co., ltd.).
The ultraviolet absorber may be used alone or in combination of two or more, and the content of the ultraviolet absorber as a whole is preferably from about 0.1 to about 5 parts by weight, more preferably from about 0.5 to about 3 parts by weight, based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer. The amount of the ultraviolet absorber added is preferably in the above range, since the ultraviolet absorbing function of the pressure-sensitive adhesive layer can be fully exhibited and the ultraviolet polymerization is not hindered when the polymerization is performed.
(1-3) silane coupling agent
In addition, a silane coupling agent may be contained in the acrylic adhesive composition used in the present invention. The amount of the silane coupling agent to be blended is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, still more preferably 0.02 to 0.6 part by weight, based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer.
Examples of the silane coupling agent include epoxy group-containing silane coupling agents such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; amino-containing silane coupling agents such as 3-aminopropyl trimethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyl dimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, and N-phenyl-gamma-aminopropyl trimethoxysilane; (meth) acryl-containing silane coupling agents such as 3-acryloxypropyl trimethoxysilane and 3-methacryloxypropyl triethoxysilane; and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyl triethoxysilane.
(1-4) Cross-linking agent
The acrylic adhesive composition used in the present invention may contain a crosslinking agent. The crosslinking agent includes an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a polysiloxane-based crosslinking agent,
Figure BDA0002728475330000201
Oxazoline-based crosslinking agents, aziridine-based crosslinking agents, silane-based crosslinking agents, alkyl etherified melamine-based crosslinking agents, metal chelate-based crosslinking agents, peroxide-based crosslinking agents, and the like. The crosslinking agent may be used singly or in combination of two or more. Among them, an isocyanate-based crosslinking agent is preferably used.
The crosslinking agent may be used alone or in combination of two or more, and the content of the crosslinking agent as a whole is preferably 5 parts by weight or less, more preferably 0.01 to 5 parts by weight, still more preferably 0.01 to 4 parts by weight, and particularly preferably 0.02 to 3 parts by weight, based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer.
The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups (including an isocyanate-regenerated functional group in which an isocyanate group is temporarily protected by blocking agent, polymerization, or the like) in one molecule. Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.
More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, and the like; an isocyanate adduct such as trimethylolpropane/toluene diisocyanate trimer adduct (trade name: CORONATE L, manufactured by Japanese polyurethane Co., ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name: CORONATE HL, manufactured by Japanese polyurethane Co., ltd.), an isocyanurate form of hexamethylene diisocyanate (trade name: CORONATE HX, manufactured by Japanese polyurethane Co., ltd.), a trimethylolpropane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui chemical Co., ltd.), and a trimethylolpropane adduct of hexamethylene diisocyanate (trade name: D160N, manufactured by Mitsui chemical Co., ltd.); polyether polyisocyanates, polyester polyisocyanates, adducts thereof with various polyols, polyisocyanates obtained by polyfunctional reaction with isocyanurate bonds, biuret bonds, allophanate bonds, and the like.
(1-5) other additives
The acrylic adhesive composition used in the present invention may contain an appropriate additive according to the application, in addition to the above-mentioned components. Examples thereof include tackifiers (e.g., substances which are solid, semisolid, or liquid at ordinary temperature, including rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, and the like); fillers such as hollow glass microspheres; a plasticizer; an anti-aging agent; antioxidants, and the like.
(1-6) method for Forming visual recognition side adhesive layer
In the present invention, the acrylic pressure-sensitive adhesive composition is preferably adjusted to a viscosity suitable for a work such as coating on a substrate. The viscosity of the acrylic adhesive composition is adjusted, for example, by adding various polymers such as a thickening additive, polyfunctional monomers, or the like, or polymerizing the monomer components in the acrylic adhesive composition. The partial polymerization may be performed before or after the addition of various polymers such as thickening additives or polyfunctional monomers. Since the viscosity of the acrylic pressure-sensitive adhesive composition varies depending on the amount of the additive or the like, the polymerization rate at the time of polymerizing the monomer component in the acrylic pressure-sensitive adhesive composition cannot be uniquely determined, and is preferably about 20% or less, more preferably about 3% to about 20%, and even more preferably about 5% to about 15% on a general basis. If the viscosity exceeds 20%, the viscosity becomes too high, and thus it is difficult to apply the coating to a substrate.
The visual recognition side adhesive layer can be formed by applying the acrylic adhesive composition to at least one side of a substrate and drying a coating film formed from the acrylic adhesive composition; alternatively, the light source may be formed by irradiation with active energy rays such as ultraviolet rays.
The substrate is not particularly limited, and various substrates such as a release film and a transparent resin film substrate, or a polarizing film described later can be suitably used as the substrate. In the case where the viewing-side adhesive layer is formed on a substrate other than the polarizing film, the viewing-side adhesive layer may be bonded and transferred to the polarizing film.
Examples of the material constituting the release film include a resin film such as polyethylene, polypropylene, polyethylene terephthalate, and polyester film, a porous material such as paper, cloth, and nonwoven fabric, a suitable thin paper (thin body) such as a net, a foam sheet, a metal foil, and a laminate thereof, and the resin film is preferably used in view of excellent surface smoothness.
Examples of the resin film include a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
The thickness of the release film is usually 5 μm to 200. Mu.m, preferably about 5 μm to about 100. Mu.m. The release film may be subjected to release and antifouling treatment with a silicone-based, fluorine-containing, long-chain alkyl-based or fatty acid amide-based release agent, silica powder or the like, or antistatic treatment such as coating-type, kneading-type, vapor deposition-type or the like, as required. In particular, the release properties from the pressure-sensitive adhesive layer can be further improved by suitably subjecting the surface of the release film to a release treatment such as a polysiloxane treatment, a long-chain alkyl treatment, or a fluorine treatment.
The transparent resin film base material is not particularly limited, and various resin films having transparency are used. The resin film is formed of one film. Examples of the material include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, and polyphenylene sulfide resins. Among these, polyester-based resins, polyimide-based resins and polyether sulfone-based resins are particularly preferable.
The thickness of the film base material is preferably 15 μm to 200 μm, more preferably 25 μm to 188 μm.
The method of applying the acrylic adhesive composition to the substrate may be any known suitable method such as roll coating, gravure coating, reverse coating, roll brush, spray coating, dip roll coating, bar coating, doctor blade coating, air knife coating, curtain coating, lip die coating, and die coater, and is not particularly limited.
When the visual inspection side pressure-sensitive adhesive layer is formed by drying a coating film formed from the acrylic pressure-sensitive adhesive composition, the drying conditions (temperature, time) are not particularly limited, and may be appropriately set depending on the composition, concentration, and the like of the pressure-sensitive adhesive composition, and for example, the pressure-sensitive adhesive layer is formed at about 60 to about 170 ℃, preferably 60 to 150 ℃ for 1 to 60 minutes, preferably 2 to 30 minutes.
In the case where the acrylic pressure-sensitive adhesive composition is an ultraviolet-curable acrylic pressure-sensitive adhesive composition and is formed by irradiating ultraviolet rays to a coating film formed from the ultraviolet-curable acrylic pressure-sensitive adhesive composition, the illuminance of the irradiated ultraviolet rays is preferably 5mW/cm 2 The above. The illuminance of the ultraviolet is less than 5mW/cm 2 In some cases, the polymerization time becomes long and the productivity is poor. The illuminance of the ultraviolet light is preferably 200mW/cm 2 The following is given. The illuminance of the ultraviolet exceeds 200mW/cm 2 In this case, since the photopolymerization initiator is consumed rapidly, the polymer may have a low molecular weight, and in particular, the retention force at high temperature may be lowered. Further, the cumulative light amount of ultraviolet rays is preferably 100mJ/cm 2 ～5000mJ/cm 2 。
The ultraviolet lamp used in the present invention is not particularly limited, and an LED lamp is preferable. The LED lamp is a lamp that emits less heat than other ultraviolet lamps, and thus can suppress the temperature in polymerization of the adhesive layer. Therefore, the polymer can be prevented from having a low molecular weight, the cohesive force of the adhesive layer can be prevented from decreasing, and the holding force at a high temperature can be improved in the case of producing the adhesive sheet. In addition, a plurality of ultraviolet lamps may be combined. The ultraviolet light may be intermittently irradiated, and a bright period during which ultraviolet light is irradiated and a dark period during which ultraviolet light is not irradiated may be provided.
In the present invention, the final polymerization rate of the monomer component in the ultraviolet curable acrylic pressure-sensitive adhesive composition is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.
In the present invention, the peak wavelength of ultraviolet light irradiated to the ultraviolet curable acrylic pressure-sensitive adhesive composition is preferably in the range of 200nm to 500nm, more preferably 300nm to 450 nm. When the peak wavelength of ultraviolet light exceeds 500nm, the photopolymerization initiator may not decompose and may not initiate polymerization. When the peak wavelength of ultraviolet light is less than 200nm, the polymer chain may be cut, and the adhesive property may be lowered.
Since the reaction is inhibited by oxygen in the air, it is preferable to form a release film or the like on a coating film formed of the ultraviolet-curable acrylic pressure-sensitive adhesive composition or to carry out photopolymerization in a nitrogen atmosphere in order to block oxygen. The release film may be the one described above. In the case of using a release film, the release film may be used as a separator for a polarizing film having an adhesive layer.
In the case where the ultraviolet curable acrylic pressure-sensitive adhesive composition used in the present invention contains a photopolymerization initiator (B), it is preferable that: a composition comprising a monomer component containing an alkyl (meth) acrylate and the photopolymerization initiator (B) (also referred to as "pre-addition polymerization initiator") is irradiated with ultraviolet light to form a partial polymer of the monomer component, and an ultraviolet light absorber and the photopolymerization initiator (A) (also referred to as "post-addition polymerization initiator") having an absorption band at a wavelength of 400nm or more are added to the partial polymer of the monomer component to produce an ultraviolet-curable acrylic pressure-sensitive adhesive composition. The polymerization rate of the partial polymer is preferably about 20% or less, more preferably about 3% to about 20%, and still more preferably about 5% to about 15%. The irradiation conditions of ultraviolet rays are as described above.
As described above, in the case where the adhesive layer is formed from the ultraviolet-curable acrylic adhesive composition containing the photopolymerization initiator (B), polymerization in two stages as described above can improve the polymerization rate of the monomer component and can improve the ultraviolet absorption function of the finally produced adhesive layer.
From the viewpoint of ensuring the ultraviolet absorbing function, the thickness of the above-mentioned viewing-side adhesive layer is preferably 2 times or more, more preferably 5 times or more, still more preferably 10 times or more the thickness of an adhesive layer on the image display portion side (image display portion side adhesive layer) of the polarizing film described later. Specifically, the thickness of the visual recognition side pressure-sensitive adhesive layer is preferably 50 μm or more, more preferably 100 μm or more, and still more preferably 150 μm or more. The upper limit of the thickness of the visual recognition side adhesive layer is not particularly limited, but is preferably 10mm or less. When the thickness of the adhesive layer exceeds 10mm, ultraviolet rays are less likely to transmit, and polymerization of the monomer component takes time, which is not preferable because of poor productivity.
The gel fraction of the viewing-side pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 35% or more, more preferably 50% or more, still more preferably 75% or more, and particularly preferably 85% or more. When the gel fraction of the visual inspection side pressure-sensitive adhesive layer is small, the cohesive force may be poor, and when the gel fraction is too large, the adhesive force may be poor.
The transmission b of the visual side pressure-sensitive adhesive layer is not particularly limited, but is preferably 3.0 or less, more preferably 1.5 or less, and further preferably 0.5 or less. The above-mentioned b is a value of b (chromaticity) in the color system of L x a x b x according to JIS Z8729, for example, a spectrophotometer (product name: U4100, manufactured by hitachi high technology, inc.).
The transmittance of the visual recognition side pressure-sensitive adhesive layer at a wavelength of 380nm is preferably 9% or less, more preferably 7% or less, still more preferably 5% or less, particularly preferably 3% or less. Since the transmittance at 380nm is in the above range, the incident ultraviolet light can be blocked more highly, and thus deterioration of optical members including liquid crystal panels, organic EL elements, polarizers, and the like can be significantly suppressed.
The transmittance of the visual recognition side pressure-sensitive adhesive layer at a wavelength of 400nm is preferably 60% or more, more preferably 70% or more, and still more preferably 75% or more. The transmittance at a wavelength of 400nm is preferably in the above range, since incident visible light can be transmitted sufficiently, and sufficient visibility can be ensured in the image display device.
In the case where the polarizing film with an adhesive layer of the present invention is used in an organic EL display device (OLED), the transmittance of the visual side adhesive layer at a wavelength of 420nm is preferably 75% or less, more preferably 50% or less, and still more preferably 40% or less. The transmittance at a wavelength of 420nm is in the above range, and is preferable from the viewpoint of protecting the light emitting element of the OLED.
In the case where the visual recognition side adhesive layer is exposed, the adhesive layer may be protected with a release film until it is put to practical use. The release film may be used as a separator for a polarizing film with an adhesive layer, and the process can be simplified.
(2) Image display side adhesive layer
The pressure-sensitive adhesive layer on the image display portion side surface of the polarizing film (image display portion side pressure-sensitive adhesive layer) is not particularly limited, and the same pressure-sensitive adhesive layer as the acrylic pressure-sensitive adhesive composition described in detail in the above-mentioned visual recognition side pressure-sensitive adhesive layer may be used, and various pressure-sensitive adhesive layers commonly used may be used.
An appropriate adhesive may be used for forming the adhesive layer on the side surface of the image display section, and the kind thereof is not particularly limited. Examples of the adhesive include rubber adhesives, acrylic adhesives, silicone adhesives, polyurethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, and cellulose adhesives. Among these adhesives, acrylic adhesives are preferably used in view of excellent optical transparency, excellent adhesion properties such as proper adhesiveness, cohesiveness and tackiness, and excellent weather resistance and heat resistance.
The acrylic adhesive has an acrylic polymer as a base polymer, and the acrylic polymer has a monomer unit of an alkyl (meth) acrylate as a main skeleton. As the alkyl (meth) acrylate constituting the main skeleton of the acrylic polymer, the same alkyl (meth) acrylate as that used in the acrylic adhesive composition for forming the visual side adhesive layer can be mentioned. The comonomer and the ratio thereof may be the same as those used in the acrylic pressure-sensitive adhesive composition.
The acrylic polymer can be produced by various known methods, and for example, a radical polymerization method such as a bulk polymerization method, a solution polymerization method, or a suspension polymerization method can be appropriately selected. As the radical polymerization initiator, various known radical polymerization initiators such as azo-based and peroxide-based ones can be used. The reaction temperature is usually set to about 50 to about 80℃and the reaction time is set to 1 to 8 hours. Among the above production methods, the solution polymerization method is preferable, and ethyl acetate, toluene, and the like are generally used as the solvent for the acrylic polymer. The solution concentration is typically set at about 20 wt% to about 80 wt%.
The adhesive may be an adhesive composition containing a crosslinking agent. The crosslinking agent may be any of the above-mentioned crosslinking agents, and isocyanate-based crosslinking agents are particularly preferable. The blending ratio of the acrylic polymer and the crosslinking agent is not particularly limited, and is generally preferably from about 0.001 to about 20 parts by weight, more preferably from about 0.01 to about 15 parts by weight, based on 100 parts by weight of the acrylic polymer (solid content).
In addition, various additives such as a tackifier, a plasticizer, a filler including glass fibers, glass beads, metal powder, other inorganic powder, etc., a pigment, a colorant, a filler, an antioxidant, an ultraviolet absorber, a silane coupling agent, etc., may be appropriately used as needed and within a range not departing from the object of the present invention. In addition, an adhesive layer or the like containing fine particles and exhibiting light diffusion may be formed. The silane coupling agent may be the one described above.
The image display-side adhesive layer is formed by applying the adhesive composition to various substrates such as a polarizing film and a release film, and drying the same. In the case of forming an adhesive layer on various substrates such as a release film, the adhesive layer may be bonded and transferred to a polarizing film. Examples of the method for applying the adhesive and the various substrates include the same method for applying the acrylic adhesive composition and the various substrates.
In the coating step, the coating amount is controlled so that the pressure-sensitive adhesive layer to be formed reaches a predetermined thickness (thickness after drying). The thickness of the image display portion side pressure-sensitive adhesive layer is not particularly limited, and is preferably 1/2 or less, preferably 1/5 or less, and more preferably 1/10 or less of the thickness of the visual recognition side pressure-sensitive adhesive layer. Specifically, the thickness of the image display section-side pressure-sensitive adhesive layer is preferably from about 1 μm to about 100 μm, more preferably from about 3 μm to about 50 μm, and even more preferably from about 5 μm to about 30 μm.
In forming the image display portion side adhesive layer, the applied adhesive is dried. The drying temperature and drying time are not particularly limited and may be appropriately set, and for example, are preferably from about 80 to about 200℃for 0.5 to 10 minutes.
In the case where the image display portion side adhesive layer is exposed, the adhesive layer may be protected with a release film until it is put to practical use. The release film may be used as a separator for a polarizing film with an adhesive layer, and the process can be simplified.
(3) Polarizing film
The polarizing film used in the present invention is characterized by comprising a polarizer and transparent protective films on both sides of the polarizer, wherein the transmittance at 380nm of the transparent protective film on the viewing side of the polarizer (viewing side transparent protective film) is less than 6%.
(3-1) visual recognition side transparent protective film
The transmittance of the transparent protective film on the viewing side used in the present invention is less than 6%, preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less at 380 nm. In the present invention, by combining the visual inspection side transparent protective film having a transmittance of less than 6% at 380nm with the visual inspection side adhesive layer (containing an ultraviolet absorber), a higher ultraviolet absorbing ability can be achieved. The lower limit of the transmittance at 380nm, which is the wavelength of the visible-side transparent protective film, is not particularly limited, but it is preferable that the transmittance is smaller from the viewpoint of the ultraviolet absorption function.
As a material for forming the viewing-side transparent protective film, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable. Examples include: and polyester polymers such AS polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such AS diacetyl cellulose and triacetyl cellulose, acrylic polymers such AS polymethyl methacrylate, styrene polymers such AS polystyrene and acrylonitrile-styrene copolymer (AS resin), and polycarbonate polymers. Examples of the polymer forming the transparent protective film include polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, polyolefin polymer such as ethylene-propylene copolymer, amide polymer such as vinyl chloride polymer, nylon or aromatic polyamide, imide polymer, sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, aromatic ester polymer, polyoxymethylene polymer, epoxy polymer, and blend of the above polymers. The transparent protective film may be formed as a cured layer of a thermosetting resin such as an acrylic, urethane, acrylic urethane, epoxy, or polysiloxane. Among them, as the viewing-side transparent protective film, at least one film selected from the group consisting of a triacetyl cellulose film, an acrylic film (a film using an acrylic polymer), a polyethylene terephthalate film, and a polyolefin film having a cyclic or norbornene structure is preferable, and a triacetyl cellulose film is more preferable.
The thickness of the viewing-side transparent protective film is not particularly limited, but is preferably 40 μm or less, more preferably 35 μm or less, and further preferably 30 μm or less. The lower limit of the thickness of the viewing-side transparent protective film is not particularly limited, but is preferably 1 μm or more. The thickness of the transparent protective film on the viewing side is preferably in the above range, since the polarizing film can be sufficiently thinned and the protective function of the polarizer is not impaired.
The polarizer and the viewing-side protective film, which will be described later, are preferably adhered via an aqueous adhesive or the like. Examples of the aqueous adhesive include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl-based latex adhesives, aqueous polyurethane, aqueous polyester, and the like. In addition to the above, examples of the adhesive for the polarizer and the viewing-side transparent protective film include: ultraviolet-curable adhesives, electron beam-curable adhesives, and the like. The adhesive for an electron beam-curable polarizing film exhibits suitable tackiness to the above-mentioned various transparent protective films on the viewing side. In addition, the adhesive used in the present invention may contain a metal compound filler.
The surface of the transparent protective film on the viewing side, which is not to be adhered, may be subjected to a hard coat layer or an antireflection treatment, and a treatment for the purpose of preventing adhesion, diffusion or antiglare.
(3-2) polarizer
The polarizer is not particularly limited, and various polarizers may be used. Examples of the polarizer include: a polarizer obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formylated polyvinyl alcohol film, or an ethylene-vinyl acetate copolymer partially saponified film after adsorbing a dichroic substance such as iodine or a dichroic dye, a polyolefin oriented film such as a dehydrated product of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride, and the like. Among them, a polarizer containing a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, and is usually about 5 μm to about 80 μm.
The polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching the film can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine, dyeing the film, and stretching the film to 3 to 7 times the original length. The aqueous solution may be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like as required. If necessary, the polyvinyl alcohol film may be immersed in water before dyeing and washed with water. The polyvinyl alcohol film is washed with water to remove stains and anti-blocking agents on the surface of the polyvinyl alcohol film, and in addition, the polyvinyl alcohol film is swelled to prevent uneven dyeing and the like. Stretching may be performed after dyeing with iodine, stretching may be performed while dyeing, and dyeing with iodine may also be performed after stretching is performed. Stretching may be performed in an aqueous solution of boric acid, potassium iodide, or the like, or in a water bath.
In the present invention, a thin polarizer having a thickness of 10 μm or less may be used. From the viewpoint of thickness reduction, the thickness is preferably 1 μm to 7 μm. Such a thin polarizer is preferable in terms of having less thickness unevenness, excellent visibility, and less dimensional change, and thus, excellent durability, and also in terms of realizing thin polarizing film thickness.
As the thin polarizer, there is typically mentioned: the thin polarizing film described in japanese patent application laid-open publication No. 51-069644, japanese patent application laid-open publication No. 2000-338329, single-file book of international publication No. 2010/100917, or japanese patent application laid-open publication No. 4751481, japanese patent application laid-open publication No. 2012-073563. These thin polarizing films can be obtained by a production method including a step of stretching a layer of a polyvinyl alcohol resin (hereinafter also referred to as PVA-based resin) and a stretching resin base material in a laminate state and a step of dyeing. With this production method, even if the PVA-based resin layer is thin, it is possible to carry out stretching without causing problems such as breakage due to stretching by being supported by the stretching resin base material.
Among the production methods including the step of stretching and the step of dyeing in the laminate, a polarizing film obtained by a production method including a step of stretching in an aqueous boric acid solution as described in the document of the single file of international publication No. 2010/100917, or the document of japanese patent No. 4751481, and the document of japanese patent application laid-open No. 2012-073563, and particularly a polarizing film obtained by a production method including a step of stretching in air as described in the document of japanese patent 4751481 and the document of japanese patent application laid-open No. 2012-073563, which is assisted by stretching in the air, are preferable.
(3-3) image display portion side transparent protective film
As the image-display-side transparent protective film, a conventionally used transparent protective film can be suitably used. Specifically, a transparent protective film formed of a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable, and examples thereof include: and polyester polymers such AS polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such AS diacetyl cellulose and triacetyl cellulose, acrylic polymers such AS polymethyl methacrylate, styrene polymers such AS polystyrene and acrylonitrile-styrene copolymer (AS resin), and polycarbonate polymers. Examples of the polymer forming the transparent protective film include polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, polyolefin polymer such as ethylene-propylene copolymer, amide polymer such as vinyl chloride polymer, nylon or aromatic polyamide, imide polymer, sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, aromatic ester polymer, polyoxymethylene polymer, epoxy polymer, and blend of the above polymers. The transparent protective film may be formed as a cured layer of a thermosetting resin such as an acrylic, urethane, acrylic urethane, epoxy, or polysiloxane.
The thickness of the protective film on the image display section side can be appropriately determined, and is usually about 1 μm to about 500 μm in view of workability such as strength and handling property, film property, and the like.
The polarizer and the transparent protective film on the image display portion side are usually adhered via an aqueous adhesive or the like. The aqueous adhesive may be the aqueous adhesive described above.
The surface of the transparent protective film on the image display portion side, which is not adhered to the polarizer, may be subjected to a hard coat layer or an antireflection treatment, and a treatment for the purpose of preventing adhesion, diffusion, or antiglare.
2. Image display device
The image display device of the present invention is characterized by using the polarizing film with an adhesive layer of the present invention.
As an example of a specific configuration of the image display device, for example, an image display device in which the layers are laminated in the following order as shown in fig. 2 to 4 is exemplified: a protective glass or protective plastic 6/a visual-recognition-side adhesive layer 2 a/a visual-recognition-side transparent protective film 3 a/a polarizer 4/an image-display-side transparent protective film 3 b/an image-display-side adhesive layer 2 b/a liquid crystal display device (LCD) or an organic EL display device (OLED) 7 (fig. 2); the protective glass or protective plastic 6/the adhesive layer 8 a/the sensor layer 9/the viewing side adhesive layer 2 a/the viewing side transparent protective film 3 a/the polarizer 4/the image display side transparent protective film 3 b/the image display side adhesive layer 2 b/the liquid crystal display device (LCD) or the organic EL display device (OLED) 7 (fig. 3); the protective glass or protective plastic 6/the adhesive layer 8 a/the sensor layer 9/the adhesive layer 8 b/the sensor layer 9/the visual-recognition-side adhesive layer 2 a/the visual-recognition-side transparent protective film 3 a/the polarizer 4/the image-display-side transparent protective film 3 b/the image-display-side adhesive layer 2 b/the liquid crystal display device (LCD) or the organic EL display device (OLED) 7 (fig. 4). The polarizing film 1 with an adhesive layer of the present invention is a portion of the above-described configuration of "viewing side adhesive layer 2 a/viewing side transparent protective film 3 a/polarizer 4/image display side transparent protective film 3 b/image display side adhesive layer 2b", and may include a retardation film or the like in addition to these portions. In the case of including the phase difference film, specifically, the phase difference film may be laminated between the image display portion side adhesive layer 2b and the liquid crystal display device (LCD) or the organic EL display device (OLED) 7 via an adhesive layer. In addition, an adhesive layer and/or an adhesive layer may be used as appropriate in the lamination of the layers.
Examples of the image display device include a liquid crystal display device, an organic EL (electroluminescence) display device, a PDP (plasma display panel), and an electronic paper, and among them, a liquid crystal display device, an organic EL (electroluminescence) display device, and the like having the above-described configuration are preferable.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The parts and% in each example are based on weight.
Production example 1 (production of acrylic adhesive composition (a-1))
A prepolymer composition (polymerization rate: 8%) was obtained by polymerizing a part of the above-mentioned monomer components by mixing 0.035 parts by weight of 1-hydroxycyclohexylphenyl ketone (trade name: IRGACURE 184, having an absorption band at a wavelength of 200nm to 370nm, manufactured by BASF Co.) as a photopolymerization initiator, 0.035 parts by weight of 2, 2-dimethoxy-1, 2-diphenylethane-1-one (trade name: IRGACURE 651, having an absorption band at a wavelength of 200nm to 380nm, manufactured by BASF Co.) with a monomer mixture composed of 78 parts by weight of 2-ethylhexyl acrylate (2 EHA), 18 parts by weight of N-vinyl-2-pyrrolidone (NVP) and 4 parts by weight of 2-hydroxyethyl acrylate (HEA) to a viscosity (measurement condition: BH viscometer No.5 rotor, 10rpm, measurement temperature 30 ℃ C.) of about 20 Pa.s. Next, 0.15 parts by weight of hexanediol diacrylate (HDDA) and 0.3 parts by weight of a silane coupling agent (trade name: KBM-403, manufactured by Xinyue chemical Co., ltd.) were added to the prepolymer composition and mixed, thereby obtaining an acrylic pressure-sensitive adhesive composition (a-1).
Production example 2 (production of acrylic adhesive composition (a-2))
To a monomer mixture composed of 72 parts by weight of 2-ethylhexyl acrylate (2 EHA), 1 part by weight of Methyl Methacrylate (MMA), 12 parts by weight of N-vinylpyrrolidone (NVP) and 15 parts by weight of hydroxyethyl acrylate (HEA), 0.2 part by weight of Azobisisobutyronitrile (AIBN) and 233 parts by weight of ethyl acetate as polymerization initiators were charged, and then a reaction was carried out at 60 ℃ for 7 hours under a nitrogen atmosphere, thereby obtaining a partial polymer in which a part of the above monomer components were polymerized. Next, 0.3 part by weight of a silane coupling agent (trade name: KBM-403, manufactured by Xinyue chemical Co., ltd.) and 0.21 part by weight of an isocyanate-based crosslinking agent (trade name: TAKENATE D N, manufactured by Sanyo chemical Co., ltd.) as a crosslinking agent were added to the partial polymer, thereby obtaining an acrylic pressure-sensitive adhesive composition (a-2).
Production example 3 (production of image display portion side pressure-sensitive adhesive layer (B-1))
Into a separable flask having a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube were charged 95 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.2 part by weight of azobisisobutyronitrile as a polymerization initiator, and 233 parts by weight of ethyl acetate, followed by introducing nitrogen gas, and nitrogen gas substitution was performed for about 1 hour while stirring. Then, the flask was heated to 60℃and reacted for 7 hours, whereby an acrylic polymer having a weight average molecular weight (Mw) of 110 ten thousand was obtained.
An adhesive composition (solution) was prepared by adding 0.8 parts by weight of trimethylolpropane toluene diisocyanate (trade name: coronate L, manufactured by Nippon polyurethane Co., ltd.) as an isocyanate-based crosslinking agent and 0.1 parts by weight of a silane coupling agent (trade name: KBM-403, manufactured by Xinyue chemical Co., ltd.) to the acrylic polymer solution (solid content: 100 parts by weight).
The resulting adhesive composition solution was applied to a separator (surface-peeled polyethylene terephthalate film) having a thickness of 38 μm in such a manner that the thickness after drying was 12 μm, and the solvent was removed by drying at 100℃for 3 minutes, thereby obtaining an adhesive layer. Then, the mixture was heated at 50℃for 48 hours to carry out a crosslinking treatment. Hereinafter, this pressure-sensitive adhesive layer is referred to as "image display portion-side pressure-sensitive adhesive layer (B-1)".
Production example 4 (production of image display side pressure-sensitive adhesive layer (B-2))
The adhesive composition solution obtained in production example 3 was applied to a separator (polyethylene terephthalate film whose surface was subjected to release treatment) having a thickness of 38 μm so that the thickness after drying was 15 μm, and the solvent was removed by drying at 100℃for 3 minutes, whereby an adhesive layer was obtained. Then, the mixture was heated at 50℃for 48 hours to carry out a crosslinking treatment. Hereinafter, this pressure-sensitive adhesive layer is referred to as "image display portion-side pressure-sensitive adhesive layer (B-2)".
Example 1
(production of adhesive composition with ultraviolet absorption function)
To the obtained acrylic adhesive composition (a-1), 1.4 parts by weight of 2, 4-bis [ {4- (4-ethylhexyl oxy) -4-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine (trade name: tinosorb S, manufactured by "ultraviolet absorber 1" in tables 1 and 2, manufactured by BASF Japanese company) and 0.2 parts by weight of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: IRGACURE 819, having an absorption band at a wavelength of 200nm to 450nm, manufactured by BASF Japanese company) were added so as to make a solid content of 15%, and stirring was carried out, thereby obtaining an adhesive composition having an ultraviolet absorbing function.
The pressure-sensitive adhesive composition having an ultraviolet absorbing function was applied to the release film so that the thickness of the pressure-sensitive adhesive layer after formation was 150. Mu.m, and then the release film was bonded to the surface of the pressure-sensitive adhesive composition layer. Then, at illuminance: 6.5mW/cm 2 Light amount: 1500mJ/cm 2 Peak wavelength: the pressure-sensitive adhesive composition layer was subjected to ultraviolet irradiation at 350nm to photo-cure the pressure-sensitive adhesive composition layer, thereby forming a visual recognition side pressure-sensitive adhesive layer (A-1).
(production of polarizing film (P-1))
A cycloolefin polymer (COP) film having a thickness of 25 μm was laminated on the viewing side of a polarizer comprising a stretched polyvinyl alcohol film having a thickness of 5 μm impregnated with iodine using a polyvinyl alcohol adhesive, and an acrylic film having a thickness of 20 μm was laminated on the image display portion side surface of the polarizer using a polyvinyl alcohol adhesive, thereby producing a polarizing film (P-1). The polarization degree of the polarizing film was 99.995.
(production of polarizing film with adhesive layer)
A viewing side adhesive layer (A-1) was laminated on the viewing side of the polarizing film (P-1) (i.e., the surface of a cycloolefin polymer (COP) film having a thickness of 25 μm). An image display side adhesive layer (B-1) was laminated on the image display side surface of the polarizing film (P-1) (i.e., the surface of an acrylic film having a thickness of 20 μm), and a retardation film (thickness: 56 μm, material: polycarbonate) and an image display side adhesive layer (B-2) were further laminated, whereby a polarizing film with an adhesive layer was formed. The resulting adhesive layer-equipped polarizing film had a constitution of visual recognition side adhesive layer (A-1)/polarizing film (P-1)/image display side adhesive layer (B-1)/retardation film/image display side adhesive layer (B-2).
Examples 2 to 3
A polarizing film with an adhesive layer was formed in the same manner as in example 1, except that the types of the acrylic adhesive composition, the amount of the ultraviolet absorber 1 added, and the thickness after formation of the visual-recognition-side adhesive layer were as shown in table 1.
Example 4
A polarizing film with an adhesive was formed in the same manner as in example 1, except that the visual-recognition-side adhesive layer was changed from the visual-recognition-side adhesive layer (a-1) to the visual-recognition-side adhesive layer (a-2) obtained as described below.
(production of visual recognition side adhesive layer (A-2))
To the acrylic pressure-sensitive adhesive composition (a-2) obtained in production example 2, 1.4 parts by weight of 2, 4-bis [ {4- (4-ethylhexyl oxy) -4-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine (trade name: tinosorb S, manufactured by BASF Japanese company) dissolved in ethyl acetate so that the solid content was 15% was added and stirred, whereby a pressure-sensitive adhesive composition having an ultraviolet absorbing function was obtained.
The above adhesive composition with an ultraviolet absorption function was applied to the peeled film of the release film in such a manner that the thickness after the formation of the adhesive layer was 150 μm, dried at 60℃for 2 minutes and at 120℃for 2 minutes, and then the peeled film was attached, whereby a visual recognition side adhesive layer (A-2) was formed.
Examples 5 to 6
A polarizing film with an adhesive layer was formed in the same manner as in example 4 except that the thickness of the adhesive layer on the visual recognition side after formation and the adhesive layer on the image display portion side were as shown in table 1.
Example 7
(production of visual recognition side adhesive layer (A-3))
To the acrylic pressure-sensitive adhesive composition (a-1) obtained in production example 1, 0.7 parts by weight of 2, 4-bis [ {4- (4-ethylhexyl oxy) -4-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine (trade name: tinosorb S, manufactured by BASF Japan Co., ltd.) so that the solid content was 15% was dissolved in butyl acrylate, 0.2 parts by weight of solvent yellow 163 (KP Plast Yellow MK, "ultraviolet absorber 2" manufactured by Ji and chemical industries Co., ltd.) and 0.2 parts by weight of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: IRGACURE 819, having an absorption band at a wavelength of 200nm to 450nm, manufactured by BASF Japan Co., ltd.) were added and stirred, thereby obtaining a pressure-sensitive adhesive composition having an ultraviolet absorbing function.
The pressure-sensitive adhesive composition having an ultraviolet absorbing function was applied to the release film so that the thickness of the pressure-sensitive adhesive layer after formation was 150. Mu.m, and then the release film was bonded to the surface of the pressure-sensitive adhesive composition layer. Then, at illuminance: 6.5mW/cm 2 Light amount: 3000mJ/cm 2 Peak wavelength: ultraviolet irradiation was performed at 350nm to photo-cure the adhesive composition layer, thereby forming a visual side adhesive layer (A-3).
A polarizing film with an adhesive was formed in the same manner as in example 1, except that the visual-recognition-side adhesive layer was changed from the visual-recognition-side adhesive layer (a-1) to the visual-recognition-side adhesive layer (a-3) obtained as described above.
Comparative example 1
A polarizing film with an adhesive layer was formed in the same manner as in example 1, except that the viewing side adhesive layer (a-1), the retardation film, and the image display portion side adhesive layer (B-2) were not formed.
Comparative example 2
A polarizing film with an adhesive layer was formed in the same manner as in example 1, except that the viewing-side adhesive layer (a-1) was not formed.
Comparative examples 3 and 4
An adhesive-equipped polarizing film was formed in the same manner as in examples 1 and 4, except that no ultraviolet absorber was added to the visual inspection side adhesive layers (a-1) and (a-2).
Comparative example 5
(production of polarizing film (P-2))
A triacetyl cellulose film having a thickness of 25 μm was laminated on the viewing side of a polarizer comprising a stretched polyvinyl alcohol film having a thickness of 12 μm impregnated with iodine using a polyvinyl alcohol adhesive, and an acrylic film having a thickness of 20 μm was laminated on the image display portion side surface of the polarizer using a polyvinyl alcohol adhesive, thereby producing a polarizing film (P-2). The polarization degree of the polarizing film was 99.995.
An adhesive-equipped polarizing film was formed in the same manner as in example 2, except that the polarizing film (P-1) in example 2 was changed to the above-described polarizing film (P-2).
The adhesive layer and the polarizing film with an adhesive layer thus obtained were evaluated as follows.
< polymerization Rate >
The release films of the visual inspection side adhesive layers obtained in examples and comparative examples were peeled off, and only the visual inspection side adhesive layer was placed on an aluminum dish whose weight was measured. The weight of the adhesive layer before drying was determined by measuring the weight of the (aluminum dish+visual side adhesive layer). The adhesive layer was dried at 130℃for 2 hours, cooled at room temperature for about 20 minutes, and the weight of the adhesive layer on the visual side after drying was determined by measuring the weight of the adhesive layer again (aluminum dish+adhesive). The polymerization rate was determined by the following calculation formula.
Figure BDA0002728475330000391
< gel fraction >
About 0.1g of the adhesive layer on the visual side obtained in examples and comparative examples was obtained by separation, and the resultant was packed in a porous tetrafluoroethylene sheet (trade name: NTF1122, manufactured by Nito electric Co., ltd.) having an average pore diameter of 0.2 μm, and then bound with kite string, and the weight (Zg) at that time was measured as the weight before impregnation. The weight before dipping was the total weight of the visual recognition side adhesive layer (the adhesive layer selected by the above collection), the tetrafluoroethylene sheet, and the kite string. In addition, the total weight (Yg) of the tetrafluoroethylene sheet and the kite string was also measured. Next, the material (referred to as "sample") in which the visual recognition side adhesive layer was wrapped with a tetrafluoroethylene sheet and bound with kite string was placed in a 50mL container filled with ethyl acetate, and allowed to stand at 23 ℃ for 7 days. Then, the sample (after ethyl acetate treatment) was taken out of the container, transferred to an aluminum cup, dried in a dryer at 130 ℃ for 2 hours to remove ethyl acetate, and then the weight (Xg) was measured, and this weight was taken as the weight after impregnation. Gel fraction was calculated from the following formula.
Gel fraction (wt%) = (X-Y)/(Z-Y) ×100
< measurement of transmittance and b-value of visual inspection side pressure-sensitive adhesive layer >
The release films of the visual recognition side adhesive layers obtained in examples and comparative examples were peeled off, and the visual recognition side adhesive layers were attached to a jig for measurement, and were measured using a spectrophotometer (product name: U4100, manufactured by Hitachi, inc.). Regarding the transmittance, the transmittance at wavelengths of 380nm, 400nm and 420nm was measured (however, for wavelengths of 420nm, only the measurement was performed in examples 2 and 7).
< residual stress >
Test pieces were produced by cutting out 30mm wide and 50mm long from the visual recognition side adhesive layers obtained in examples and comparative examples, and making them into a tube shape. The test piece was stretched at a stretching speed of 200 mm/min by setting it at a grip pitch of 20mm by 60mm (300%) (the grip pitch after stretching was 80 mm). The specimen was fixed (held) at a position of 60mm for 300 seconds, and the stress value (N) after 300 seconds was measured. Residual stress was determined by the following equation.
Residual stress after 300 seconds = stress value after 300 seconds (N)/(4 x thickness of test piece/10)
< optical reliability >
The viewing side adhesive layers obtained in examples 1 to 7 and comparative examples 3 to 5 were bonded to the COP film of the polarizing film (P-1) used in example 1. Further, a 56 μm retardation film (manufactured by Nitton electric Co., ltd.) having an adhesive of 15 μm was bonded to the opposite side (acrylic film side) of the polarizing film to which the viewing side adhesive layer was bonded. The sample was bonded on both sides to glass (trade name: S200200, thickness: 1.3mm, size: 45 mm. Times.50 mm, manufactured by Song Nitro Co., ltd.) and subjected to autoclave treatment (air pressure: 0.5MPa, temperature: 50 ℃ C.) for 15 minutes. Then, the transmittance was measured by using a spectral transmittance measuring device (product name: DOT-3, manufactured by color technology research, inc.) under the following various reliability conditions. The amount of change in transmittance from the initial value was obtained. The evaluation was performed according to the following evaluation criteria.
(various reliability conditions)
(condition 1) 85 ℃ C. For 500 hours
(condition 2) 60 ℃ C., 95%. Times.500 hours
(condition 3) thermal shock (HS) (-40 ℃ to 85 ℃) for 300 times of circulation
(condition 4) UV irradiation for 100 hours, illuminance: 500W/cm 2 (300 nm-700 nm), ambient temperature: 60-65 ℃ and environmental humidity: 50 percent of
(condition 5) xenon lamp irradiation for x 300 hours, illuminance: 2.40W/cm 2 (420 nm), ambient temperature: 50 ℃, environmental humidity: 30%
(evaluation criteria)
O: the transmittance change amount is 2.0% or less.
Delta: the transmittance change amount exceeds 2.0% and is 3.0% or less.
X: the transmittance variation exceeds 3.0%.
< glue stain, dimensional accuracy, end appearance >
The adhesive layer-carrying polarizing films obtained in examples and comparative examples were cut into dimensions of 25mm×30mm using a super cutter. Then, four sides of the cut piece were subjected to 0.05mm cutting by an end face processor (manufactured by MEGARO techenica corporation), and samples were produced. Regarding the gummy stain, the side surface of the sample was visually checked to confirm the presence or absence of the gummy stain. The dimensional accuracy and the end appearance were observed with an optical microscope, and evaluated according to the following evaluation criteria.
(dimensional accuracy)
O: within + -0.3 mm
X: exceeding + -0.3 mm
(end appearance)
O: no end sticking when touched by hand
X: case of end tackiness when touched by hand
< curl measurement >
The samples cut to 50mm by 40mm were placed on a flat table and the curl was measured using a feeler gauge.
(crimping)
O: within + -1.0 mm
Delta: is more than +/-1.0 mm and less than +/-2.0 mm
X: greater than + -2.0 mm
Figure BDA0002728475330000421
/>
Figure BDA0002728475330000431
In Table 1, P-1 represents a polarizing film (P-1), P-2 represents a polarizing film (P-2), a-1 represents an acrylic adhesive composition (a-1) obtained in production example 1, a-2 represents an acrylic adhesive composition (a-2) obtained in production example 2, ultraviolet absorber 1 represents 2, 4-bis [ {4- (4-ethylhexyl oxy) -4-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine (trade name: tinosorb S, manufactured by BASF Japanese Co., ltd.), ultraviolet absorber 2 represents solvent yellow 163 (KP Plast Yellow MK, manufactured by Ji and chemical industry Co., ltd.), B-1 represents an image display side adhesive layer (B-1) obtained in production example 3, and B-2 represents an image display side adhesive layer (B-2) obtained in production example 4.
Reference numerals
1. Polarizing film with adhesive layer
2a visual recognition side adhesive layer
2b image display side adhesive layer
3a visual recognition side transparent protective film
3b image display portion side transparent protective film
4. Polarizer
5 polarizing film
6. Protective glass or protective plastic
7. Liquid Crystal Display (LCD) or organic EL display (OLED)
8a, 8b adhesive layer
9. Sensor layer

Claims (9)

1. A polarizing film with an adhesive layer for use in an image display device at a position closer to the viewing side than an image display portion, characterized in that,
the adhesive layer-equipped polarizing film has a polarizing film and adhesive layers on both sides of the polarizing film,
the polarizing film has a polarizer and transparent protective films on both sides of the polarizer,
the transmittance of the transparent protective film on the visual recognition side of the polarizer at 380nm is less than 6%,
the adhesive layer on the viewing side of the polarizing film has an ultraviolet absorbing function,
the adhesive layer on the visual recognition side of the polarizing film contains one or more of triazine ultraviolet absorbent, benzotriazole ultraviolet absorbent, benzophenone ultraviolet absorbent, hydroxybenzophenone ultraviolet absorbent, salicylate ultraviolet absorbent and cyanoacrylate ultraviolet absorbent and dye as ultraviolet absorbent, and
The transparent protective film on the viewing side of the polarizer is at least one film selected from the group consisting of a triacetyl cellulose film and a polyolefin film having a cyclic or norbornene structure.
2. The adhesive layer-carrying polarizing film according to claim 1, wherein the transparent protective film on the viewing side of the polarizer has a thickness of 40 μm or less.
3. The polarizing film with an adhesive layer according to claim 1, wherein the thickness of the adhesive layer on the viewing side of the polarizing film is 2 times or more the thickness of the adhesive layer on the image display portion side of the polarizing film.
4. The polarizing film with an adhesive layer according to claim 1, wherein the adhesive layer on the viewing side of the polarizing film has a transmittance of 9% or less at a wavelength of 380nm and a transmittance of 60% or more at a wavelength of 400 nm.
5. The polarizing film with an adhesive layer according to claim 1, wherein the adhesive layer on the viewing side of the polarizing film has a transmittance of 9% or less at a wavelength of 380nm and a transmittance of 75% or less at a wavelength of 420 nm.
6. The adhesive layer-carrying polarizing film according to claim 1, wherein the b-x value of the adhesive layer on the viewing side of the polarizing film is 3.0 or less.
7. The polarizing film with an adhesive layer according to claim 1, wherein the adhesive layer on the viewing side of the polarizing film contains an acrylic polymer as a base polymer.
8. The adhesive layer-attached polarizing film according to any one of claims 1 to 7, wherein the adhesive layer-attached polarizing film is used for a liquid crystal display device or an organic EL display device.
9. An image display device using the polarizing film with an adhesive layer according to any one of claims 1 to 8 at a position closer to the viewing side than the image display portion.
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