CN116179119A - Adhesive composition and adhesive layer for organic EL display device, polarizing film with adhesive layer, and organic EL display device - Google Patents

Adhesive composition and adhesive layer for organic EL display device, polarizing film with adhesive layer, and organic EL display device Download PDF

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CN116179119A
CN116179119A CN202310144066.7A CN202310144066A CN116179119A CN 116179119 A CN116179119 A CN 116179119A CN 202310144066 A CN202310144066 A CN 202310144066A CN 116179119 A CN116179119 A CN 116179119A
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adhesive layer
organic
display device
wavelength
film
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Inventor
形见普史
山本真也
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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    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising 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
    • 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
    • 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
    • G09F9/33—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 being semiconductor devices, e.g. diodes
    • G09F9/335—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 being semiconductor devices, e.g. diodes being organic light emitting diodes [OLED]
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Polarising Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Optical Filters (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The present invention relates to an adhesive composition and an adhesive layer for an organic EL display device, a polarizing film with an adhesive layer, and an organic EL display device. The adhesive composition for an organic EL display device of the present invention comprises a base polymer, an ultraviolet absorber, and a pigment compound, wherein the maximum absorption wavelength of the absorption spectrum of the pigment compound is within the wavelength range of 380nm to 430 nm. The adhesive composition for an organic EL display device of the present invention can form an adhesive layer for an organic EL display device, which can suppress deterioration of an organic EL element and has high transparency when used in an organic EL display device. In addition, an adhesive layer for an organic EL display device, a polarizing film with an adhesive layer having a polarizing film and an adhesive layer for an organic EL display device, and an organic EL display device including the adhesive layer and/or the polarizing film with an adhesive layer, each of which is formed from the adhesive composition, can be provided.

Description

Adhesive composition and adhesive layer for organic EL display device, polarizing film with adhesive layer, and organic EL display device
The present application is a divisional application of chinese patent application with application number 201680075203.4, which is the application date 2016, 12 and 22.
Technical Field
The present invention relates to an adhesive composition for an organic EL (electroluminescent) display device (OLED). The present invention also relates to an adhesive layer for an organic EL display device, which is formed from the adhesive composition for an organic EL display device, and a polarizing film with an adhesive layer, which has the adhesive layer. The present invention also relates to an organic EL display device using the adhesive layer and/or the polarizing film.
Background
In recent years, organic EL display devices having organic EL panels mounted thereon have been widely used in various applications such as mobile phones, navigation devices, monitors for personal computers, and televisions. In general, in order to suppress reflection of external light by a metal electrode (cathode) and to view the external light as a mirror surface, a circular polarizing plate (a laminate of a polarizing plate and a 1/4 wave plate, etc.) is disposed on a viewing side surface of an organic EL panel. In addition, a decorative panel or the like may be further laminated on a circularly polarizing plate laminated on the viewing side surface of the organic EL panel. The constituent members of the organic EL display device such as the circularly polarizing plate and the decorative panel are generally laminated via a bonding material such as an adhesive layer or an adhesive layer.
In image display devices such as organic EL display devices, it is known that components and the like in the image display devices are degraded by incident ultraviolet light, and a layer containing an ultraviolet absorber is provided to suppress such degradation by ultraviolet light. Specifically, for example, the following adhesive sheets are known: a transparent double-sided adhesive sheet for an image display device, which has at least one ultraviolet absorbing layer, has a light transmittance of 30% or less at a wavelength of 380nm, and has a visible light transmittance of 80% or more at a longer wavelength side than at a wavelength of 430nm (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).
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
Disclosure of Invention
Problems to be solved by the invention
The pressure-sensitive adhesive sheets described in patent documents 1 and 2 can control the transmittance of light having a wavelength of 380nm, but when the pressure-sensitive adhesive sheets are used in an organic EL display device, the organic EL element may be deteriorated due to long-term use, and thus the pressure-sensitive adhesive sheets are not satisfactory. This is considered to be because the pressure-sensitive adhesive sheets described in patent documents 1 and 2 can absorb light having a wavelength of 380nm, but the light having a wavelength range (380 nm to 430 nm) closer to the short wavelength side than the light emission range (longer wavelength side than 430 nm) of the organic EL element is not sufficiently absorbed, and the transmitted light is degraded.
Therefore, in order to suppress degradation of the organic EL element, it is necessary to use a layer in the organic EL display device that suppresses transmission of light having a wavelength (380 nm to 430 nm) closer to the short wavelength side than the light emission range (closer to the long wavelength side than 430 nm) of the organic EL element, and that can sufficiently ensure transmittance of visible light in the light emission range of the organic EL element and that has high transparency.
Accordingly, an object of the present invention is to provide an adhesive composition for an organic EL display device capable of forming an adhesive layer for an organic EL display device, which is used for an organic EL display device, can suppress degradation of an organic EL element, and has high transparency. The present invention also provides an adhesive layer for an organic EL display device, an adhesive layer-equipped polarizing film having a polarizing film and an adhesive layer for an organic EL display device, which is formed from the adhesive composition, and an organic EL display device comprising the adhesive layer and/or the adhesive layer-equipped polarizing film.
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 adhesive composition for an organic EL display device, and have completed the present invention.
Specifically, the present invention relates to an adhesive composition for an organic EL display device, which comprises a base polymer, an ultraviolet absorber, and a dye compound, wherein the dye compound has an absorption spectrum with a maximum absorption wavelength in the wavelength range of 380nm to 430 nm.
Preferably, the base polymer is a (meth) acrylic polymer.
Preferably, the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is in a wavelength range of 300nm to 400 nm.
The present invention also relates to an adhesive layer for an organic EL display device, which is characterized by being formed from the adhesive composition for an organic EL display device.
In the adhesive layer for an organic EL display device, the average transmittance at a wavelength of 300nm to 400nm is preferably 5% or less, the average transmittance at a wavelength of 450nm to 500nm is preferably 70% or more, and the average transmittance at a wavelength of 500nm to 780nm is preferably 80% or more.
The average transmittance may be 5% or less in the wavelength range of 300nm to 400nm, 30% or less in the wavelength range of 400nm to 430nm, 70% or more in the wavelength range of 450nm to 500nm, or 80% or more in the wavelength range of 500nm to 780 nm.
The average transmittance may be 5% or less in the range of 300nm to 400nm, 30% or more to 75% or less in the range of 400nm to 430nm, 80% or more in the range of 450nm to 500nm, or 80% or more in the range of 500nm to 780 nm.
The present invention also relates to a polarizing film having an adhesive layer for an organic EL display device, wherein the polarizing film having an adhesive layer for an organic EL display device includes a polarizing film and the adhesive layer for an organic EL display device.
Preferably, the polarizing film is a polarizing film having a transparent protective film provided on one surface of a polarizer and a retardation film provided on the other surface, and the adhesive layer for an organic EL display device is provided on a surface of the retardation film opposite to a surface contacting the polarizer and/or on a surface of the transparent protective film opposite to a surface contacting the polarizer.
Preferably, the polarizing film with an adhesive layer for an organic EL display device includes, in order, a first adhesive layer, a transparent protective film, a polarizer, a second adhesive layer, a retardation film, and a third adhesive layer, and
At least one of the first, second and third adhesive layers is the adhesive layer for an organic EL display device.
Preferably, the retardation film is a 1/4 wave plate, and the polarizing film is a circular polarizing film.
The present invention also relates to an organic EL display device using at least one of the adhesive layer for an organic EL display device and the polarizing film with the adhesive layer for an organic EL display device.
Effects of the invention
The adhesive composition for an organic EL display device of the present invention can form an adhesive layer for an organic EL display device, which can suppress deterioration of an organic EL element and has high transparency when used in an organic EL display device. Therefore, the organic EL display device using the adhesive layer for an organic EL display device and/or the polarizing film with an adhesive layer containing the adhesive layer for an organic EL display device of the present invention has excellent weather degradation resistance, and can realize a long lifetime.
Drawings
Fig. 1 (a) to (c) are cross-sectional views schematically showing one embodiment of the polarizing film with an adhesive layer for an organic EL display device of the present invention.
Fig. 2 is a cross-sectional view schematically showing one embodiment of the organic EL display device of the present invention.
Fig. 3 is a cross-sectional view schematically showing one embodiment of the organic EL display device of the present invention.
Fig. 4 is a cross-sectional view schematically showing one embodiment of the organic EL display device of the present invention.
Detailed Description
1. Adhesive composition for organic EL display device
The adhesive composition for an organic EL display device of the present invention is characterized by comprising a base polymer, an ultraviolet absorber, and a pigment compound, wherein the maximum absorption wavelength of the absorption spectrum of the pigment compound is within the wavelength range of 380nm to 430 nm. Here, the maximum absorption wavelength means an absorption maximum wavelength that exhibits maximum absorbance when a plurality of absorption maxima exist in the spectroscopic absorption spectrum in the wavelength range of 300nm to 460 nm.
The base polymer used in the present invention is not particularly limited, and examples of the type of the adhesive composition include rubber adhesives, acrylic adhesives, silicone adhesives, polyurethane adhesives, vinyl alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinyl pyrrolidone adhesives, polyacrylamide adhesives, cellulose adhesives, and the like. 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. In the present invention, an acrylic adhesive composition containing a (meth) acrylic polymer as a base polymer is preferable.
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, an ultraviolet absorber, and a pigment compound.
(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 "(meth) alkyl acrylate" means alkyl acrylate and/or alkyl methacrylate, and the term "methyl" as used herein means the same.
The alkyl (meth) acrylate includes the linear or branched alkyl (meth) acrylate having 1 to 24 carbon atoms. Among them, alkyl (meth) acrylates having 1 to 9 carbon atoms are preferable, alkyl (meth) acrylates having 4 to 9 carbon atoms are more preferable, and alkyl (meth) acrylates having 4 to 9 carbon atoms are still more preferable. The alkyl (meth) acrylate is preferable in terms of easily obtaining a balance of adhesive properties. For example, specific examples of the alkyl (meth) acrylate having 4 to 9 carbon atoms include n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-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, 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 BDA0004088561440000071
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 Alkyl (meth) acrylate represented by a substituted alkyl group having 1 to 3 carbon atoms and 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% by weight or less, preferably 45% by weight or less, more preferably 40% by weight or less, and still more preferably 35% by weight 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, the polymerization initiator is added under a flow of an inert gas such as nitrogen, and the reaction is usually carried out under a reaction condition of about 50℃to about 70℃and about 5 hours 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, a pigment compound, 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 is not particularly limited, and preferably includes a photopolymerization initiator (A) having an absorption band at a wavelength of 400nm or more. When the ultraviolet absorber and the pigment compound are contained in the adhesive composition, ultraviolet light is absorbed by the ultraviolet absorber and the pigment compound during ultraviolet polymerization, and thus polymerization cannot be sufficiently performed. However, if the photopolymerization initiator (A) has an absorption band at a wavelength of 400nm or more, the polymerization can be sufficiently carried out even if the ultraviolet absorber or the pigment compound is contained, and therefore, it is preferable.
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) and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide (LUCIRIN TPO, manufactured by BASF).
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 or the pigment compound described later, and is preferably about 0.005 to about 1 part by weight, more preferably about 0.02 to about 0.8 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) 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 0.2 parts by weight, based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer, within a range not impairing 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, an ultraviolet absorber and a pigment compound 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.
(2) Ultraviolet absorber
Examples of the ultraviolet absorber include, but are not particularly limited to, triazine ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, hydroxybenzophenone ultraviolet absorbers, salicylate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers, and these ultraviolet absorbers may be used singly or in combination. 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.
Specific examples of the triazine ultraviolet light absorber having two or more hydroxyl groups in one molecule 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.
The maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in the wavelength range of 300nm to 400nm, more preferably in the wavelength range of 320nm to 380 nm. The method for measuring the maximum absorption wavelength is the same as the method for measuring the dye-based compound described later.
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.
(3) Pigment compound
The pigment compound used in the present invention is not particularly limited as long as it has a maximum absorption wavelength of an absorption spectrum within a wavelength range of 380nm to 430 nm. The maximum absorption wavelength of the absorption spectrum of the dye compound is more preferably in the wavelength range of 380nm to 420 nm. In the present invention, by using such a pigment compound in combination with the above-described ultraviolet absorber, light in a range (wavelength 380nm to 430 nm) that does not affect the light emission of the organic EL element can be sufficiently absorbed, and the light emission range (on the long wavelength side than 430 nm) of the organic EL element can be sufficiently transmitted, and as a result, deterioration of the organic EL element due to external light can be suppressed. The pigment compound is not particularly limited as long as it has the above wavelength characteristics, and a material which does not interfere with the display properties of the organic EL element and does not have fluorescence or phosphorescence properties (photoluminescence) is preferable.
The half-width of the dye compound is not particularly limited, but is preferably 80nm or less, more preferably 5nm to 70nm, and still more preferably 10nm to 60nm. By the half-width of the dye compound falling within the above range, the following control can be performed: light in a range not affecting light emission of the organic EL element is sufficiently absorbed, and light on a longer wavelength side than 430nm is sufficiently transmitted, so that it is preferable. The half-width measurement method was as follows.
< method for measuring half Peak Width >
The half-width of the dye compound was measured by using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi high technology, inc.) under the following conditions from the transmission absorption spectrum of the dye compound solution. The half-width of the dye compound was defined as the distance between the two points at which 50% of the peak value was reached (full width at half maximum) from the spectrum measured by adjusting the concentration so that the absorbance at the maximum absorption wavelength was 1.0.
(measurement conditions)
Solvent: toluene or chloroform
Cuvette(s): quartz cuvette
Optical path length: 10mm of
The dye compound is not particularly limited in structure, as long as it has a maximum absorption wavelength of an absorption spectrum within a wavelength range of 380nm to 430 nm. Examples of the dye compound include organic dye compounds and inorganic dye compounds, and among them, organic dye compounds are preferable from the viewpoints of maintaining dispersibility in a resin component such as a base polymer and maintaining transparency.
Examples of the organic dye compound include azomethine compounds, indole compounds, cinnamic acid compounds, pyrimidine compounds, and porphyrin compounds.
As the organic dye compound, commercially available organic dye compounds can be suitably used, specifically, as the indole compounds, BONASORB UA3911 (trade name, maximum absorption wavelength of absorption spectrum: 398nm, manufactured by Orient chemical industry Co., ltd.), BONASORB UA3912 (trade name, maximum absorption wavelength of absorption spectrum: 386nm, half-peak width: 53nm, manufactured by Orient chemical industry Co., ltd.), SOM-5-0106 (trade name, maximum absorption wavelength of absorption spectrum: 416nm, half-peak width: 50nm, manufactured by Orient chemical industry Co., ltd.), and as the porphyrin compounds, FDB-001 (trade name, maximum absorption wavelength of absorption spectrum: 420nm, half-peak width: 14nm, manufactured by mountain chemical industry Co., ltd.) and the like can be cited.
The pigment compound may be used alone or in combination of two or more, and the content of the pigment compound as a whole is preferably from about 0.01 to about 10 parts by weight, more preferably from about 0.02 to about 5 parts by weight, based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer. The addition amount of the pigment compound is preferably set to the above range, since light in a range not affecting the light emission of the organic EL element can be sufficiently absorbed, and the use of the adhesive layer formed of the adhesive composition can suppress the deterioration of the organic EL element.
(4) Silane coupling agent
In addition, a silane coupling agent may be contained in the adhesive composition of 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.
(5) Crosslinking agent
The adhesive composition of 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 BDA0004088561440000211
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.
(6) Other additives
The adhesive composition of the present invention may contain an appropriate additive in addition to the above components depending on the application. 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; light Stabilizers (HALS); antioxidants, and the like.
In the present invention, the adhesive composition is preferably adjusted to a viscosity suitable for an operation such as coating on a substrate. The viscosity of the 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 adhesive composition. The partial polymerization may be performed before or after the addition of various polymers such as thickening additives or polyfunctional monomers. The viscosity of the adhesive composition varies depending on the amount of the additive or the like, and therefore, the polymerization rate at the time of polymerizing the monomer component in the adhesive composition cannot be determined uniquely, and is preferably about 20% or less, more preferably about 3% to about 20%, and still more preferably about 5% to about 15% on a general basis. If the amount is more than 20%, the viscosity becomes too high, and thus it is difficult to apply the coating to a substrate.
2. Adhesive layer for organic EL display device
The adhesive layer for an organic EL display device of the present invention is characterized in that the adhesive layer for an organic EL display device is formed from the adhesive composition for an organic EL display device.
The method for forming the adhesive layer is not particularly limited, and it can be formed by a method generally used in the art. Specifically, the adhesive composition can be formed by applying the adhesive composition to at least one surface of a substrate, and drying a coating film formed from the 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.
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, vinyl acetate resins, polyether sulfone 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 adhesive composition to the substrate may be any known suitable method such as roll coating, gravure coating, reverse coating, roll brushing, 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 pressure-sensitive adhesive layer is formed by drying a coating film formed from the 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 are, for example, 1 minute to 60 minutes, preferably 2 minutes to 30 minutes at a temperature of about 60 ℃ to about 170 ℃, preferably 60 ℃ to 150 ℃.
In the case where the adhesive composition is an ultraviolet-curable adhesive composition and is formed by irradiating ultraviolet rays to a coating film formed from the ultraviolet-curable 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 is greater than 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 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 the ultraviolet light irradiated to the ultraviolet curable adhesive composition is preferably in the range of 200nm to 500nm, more preferably in the range of 300nm to 450 nm. When the peak wavelength of ultraviolet light is more than 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 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, a pigment compound, 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 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 adhesive composition containing the photopolymerization initiator (B), polymerization is performed in two stages as described above, so that the polymerization rate of the monomer component can be increased and the ultraviolet absorption function of the finally produced adhesive layer can be improved.
The thickness of the pressure-sensitive adhesive layer is preferably 12 μm or more, more preferably 50 μm or more, still more preferably 100 μm or more, particularly preferably 150 μm or more, from the viewpoint of ensuring the function of absorbing light having a wavelength of less than 430 nm. The upper limit of the thickness of the adhesive layer is not particularly limited, but is preferably 1mm or less. When the thickness of the pressure-sensitive adhesive layer is larger than 1mm, ultraviolet light is less likely to transmit, polymerization of the monomer component takes time, and there are problems in workability, winding in the process, and transportation properties, and productivity is sometimes poor, which is not preferable.
The gel fraction of the 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 pressure-sensitive adhesive layer is small, the cohesive force is poor, and there are cases where the workability and the handleability are problematic.
The haze value of the pressure-sensitive adhesive layer measured at a thickness of 25 μm is preferably 2% or less, more preferably 0 to 1.5%, and still more preferably 0 to 1%. The haze is in the above range, and the adhesive layer has high transparency, so that it is preferable.
The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 300nm to 400nm is preferably 5% or less, more preferably 2% or less. When the transmittance of the adhesive layer is within the above range, light in a range that does not affect the light emission of the organic EL element can be sufficiently absorbed, and deterioration of the organic EL element can be suppressed.
The average transmittance of the pressure-sensitive adhesive layer at a wavelength of 450nm to 500nm is preferably 70% or more, more preferably 75% or more, and the average transmittance at a wavelength of 500nm to 780nm is preferably 80% or more, more preferably 85% or more. When the transmittance of the adhesive layer is within the above range, light can be sufficiently transmitted in the light emission range (on the long wavelength side of 430 nm) of the organic EL element, and an organic EL display device using the adhesive layer can sufficiently emit light.
The adhesive layer may have an average transmittance of 400nm to 430nm or less, and may be designed according to the characteristics required for the organic EL display device. For example, the adhesive layer preferably has an average transmittance of 30% or less, more preferably 20% or less at a wavelength of 400nm to 430nm, from the viewpoint of sufficiently absorbing light in a range not affecting the light emission of the organic EL element and suppressing the degradation of the organic EL element for protection. On the other hand, from the viewpoint of protecting the organic EL element from ultraviolet light and suppressing coloring of the organic EL element, the average transmittance of the adhesive layer at a wavelength of 400nm to 430nm is preferably greater than 30% and equal to or less than 75%, more preferably greater than 30% and equal to or less than 65%.
The term "average transmittance at a wavelength of 300nm to 400 nm" as used herein refers to an average transmittance obtained by measuring transmittance at a pitch of 1nm in a wavelength range of 300nm to 400 nm. The same applies to the average transmittance in other wavelength ranges.
The pressure-sensitive adhesive layer of the present invention can sufficiently absorb light in a range that does not affect the light emission of the organic EL element by having the above transmittance, and can sufficiently transmit the light emission range (on the long wavelength side of 430 nm) of the organic EL element, thereby suppressing degradation of the organic EL element due to external light.
In the case where the adhesive layer is exposed, the adhesive layer may be protected with a release film until it is put to practical use.
3. Polarizing film with adhesive layer for organic EL display device
The polarizing film with an adhesive layer for an organic EL display device of the present invention is characterized by comprising a polarizing film and the adhesive layer for an organic EL display device.
The adhesive layer for an organic EL display device can be suitably used. In addition, in the case where the adhesive layer is formed on a substrate other than the polarizing film, the adhesive layer may be bonded and transferred to the polarizing film. In addition, the release film can be used as a separator for a polarizing film having an adhesive layer, and simplification of the process can be achieved.
The polarizing film is not particularly limited, and examples thereof include a polarizing film having a polarizer and a transparent protective film on at least one surface of the polarizer.
(1) 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 formalized 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.
(2) Transparent protective film
As the 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 transparent protective film 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 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, as an adhesive for a polarizer and a transparent protective film, there may be mentioned: 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, to which the polarizer is not adhered, may be subjected to a hard coat layer or an antireflection treatment, and a treatment for preventing adhesion, diffusion or antiglare.
As the transparent protective film, a transparent protective film having a phase difference and capable of functioning as an optical compensation layer can be used. In the case of using a transparent protective film having a phase difference, its phase difference characteristic can be appropriately adjusted to a value required for optical compensation. As the retardation film, a stretched film can be suitably used. In the retardation film, when the refractive index in the slow axis direction is nx, the refractive index in the in-plane fast axis direction is ny, and the refractive index in the thickness direction is nz, a retardation film satisfying the relationships of nx=ny > nz, nx > ny > nz, nx > ny=nz, nx > nz > ny, nz=nx > ny, nz > nx > nx=ny is selected and used according to various applications. It should be noted that nx=ny includes not only the case where nx is identical to ny but also the case where nx is substantially identical to ny. In addition, ny=nz includes not only the case where ny is the same as nz but also the case where ny is substantially the same as nz.
When the polarizing film used in the present invention is used as a circularly polarizing plate for antireflection of an organic EL display device, the retardation film is preferably a 1/4 wave plate in which the front retardation of the transparent protective film is set to 1/4 wavelength (about 100nm to about 170 nm).
In the case of using a retardation film as the transparent protective film, a polarizing film having a transparent protective film provided on one surface of the polarizer and a retardation film provided on the other surface can be suitably used. In this case, the position of the pressure-sensitive adhesive layer is not particularly limited, and the pressure-sensitive adhesive layer may be provided on the surface of the transparent protective film opposite to the surface contacting the polarizer, or may be provided on the surface of the retardation film opposite to the surface contacting the polarizer, and is preferably provided on at least one surface or on both surfaces from the viewpoint of suppressing degradation of the organic EL element.
Fig. 1 (a) to (c) show an example of a specific structure of the polarizing film with an adhesive layer for an organic EL display device of the present invention. A polarizing film 1 with an adhesive layer for an organic EL display device, which is obtained by stacking the layers in the order of the adhesive layer 2/transparent protective film 3/polarizer 4/retardation film 5, as shown in fig. 1 (a), in the order of the transparent protective film 3/polarizer 4/retardation film 5/adhesive layer 2, as shown in fig. 1 (b), and in the order of the adhesive layer 2/transparent protective film 3/polarizer 4/retardation film 5/adhesive layer 2, as shown in fig. 1 (c), is exemplified. In fig. 1 (a) and (b), the adhesive layer 2 is an adhesive layer for an organic EL display device of the present invention, and in fig. 1 (c), at least one of the two adhesive layers 2 may be an adhesive layer for an organic EL display device of the present invention, or both may be an adhesive layer for an organic EL display device of the present invention. In fig. 1, the polarizing film 6 is a single-sided protective polarizing film composed of the polarizer 4 and the transparent protective film 3, but the present invention is not limited to this, and may be a double-sided protective polarizing film having a transparent protective film between the polarizer 4 and the retardation film 5. As described above, various functional layers such as a hard coat layer may be formed on the surface of the transparent protective film 3 which is not in contact with the polarizer 4.
In the case where the retardation film is laminated on the polarizer via the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer may be the pressure-sensitive adhesive layer for an organic EL display device of the present invention. That is, the polarizing film having the adhesive layer for an organic EL display device may include, in order, a first adhesive layer, a transparent protective film, a polarizer, a second adhesive layer, a retardation film, and a third adhesive layer, wherein at least one of the first adhesive layer, the second adhesive layer, and the third adhesive layer is the adhesive layer for an organic EL display device.
4. Organic EL display device
The organic EL display device of the present invention is characterized by using at least one of the adhesive layer for an organic EL display device of the present invention and/or the polarizing film with the adhesive layer for an organic EL display device of the present invention.
As an example of a specific configuration of the organic EL display device, for example, an organic EL display device in which the layers are laminated in the following order as shown in fig. 2 to 4 is exemplified: protective glass or protective plastic 7/adhesive layer 2/transparent protective film 3/polarizer 4/retardation film 5/adhesive layer 2/organic EL display panel (OLED element panel) 8 (fig. 2); protective glass or protective plastic 7/adhesive layer 9/transparent protective film 3/polarizer 4/retardation film 5/adhesive layer 2/organic EL display panel 8 (fig. 3); the protective glass or protective plastic 7/the adhesive layer 2/the sensor layer 10/the adhesive layer 2/the transparent protective film 3/the polarizer 4/the retardation film 5/the adhesive layer 2/the organic EL display panel 8 (fig. 4). At least one of the adhesive layers 2 in the above-described respective configurations may be the adhesive layer of the present invention, or all of the adhesive layers 2 may be the adhesive layer of the present invention. The organic EL display device of the present invention may further include various functional layers such as a protective film and a hard coat layer, in addition to the above. In addition, an adhesive layer and/or an adhesive layer may be suitably used in the lamination of the layers. As the adhesive layer other than the adhesive layer of the present invention, a usual adhesive layer used in the art can be suitably used.
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))
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 in the wavelength range 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 in the wavelength range 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 15 parts by weight of 2-hydroxyethyl acrylate (HEA) until the viscosity (measurement condition: BH viscometer No.5 rotor, 10rpm, measurement temperature 30 ℃) was 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).
Production example 2 (production of acrylic adhesive composition (b))
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.
A solution of an adhesive composition (b) 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).
Production example 3 (production of adhesive layer (B1-1))
The adhesive composition (b) solution obtained in production example 2 was applied to a separator (surface-peeled polyethylene terephthalate-based film) having a thickness of 38 μm so 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 adhesive layer is referred to as "organic EL display panel-side adhesive layer (B1-1)".
Production example 4 (production of adhesive layer (B1-2))
The adhesive composition (b) solution obtained in production example 2 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 23 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 adhesive layer is referred to as an "organic EL display panel-side adhesive layer (B1-2)".
Example 1
(production of adhesive composition (A))
To the acrylic pressure-sensitive adhesive composition (a) obtained in production example 1 (the monomer component forming the acrylic polymer was 100 parts by weight), 0.7 part by weight (solid content weight) of 2, 4-bis [ {4- (4-ethylhexyl oxy) -4-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine (trade name: tinosorb S, the "ultraviolet absorber (b 1)" in tables 1 and 2, the maximum absorption wavelength of the absorption spectrum: 346nm, manufactured by BASF Japanese Co., ltd.), 0.3 part by weight of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide (trade name: IRGACURE 819, having an absorption band in the wavelength range of 200nm to 450nm, manufactured by BASF Japanese Co., ltd.) and BOSORB 3911 (trade name, indole class 1, the maximum absorption wavelength of 2, the "pigment compound in the spectral table 1, the maximum absorption of 2 nm (trade name: 48nm, manufactured by BASF Japanese Co., ltd.) were added so that the solid content was 5%, and the pressure-sensitive adhesive composition (industry: 5 parts by chemical industry: 5 nm, the maximum absorption spectral composition was obtained).
The pressure-sensitive adhesive composition (A) was applied to the release film-treated film so that the thickness of the pressure-sensitive adhesive layer after formation was 150. Mu.m, and then a 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 adhesive layer (A-1) was formed by photo-curing the adhesive composition layer by ultraviolet irradiation at 350 nm.
Example 2
An adhesive layer (A-2) was formed in the same manner as in example 1, except that the dye compound (c) was prepared so that BONASORB UA3912 (trade name, indole compound, "dye compound (c 2)" in tables 1 and 2, maximum absorption wavelength of absorption spectrum: 386nm, half-width: 53nm, manufactured by Orient chemical industry Co., ltd.) was dissolved in N-vinyl-2-pyrrolidone (NVP) so that the solid content was 10%, and the coating was performed so that the thickness after the formation of the adhesive layer was 100. Mu.m.
Example 3
The type of the ultraviolet absorber of example 1 was changed to 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1, 3-tetramethylbutyl) phenol (trade name: tinuvin 928, the "ultraviolet absorber (b 2)" of tables 1 and 2, the maximum absorption wavelength of absorption spectrum: 349nm, manufactured by BASF Japan Co., ltd.) dissolved in butyl acrylate so that the solid content was 15%, and the addition amount was set to 1.5 parts by weight (solid content weight). An adhesive layer (A-3) was formed in the same manner as in example 1, except that the type of the dye compound was changed to a cinnamic acid compound (sample name: SOM-5-0103, "dye compound (c 3)" in tables 1 and 2, maximum absorption wavelength of absorption spectrum: 416nm, half-width: 50nm, manufactured by Orient chemical Co., ltd.) and 0.2 part by weight (solid content weight) was directly added to the resultant mixture to apply the mixture so that the thickness after the formation of the adhesive layer was 100. Mu.m.
Example 4
An adhesive layer (A-4) was formed in the same manner as in example 1 except that the amount of the ultraviolet absorber (b 1) in example 1 was changed to 3.0 parts by weight (solid content weight), the type of the pigment compound was set to 0.1 part by weight (solid content weight) of the porphyrin compound (sample name: FDB-001, "pigment compound (c 4)" in tables 1 and 2) dissolved in N-vinyl-2-pyrrolidone (NVP) so that the solid content was 1%, the maximum absorption wavelength of the absorption spectrum was 420nm, the half-width was 14nm, and the thickness after formation of the adhesive layer was 100 μm by coating.
Example 5
(production of adhesive composition (B))
To the adhesive composition (B) solution obtained in production example 2 (100 parts by weight of the monomer component forming the acrylic polymer), 3 parts by weight (solid content weight) of 2, 4-bis [ {4- (4-ethylhexyl oxy) -4-hydroxy } phenyl ] -6- (4-methoxyphenyl) -1,3, 5-triazine (trade name: tinosorb S, "ultraviolet absorber (B1)" in tables 1 and 2, maximum absorption wavelength of absorption spectrum: 346nm, manufactured by BASF Japanese company) and BONASORB UA3912 (trade name, indole compound, pigment compound (c 2) in tables 1 and 2), maximum absorption wavelength of absorption spectrum: 386nm, half-width: 53nm, manufactured by Orient chemical industry Co., ltd.) were directly added and stirred, thereby obtaining an adhesive composition (B) solution.
The resulting adhesive composition (B) solution was applied to a separator (surface-treated polyethylene terephthalate film) having a thickness of 38 μm so that the thickness after drying was 25 μm, and the solvent was removed by drying at 120 ℃ for 3 minutes, thereby obtaining an adhesive layer. Then, the mixture was heated at 50℃for 48 hours to carry out a crosslinking treatment. An adhesive layer (B) is formed.
Comparative example 1
An adhesive layer (A1-1) was formed in the same manner as in example 1, except that the ultraviolet absorber (b 1) and the pigment compound (c 1) of example 1 were not contained, and only the acrylic adhesive composition (a) was used.
Comparative example 2
The organic EL display panel-side adhesive layer (B1-2) of production example 3 was used.
Comparative example 3
The pressure-sensitive adhesive layers (A1-2) were formed in the same manner as in example 1, except that the pressure-sensitive adhesive layer was applied so that the thickness after formation of the pressure-sensitive adhesive layer was 100. Mu.m, without containing the pigment compound (c 1) of example 1.
Comparative example 4
An adhesive layer (A1-3) was formed in the same manner as in example 3, except that the pigment compound (c 3) was not contained and the adhesive layer was applied so that the thickness after the formation of the adhesive layer was 150. Mu.m.
Comparative example 5
The pressure-sensitive adhesive layers (A1-4) were formed in the same manner as in example 1, except that the ultraviolet absorber (b 1) of example 1 was not contained, and the amount of the pigment compound (c 1) added was set to 0.3 part by weight (solid content weight) and the pressure-sensitive adhesive layer was applied so that the thickness after the formation of the pressure-sensitive adhesive layer was 100. Mu.m.
Comparative example 6
The pressure-sensitive adhesive layers (A1-5) were formed in the same manner as in example 2, except that the ultraviolet absorber (b 1) of example 2 was not contained, and the amount of the pigment compound (c 2) added was set to 0.5 parts by weight (solid content weight).
Comparative example 7
Adhesive layers (A1-6) were formed in the same manner as in example 3, except that the ultraviolet absorber (b 2) of example 3 was not contained.
Comparative example 8
The adhesive layers (A1-7) were formed in the same manner as in example 4, except that the ultraviolet absorber (b 1) of example 4 was not contained.
Example 6
(production of adhesive layer (A-5))
An adhesive layer (A-5) was formed in the same manner as in example 1 except that the pigment compound (c 1) of example 1 was added in an amount of 0.7 parts by weight (solid content weight) and the adhesive layer was applied so that the thickness after the formation of the adhesive layer was 100. Mu.m.
(production of polarizing film (P))
On the visual inspection side of a polarizer comprising a stretched polyvinyl alcohol film having a thickness of 5 μm impregnated with iodine, a cycloolefin polymer (COP) film having a thickness of 25 μm was bonded using a polyvinyl alcohol adhesive, and an acrylic film having a thickness of 20 μm was laminated on the organic EL display panel side surface of the polarizer using a polyvinyl alcohol adhesive, thereby producing a polarizing film (P). The polarization degree of the polarizing film was 99.995.
(production of polarizing film with adhesive layer)
The adhesive layer (A-5) produced as described above was laminated on the viewing side of the polarizing film (P) (i.e., the surface of a cycloolefin polymer (COP) film having a thickness of 25 μm). An image display portion side adhesive layer (B1-1) was laminated on the surface of the above-mentioned polarizing film (P) on the side of the organic EL display panel (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 portion side adhesive layer (B1-2) were further laminated, whereby a polarizing film with an adhesive layer was formed. The resulting adhesive layer-equipped polarizing film had a structure of adhesive layer (A-5)/polarizing film (P)/organic EL display panel-side adhesive layer (B1-1)/retardation film/organic EL display panel-side adhesive layer (B1-2).
Example 7
An adhesive layer (a-6) was formed in the same manner as in example 2 except that the addition amount of the pigment compound (c 2) of example 2 was set to 0.5 parts by weight (solid content weight). In addition, a polarizing film with an adhesive layer was formed in the same manner as in example 6, except that the above-mentioned adhesive layer (a-6) was used.
Comparative example 9
The adhesive layer (A1-8) was formed in the same manner as in example 6, except that the adhesive layer (A-5) of example 6 did not contain the pigment compound (c 1). In addition, a polarizing film with an adhesive layer was formed in the same manner as in example 6, except that the above-mentioned adhesive layers (A1-8) were used.
The adhesive layer and the polarizing film with the adhesive layer thus obtained were evaluated as follows.
< measurement of transmittance of adhesive layer >
The release films of the adhesive layers obtained in examples and comparative examples were peeled off, and the 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 in the wavelength range of 300nm to 780nm was measured.
< measurement of transmittance of polarizing film with adhesive layer >
The release films of the polarizing films with an adhesive layer obtained in examples and comparative examples were peeled off and measured using a spectrophotometer (product name: U4100, manufactured by Hitachi, inc.). Regarding the transmittance, the transmittance in the wavelength range of 350nm to 780nm was measured.
< tackiness >
Sheets having a length of 100mm and a width of 20mm were cut out from the adhesive layers obtained in examples and comparative examples. Then, one of the release films of the adhesive layer was peeled off, and a PET film (trade name: lumirrorS-10, thickness: 25 μm, manufactured by Toli Co., ltd.) was attached (lining). Then, the other release film was peeled off and pressed onto a glass plate (trade name: soda lime glass #0050, manufactured by Song Nitro Corp Co., ltd.) as a test plate under pressure conditions of one round trip of a 2kg roller, whereby a sample composed of the test plate/the adhesive layer (A)/the PET film was produced. The obtained sample was autoclaved (50 ℃ C., 0.5 MPa., 15 minutes) and then naturally cooled for 30 minutes in an atmosphere of 50% R.H. at 23 ℃. After the film was naturally cooled, the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer/PET film) was peeled from the test sheet by using a tensile tester (apparatus name: autograph AG-IS, manufactured by Shimadzu corporation) under the conditions of a tensile speed of 300 mm/min and a peeling angle of 180℃in an atmosphere of 50% R.H. at 23℃in accordance with JIS Z0237, and the 180℃peel adhesion (N/20 mm) was measured.
< total light transmittance, haze >
A release film was peeled off from the adhesive layers obtained in examples and comparative examples and bonded to a glass slide (trade name: white polishing No.1, thickness: 0.8mm to 1.0mm, total light transmittance: 92%, haze: 0.2%, manufactured by Song Nitro Co., ltd.). The other release film was further peeled off to prepare a test piece having a layer structure of an adhesive layer/slide glass. The total light transmittance and haze value of the test piece in the visible light range were measured by using a haze meter (device name: HM-150, manufactured by color research Co., ltd.).
Figure BDA0004088561440000411
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Figure BDA0004088561440000421
Reference numerals
1 polarizing film having adhesive layer for organic EL display device
2 adhesive layer
3 transparent protective film
4 polarizer
5 phase difference film
6 polarizing film
7 protective glass or protective plastic
8 organic EL panel
9 adhesive layer
10 sensor layer

Claims (11)

1. An adhesive composition for an organic EL display device, characterized in that,
the adhesive composition for an organic EL display device comprises a base polymer, an ultraviolet absorber, and a pigment compound, wherein the maximum absorption wavelength of the absorption spectrum of the pigment compound is in the wavelength range of 380 nm-430 nm,
the ultraviolet absorbent is one or more than two of triazine ultraviolet absorbent, benzotriazole ultraviolet absorbent, benzophenone ultraviolet absorbent, hydroxybenzophenone ultraviolet absorbent, salicylate ultraviolet absorbent and cyanoacrylate ultraviolet absorbent,
The base polymer is a (meth) acrylic polymer,
the ultraviolet absorber is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer.
2. The adhesive composition for an organic EL display device according to claim 1, wherein the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is in a wavelength range of 300nm to 400 nm.
3. An adhesive layer for an organic EL display device, characterized in that the adhesive layer for an organic EL display device is formed from the adhesive composition for an organic EL display device according to claim 1 or 2.
4. The adhesive layer for an organic EL display device according to claim 3, wherein the adhesive layer for an organic EL display device
The average transmittance at a wavelength of 300nm to 400nm is 5% or less,
the average transmittance at a wavelength of 450nm to 500nm is 70% or more,
the average transmittance at wavelengths of 500nm to 780nm is 80% or more.
5. The adhesive layer for an organic EL display device according to claim 4, wherein the adhesive layer for an organic EL display device
The average transmittance at a wavelength of 300nm to 400nm is 5% or less,
The average transmittance at a wavelength of 400nm to 430nm is 30% or less,
the average transmittance at a wavelength of 450nm to 500nm is 70% or more,
the average transmittance at wavelengths of 500nm to 780nm is 80% or more.
6. The adhesive layer for an organic EL display device according to claim 4, wherein the adhesive layer for an organic EL display device
The average transmittance at a wavelength of 300nm to 400nm is 5% or less,
the average transmittance of the wavelength 400 nm-430 nm is more than 30% and less than or equal to 75%,
the average transmittance at a wavelength of 450nm to 500nm is 80% or more,
the average transmittance at wavelengths of 500nm to 780nm is 80% or more.
7. A polarizing film with an adhesive layer for an organic EL display device, characterized in that the polarizing film with an adhesive layer for an organic EL display device has a polarizing film and the adhesive layer for an organic EL display device according to any one of claims 3 to 6.
8. The polarizing film with an adhesive layer for an organic EL display device according to claim 7, wherein the polarizing film is a polarizing film having a transparent protective film provided on one surface of a polarizer and a phase difference film provided on the other surface,
the adhesive layer for an organic EL display device is provided on the surface of the retardation film on the opposite side of the surface contacting the polarizer and/or on the surface of the transparent protective film on the opposite side of the surface contacting the polarizer.
9. The polarizing film with an adhesive layer for an organic EL display device according to claim 7, wherein the polarizing film with an adhesive layer for an organic EL display device comprises, in order, a first adhesive layer, a transparent protective film, a polarizer, a second adhesive layer, a retardation film, and a third adhesive layer,
at least one of the first, second and third adhesive layers is the adhesive layer for an organic EL display device.
10. The polarizing film with an adhesive layer for an organic EL display device according to claim 8 or 9, wherein the phase difference film is a 1/4 wave plate, and the polarizing film is a circular polarizing film.
11. An organic EL display device using at least one of the adhesive layer for an organic EL display device according to any one of claims 3 to 6 or the polarizing film with the adhesive layer for an organic EL display device according to any one of claims 7 to 10.
CN202310144066.7A 2015-12-25 2016-12-22 Adhesive composition and adhesive layer for organic EL display device, polarizing film with adhesive layer, and organic EL display device Pending CN116179119A (en)

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