KR20200021915A - The polarizing film provided with the adhesive composition for organic electroluminescent display, the adhesive layer for organic electroluminescent display, the adhesive layer for organic electroluminescent display, and organic electroluminescence display - Google Patents

Abstract

The present invention is selected from the base polymer, the radical generator, and the ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure, and the dye compound (b) in which the maximum absorption wavelength of the absorption spectrum exists in the wavelength region of 380 to 430 nm. It relates to the adhesive composition for organic electroluminescence displays containing at least 1 sort (s) of compound (A). The adhesive composition for organic electroluminescent display of this invention can suppress deterioration of organic electroluminescent element, and can suppress an external appearance yield fall, generation | occurrence | production of foaming in heating durability, etc. by using for the organic electroluminescence display. .

Description

The polarizing film provided with the adhesive composition for organic electroluminescent display, the adhesive layer for organic electroluminescent display, the adhesive layer for organic electroluminescent display, and organic electroluminescence display

The present invention relates to a pressure-sensitive adhesive composition for organic EL (electroluminescence) display device (OLED). Moreover, this invention relates to the polarizing film provided with the adhesive layer for organic electroluminescent display devices formed from the adhesive composition for organic electroluminescent display devices, and the adhesive layer which has this adhesive layer. Moreover, this invention relates to the organic electroluminescence display using the said adhesive layer and / or the said polarizing film.

In recent years, organic electroluminescent display apparatus equipped with an organic electroluminescent panel became widely used in various uses, such as a mobile telephone, a car navigation apparatus, the monitor for personal computers, and a television. In order to suppress that external light is reflected by a metal electrode (cathode) and is recognized like a mirror surface, an organic electroluminescence display normally has a circularly polarizing plate (a laminated body of a polarizing plate and a quarter wave plate, etc.) on the visual side of an organic EL panel. ) Is placed. In addition, a decorative panel etc. may be further laminated by the circularly polarizing plate laminated | stacked on the visual side of the organic electroluminescent panel. The structural members of organic electroluminescent display devices, such as said circular polarizing plate and a decorative panel, are laminated | stacked normally through bonding materials, such as an adhesive layer and an adhesive bond layer.

In image display apparatuses, such as an organic electroluminescence display, the structural member etc. in an image display apparatus may deteriorate by the incident ultraviolet light, and in order to suppress deterioration by the said ultraviolet light, the layer containing a ultraviolet absorber is provided. It is known to arrange. Specifically, the transparent double-sided adhesive sheet for image display device which has at least 1 ultraviolet-ray absorption layer, the light transmittance of wavelength 380nm is 30% or less, and the visible light transmittance in the long wavelength side is 80% or more than wavelength 430 nm. (For example, refer patent document 1).

Japanese Patent Laid-Open No. 2012-211305

Generally, the adhesive composition applied to the transparent double-sided adhesive sheet for image display apparatus contains base polymers, such as a (meth) acrylic-type polymer, for example. In addition, the adhesive composition may form the adhesive layer which carried out radical crosslinking in addition to a base polymer using a radical generator (for example, a peroxide) as a crosslinking agent. Moreover, when using a (meth) acrylic-type polymer as said base polymer, in the said (meth) acrylic-type polymer, since a monomer component is prepared by heat or radiation hardening, the radical polymerization initiator is contained in the said adhesive composition.

However, when an ultraviolet absorber is contained in the adhesive composition containing the said radical generator, there exists a tendency for the gel fraction (crosslinking degree) of the adhesive layer formed from the said adhesive composition to fall depending on a ultraviolet absorber. When the fall of the gel fraction (crosslinking degree) of the said adhesive layer became large, the said adhesive layer had defects, such as the fall of the external appearance yield by adhesive scratch at the time of adhesive scratch or processing, and foaming in heating durability.

Therefore, this invention can use the organic electroluminescent display apparatus, and can suppress deterioration of an organic electroluminescent element, and also can suppress the fall of external appearance yield, the occurrence of foaming in heat durability, etc. adhesive for organic electroluminescent display apparatuses. It is an object to provide a composition.

Moreover, this invention provides the adhesive layer for organic electroluminescent display devices formed from the said adhesive composition, providing the polarizing film provided with the adhesive layer which has a polarizing film and the adhesive layer for organic electroluminescent display devices, The said adhesive layer And / or it aims at providing the organic electroluminescence display containing the polarizing film provided with the said adhesive layer.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered the following adhesive composition for organic electroluminescent display devices, and came to complete this invention.

That is, the present invention relates to a base polymer, a radical generator, and a ultraviolet ray absorbent (a) having 0 to 3 hydroxyl groups in its molecular structure, and a dye compound (b) having a maximum absorption wavelength in the absorption spectrum of 380 to 430 nm. It relates to the adhesive composition for organic electroluminescence displays containing at least 1 sort (s) of compound (A) chosen from.

In the adhesive composition for organic electroluminescent display devices, it is preferable that the said compound (A) contains both the said ultraviolet absorber (a) and the said dye compound (b).

In the pressure-sensitive adhesive composition for organic EL display devices, it is preferable that the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) is present in a wavelength range of 300 to 400 nm.

In the pressure-sensitive adhesive composition for organic EL display devices, the radical generator may use a peroxide.

In the said adhesive composition for organic electroluminescent display devices, a (meth) acrylic-type polymer can be used for the said base polymer.

In the adhesive composition for an organic EL display device, it is preferable to contain 0.01 to 2 parts by weight of the radical generator with respect to 100 parts by weight of the base polymer.

In the said adhesive composition for organic electroluminescent display devices, it is preferable to contain 0.1-25 weight part of said compounds (A) with respect to 100 weight part of said base polymers.

The pressure-sensitive adhesive composition for organic EL display devices may further include an antioxidant.

The pressure-sensitive adhesive composition for organic EL display devices may further include a crosslinking agent.

Moreover, this invention relates to the adhesive layer for organic electroluminescent display characterized by being formed from the said adhesive composition for organic electroluminescent display.

The pressure-sensitive adhesive layer for the organic EL display device preferably has an average transmittance of 12% or less at a wavelength of 300 to 400 nm, an average transmittance of 30% or less at a wavelength of 400 nm to 430 nm, and an average transmittance of 70% or more at a wavelength of 430 to 450 nm. .

The pressure-sensitive adhesive layer for the organic EL display device has an average transmittance of 12% or less at a wavelength of 300 to 400 nm, an average transmittance of more than 30% at a wavelength of 400 nm to 430 nm, and 95% or less, and an average transmittance of 80 at a wavelength of 430 to 450 nm. It is preferable that it is% or more.

Moreover, this invention has a polarizing film and the polarizing film provided with the adhesive layer for organic electroluminescent display characterized by having the said adhesive layer for organic electroluminescent display devices.

In the polarizing film provided with the adhesive layer for organic electroluminescent display devices, the said polarizing film is provided with the transparent protective film in one side of a polarizer, has a phase difference film in the other side, and the adhesive layer for said organic electroluminescence display It is preferable to provide in the surface on the opposite side to the surface which contact | connects the polarizer of this retardation film, and / or the surface on the opposite side to the surface which contact | connects the polarizer of the said transparent protective film.

The polarizing film provided with the adhesive layer for organic electroluminescent display devices contains the 1st adhesive layer, a transparent protective film, a polarizer, a 2nd adhesive layer, a retardation film, and a 3rd adhesive layer in this order. It is a polarizing film provided with

It is preferable that at least one adhesive layer of the said 1st adhesive layer, a 2nd adhesive layer, and a 3rd adhesive layer is the said adhesive layer for organic electroluminescent display devices.

In the polarizing film provided with the adhesive layer for organic electroluminescent display devices, it is preferable that the said retardation film is a quarter wave plate, and the said polarizing film is a circularly polarizing film.

Moreover, this invention used the polarizing film provided with the said adhesive layer for organic electroluminescent display, or the said adhesive layer for organic electroluminescent display, It is related with the organic electroluminescent display characterized by the above-mentioned.

The adhesive composition for organic electroluminescent display of this invention contains a ultraviolet absorber (a) other than a base polymer. By a ultraviolet absorber (a), deterioration by ultraviolet light can be suppressed and deterioration of an organic EL element can be suppressed. Moreover, in the adhesive composition for organic electroluminescent display of this invention, instead of the said ultraviolet absorber (a) or in combination with the said ultraviolet absorber (a), the pigment compound in which the maximum absorption wavelength of an absorption spectrum exists in a wavelength range of 380-430 nm. (b) is contained. Also with the said dye compound (b), deterioration by ultraviolet light can be suppressed and deterioration of organic electroluminescent element can be suppressed.

Moreover, the adhesive composition for organic electroluminescent display of this invention contains radical generators, such as a peroxide. The said radical generating agent functions as a crosslinking agent with respect to base polymers, such as a (meth) acrylic-type polymer, for example, can control the gel fraction of the adhesive layer formed from the said adhesive composition to a desired range, The adhesive layer of a favorable external appearance Can be formed.

As mentioned above, since the ultraviolet absorber and / or a dye compound and a radical generator coexist in the adhesive composition for organic electroluminescent display of this invention, the fall of the gel fraction of the adhesive layer obtained is concerned. However, in the adhesive composition for organic electroluminescent display of this invention, as an ultraviolet absorber, the ultraviolet absorber (a) which is 0-3 of hydroxyl groups in a molecular structure is selected and used. That is, in the present invention, the decrease in the gel fraction is caused by the decrease in the degree of crosslinking due to the deactivation of radicals generated from the radical generator, and the cause of deactivation of the radicals is considered to be a hydrogen donor group possessed by the ultraviolet absorber. The hydroxyl group related to the hydrogen donor group suppresses the crosslinking inhibition of the radical generator by the ultraviolet absorber by selecting and using three or less ultraviolet absorbers (a).

As a result, according to the adhesive composition for organic electroluminescent display of this invention, the adhesive layer for organic electroluminescent display devices which can suppress an external yield yield, generation | occurrence | production of foaming in heat durability, etc. are obtained. Therefore, the organic electroluminescence display using the polarizing film provided with the adhesive layer containing the adhesive layer for organic electroluminescent display and / or the adhesive layer for organic electroluminescent display of this invention has the outstanding weather resistance, and it is long life. Can be.

FIG. 1: is sectional drawing which shows typically one Embodiment of the polarizing film provided with the adhesive layer for organic electroluminescent display of this invention (a)-(c).
2 is a cross-sectional view schematically showing one embodiment of the organic EL display device of the present invention.
3 is a cross-sectional view schematically showing an embodiment of the organic EL display device of the present invention.
4 is a cross-sectional view schematically showing one embodiment of the organic EL display device of the present invention.

1. Adhesive composition for organic electroluminescence display

In the pressure-sensitive adhesive composition for an organic EL display device of the present invention, the base polymer, the radical generator, and the ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure and the maximum absorption wavelength of the absorption spectrum are present in the wavelength region of 380 to 430 nm. It is characterized by including at least 1 sort (s) of compound (A) chosen from the pigment compound (b).

The adhesive composition for organic electroluminescent display of this invention contains a base polymer as a main component. A main component refers to the component with the most content rate among the total solid contained in an adhesive composition, For example, it is a component which occupies more than 50 weight% of the total solid contained in an adhesive composition, Furthermore, it refers to the component which occupies more than 70 weight%. .

It does not specifically limit as a base polymer used by this invention, As a kind of adhesive composition, for example, a rubber type adhesive, an acrylic type adhesive, a silicone type adhesive, a urethane type adhesive, a vinyl alkyl ether type adhesive, a polyvinyl alcohol-type adhesive, polyvinyl Pyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives and the like. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit moderate adhesiveness, cohesiveness, and adhesive adhesion characteristics, and are excellent in weather resistance, heat resistance, and the like. In this invention, it is preferable that it is an acrylic adhesive composition containing a (meth) acrylic-type polymer as a base polymer.

<(Meth) acrylic polymer>

The said (meth) acrylic-type polymer normally contains an alkyl (meth) acrylate as a main component as a monomer unit. In addition, (meth) acrylate means an acrylate and / or methacrylate, and (meth) of this invention is the same meaning.

As an alkyl (meth) acrylate which comprises the main skeleton of the said (meth) acrylic-type polymer, what has C1-C18 linear or branched alkyl groups can be illustrated. These may be used alone or in combination. It is preferable that the average carbon number of these alkyl groups is 3-9.

Moreover, alkyl (meth) acrylate containing aromatic rings, such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate, can be used from a viewpoint of adhesive property, durability, retardation adjustment, refractive index adjustment, etc. have.

In the (meth) acrylic polymer, at least one copolymerization monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group may be introduced by copolymerization for the purpose of improving adhesion or heat resistance. Can be. As a specific example of such a copolymerization monomer, (meth) acrylic-acid 2-hydroxyethyl, (meth) acrylic-acid 3-hydroxypropyl, (meth) acrylic-acid 4-hydroxybutyl, (meth) acrylic acid 6-hydroxy Hydroxides such as hexyl, 8-hydroxyoctyl (meth) acrylic acid, 10-hydroxydecyl (meth) acrylic acid, 12-hydroxylauryl (meth) acrylic acid and (4-hydroxymethylcyclohexyl) -methylacrylate Actual group-containing monomers; Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Caprolactone adducts of acrylic acid; Sulfonic acid groups such as styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalenesulfonic acid Containing monomers; Phosphoric acid group containing monomers, such as 2-hydroxyethyl acryloyl phosphate, etc. are mentioned.

Furthermore, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol propane (meth) acrylamide, etc. (N-substituted) amide monomers; Alkyl (meth) acrylate alkylaminoalkyl monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate; Alkoxy (meth) acrylate alkyl monomers, such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, N Succinimide monomers such as acryloyl morpholine; Maleimide monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide and N-phenyl maleimide; N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itacon Itaconic imide type monomers, such as mead and N-lauryl itaconimide, etc. are mentioned as a monomer example for a purpose of modification.

Furthermore, as modified monomers, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, Vinyl monomers such as vinyl oxazole, vinyl morpholine, N-vinyl carboxylic acid amides, styrene, α-methyl styrene, and N-vinyl caprolactam; Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; Glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; Acrylic acid ester system monomers, such as (meth) acrylic acid tetrahydrofurfuryl, a fluorine (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate, can also be used. Furthermore, isoprene, butadiene, isobutylene, vinyl ether, etc. are mentioned.

Moreover, the silane type monomer containing a silicon atom, etc. are mentioned as a monomer which can be copolymerized other than the above. Examples of the silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-. Vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltri Ethoxysilane, 10-acryloyl oxydecyl triethoxysilane, etc. are mentioned.

Moreover, as a copolymerization monomer, a tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) Acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth (Meth) acryloyl groups, such as esterified products of (meth) acrylic acid and a polyhydric alcohol, such as acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone modified dipentaerythritol hexa (meth) acrylate As a functional group similar to a monomer component to the polyfunctional monomer which has two or more unsaturated double bonds, such as a group, and a skeleton, such as polyester, an epoxy, a urethane, ) Can also be used with an acrylic group, a vinyl group, and the like of the unsaturated double bond of two or more additional polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like.

Although the said (meth) acrylic-type polymer has alkyl (meth) acrylate as a main component in the weight ratio of all the constituent monomers, the ratio of the said copolymerization monomer in a (meth) acrylic-type polymer is not specifically limited, However, It is preferable that a ratio is about 0 to 20%, about 0.1 to 15%, and also about 0.1 to 10% in the weight ratio of all the constituent monomers.

Among these copolymerization monomers, from the viewpoint of adhesion and durability, hydroxyl group-containing monomers and carboxyl group-containing monomers are preferably used. A hydroxyl group containing monomer and a carboxyl group containing monomer can be used together. These copolymerization monomers become a reaction point with a crosslinking agent, when an adhesive composition contains a crosslinking agent. Since a hydroxyl group containing monomer, a carboxyl group containing monomer, etc. are rich in reactivity with an intermolecular crosslinking agent, it is used preferably for the improvement of the cohesiveness and heat resistance of the adhesive layer obtained. The hydroxyl group-containing monomer is preferable in view of reworkability, and the carboxyl group-containing monomer is preferable in that both durability and reworkability are achieved.

When a hydroxyl group containing monomer is contained as said copolymerization monomer, 0.01-15 weight% is preferable, as for the ratio, 0.03-10 weight% is more preferable, Furthermore, 0.05-7 weight% is preferable. As said copolymerization monomer, when it contains a carboxyl group-containing monomer, 0.05-10 weight% is preferable, as for the ratio, 0.1-8 weight% is more preferable, Furthermore, 0.2-6 weight% is preferable.

As for the (meth) acrylic-type polymer of this invention, the thing of the range of 500,000-3 million in weight average molecular weight is used normally. In consideration of durability, particularly heat resistance, it is preferable to use a weight average molecular weight of 700,000 to 2.7 million. Furthermore, it is preferable that they are 800,000-2,500,000. If the weight average molecular weight is smaller than 500,000, it is not preferable from the viewpoint of heat resistance. Moreover, when a weight average molecular weight becomes larger than 3 million, in order to adjust to the viscosity for coating, a large amount of diluting solvent is needed and it is unpreferable in that it will become a cost increase. In addition, a weight average molecular weight means the value measured by GPC (gel permeation chromatography) and computed by polystyrene conversion.

In the production of such a (meth) acrylic polymer, a known production method such as radiation polymerization such as solution polymerization or UV polymerization, bulk polymerization, emulsion polymerization or various radical polymerization can be appropriately selected. In addition, any of a random copolymer, a block copolymer, a graft copolymer, etc. may be sufficient as the obtained (meth) acrylic-type polymer.

In solution polymerization, for example, ethyl acetate, toluene or the like is used as the polymerization solvent. As a specific solution polymerization example, reaction is added under inert gas streams, such as nitrogen, and a polymerization initiator is normally performed on reaction conditions for about 5 to 30 hours at about 50-70 degreeC.

The polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization are not specifically limited, It can select suitably and can use. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount and reaction conditions of a polymerization initiator, a chain transfer agent, and the usage-amount is adjusted suitably according to these types.

As the radical polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5 -Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) sulfate, 2,2'-azobis (N, N'- Azo initiators, such as dimethylene isobutyl amidine) and 2,2'- azobis [N- (2-carboxyethyl) -2-methylpropion amidine] hydrate (made by Wako Pure Chemical Industries, Ltd., VA-057); Persulfates, such as potassium sulfate and ammonium persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate , t-butylperoxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3 Tetramethylbutylperoxy-2-ethylhexanoate, di (4-meth Peroxide initiators such as benzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexylperoxy) cyclohexane, t-butylhydroperoxide, hydrogen peroxide, persulfate and Although redox type initiator which combined peroxide and a reducing agent, such as the combination of sodium hydrogen sulfite and the combination of a peroxide and sodium ascorbate, etc. are mentioned, It is not limited to these.

Although the said radical polymerization initiator may be used independently and may mix and use 2 or more types, it is preferable that content as a whole is about 0.005-1 weight part with respect to 100 weight part of monomers, and 0.02-0.5 weight part It is more preferable that it is a degree.

Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, thioglycolic acid 2-ethylhexyl, and 2,3-dimercapto-1-propanol. Can be mentioned. Although a chain transfer agent may be used independently and may be used in mixture of 2 or more type, content as a whole is about 0.1 weight part or less with respect to 100 weight part of whole quantities of a monomer component.

Moreover, as an emulsifier used when emulsion-polymerizing, anionic emulsifiers, such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene alkyl ether ammonium sulfate, and polyoxyethylene alkyl phenyl ether sodium sulfate, for example And nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer. These emulsifiers may be used independently or may use 2 or more types together.

Moreover, as an emulsifier into which radically polymerizable functional groups, such as a propenyl group and an allyl ether group, were introduce | transduced as a reactive emulsifier, For example, aqualon HS-10, HS-20, KH-10, BC-05, BC -10, BC-20 (all are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Adekaria Soap SE10N (manufactured by Asahi Denka Takumi Co., Ltd.). Since a reactive emulsifier is introduce | transduced into a polymer chain after superposition | polymerization, water resistance improves and it is preferable. As for the usage-amount of an emulsifier, 0.5-1 weight part is more preferable from 0.3-5 weight part, polymerization stability, and mechanical stability with respect to 100 weight part of whole quantity of a monomer component.

<Radical generator>

As a radical generator mix | blended with the adhesive composition of this invention, the radical polymerization initiator used at the time of manufacture of the said (meth) acrylic-type polymer can be illustrated. Among the radical polymerization initiators, the radical generator blended with the pressure-sensitive adhesive composition is preferably a peroxide.

A radical generating agent can generate radical active species by heating or light irradiation, and can advance bridge | crosslinking of the (meth) acrylic-type polymer in an adhesive composition. As a radical generator, in view of workability and stability, it is preferable to use peroxide whose half life temperature is 80 degreeC-160 degreeC for 1 minute, and it is more preferable to use a peroxide which is 90 degreeC-140 degreeC.

As the peroxide, for example, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half life temperature: 92.1 ° C.), di-sec-butyl peroxy dicarbonate (1 minute half life temperature: 92.4 ° C.) ), t-butylperoxy neodecanoate (1 minute half-life temperature: 103.5 ° C.), t-hexyl peroxy pivalate (1 minute half-life temperature: 109.1 ° C.), t-butylperoxy pivalate (1 minute half-life temperature) : 110.3 ° C.), dilauroyl peroxide (1 minute half life temperature: 116.4 ° C.), di-n-octanoyl peroxide (1 minute half life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutyl Peroxy-2-ethylhexanoate (1 minute half-life temperature: 124.3 ° C), di (4-methylbenzoyl) peroxide (1 minute half-life temperature: 128.2 ° C), dibenzoylperoxide (1 minute half-life temperature: 130.0 ° C) ), t-butylperoxy isobutyrate (1 minute half-life temperature: 136.1 ° C.), 1,1-di (t-hexylperoxy) cyclohexane (1 minute half-life temperature: 149.2 ° C.), and the like. Among them, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C) and dilauroyl peroxide (1 minute half-life temperature: 116.4), in particular, in terms of excellent crosslinking reaction efficiency. C), dibenzoyl peroxide (1 minute half life temperature: 130.0 degreeC), etc. are used preferably.

The half-life of the peroxide is an index indicating the decomposition rate of the peroxide, and means the time until the remaining amount of the peroxide is half. The decomposition temperature for obtaining the half life at any time and the half life time at any temperature are described in the manufacturer's catalog and the like, and are described in, for example, Nihon Yushi Co., Ltd. Month ”).

The content of the radical generator (particularly peroxide) in the pressure-sensitive adhesive composition of the present invention takes into account the gel fraction and the like for adjustment of processability, reworkability, crosslinking stability, peelability, and the like of the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition. Is determined. When the content of the radical generator (particularly peroxide) is increased, it is preferable to secure the gel fraction (crosslinking degree) of the pressure-sensitive adhesive layer obtained. However, when the content is excessively high, the peeling force of the release film (separator) applied to the pressure-sensitive adhesive layer is increased. There is a tendency. Usually, it is preferable that content of a radical generator is 0.01-2 weight part with respect to 100 weight part of said base polymers (for example, a (meth) acrylic-type polymer), Furthermore, it is preferable that it is 0.01-1 weight part, Furthermore, 0.05 To 0.8 weight part is preferable, Furthermore, 0.1 to 0.6 weight part is preferable.

Moreover, in the said (meth) acrylic-type polymer, the radical polymerization initiator (radical generator) which is not used for a polymerization reaction at the time of manufacture of the said (meth) acrylic-type polymer may exist. The said residual radical generator can be used as a radical generator in the said adhesive composition. In that case, the quantity of a residual radical generator can be quantified, and a radical generator can be mix | blended suitably according to content of a residual radical generator.

In addition, the residual amount of peroxide decomposition after the reaction treatment can be measured, for example, by HPLC (high speed liquid chromatography).

More specifically, for example, about 0.2 g of the pressure-sensitive adhesive composition after the reaction treatment is taken out, immersed in 10 mL of ethyl acetate, shaken and extracted at 120 rpm for 3 hours at 25 ° C with a shaker, and then left at room temperature for 3 days. Subsequently, 10 mL of acetonitrile was added, the mixture was shaken at 120 rpm for 30 minutes at 25 ° C., and about 10 μL of the extract obtained by filtration with a membrane filter (0.45 μm) was injected into the HPLC, and analyzed. .

<Compound (A)>

The pressure-sensitive adhesive composition of the present invention includes at least one kind selected from the ultraviolet absorbent (a) having 0 to 3 hydroxyl groups in the molecular structure and the dye compound (b) having a maximum absorption wavelength in the absorption spectrum in the wavelength range of 380 to 430 nm. Compound (A) is compounded. Regarding the ultraviolet absorbent (a), the hydroxyl groups in the molecular structure having 0 to 3 are effective in suppressing the crosslinking inhibition of the radical generator by reducing the hydrogen donor group which is the cause of deactivating radicals as described above. Do. Moreover, when the hydroxyl group is 0-3, for example, when mix | blending an isocyanate type crosslinking agent etc. which have reactivity with a hydroxyl group, it is preferable also in suppressing crosslinking inhibition by the said crosslinking agent. Moreover, it is preferable to use the compound which does not have a phenyl group in molecular structure as said ultraviolet absorber (a) as a hydrogen donor group which deactivates radicals other than a hydroxyl group. Moreover, not a phenyl group which does not have in the molecular structure, represents a phenyl (-C ₆ H ₅₎ having no substituent, excluding the substituents having a phenyl group or phenylene group and the like. In addition, also in the said dye compound (b), similarly to the said ultraviolet absorber (a), hydrogen donor groups, such as a hydroxyl group and a phenyl group, are small in a molecular structure from a viewpoint of preventing the crosslinking inhibition of a radical generating agent (the hydroxyl group is 0 To 3) or a compound having no).

The compounding quantity as said compound (A) regarding the said ultraviolet absorber (a) and / or a dye compound (b) is 0.1-25 weight part with respect to 100 weight part of base polymers (for example, (meth) acrylic-type polymer). It is preferable that it is about 0.5-20 weight part, and it is more preferable that it is about 2-10 weight part further.

The said ultraviolet absorber (a) may be used independently, and may mix and use 2 or more types. When using only the said ultraviolet absorber (a) as said compound (A), content as a whole of the said ultraviolet absorber (a) is 0.1-100 weight part with respect to 100 weight part of base polymers (for example, a (meth) acrylic-type polymer). It is preferable that it is 20 weight part, It is preferable that it is 0.1-10 weight part, It is preferable that it is 0.1-5 weight part, It is more preferable that it is 0.5-3 weight part. By making the addition amount of a ultraviolet absorber (a) into the said range, since the ultraviolet absorbing function of an adhesive layer can fully be exhibited, and ultraviolet-ray polymerization does not interfere with the said polymerization, it is preferable.

The said dye compound (b) may be used independently, and may mix and use 2 or more types. When using only the said dye compound (b) as said compound (A), content as a whole of the said dye compound (b) is 0.1-100 with respect to 100 weight part of base polymers (for example, (meth) acrylic-type polymer). It is preferable that it is 20 weight part, It is preferable that it is 0.1-10 weight part, It is preferable that it is 0.1-5 weight part, It is more preferable that it is 0.5-3 weight part. By making the addition amount of a dye compound (b) into the said range, the light of the area | region which does not affect light emission of an organic electroluminescent element can fully be absorbed, and deterioration of an organic electroluminescent element is used by using the adhesive layer formed from the said adhesive composition. Since it can suppress, it is preferable.

Although the said ultraviolet absorber (a) and a pigment compound (b) can use either, It is preferable to use the said ultraviolet absorber (a) and a pigment compound (b) together. According to the ultraviolet absorber (a), for example, light having a wavelength of 380 nm can be absorbed, but light in the wavelength region (380 nm to 430 nm) on the short wavelength side is sufficiently higher than the light emitting region (longer wavelength side than 430 nm) of the organic EL element. Not absorbed, deterioration may occur due to the transmitted light. The said dye compound (b) can suppress the permeation | transmission of light of wavelength (380 nm-430 nm) of the short wavelength side rather than the light emitting area | region (longer wavelength side than 430 nm) of an organic electroluminescent element, The said ultraviolet absorber (a) and a dye compound (b) ) Together, the transmittance of visible light in the light emitting region of the organic EL device can be sufficiently secured.

In the present invention, by using such a dye compound (b) and the ultraviolet absorber (a2) in combination, light of a region (wavelengths of 380 nm to 430 nm) that does not affect the light emission of the organic EL element can be sufficiently absorbed, In addition, the light emitting region (longer wavelength side than 430 nm) of the organic EL element can sufficiently transmit, and as a result, deterioration due to external light of the organic EL element can be suppressed. When using together the said ultraviolet absorber (a) and a dye compound (b), it is preferable to control so that the total amount of the said ultraviolet absorber (a) and a dye compound (b) may be in the range of the compounding quantity as said compound (A). It is preferable that it is 0.1-10 weight part with respect to 100 weight part of base polymers (for example, a (meth) acrylic-type polymer), It is preferable that it is 0.1-5 weight part, and the said ultraviolet absorber (a) is 0.5-3 weight part It is more preferable. It is preferable that it is about 0.1-10 weight part with respect to 100 weight part of base polymers (for example, a (meth) acrylic-type polymer), and, as for the said dye compound (b), it is more preferable that it is about 0.1-5 weight part, It is more preferable that it is 0.5-3 weight part.

<Ultraviolet absorber (a)>

The ultraviolet absorbent (a) is not particularly limited as long as it has 0 to 3 hydroxyl groups in the molecular structure, but for example, a triazine ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, an oxybenzophenone ultraviolet absorber, A salicylic acid ester ultraviolet absorber, a cyanoacrylate ultraviolet absorber, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Among these, a triazine ultraviolet absorber and a benzotriazole ultraviolet absorber are preferable, a triazine ultraviolet absorber having two or less hydroxyl groups in one molecule, and a benzotriazole ultraviolet absorber having one benzotriazole skeleton in one molecule. It is preferable that it is at least 1 type of ultraviolet absorber chosen from the group which consists of since it has the favorable solubility with respect to the monomer used for formation of an acrylic adhesive composition, and its ultraviolet absorption ability in wavelength vicinity is high about 380 nm.

As a triazine-type ultraviolet absorber which has two or less hydroxyl groups in 1 molecule, specifically, 2, 4-bis- [{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6 -(4-methoxyphenyl) -1,3,5-triazine (Tinosorb S, manufactured by BASF), 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4 -Dibutoxyphenyl) -1,3,5-triazine (TINUVIN 460, made by BASF), 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2 Reaction product of -yl) -5-hydroxyphenyl with [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxirane (TINUVIN400, manufactured by BASF), 2- [4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydrate Roxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester reaction product (TINUVIN405, made by BASF), 2 -(4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (TINUVIN1577, manufactured by BASF), 2- (4,6-diphenyl -1,3,5-triazin-2-yl ) -5- [2- (2-ethylhexanoyloxy) ethoxy] -phenol (ADK STAB LA46, manufactured by ADEKA), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl ) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (TINUVIN479, BASF Corporation) etc. are mentioned.

Moreover, as a benzotriazole type ultraviolet absorber which has one benzotriazole skeleton in 1 molecule, 2- (2H- benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- ( 1,1,3,3-tetramethylbutyl) phenol (TINUVIN 928, manufactured by BASF Corporation), 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (TINUVIN PS, manufactured by BASF Corporation) ), Benzenepropanoic acid and ester compounds of 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 branched and straight chain alkyl) (TINUVIN384-) 2, BASF Corporation), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN900, BASF Corporation), 2- (2H- Benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN928, manufactured by BASF), methyl-3- Reaction product of (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 (TINUVIN1130, manufactured by BASF), 2- (2H- Benzotriazol-2-yl) -p-cresol (TINUVIN P, manufactured by BASF), 2 (2H) -Benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN234, manufactured by BASF), 2- [5-chloro (2H) -benzotriazole-2- Yl] -4-methyl-6- (tert-butyl) phenol (TINUVIN326, BASF Corporation make), 2- (2H- benzotriazol-2-yl) -4, 6- di-tert- pentyl phenol (TINUVIN328, BASF Corporation make), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3- tetramethylbutyl) phenol (TINUVIN329, BASF make), methyl 3- (3- ( Reaction product of 2H- benzotriazol-2-yl) -5-tert- butyl- 4-hydroxyphenyl) propionate and polyethyleneglycol 300 (TINUVIN213, BASF Corporation make), 2- (2H- benzotriazole- 2-yl) -6-dodecyl-4-methylphenol (TINUVIN571, manufactured by BASF), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5- Methylphenyl] benzotriazole (Sumisorb250, Sumitomo Chemical Co., Ltd. product) etc. are mentioned.

Moreover, as said benzophenone type ultraviolet absorber (benzophenone type compound) and an oxybenzophenone type ultraviolet absorber (oxybenzophenone type compound), it is 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-, for example. 4-methoxybenzophenone-5-sulfonic acid (anhydride and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydride Hydroxybenzophenone, 2,2'-dihydroxy-4,4-dimethoxybenzophenone, etc. are mentioned.

Moreover, as said salicylic acid ester ultraviolet absorber (salicylic acid ester type compound), it is 2, 4- di-tert- butylphenyl-3, 5-di-tert- butyl- 4-hydroxy benzoate (TINUVIN120, BASF company, for example). Production), and the like.

As said cyanoacrylate type ultraviolet absorber (cyanoacrylate type compound), an alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, Alkenyl-2-cyanoacrylate, alkynyl-2-cyanoacrylate, etc. are mentioned.

It is preferable to exist in the wavelength range of 300-400 nm, and, as for the maximum absorption wavelength of the absorption spectrum of the said ultraviolet absorber (a), it is more preferable to exist in the wavelength range of 320-380 nm. The measuring method of the maximum absorption wavelength is the same as the measuring method of the dye compound mentioned later.

<Color Compound (b)>

The dye compound (b) should just be a compound which exists in the wavelength range of 380-430 nm of the maximum absorption wavelength of an absorption spectrum, Although it does not specifically limit, Like a said ultraviolet absorber (a), a hydroxyl group, a phenyl group, etc. are contained in a molecular structure. It is preferable that it is a compound with few or no hydrogen donor groups. In addition, the maximum absorption wavelength means the absorption maximum wavelength which shows the largest absorbance among them when there exist several absorption maximum in the spectral absorption spectrum in 300-460 nm wavelength range.

As for the maximum absorption wavelength of the absorption spectrum of a dye compound (b), it is more preferable to exist in the wavelength range of 380-420 nm. The dye compound (b) is not particularly limited as long as the dye compound (b) has the above-described wavelength characteristics, but a material having no fluorescence and phosphorescence performance (photoluminescence), which does not impair displayability of the organic EL device, is preferable.

In addition, although the half value width of the said pigment compound (b) is not specifically limited, It is preferable that it is 80 nm or less, It is more preferable that it is 5-70 nm, It is further more preferable that it is 10-60 nm. Since the half value width of a dye compound exists in the said range, since the light of the wavelength side longer than 430 nm can be fully transmitted while being able to fully absorb the light of the area | region which does not affect the light emission of organic electroluminescent element, it is preferable. In addition, the measuring method of half value width is based on the method described below.

<Measuring method of half value width>

The half value width of the dye compound (b) was measured from the transmission absorption spectrum of the solution of the dye compound under the following conditions using an ultraviolet visible spectrophotometer (U-4100, manufactured by Hitachi Hi-Tech Science Co., Ltd.). From the spectral spectrum measured by adjusting concentration so that the absorbance of a maximum absorption wavelength might be 1.0, the space | interval (half value full width) between two points used as 50% of a peak value was made into the half value width of the pigment compound.

(Measuring conditions)

Solvent: Toluene or Chloroform

Cell: quartz cell

Optical path length: 10mm

As said pigment compound (b), an organic pigment compound and an inorganic pigment compound are mentioned, for example, Among these, an organic pigment compound is preferable from a viewpoint of dispersibility and transparency of resin components, such as a base polymer.

Examples of the organic dye compound include azomethine compounds, indole compounds, cinnamic acid compounds, pyrimidine compounds, porphyrin compounds, cyanine compounds, and the like.

As said organic pigment compound, a commercially available thing can be used suitably, Specifically, as said indole type compound, it is BONASORB UA3911 (brand name, the maximum absorption wavelength of an absorption spectrum: 398nm, half value width: 48nm, Orient Kagaku Kogyo ( Manufacture)

As a cinnamic acid type compound, SOM-5-0106 (brand name, the maximum absorption wavelength of an absorption spectrum: 416 nm, half-value width: 50 nm, Orient Kagaku Kogyo Co., Ltd. product) is a FDB-001 (brand name, absorption) as a porphyrin type compound. Maximum absorption wavelength of a spectrum: 420 nm, half value width: 14 nm, Yamada Kagaku Kogyo Co., Ltd. is a cyanine compound, and a melancyanine compound (brand name: FDB-009, maximum absorption wavelength of an absorption spectrum: 394 nm, half value) Width: 43 nm, Yamada Kagaku Kogyo Co., Ltd.), a polymethine compound (brand name: DAA-247, the maximum absorption wavelength of an absorption spectrum: 389 nm, half value width: 49.5 nm, Yamada Kagaku Kogyo Co., Ltd. make), etc. Among them, the cyanine compound is preferable, and a polymethine compound is particularly preferable from the viewpoint of crosslinking inhibition inhibition and optical reliability.

Antioxidant

Antioxidant mix | blended with the adhesive composition of this invention can be mix | blended. Antioxidant prevents the inhibition of the radicals generated from the radical generator by oxygen, ensures a stable gel fraction (crosslinking degree), and increases the peeling force of the release film (separator) applied to the pressure-sensitive adhesive layer. It is possible to increase the gel fraction while suppressing this.

As said antioxidant, antioxidant, a phenol type, phosphorus type | system | group, sulfur type, and an amine type, is mentioned, for example, Any at least 1 sort (s) chosen from these is used. Among these, a phenolic antioxidant is preferable.

As a specific example of a phenolic antioxidant, as a monocyclic phenol compound, 2, 6- di- t- butyl- p- cresol, 2, 6- di- t- butyl- 4-ethyl phenol, 2, 6- dicyclohexyl- 4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2- Isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL-α-tocopherol, stearylβ- (3,5 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'- as a dicyclic phenolic compound -di-t-butyl-4-hydroxyphenyl) propionate etc. Butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-thiobis (4-methyl-6 -t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidene ratio (4,6-di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis [3- (3- t-butyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6 -Hexanediolbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylenebis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3 as a tricyclic phenol compound; , 5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3,5-tris [(3,5-di-t-butyl-4-hydrate Oxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4, 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like are tetrakis [methylene-3- (3,5-di-t as tetracyclic phenol compounds; -Butyl-4-hydroxyphenyl) propionate] methane and the like as bis (3,5-di-t-butyl-4-hydroxybenzylphosphonic acid) calcium, bis (3, 5-di-t-butyl-4-hydroxybenzyl phosphonate) nickel etc. are mentioned.

Specific examples of the phosphorus antioxidant include trioctyl phosphite, trilauryl phosphite, tristridecyl phosphite, trisisodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, and phenyl di (tridecyl) Phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) Phosphite, tris (butoxyethyl) phosphite, tetratridecyl-4,4'-butylidenebis (3-methyl-6-t-butylphenol) -diphosphite, 4,4'-isopropylidene- Diphenol alkyl phosphite (However, alkyl is about 12 to 15 carbon atoms), 4,4'-isopropylidenebis (2-t- butylphenol), di (nonylphenyl) phosphite, tris (biphenyl) phosphite , Tetra (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butanediphosphpy , Tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4 ' -Butylidenebis (3-methyl-6-t-butylphenol)] 1,6-hexanedioldiphosphite, hexatridecyl-1,1,3-tris (2-methyl-4-hydroxy-5 -t-butylphenol) diphosphite, tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite, tris (1,3-distearoyloxyisopropyl) phosphite, 9, 10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, distearylpentaerythritol Diphosphite, di (nonylphenyl) pentaerythritoldiphosphite, phenyl 4,4'-isopropylidenediphenol pentaerythritoldiphosphite, bis (2,4-di-t-butylphenyl) pentaerythritoldipotho Spite, Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritoldiphosphite and phenyl ratio Sphenol-A- pentaerythritol diphosphite etc. are mentioned.

As a sulfur type antioxidant, it is preferable to use the polyhydric alcohol ester of dialkylthio dipropionate and alkylthio propionic acid. As the dialkylthiodipropionate used herein, a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms is preferable, and as the polyhydric alcohol ester of alkylthiopropionic acid, an alkyl having a alkyl group having 4 to 20 carbon atoms is used. Polyhydric alcohol esters of thiopropionic acid are preferred. In this case, examples of the polyhydric alcohol constituting the polyhydric alcohol ester include glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, trishydroxyethyl isocyanurate, and the like. Examples of such dialkylthiodipropionate include dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, and the like. On the other hand, as polyhydric alcohol ester of alkylthio propionic acid, glycerol tributyl thio propionate, glycerol trioctyl thio propionate, glycerin trilauryl thio propionate, glycerin tri stearyl thio propionate, trimethylol, for example. Ethanetributylthiopropionate, trimethylolethanetrioctylthiopropionate, trimethylolethanetrilaurylthiopropionate, trimethylolethanetristearylthiopropionate, pentaerythritol tetrabutylthiopropionate, Pentaerythritol tetraoctyl thio propionate, pentaerythritol tetralauryl thio propionate, pentaerythritol tetrastearyl thio propionate, etc. are mentioned.

Specific examples of the amine antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2, Polycondensates of 2,6,6-tetramethylpiperidineethanol, N, N ', N ", N"'-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2, 6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine.1,3,5-tri Azine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4- Polycondensates of piperidyl) butylamine, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2 , 6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2, 6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis- ( 1,2,6,6-pentamethyl-4-pepyridyl) -2 -(3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), (mix 2,2,6,6-tetramethyl-4-pi Ferridyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mix 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2, 3,4-butanetetracarboxylate, mix [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4 , 8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, mix [1,2,2,6,6-pentamethyl-4 Piperidyl / β, β, β ', β'-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2, 3,4-butanetetracarboxylate, N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl -4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, poly [6-N-morphoryl- 1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetra Methyl-4-piperidyl) imide], condensation of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 1,2-dibromoethane Water, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) imino ] Propionamide, etc. are mentioned.

Content of antioxidant in the adhesive composition of this invention is determined from a viewpoint of preventing the discoloration of the pigment | dye by the said radical generator. Usually, it is preferable to make content of antioxidant into the range of 0.03 weight part or more with respect to 100 weight part of said (meth) acrylic-type polymers. On the other hand, when content of the said antioxidant increases, the ratio which captures the radical which generate | occur | produces from a radical generator increases. As a result, it becomes easy to cause crosslinking inhibition of the adhesive layer formed from the said adhesive composition, the gel fraction of an adhesive layer falls, and it exists in the tendency to generate an appearance defect. From such a viewpoint, it is preferable to make content of antioxidant into the range of 5 weight part or less and further 1.5 weight part or less with respect to 100 weight part of said (meth) acrylic-type polymers. From the viewpoint of achieving both the above-mentioned gel fraction and preventing the fading of the dye, the content of the antioxidant is preferably 0.05 to 1.5 parts by weight based on 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). Furthermore, 0.1-1.0 weight part is preferable, Furthermore, 0.3-0.8 weight part is preferable.

<Bridge school>

Moreover, the adhesive composition of this invention can contain a crosslinking agent (except the said radical generator). In the present invention, when an isocyanate crosslinking agent is used together as a crosslinking agent, an isocyanate crosslinking agent can efficiently form a three-dimensional crosslinking network of the pressure-sensitive adhesive layer while effectively inhibiting radical crosslinking inhibition by oxygen with an antioxidant. have. As a result, generation | occurrence | production of the external appearance abnormality in a polarizing film edge part can be prevented more effectively.

Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, a silicone crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a silane crosslinking agent, an alkyl etherified melamine crosslinking agent, and a crosslinking agent of a metal chelate crosslinking agent. A crosslinking agent can be used individually by 1 type or in combination of 2 or more type. Among these, an isocyanate crosslinking agent is used preferably.

Although the said crosslinking agent may be used individually by 1 type, and may mix and use 2 or more types, content as a whole is 5 weight part with respect to 100 weight part of base polymers (for example, a (meth) acrylic-type polymer). It is preferable that it is the following, It is more preferable that it is 0.01-5 weight part, 0.01-4 weight part is further more preferable, 0.02-3 weight part is especially preferable.

An isocyanate type crosslinking agent means the compound which has two or more isocyanate groups (including the isocyanate regeneration type functional group which temporarily protected the isocyanate group by blocking agent or quantification etc.) in 1 molecule. As an isocyanate type crosslinking agent, aromatic isocyanate, such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanate, such as isophorone diisocyanate, aliphatic isocyanate, such as hexamethylene diisocyanate, etc. are mentioned.

More specifically, Lower aliphatic polyisocyanates, such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates, such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2, 4-, for example Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, Nippon Polyurethane High Bridge Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate trimer adduct (brand name: coronate HL, Nippon Polyurethane High Bridge Co., Ltd. product), isocyanurate body of hexamethylene diisocyanate ( Product name: Coronate HX, Nippon Polyurethane High Isocyanate adducts, such as (manufactured by Co., Ltd.), trimethylolpropane adducts of xylylene diisocyanate (trade name: D110N, Mitsui Chemical Industries, Ltd.), trimethylolpropane adducts of hexamethylene diisocyanate (trade name: D160N, Mitsui Chemicals Co., Ltd. product); Polyether polyisocyanate, polyester polyisocyanate, and adducts of these and various polyols, polyisocyanates polyfunctionalized with isocyanurate bonds, biuret bonds, allophanate bonds and the like.

Moreover, the adhesive composition of this invention can contain a silane coupling agent. It is preferable that it is 1 weight part or less with respect to 100 weight part of monofunctional monomer components which form a (meth) acrylic-type polymer, as for the compounding quantity of a silane coupling agent, 0.01-1 weight part is more preferable, 0.02-0.6 weight part is more preferable.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclo Epoxy group-containing silane coupling agents such as hexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N Amino group-containing silane coupling agents such as-(1,3-dimethylbutylidene) propylamine and N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyl Isocyanate group containing silane coupling agents, such as (meth) acryl group containing silane coupling agents, such as a triethoxysilane, and 3-isocyanate propyl triethoxysilane, etc. are mentioned.

In addition to the said component, the adhesive composition of this invention may contain the suitable additive according to a use. For example, Tackifier (The thing which is solid, semisolid, or liquid at normal temperature which consists of rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.); Fillers such as hollow glass balloons; Plasticizers; Anti-aging agents; Light stabilizers (HALS); Antioxidant, and the like.

2. Adhesive layer for organic EL display device

The adhesive layer for organic electroluminescent display of this invention is formed from the said adhesive composition for organic electroluminescent display, It is characterized by the above-mentioned.

It does not specifically limit as a formation method of an adhesive layer, Usually, it can form by the method used in this field. Specifically, the pressure-sensitive adhesive composition may be coated on at least one side of the substrate, and the coating film formed of the pressure-sensitive adhesive composition may be dried and formed, or may be formed by irradiating active energy rays such as ultraviolet rays.

It does not specifically limit as said base material, For example, various base materials, such as a release film and a transparent resin film base material, and the polarizing film mentioned later can also be used suitably as a base material.

As a constituent material of the said release film, For example, resin materials, such as polyethylene, a polypropylene, a polyethylene terephthalate, a polyester film, porous materials, such as paper, a cloth, and a nonwoven fabric, a net, a foam sheet, a metal foil, and these laminated bodies Although an appropriate thin body etc. are mentioned, A resin film is used suitably from the point which is excellent in surface smoothness.

As the resin film, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film , Polyurethane films, ethylene-vinyl acetate copolymer films, and the like.

The thickness of the said release film is 5-200 micrometers normally, Preferably it is about 5-100 micrometers. If necessary, the release film may be subjected to release and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, or the like, or an antistatic treatment such as a coating type, a dough type, or a deposition type. . In particular, the peelability from the pressure-sensitive adhesive layer can be further improved by appropriately performing a peeling treatment such as silicone treatment, long chain alkyl treatment, or fluorine treatment on the surface of the release film.

Although it does not restrict | limit especially as said transparent resin film base material, Various resin films which have transparency are used. The said resin film is formed of the film of one layer. For example, as the material, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, and polyolefins Resin, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin and the like. Among these, especially preferable are polyester resin, polyimide resin, and polyether sulfone resin.

It is preferable that it is 15-200 micrometers, and, as for the thickness of the said film base material, it is more preferable that it is 25-188 micrometers.

The method for applying the pressure-sensitive adhesive composition on the substrate includes a roll coat, a kiss roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, a dip roll coat, a bar coat, a knife coat, an air knife coat, a curtain coat, a lip A well-known suitable method, such as a coat and a die coater, can be used and it does not restrict | limit in particular.

When the pressure-sensitive adhesive layer is formed by drying the coating film formed of the pressure-sensitive adhesive composition, the drying conditions (temperature, time) are not particularly limited and can be appropriately set according to the composition, concentration, etc. of the pressure-sensitive adhesive composition, For example, it is about 60-170 degreeC, Preferably it is 60-150 degreeC, for 1 to 60 minutes, Preferably it is 2 to 30 minutes. In addition, when the said adhesive composition is an ultraviolet curable adhesive composition, an adhesive layer can be formed by irradiating an ultraviolet-ray to a coating film.

It is preferable that it is 5 micrometers or more, It is more preferable that it is 50 micrometers or more, It is still more preferable that it is 100 micrometers or more, Especially preferably, the thickness of an adhesive layer is 50 micrometers or more from a viewpoint of ensuring the function which absorbs the light of wavelength less than 430 nm. Do. Although the upper limit of the thickness of an adhesive layer is not specifically limited, It is preferable that it is 1 mm or less. When the thickness of the pressure-sensitive adhesive layer exceeds 1 mm, it becomes difficult to transmit ultraviolet rays, which takes time to polymerize the monomer component, and may cause problems in workability, winding in the process and transportability, and thus may lower productivity. Not.

Although the adhesive layer gel fraction of this invention is not specifically limited, It is preferable that it is 40% or more, It is more preferable that it is 60% or more, It is further more preferable that it is 75% or more, It is especially preferable that it is 85% or more. When the gel fraction of an adhesive layer is small, cohesion force may fall and a problem may arise in workability and handling property. Moreover, it is preferable that it is 60% or more from a viewpoint of preventing the external appearance defects, such as an adhesive scratch, and the gel fraction immediately after forming an adhesive layer by heat-drying or ultraviolet irradiation of the coating film of an adhesive composition, and it is more preferable that it is 63% or more. And it is more preferable that it is 66% or more, and it is especially preferable that it is 70% or more.

It is preferable that the haze value measured at 25 micrometers of thickness is 2% or less, It is more preferable that it is 0 to 1.5%, It is still more preferable that the said adhesive layer is 0 to 1%. Since the adhesive layer has high transparency, it is preferable because a haze exists in the said range.

It is preferable that the average transmittance | permeability of wavelength 300-400 nm of the said adhesive layer is 12% or less, Furthermore, it is preferable that it is 5% or less, and it is more preferable that it is 2% or less. If the transmittance | permeability of an adhesive layer is the said range, the light of the area | region which does not affect light emission of an organic EL element can fully be absorbed, and deterioration of an organic EL element can be suppressed.

It is preferable that the average transmittance of wavelength 430-450 nm of the said adhesive layer is 70% or more, It is more preferable that it is 75% or more, It is preferable that the average transmittance of wavelength 500-780 nm is 80% or more, It is more preferable that it is 85% or more. When the transmittance of the pressure-sensitive adhesive layer is in the above range, light can be sufficiently transmitted in the light emitting region (longer wavelength side than 430 nm) of the organic EL element, and the organic EL display device using the pressure-sensitive adhesive layer can perform sufficient light emission.

In addition, the average transmittance of wavelength 400-430 nm or less of the said adhesive layer can be designed according to the characteristic calculated | required by the organic electroluminescence display. For example, from the viewpoint of sufficiently absorbing light in a region that does not affect the light emission of the organic EL element, suppressing and protecting the deterioration of the organic EL element, the average transmittance of the wavelength of 400 to 430 nm or less of the pressure-sensitive adhesive layer is 30. It is preferable that it is% or less, and it is more preferable that it is 20% or less. On the other hand, from the viewpoint of suppressing coloring of the organic EL device while protecting the organic EL device from ultraviolet light, the average transmittance of the wavelength of 400 to 430 nm or less of the pressure-sensitive adhesive layer is preferably more than 30% and 95% or less, and 50% It is more preferable that it exceeds 90% or less.

Here, the said "average transmittance of wavelength 300-400 nm" means the average value of the transmittance | permeability which measured the transmittance by 1 nm pitch in the area | region of wavelength 300-400 nm. The same applies to the average transmittance in other wavelength ranges.

By having the said transmittance | permeability, the adhesive layer of this invention can fully absorb the light of the area | region which does not affect the light emission of organic electroluminescent element, and the light emission area | region (long wavelength side rather than 430 nm) of organic electroluminescent element is fully transmitted. It is possible to suppress deterioration due to external light of the organic EL element.

When the said adhesive layer is exposed, you may protect an adhesive layer with a release film until it is provided for practical use.

3. Polarizing film provided with pressure-sensitive adhesive layer for organic EL display device

The polarizing film provided with the adhesive layer for organic electroluminescent display of this invention has a polarizing film and the adhesive layer for said organic electroluminescent display, It is characterized by the above-mentioned.

As an adhesive layer for organic electroluminescent display apparatuses, the above-mentioned thing can be used suitably. In addition, when an adhesive layer is formed in base materials other than a polarizing film, the said adhesive layer can be bonded and transferred to a polarizing film. In addition, the said release film can be used as a separator of the polarizing film provided with an adhesive layer as it is, and can simplify in a process surface.

Although it does not specifically limit as said polarizing film, What has a transparent protective film on at least one side of a polarizer and the said polarizer is mentioned.

(1) polarizer

A polarizer is not specifically limited, Various things can be used. As a polarizer, the dichroic substance of iodine or a dichroic dye is made to adsorb | suck to hydrophilic polymer films, such as a polyvinyl alcohol-type film, a partially formalized polyvinyl alcohol-type film, and an ethylene-vinyl acetate copolymerization system partial saponification film, for example. A polyene oriented film, such as an axial stretched thing, the dehydration process of polyvinyl alcohol, and the dehydrochlorination process of polyvinyl chloride, etc. are mentioned. Among these, the polarizer which consists of dichroic substances, such as a polyvinyl alcohol-type film and iodine, is suitable. Although the thickness in particular of these polarizers is not restrict | limited, Usually, it is about 5-80 micrometers.

The polarizer which uniaxially stretched the polyvinyl alcohol-type film by iodine can be produced by dyeing polyvinyl alcohol by immersing it in the aqueous solution of iodine, and extending | stretching 3 to 7 times the original length, for example. As needed, it can also be immersed in aqueous solution, such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride, etc. If necessary, the polyvinyl alcohol-based film may be dipped in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the contamination of the polyvinyl alcohol-based film with the antiblocking agent can be washed, and the polyvinyl alcohol-based film is swelled to prevent unevenness such as dyeing. Stretching may be performed after dyeing with iodine, or may be performed while dyeing, or may be dyed with iodine after stretching. It can extend | stretch also in aqueous solution, such as boric acid and potassium iodide, or a water bath.

Moreover, in this invention, the thin polarizer whose thickness is 10 micrometers or less can also be used. It is preferable that the said thickness is 1-7 micrometers from the viewpoint of thickness reduction. It is preferable that such a thin polarizer has little thickness unevenness, is excellent in visibility, and has little dimensional change, which is excellent in durability, and further, the thickness as a polarizing film can be reduced in thickness.

As a thin polarizer, Unexamined-Japanese-Patent No. 51-069644, Unexamined-Japanese-Patent No. 2000-338329, International Publication No. 2010/100917 Pamphlet, International Publication No. 2010/100917 Pamphlet, or Patent 4751481 The thin polarizing film described in Unexamined-Japanese-Patent No. 2012-073563. These thin polarizing films can be obtained by the manufacturing method including the process of extending | stretching and dyeing a polyvinyl alcohol-type resin (henceforth a PVA-type resin) layer, and the extending | stretching resin base material in the state of a laminated body. If it is this manufacturing method, even if a PVA system resin layer is thin, it can support extending | stretching without a problem, such as a fracture by extending | stretching by being supported by the resin base material for extending | stretching.

As said thin polarizing film, in the manufacturing method which includes the process of extending | stretching in the state of a laminated body, and the process of dyeing, it can extend | stretch at high magnification, and can improve polarization performance, International Publication No. 2010/100917 Pamphlet, International It is preferable that it is obtained by the manufacturing method including the process of extending | stretching in the aqueous solution of boric acid described in Unexamined-Japanese-Patent No. 2010/100917 pamphlet, or the patent 4751481 specification, and Unexamined-Japanese-Patent No. 2012-073563, Especially patent specification 4751481 and Japan It is preferable that it is obtained by the manufacturing method including the process of assisting to draw in air before extending | stretching in the aqueous solution of boric acid described in Unexamined-Japanese-Patent No. 2012-073563.

(2) transparent protective film

About the transparent protective film, what is conventionally used can be used suitably. Specifically, a transparent protective film formed of a material having excellent transparency, mechanical strength, thermal stability, moisture barrier property, and isotropy is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, diacetyl Cellulose polymers such as cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene and acrylonitrile styrene copolymer (AS resin), and polycarbonate polymers. have. Polyolefin polymers such as polyethylene, polypropylene, cycloolefin or norbornene structures, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamides, imide polymers and liquors Phone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, Epoxy-based polymers, blends of the polymers, and the like can also be cited as examples of the polymer forming the transparent protective film. The transparent protective film can also be formed as a thermosetting or ultraviolet curable resin cured layer such as acrylic, urethane, acrylic urethane, epoxy, or silicone.

Although the thickness of a transparent protective film can be suitably determined, it is generally about 1-500 micrometers from a viewpoint of workability, thin film property, etc., such as strength and handleability.

It is preferable that the said polarizer and a transparent protective film adhere closely through an aqueous adhesive etc. As an aqueous adhesive agent, an isocyanate adhesive, a polyvinyl alcohol adhesive, a gelatin adhesive, a vinyl latex type, an aqueous polyurethane, an aqueous polyester, etc. can be illustrated. In addition to the above, an ultraviolet curable adhesive, an electron beam curable adhesive, etc. are mentioned as an adhesive agent of a polarizer and a transparent protective film. The adhesive agent for electron beam hardening type polarizing films shows suitable adhesiveness with respect to the said various visual recognition side transparent protective films. Moreover, a metal compound filler can be contained in the adhesive agent used by this invention.

The surface which does not adhere | attach the polarizer of the said transparent protective film may be the thing which performed the process for the purpose of a hard-coat layer, an antireflection process, sticking prevention, and diffusive or antiglare.

Moreover, as said transparent protective film, any of what has a phase difference and can function as an optical compensation layer can be used. When using the transparent protective film which has retardation, the retardation characteristic can be suitably adjusted to the value required for optical compensation. As this retardation film, a stretched film can be used suitably. The retardation film is nx = ny> nz, nx> ny> nz and nx> ny = when the refractive index in the slow axis direction is nx, the refractive index in the in-plane fastening direction is ny, and the refractive index in the thickness direction is nz. Satisfying the relationship of nz, nx> nz> ny, nz = nx> ny, nz> nx> ny, and nz> nx = ny is selected and used according to various uses. In addition, nx = ny includes not only the case where nx and ny are exactly the same, but also the case where nx and ny are substantially the same. In addition, ny = nz includes not only the case where ny and nz are exactly the same, but also the case where ny and nz are substantially the same.

When using the polarizing film used by this invention as an anti-reflective circular polarizing plate of an organic electroluminescent display, the said retardation film is 1 / which made the front side retardation of a transparent protective film into 1/4 wavelength (about 100-170 nm). It is preferable that it is four wavelength plates.

When using a retardation film as a transparent protective film, the transparent protective film is provided in one side of a polarizer, and what has a retardation film in the other side can be used suitably. In addition, in that case, the installation place of the said adhesive layer is not specifically limited, Even if it is provided in the surface on the opposite side to the surface which contact | connects the polarizer of the said transparent protective film, or may be provided in the surface on the opposite side to the surface which contact | connects the polarizer of the retardation film. However, from the viewpoint of suppressing deterioration of the organic EL element, it is preferable to be provided on at least one surface or both surfaces.

An example of the specific structure of the polarizing film provided with the adhesive layer for organic electroluminescent display of this invention is shown to FIG. 1 (a)-(c). As shown to Fig.1 (a), as shown to the adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5, FIG. 1 (b), transparent protection Film 3 / polarizer 4 / phase difference film 5 / adhesive layer 2, as shown in Fig. 1 (c), pressure-sensitive adhesive layer (2) / transparent protective film (3) / polarizer (4) ) / Retardation film 5 / adhesive layer 2; The polarizing film 1 provided with the adhesive layer for organic electroluminescent display in which each layer was laminated | stacked in this order is mentioned. In (a) and (b) of FIG. 1, the pressure-sensitive adhesive layer 2 is the pressure-sensitive adhesive layer for the organic EL display device of the present invention, and in FIG. 1C, at least one of the two pressure-sensitive adhesive layers 2 is present. One may be an adhesive layer for organic electroluminescent display of this invention, and both may be an adhesive layer for organic electroluminescent display of this invention. In addition, in FIG. 1, although the polarizing film 6 is a single protection polarizing film comprised from the polarizer 4 and the transparent protective film 3, it is not limited to this, The polarizer 4 and retardation film 5 Both protective polarizing films which further have a transparent protective film in between may be sufficient. Moreover, as mentioned above, various functional layers, such as a hard-coat layer, can also be formed in the surface which is not in contact with the polarizer 4 of the transparent protective film 3.

Moreover, when the said phase difference film is laminated | stacked on a polarizer through an adhesive layer, the said adhesive layer may be the adhesive layer for organic electroluminescent display of this invention. That is, the polarizing film provided with the adhesive layer for organic electroluminescent display devices has a 1st adhesive layer, a transparent protective film, a polarizer, a 2nd adhesive layer, a retardation film, and a 3rd adhesive layer in this order,

At least one adhesive layer of a said 1st adhesive layer, a 2nd adhesive layer, and a 3rd adhesive layer should just be the said adhesive layer for organic electroluminescent display devices.

4. organic EL display

The organic electroluminescence display of this invention used the polarizing film provided with the adhesive layer for organic electroluminescent display of this invention, and / or the adhesive layer for organic electroluminescence display of this invention, It is characterized by the above-mentioned.

As an example of the specific structure of an organic electroluminescence display, as shown, for example in FIGS. 2-4, a cover glass or cover plastics 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); Cover glass or cover plastic (7) / adhesive layer (9) / transparent protective film (3) / polarizer (4) / retardation film (5) / adhesive layer (2) / organic EL display panel (8) (FIG. 3) ; Cover glass or cover plastic (7) / adhesive layer (2) / sensor layer (10) / adhesive layer (2) / transparent protective film (3) / polarizer (4) / retardation film (5) / adhesive layer (2) As in the organic EL display panel 8 (Fig. 4), an organic EL display device in which each layer is laminated in this order is mentioned. At least one of the adhesive layers 2 in each said structure should just be the adhesive layer of this invention, and all the adhesive layers 2 may be the adhesive layer of this invention. Moreover, the organic electroluminescence display of this invention may contain various functional layers, such as a protective film and a hard-coat layer, in addition to the above. In addition, in lamination | stacking of each layer, an adhesive layer and / or an adhesive bond layer can be used suitably. As an adhesive layer other than the adhesive layer of this invention, the normal adhesive layer used in this field can be used suitably.

Example

Although an Example demonstrates this invention concretely below, this invention is not limited by these Examples. In addition, all the parts and% in each case are a basis of weight.

<Measurement of the weight average molecular weight of the (meth) acrylic polymer>

The weight average molecular weight (Mw) of the (meth) acrylic polymer was measured by GPC (gel permeation chromatography). Also about Mw / Mn, it measured similarly.

Analysis equipment: manufactured by Tosoh Corporation, HLC-8120GPC

Column: manufactured by Tosoh Corporation, G7000HXL + GMHXL + GMHXL

Column size: Each 7.8mmφ × 30cm total 90cm

Column temperature: 40 ℃

Flow rate: 0.8 mL / min

Injection volume: 100 μL

Eluent: tetrahydrofuran

Detector: Differential Refractometer (RI)

Standard sample: polystyrene

<Preparation of (meth) acrylic polymer (1)>

A monomer mixture containing 99 parts of butyl acrylate (BA) and 1 part of 4-hydroxybutyl acrylate (HBA) was introduced into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device. Further, 0.1 part of 2,2'-azobisisobutyronitrile was added together with 100 parts of ethyl acetate with respect to 100 parts of the monomer mixture, 100 parts of ethyl acetate was introduced, nitrogen gas was introduced with gentle stirring, and the flask was replaced with a flask. The liquid temperature inside was hold | maintained at 55 degreeC, and the polymerization reaction was performed for 8 hours, and the solution (solid content concentration 30 weight%) of the weight average molecular weight (Mw) 1.8 million and the acrylic polymer of Mw / Mn = 4.1 was prepared.

<Preparation of (meth) acrylic polymer (2)>

A monomer mixture containing 94.8 parts of butyl acrylate (BA), 5 parts of acrylic acid (AA), and 0.2 parts of 2-hydroxyethyl (HEA) was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device. It was. To 100 parts of the monomer mixture, 0.3 part of benzoyl peroxide (Nipper BMT manufactured by Nippon Yushi Co., Ltd.) was added together with 100 parts of ethyl acetate as a polymerization initiator, and nitrogen gas was introduced while nitrogen was introduced while gently stirring. The polymerization was carried out for 8 hours while maintaining the liquid temperature in the flask at about 55 ° C to prepare a solution (solid content concentration of 30% by weight) of an acrylic polymer having a weight average molecular weight (Mw) of 2.2 million and Mw / Mn = 4.1.

<Preparation of (meth) acrylic polymer (3)>

73.3 parts of butyl acrylate (BA), 21 parts of phenoxyethyl acrylate (PEA), 5 parts of N-vinylpyrrolidone (NVP) to a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, A monomer mixture containing 0.3 part of acrylic acid (AA) and 0.4 part of 4-hydroxybutyl acrylate (HBA) was added. 0.1 part of 2,2'-azobisisobutyronitrile was added together with 100 parts of ethyl acetate with respect to 100 parts of said monomer mixture (solid content), and nitrogen-substituted by nitrogen gas introduction, stirring gently. Thereafter, the liquid temperature in the flask was maintained at about 55 ° C. to carry out the polymerization reaction for 8 hours to prepare a solution (solid content concentration of 28% by weight) of an acrylic polymer having a weight average molecular weight (Mw) of 1.6 million and Mw / Mn = 3.8.

Example 1

(Preparation of Adhesive Composition)

About 100 parts of solid content of the solution of the acrylic polymer (1) manufactured above,

0.3 parts of radical generators (benzoyl peroxide, Nippon Yushi Co., Ltd. brand name Niper BMT)

0.1 part of an isocyanate type crosslinking agent (trade name Takeate D110N by Mitsui Chemicals, Inc.),

As ultraviolet absorber (a), 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5 Triazine (trade name: Tinosorb S, manufactured by BASF), and 2 parts

0.1 part of silane coupling agents (KBM403 by Shin-Etsu Chemical Co., Ltd. product) were mix | blended, and the adhesive composition was obtained.

(Production of adhesive layer)

The pressure-sensitive adhesive composition was applied on a separator having a thickness of 38 μm (a polyethylene terephthalate-based film having a surface peeled off: release film) so as to have a thickness of 20 μm after drying, and dried at 155 ° C. for 1 minute to remove the solvent. And an adhesive layer (A) were obtained.

Immediately after the pressure-sensitive adhesive layer (A) was formed, the separator in which the pressure-sensitive adhesive layer (A) was formed had a phase difference film having a configuration of a cycloolefin polymer film / polarizer / acrylic resin film / adhesive layer (B) / retardation film. It adhere | attached on the polarizing film and produced the polarizing film provided with the adhesive layer. The structure of the polarizing film provided with the obtained adhesive layer is a cycloolefin polymer film / polarizer / acrylic resin film / adhesive layer (B) / retardation film / adhesive layer (A).

Moreover, the cycloolefin polymer film and acrylic resin film of both sides of the polarizer were bonded together using the polyvinyl alcohol-type adhesive agent, and the polarizing film was obtained. In preparation of the polarizing film provided with the adhesive layer which has retardation film, the polarizing film and retardation film were bonded through the adhesive layer (B).

In addition, the structural member of the polarizing film which has retardation film is as follows.

(Cycloolefin polymer film)

A 25-micrometer-thick cycloolefin polymer film (trade name Zeonoa Film, manufactured by Nippon Xeon Co., Ltd.) was used.

(Manufacture of Polarizer)

A polarizer made of a stretched polyvinyl alcohol film having a thickness of 5 μm impregnated with iodine was used. The single-crystal transmittance Y value of the polarizer (or the polarizing film which bonded the protective film) was 42.4%, and the polarization degree was 99.995.

(Acrylic resin film)

The resin pellet which consists of 100 weight part of imidized MS resin of Unexamined-Japanese-Patent No. 2010-284840 is dried for 12 hours at 100.5 kPa and 100 degreeC, and it is made from a T die at the die temperature of 270 degreeC by the single screw extruder. It extruded and shape | molded to film shape (thickness 80 micrometers). Furthermore, the said film was extended | stretched in 150 degreeC atmosphere in the conveyance direction (40 micrometers in thickness), and then extended in 150 degreeC atmosphere in the direction orthogonal to a film conveyance direction, and the acrylic resin film of 20 micrometers in thickness was obtained.

(Retardation film)

A polycarbonate film (Nitto Denko Co., Ltd. "NRF", in-plane retardation Re (550): 135 nm) of 56 micrometers in thickness was used.

(Preparation of the adhesive composition which forms an adhesive layer (B))

In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube, 95 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, and 233 parts by weight of ethyl acetate After adding the part, nitrogen gas was flowed and nitrogen substitution was performed for about 1 hour, stirring. Thereafter, the flask was heated to 60 ° C. and reacted for 7 hours to obtain a weight average molecular weight (Mw) of 1.1 million acrylic polymer. 0.8 parts by weight of trimethylol-propantolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.), as a isocyanate-based crosslinking agent, in the acrylic polymer solution (containing 100 parts by weight of solid content), a silane coupling agent (brand name) : KBM-403, Shin-Etsu Chemical Co., Ltd. make) 0.1 weight part was added, and the adhesive composition (solution) was prepared.

(Manufacture of an adhesive layer (B))

The pressure-sensitive adhesive composition (solution) was coated on a 38-μm-thick separator (polyethylene terephthalate-based film: release film whose surface was peeled off) so as to have a thickness of 15 μm after drying, and dried at 100 ° C. for 3 minutes. The solvent was removed to obtain an adhesive layer (B).

Examples 2 to 13, Comparative Examples 1 to 3

In Example 1, in preparation of an adhesive composition, the kind of (meth) acrylic-type polymer, the kind or compounding quantity of a crosslinking agent, the kind or compounding quantity of a ultraviolet absorber, the kind or compounding quantity of a pigment compound, and the compounding quantity of antioxidant are shown in Table 1 Except having changed as mentioned above, it carried out similarly to Example 1, and formed the adhesive layer. Moreover, the polarizing film provided with the adhesive layer was produced similarly to Example 1.

The following evaluation was performed about the adhesive layer (A) obtained by the said Example and comparative example and the polarizing film provided with an adhesive layer. The evaluation results are shown in Table 1.

<Measurement of transmittance of the adhesive layer>

The separator was peeled off from the pressure-sensitive adhesive layer (A) obtained in the examples and the comparative examples, the pressure-sensitive adhesive layer (A) was placed on a measuring jig, and measured with a spectrophotometer (product name: U4100, manufactured by Hitachi High Technologies Co., Ltd.). . The transmittance | permeability measured the transmittance in the range of wavelength 300nm-450nm. Table 1 shows the average transmittances of wavelengths of 300 nm to 400 nm, wavelengths of 400 nm to 430 nm, and wavelengths of 430 nm to 450 nm.

<Measurement of gel fraction>

The gel fraction is 0.2g of the pressure-sensitive adhesive layer (A), wrapped in a fluorine resin (TEMISH NTF-1122 manufactured by Nitto Denko Co., Ltd.) (Wa), and weighed in advance so as not to leak the pressure-sensitive adhesive, and then the weight ( Wb) was measured and placed in a sample bottle. 40 cc of ethyl acetate was added, and it left to stand for 7 days. Thereafter, the fluorine resin was taken out, dried at 130 ° C. for 2 hours on an aluminum cup, the weight (Wc) of the fluorine resin containing the sample was measured, and the gel fraction was determined by the following formula (I).

Formula (I): gel fraction = (Wc-Wa) / (Wb-Wa) x 100 (weight%)

The gel fraction was measured immediately after the pressure-sensitive adhesive layer (A) was formed (within 4 hours) and after the pressure-sensitive adhesive layer (A) was formed, and then left at room temperature (23 ° C.) for 1 week.

<Appearance yield>

About punching the obtained polarizing film with an adhesive layer in the square whose side length is 270 mm, the adhesive scratch of the adhesive layer (A), the adhesive shortage of an edge part, and the adhesive contamination of the edge part were evaluated on the following references | standards.

○…. No problem.

Δ. Some appearance defects due to lack of adhesive, adhesive contamination, adhesive scratches.

×… Significant appearance defects due to lack of adhesives, adhesive contamination and adhesive scratches.

<Durability>

The separator was peeled from the obtained polarizing film (290 mm x 220 mm) provided with the adhesive layer, and the adhesive layer (A) side was adhere | attached on both surfaces of the alkali free glass plate of thickness 0.7mm so that it might become a cross nicol state. Subsequently, autoclave process was performed at 50 degreeC and 5atm for 15 minutes, and it fully adhered and the sample was prepared. After 500 hours of treatment of the sample under 85 conditions, the state of foaming, peeling and lifting was visually observed based on the following criteria.

○…. No foaming, peeling or lifting

Δ. There is no problem in practical use, but it is a little bad level visually.

×… There is a problem in practical use.

Peeling force

The sheet piece of length 100mm and width 50mm was cut out from the polarizing film provided with the obtained adhesive layer as a sample. Tensile rate 300 mm / min was carried out in the atmosphere of 23 degreeC and 50% RH based on JISZ0237 about the obtained sample using the tension tester (device name: Autograph AG-IS, the Shimadzu Corporation make). The separator was peeled off from the sample on the conditions of 180 degree peeling angle, and 180 degree peeling peeling force (N / 50mm) was measured.

As for the said separator peeling force, 0.02-1.0 (N / 50mm) is preferable. It is preferable that the said separator peeling force is 0.02 (N / 50mm) or more in suppressing the external appearance defect by the lift of a separator at the time of processing or handling. On the other hand, it is preferable that the said separator peeling force is 1.0 (N / 50mm) or less in suppressing the peeling defect of a separator. The separator peel force is more preferably 0.04 to 0.5 (N / 50 mm), still more preferably 0.06 to 0.2 (N / 50 mm), and particularly preferably 0.08 to 0.15 (N / 50 mm).

In Table 1,

Radical generators include benzoyl peroxide (trade name Naifer BMT manufactured by Nippon Yushi Co., Ltd.);

D110N isocyanate type crosslinking agent (Brand name Takeate D110N by Mitsui Chemicals, Inc.);

C / L is an isocyanate crosslinking agent (trade name Coronate L manufactured by Tosoh Corporation);

A1 which is a ultraviolet absorber is 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5- Triazine (trade name: Tinosorb S, manufactured by BASF);

A2 which is a ultraviolet absorber is 2,2 ', 4,4' tetrahydroxy benzophenone (brand name: SeeSorb 106, the product made by Cipro Kasei);

B1, which is a dye compound, is a melocyanine compound (trade name: FDB-009, maximum absorption wavelength of an absorption spectrum: 394 nm, half-value width: 43 nm, manufactured by Yamada Kagaku Kogyo Co., Ltd.);

B2 which is a pigment compound is a polymethine compound (brand name: DAA-247, the maximum absorption wavelength of an absorption spectrum: 389 nm, half value width: 49.5 nm, Yamada Kagaku Kogyo Co., Ltd. product);

B3, which is a dye compound, is an alkylphenyl indolinocyanate derivative (indole compound) (trade name: BONASORB UA3912, maximum absorption wavelength of an absorption spectrum: 386 nm, half-value width: 53 nm, manufactured by Orient Chemical Co., Ltd.);

The antioxidant represents a phenolic antioxidant (trade name IRGANOX 1010 manufactured by BASF Japan).

1: Polarizing film provided with adhesive layer for organic electroluminescence display
2: adhesive layer
3: transparent protective film
4: polarizer
5: retardation film
6: polarizing film
7: cover glass or cover plastic
8: organic EL panel
9: adhesive layer
10: sensor layer

Claims (17)

At least one selected from the base polymer, the radical generator, and the ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure and the dye compound (b) in which the maximum absorption wavelength of the absorption spectrum exists in the wavelength region of 380 to 430 nm. Compound (A) is contained, The adhesive composition for organic electroluminescent display devices characterized by the above-mentioned. The method of claim 1,
The said compound (A) contains both the said ultraviolet absorber (a) and the said dye compound (b), The adhesive composition for organic electroluminescent display apparatuses characterized by the above-mentioned. The method according to claim 1 or 2,
The maximum absorption wavelength of the absorption spectrum of the said ultraviolet absorber (a) exists in the wavelength range of 300-400 nm, The adhesive composition for organic electroluminescent display apparatuses characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The said radical generator is a peroxide, The adhesive composition for organic electroluminescent display apparatuses characterized by the above-mentioned. The method according to any one of claims 1 to 4,
The said base polymer is a (meth) acrylic-type polymer, The adhesive composition for organic electroluminescent displays characterized by the above-mentioned. The method according to any one of claims 1 to 5,
0.01-2 weight part of said radical generators are contained with respect to 100 weight part of said base polymers, The adhesive composition for organic electroluminescent display apparatuses characterized by the above-mentioned. The method according to any one of claims 1 to 6,
0.1-25 weight part of said compound (A) is contained with respect to 100 weight part of said base polymers, The adhesive composition for organic electroluminescent display apparatuses characterized by the above-mentioned. The method according to any one of claims 1 to 7,
The adhesive composition for organic electroluminescent display further containing antioxidant. The method according to any one of claims 1 to 8,
The adhesive composition for organic electroluminescent display further containing a crosslinking agent. It is formed with the adhesive composition for organic electroluminescent display of any one of Claims 1-9, The adhesive layer for organic electroluminescence display characterized by the above-mentioned. The method of claim 10,
The average transmittance of wavelength 300-400 nm is 12% or less, the average transmittance of wavelength 400 nm-430 nm is 30% or less, and the average transmittance of wavelength 430-450 nm is 70% or more, The adhesive layer for organic electroluminescent display apparatuses characterized by the above-mentioned. The method of claim 10,
An organic EL display device having an average transmittance of wavelength 300 to 400 nm of 12% or less, an average transmittance of wavelength 400 nm to 430 nm of more than 30% and 95% or less, and an average transmittance of wavelength 430 to 450 nm of 80% or more. Pressure-sensitive adhesive layer. It has a polarizing film and the adhesive layer for organic electroluminescent display of any one of Claims 10-12, The polarizing film provided with the adhesive layer for organic electroluminescent display characterized by the above-mentioned. The method of claim 13,
The said polarizing film is provided with the transparent protective film in one surface of a polarizer, has a retardation film in the other surface, the surface on the opposite side to the surface which the said adhesive layer for organic electroluminescent devices contacts with the polarizer of the said retardation film, And / or a surface on the side opposite to the surface in contact with the polarizer of the transparent protective film. The polarizing film provided with the pressure-sensitive adhesive layer for organic EL display device. The method of claim 13,
It is a polarizing film provided with the adhesive layer for organic electroluminescent display devices which has a 1st adhesive layer, a transparent protective film, a polarizer, a 2nd adhesive layer, a retardation film, and a 3rd adhesive layer in this order,
At least one adhesive layer of the said 1st adhesive layer, the 2nd adhesive layer, and the 3rd adhesive layer is an adhesive layer for said organic electroluminescent display devices, The polarizing film provided with the adhesive layer for organic electroluminescent display devices. . The method according to claim 14 or 15,
The said retardation film is a quarter wave plate, and the said polarizing film is a circularly polarizing film, The polarizing film provided with the adhesive layer for organic electroluminescence display characterized by the above-mentioned. At least one polarizing film provided with the adhesive layer for organic electroluminescent display of any one of Claims 10-12, or the adhesive layer for organic electroluminescent display of any one of Claims 13-16. It was used, The organic electroluminescence display characterized by the above-mentioned.

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