TWI772439B - Adhesive composition for organic EL display device, adhesive layer for organic EL display device, polarizing film with adhesive layer for organic EL display device, and organic EL display device - Google Patents

Abstract

The present invention relates to an adhesive composition for an organic EL display device, which is characterized by comprising: a base polymer, a radical generator, and a compound (A), wherein the compound (A) is selected from the group consisting of hydroxyl groups in the molecular structure being 0 At least one of the ultraviolet absorbers (a) of ~3 and the pigment compounds (b) of which the maximum absorption wavelength of the absorption spectrum exists in the wavelength region of 380 to 430 nm. When the adhesive composition for organic EL display devices of the present invention is used in an organic EL display device, deterioration of organic EL elements can be suppressed, and reduction in appearance yield and generation of foaming due to heating durability can be suppressed.

Description

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

The present invention relates to an adhesive composition for an organic EL (Electroluminescence, electroluminescence) display device (OLED (organic light emitting diode, organic light emitting diode)). Furthermore, the present invention relates to an adhesive layer for an organic EL display device formed from the above-mentioned adhesive composition for an organic EL display device, and a polarizing film having the adhesive layer of the adhesive layer. Furthermore, the present invention relates to an organic EL display device using the above-mentioned adhesive layer and/or the above-mentioned polarizing film.

In recent years, organic EL display devices incorporating organic EL panels have been widely used in various applications such as mobile phones, car navigation devices, monitors for personal computers, and televisions. In order to prevent the external light from being reflected by the metal electrode (cathode) and be seen as a mirror surface, the organic EL display device is usually equipped with a circular polarizing plate (a laminate of a polarizing plate and a quarter-wave plate, etc.) on the visible side surface of the organic EL panel. . Moreover, there exists a case where the circular polarizing plate laminated|stacked on the visible side surface of an organic electroluminescent panel is further laminated|stacked with a decorative panel, etc. The constituent members of the organic EL display device such as the circularly polarizing plate and the decorative panel are usually laminated through a bonding material such as an adhesive layer or an adhesive layer.

In an image display device such as an organic EL display device, the components in the image display device may deteriorate due to incident ultraviolet light. Floor. Specifically, for example, there is known a transparent double-sided adhesive sheet for an image display device, which has at least one ultraviolet absorbing layer, the transmittance of light with a wavelength of 380 nm is 30% or less, and the wavelength is longer than that with a wavelength of 430 nm. The visible light transmittance of the side is 80% or more (for example, refer to Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-211305

[Problems to be Solved by Invention]

Usually, the adhesive composition applied to the transparent double-sided adhesive sheet for image display devices contains, for example, a base polymer such as a (meth)acrylic polymer. Moreover, in an adhesive composition, in addition to a base polymer, a radical generator (for example, a peroxide) is used as a crosslinking agent, and the adhesive layer which performs radical crosslinking may be formed. In addition, in the case of using a (meth)acrylic polymer as the above-mentioned base polymer, in order to prepare a monomer component by heat or radiation curing in the (meth)acrylic polymer, the above-mentioned adhesive is combined with Contains free radical polymerization initiators.

However, in the case where an ultraviolet absorber is contained in the above-mentioned adhesive composition containing a radical generator, the presence of the ultraviolet absorber causes the gel fraction (crosslinking degree) of the adhesive layer formed from the adhesive composition. tendency to decrease. If the decrease in the gel fraction (degree of crosslinking) of the adhesive layer becomes large, the adhesive layer may have a decrease in the appearance yield due to paste dents or paste stains during processing, or heat durability. Abnormalities such as the generation of foaming.

Therefore, an object of the present invention is to provide an adhesive composition for an organic EL display device, which can suppress the deterioration of the organic EL element, and can suppress the deterioration of the appearance yield or the heat durability by being used in the organic EL display device. The generation of foaming, etc.

Furthermore, the object of the present invention is to provide an adhesive layer for organic EL display devices formed from the above-mentioned adhesive composition, to provide a polarizing film and a polarizing film having the adhesive layer for organic EL display devices, and to provide a polarizing film containing the above-mentioned adhesive layer. The organic EL display device of the adhesive layer and/or the polarizing film of the above-mentioned adhesive layer. [Technical means to solve problems]

In order to solve the above-mentioned problems, the inventors of the present invention have repeatedly conducted intensive studies, found the following adhesive composition for an organic EL display device, and completed the present invention.

That is, the present invention relates to an adhesive composition for an organic EL display device, characterized by comprising: a base polymer, a radical generator, and a compound (A) selected from hydroxyl groups in a molecular structure At least one of 0 to 3 ultraviolet absorbers (a) and pigment compounds (b) whose maximum absorption wavelength of the absorption spectrum exists in the wavelength region of 380 to 430 nm.

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

It is preferable that the maximum absorption wavelength of the absorption spectrum of the said ultraviolet absorber (a) exists in the wavelength region of 300-400 nm in the said adhesive composition for organic electroluminescent display apparatuses.

In the above-mentioned adhesive composition for organic EL display devices, a peroxide can be used as the above-mentioned radical generator.

A (meth)acrylic-type polymer can be used for the said base polymer in the said adhesive composition for organic electroluminescent display apparatuses.

It is preferable to contain 0.01-2 weight part of said radical generators with respect to 100 weight part of said base polymers in the said adhesive composition for organic electroluminescent display apparatuses.

It is preferable to contain 0.1-25 weight part of said compound (A) with respect to 100 weight part of said base polymers in the said adhesive composition for organic electroluminescent display apparatuses.

The above-mentioned adhesive composition for organic EL display devices may further contain an antioxidant.

The above-mentioned adhesive composition for organic EL display devices may further contain a crosslinking agent.

Furthermore, the present invention relates to an adhesive layer for an organic EL display device, characterized in that it is formed from the above-mentioned adhesive composition for an organic EL display device.

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

The above-mentioned adhesive layer for an organic EL display device preferably has an average transmittance of 300 to 400 nm in wavelength of 12% or less, an average transmittance of 400 to 430 nm in wavelength of more than 30% and 95% or less, and a wavelength of 430 to 450 nm. The average transmittance is above 80%.

Furthermore, the present invention relates to a polarizing film with an adhesive layer for organic EL display devices, characterized by having a polarizing film and the above-mentioned adhesive layer for organic EL display devices.

The above-mentioned polarizing film with an adhesive layer for an organic EL display device preferably has a transparent protective film on one side of the polarizing element and a retardation film on the other side of the polarizing film, and the above-mentioned adhesive layer for an organic EL display device is provided on the The surface on the opposite side of the retardation film and the polarizing element, and/or the surface on the opposite side of the transparent protective film and the polarizing element.

The polarizing film with the adhesive layer for an organic EL display device preferably has a first adhesive layer, a transparent protective film, a polarizing element, a second adhesive layer, a retardation film, and a third adhesive layer in this order, And at least one adhesive layer among the said 1st adhesive bond layer, the 2nd adhesive bond layer, and the 3rd adhesive bond layer is the said adhesive bond layer for organic EL display devices.

In the polarizing film with the adhesive layer for organic EL display devices, it is preferable that the retardation film is a quarter wave plate, and the polarizing film is a circular polarizing film.

Furthermore, the present invention relates to an organic EL display device characterized by using at least one of the above-mentioned adhesive layer for an organic EL display device or a polarizing film with the above-mentioned adhesive layer for an organic EL display device. [Effect of invention]

The adhesive composition for organic EL display devices of this invention contains an ultraviolet absorber (a) in addition to a base polymer. By the ultraviolet absorber (a), the deterioration by ultraviolet light can be suppressed, and the deterioration of an organic EL element can be suppressed. Moreover, the adhesive composition for organic EL display devices of the present invention contains a pigment compound (b) whose absorption spectrum has a maximum absorption wavelength in the wavelength region of 380 to 430 nm in place of the above-mentioned ultraviolet absorber (a), or in combination with the above-mentioned ultraviolet absorber. Agent (a) is used in combination. Deterioration by ultraviolet light can also be suppressed by this dye compound (b), and the deterioration of an organic EL element can also be suppressed.

Moreover, the adhesive composition for organic EL display devices of this invention contains a radical generator, such as a peroxide. This radical generator functions as, for example, a crosslinking agent for base polymers such as (meth)acrylic polymers, and can control the gel fraction of the adhesive layer formed from the above-mentioned adhesive composition to a desired level range, can form an adhesive layer with good appearance.

As described above, since the ultraviolet absorber and/or the dye compound and the radical generator coexist in the adhesive composition for organic EL display devices of the present invention, there is a concern that the gel fraction of the obtained adhesive layer will decrease. However, in the adhesive composition for organic EL display devices of the present invention, the ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure is selected and used as the ultraviolet absorber. That is, in the present invention, it is considered that the decrease in the gel fraction is caused by the decrease in the degree of crosslinking due to the deactivation of the radicals generated by the radical generator, and the reason for deactivating the radicals is the hydrogen contained in the ultraviolet absorber. As the donating group, by selecting and using the ultraviolet absorber (a) in which the hydroxyl group of the hydrogen donating group is 3 or less, the crosslinking inhibition of the radical generator by the ultraviolet absorber is suppressed.

As a result, according to the adhesive composition for organic EL display devices of the present invention, it is possible to obtain an adhesive layer for organic EL display devices that can suppress the decrease in appearance yield and the generation of foaming due to heating durability. Therefore, the organic EL display device using the adhesive layer for organic EL display devices and/or the polarizing film containing the adhesive layer for organic EL display devices of the present invention has excellent weathering resistance and can have a longer life. .

1. Adhesive composition for organic EL display devices The adhesive composition for organic EL display devices of the present invention is characterized in that it contains: a base polymer, a radical generator, and a compound (A), and the compound (A) is selected from At least one of the ultraviolet absorber (a) having 0 to 3 hydroxyl groups in its molecular structure and the pigment compound (b) having the maximum absorption wavelength of the absorption spectrum in the wavelength region of 380 to 430 nm.

The adhesive composition for organic EL display devices of this invention contains a base polymer as a main component. The so-called main component refers to the component with the largest proportion in the total solid content contained in the adhesive composition, for example, it refers to the component that accounts for more than 50% by weight of the total solid content contained in the adhesive composition, and further refers to the More than 70% by weight of ingredients.

The base polymer used in the present invention is not particularly limited, and examples of the type of the adhesive composition include rubber-based adhesives, acrylic-based adhesives, polysiloxane-based adhesives, and urethane-based adhesives. Adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, etc. Among these adhesives, acrylic adhesives are preferably used in terms of having excellent optical transparency, exhibiting suitable adhesive properties of adhesion, cohesion, and adhesiveness, and being excellent in weather resistance and heat resistance. . In the present invention, an acrylic adhesive composition containing a (meth)acrylic polymer as a base polymer is preferred.

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

As the alkyl (meth)acrylate constituting the main skeleton of the (meth)acrylic polymer, those having 1 to 18 carbon atoms in a linear or branched alkyl group can be exemplified. These may be used alone, or may be used in combination. The average carbon number of these alkyl groups is preferably 3-9.

In addition, in terms of adhesive properties, durability, adjustment of retardation, adjustment of refractive index, etc., aromatic ring-containing compounds such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate can be used. Alkyl (meth)acrylate.

In order to improve adhesiveness or heat resistance, one or more types of polymerizable functions having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group can be introduced into the (meth)acrylic polymer by copolymerization. base comonomer. Specific examples of such comonomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylate ) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate or (4-hydroxymethylcyclohexyl acrylate) ) Hydroxyl-containing monomers such as methyl ester; (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itonic acid, maleic acid, fumaric acid, crotonic acid, etc. Monomers containing carboxyl groups; monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; styrene sulfonic acid or allyl sulfonic acid, 2-(meth)acrylamide -2-Methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, (meth)acrylic acid sulfopropyl ester, (meth)acryloyloxynaphthalenesulfonic acid and other sulfonic acid group-containing monomers; acrylic acid 2-Hydroxyethyl phosphate and other monomers containing phosphoric acid groups, etc.

Moreover, as an example of the monomer for the purpose of modification, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, or (N-substituted) amide-based monomers such as N-methylol (meth)acrylamide, N-methylolpropane (meth)acrylamide, etc.; aminoethyl (meth)acrylate, (methyl) (meth)acrylic acid alkylamino alkyl ester monomers such as N,N-dimethylaminoethyl acrylate, tert-butylaminoethyl (meth)acrylate, etc.; (meth)acrylic acid (meth)acrylic acid alkoxyalkyl ester monomers such as methoxyethyl ester and (meth)acrylic acid ethoxyethyl ester; N-(meth)acryloyloxymethylenesuccinimide or N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyoctamethylenesuccinimide, N-acryloylidene Succinimide-based monomers such as succinimide; N-cyclohexylmaleimide or N-isopropylmaleimide, N-laurylmaleimide or N-phenylmaleimide Maleimide monomers such as imine Iconimide monomers such as amine, N-2-ethylhexyliconimide, N-cyclohexyliconimide, N-lauryliconimide, etc.

Furthermore, as a modification monomer, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine can also be used , vinylpiperidine, vinylpyrrole, vinylpyrrole, vinylimidazole, vinyloxazole, vinylpyridine, N-vinylcarboxyamide, styrene, α-methylstyrene, N- Vinyl-based monomers such as vinyl caprolactam; cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; epoxy-containing acrylic-based monomers such as glycidyl (meth)acrylate; polyethylene glycol Alcohol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate and other glycol-based acrylate monomers; Acrylate monomers such as tetrahydrofurfuryl (meth)acrylate, fluorine-containing (meth)acrylate, polysiloxane (meth)acrylate, and 2-methoxyethyl acrylate, and the like. Furthermore, isoprene, butadiene, isobutylene, vinyl ether, etc. are mentioned.

Furthermore, as a copolymerizable monomer other than the above, the silane type monomer containing a silicon atom, etc. are mentioned. As the silane-based monomer, for example, 3-propenyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 4-vinylbutyltrimethoxysilane may be mentioned. Silane, 4-Vinylbutyltriethoxysilane, 8-Vinyloctyltrimethoxysilane, 8-Vinyloctyltriethoxysilane, 10-Methacryloyloxy Decyltrimethoxysilane, 10-propenyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-propenyloxydecyltriethoxy Silane etc.

Moreover, as a comonomer, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol can also be used A diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. (meth)acrylic acid and polyol Polyfunctional monomers having 2 or more (meth)acryloyl, vinyl, etc. unsaturated double bonds, such as esters, or adding 2 to the skeleton of polyester, epoxy, urethane, etc. Polyester (meth)acrylates, epoxy (meth)acrylates, (meth)acrylates in which unsaturated double bonds such as the above (meth)acryloyl and vinyl groups are the same functional groups as the monomer components ) acrylic urethane, etc.

The above-mentioned (meth)acrylic polymer has alkyl (meth)acrylate as the main component in the weight ratio of all the constituent monomers, and the ratio of the above-mentioned comonomer in the (meth)acrylic polymer is not In particular, the ratio of the above-mentioned comonomers is preferably about 0~20%, about 0.1~15%, and more preferably about 0.1~10% in the weight ratio of all the constituent monomers.

Among these comonomers, a hydroxyl group-containing monomer and a carboxyl group-containing monomer can be preferably used in terms of adhesion and durability. A hydroxyl group-containing monomer and a carboxyl group-containing monomer may be used in combination. These comonomers become reaction sites with the cross-linking agent when the adhesive composition contains the cross-linking agent. Since hydroxyl group-containing monomers, carboxyl group-containing monomers, etc. are rich in reactivity with intermolecular crosslinking agents, they can be preferably used to improve the cohesiveness or heat resistance of the obtained adhesive layer. The hydroxyl group-containing monomer is preferable in terms of secondary processability, and the carboxyl group-containing monomer is preferable in terms of both durability and secondary processability.

When a hydroxyl group-containing monomer is used as the above-mentioned comonomer, the ratio thereof is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and still more preferably 0.05 to 7% by weight. When a carboxyl group-containing monomer is used as the above-mentioned comonomer, the ratio thereof is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and still more preferably 0.2 to 6% by weight.

The (meth)acrylic polymer of the present invention is generally used in the range of the weight average molecular weight of 500,000 to 3,000,000. In consideration of durability, especially heat resistance, it is preferable to use those having a weight average molecular weight of 700,000 to 2,700,000. More preferably, it is 800,000 to 2,500,000. If the weight average molecular weight is less than 500,000, it is unfavorable in terms of heat resistance. In addition, when the weight average molecular weight exceeds 3 million, in order to adjust the viscosity for coating, a large amount of a diluting solvent is required, and the cost increases, which is not preferable. In addition, the weight average molecular weight means the value calculated by GPC (gel permeation chromatography), and calculated by polystyrene conversion.

For the production of such a (meth)acrylic polymer, known production methods such as solution polymerization, radiation polymerization such as UV (ultraviolet) polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected. In addition, the obtained (meth)acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

In addition, in solution polymerization, as a polymerization solvent, ethyl acetate, toluene, etc. can be used, for example. As a specific example of solution polymerization, the reaction is carried out under the flow of inert gas such as nitrogen, adding a polymerization initiator, usually at about 50 to 70° C. for about 5 to 30 hours.

The polymerization initiator, chain transfer agent, emulsifier, etc. used in the radical polymerization are not particularly limited, and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth)acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator, a chain transfer agent, and reaction conditions, and the usage-amount can be 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-amidinopropane)dihydrochloride, Azabis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2 '-Azobis(N,N'-dimethyleneisobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate ( Azo-based initiators such as VA-057, manufactured by Wako Pure Chemical Industries, Ltd.; persulfates such as potassium persulfate and ammonium persulfate; 4-tert-butylcyclohexyl) ester, di-2-butyl peroxydicarbonate, 3-butyl peroxyneodecanoate, 3-hexyl peroxypivalate, 3rd-butyl peroxypivalate , Dilaurin peroxide, di-n-octyl peroxide, (2-ethylhexanoic acid) 1,1,3,3-tetramethylbutyl peroxide, bis(4-methylbenzyl peroxide) , Dibenzyl peroxide, tert-butyl peroxyisobutyrate, 1,1-bis(tert-hexyl peroxy) cyclohexane, tert-butyl hydroperoxide, hydrogen peroxide and other peroxides It is an initiator; a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, etc. Redox-based initiators, etc., which are combined with a peroxide and a reducing agent, etc., but are not limited to the Wait.

The above-mentioned radical polymerization initiators can be used alone, or can be used in a mixture of two or more kinds, and the content as a whole is preferably about 0.005 to 1 part by weight, more preferably 0.02 to 0.5 part by weight relative to 100 parts by weight of the monomers. around.

Examples of chain transfer agents include lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolic acid, 2,3-dimercapto- 1-Propanol, etc. The chain transfer agent may be used alone or in combination of two or more, and the total content thereof is about 0.1 part by weight or less with respect to 100 parts by weight of the total amount of the monomer components.

Moreover, as an emulsifier used when carrying out the emulsion polymerization, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, polyoxyethylene Anionic emulsifiers such as oxyethylidene alkyl phenyl ether sodium sulfate; polyoxyethylidene alkyl ether, polyoxyethylidene alkyl phenyl ether, polyoxyethylidene fatty acid ester, Nonionic emulsifiers such as polyoxypropylene block polymers, etc. These emulsifiers may be used alone or in combination of two or more.

Furthermore, as a reactive emulsifier, as an emulsifier into which a radical polymerizable functional group such as acryl group and allyl ether group is introduced, specifically, there are, for example, AQUALON HS-10, HS-20, KH-10, BC- 05. BC-10, BC-20 (the above are all manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), ADEKA REASOAP SE10N (manufactured by Asahi Electric Chemical Co., Ltd.), etc. Since the reactive emulsifier is taken into the polymer chain after the polymerization, it is preferable that the water resistance becomes good. The use amount of the emulsifier is 0.3 to 5 parts by weight with respect to 100 parts by weight of the total amount of the monomer components, and more preferably 0.5 to 1 part by weight in terms of polymerization stability or mechanical stability.

<Radical generator> The radical polymerization initiator used at the time of manufacture of the said (meth)acrylic-type polymer as a radical generator mix|blended with the adhesive composition of this invention can be illustrated. Among the above-mentioned free radical polymerization initiators, the free radical generator formulated in the adhesive composition is preferably a peroxide.

The free-radical generator can generate free-radical active species by heating or light irradiation to perform crosslinking of the (meth)acrylic polymer in the adhesive composition. As the radical generator, in consideration of workability and stability, a peroxide having a half-life temperature of 80°C to 160°C for 1 minute is preferably used, and a peroxide having a half-life temperature of 90°C to 140°C is more preferably used.

Examples of the above-mentioned peroxides include bis(4-tert-butylcyclohexyl)peroxydicarbonate (1-minute half-life temperature: 92.1°C), di-2-butylperoxydicarbonate (1-minute half-life temperature : 92.4°C), 3-butyl peroxyneodecanoate (1-minute half-life temperature: 103.5°C), 3-hexyl peroxypivalate (1-minute half-life temperature: 109.1°C), 3rd pivalate peroxy Butyl ester (1-minute half-life temperature: 110.3°C), dilaurin peroxide (1-minute half-life temperature: 116.4°C), di-n-octyl peroxide (1-minute half-life temperature: 117.4°C), peroxide (2-ethyl acetate) Caproic acid) 1,1,3,3-tetramethylbutyl ester (1-minute half-life temperature: 124.3°C), bis(4-methylbenzyl) peroxide (1-minute half-life temperature: 128.2°C), peroxide Dibenzyl (1-minute half-life temperature: 130.0°C), 3-butyl peroxyisobutyrate (1-minute half-life temperature: 136.1°C), 1,1-bis(tert-hexylperoxy)cyclohexane ( 1 minute half-life temperature: 149.2°C) and so on. Among them, bis(4-tert-butylcyclohexyl)peroxydicarbonate (1-minute half-life temperature: 92.1°C), dilauryl peroxide, bis(4-tert-butylcyclohexyl)peroxydicarbonate, and Acrylic acid (1-minute half-life temperature: 116.4°C), dibenzyl peroxide (1-minute half-life temperature: 130.0°C), and the like.

The above-mentioned so-called half-life of peroxide is an index indicating the decomposition rate of peroxide, and refers to the time until the residual amount of peroxide becomes half. The decomposition temperature for obtaining the half-life at an arbitrary time, or the half-life time at an arbitrary temperature, is described in the manufacturer's catalog, etc., for example, in "Organic Peroxide Catalog 9th Edition (May 2003)" month)" etc.

The content of the radical generator (especially peroxide) in the adhesive composition of the present invention is for the purpose of processability, secondary processability, crosslinking stability, and peelability of the adhesive layer formed from the above-mentioned adhesive composition. Such adjustment is determined in consideration of the gel fraction and the like. If the content of the radical generator (especially peroxide) is large, it is preferable in terms of ensuring the gel fraction (crosslinking degree) of the obtained adhesive layer, but if it is too large, there will be problems There is a tendency for the peeling force of the release film (separator film) to be applied to the adhesive layer to increase. Usually, the content of the free radical generator is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and more Preferably it is 0.05-0.8 weight part, More preferably, it is 0.1-0.6 weight part.

In addition, there is a case where a radical polymerization initiator (radical generator) which is not used in the polymerization reaction at the time of preparing the (meth)acrylic polymer remains in the (meth)acrylic polymer. The residual free radical generator can be used as a free radical generator in the above-mentioned adhesive composition. In this case, the amount of the residual radical generator can be quantified, and the radical generator can be appropriately prepared according to the content of the residual radical generator.

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

More specifically, for example, the adhesive composition after the reaction treatment can be taken out in a manner of about 0.2 g each time, immersed in 10 mL of ethyl acetate, and extracted by shaking at 120 rpm for 3 hours at 25° C. with a shaker. After that, it was left to stand at room temperature for 3 days. Next, 10 mL of acetonitrile was added, the mixture was shaken at 120 rpm for 30 minutes at 25°C, filtered through a membrane filter (0.45 μm), and about 10 μL of the obtained extract was injected into HPLC for analysis, and set as after reaction treatment. the amount of peroxide.

<Compound (A)> In the adhesive composition of the present invention, an ultraviolet absorber (a) selected from the group consisting of 0 to 3 hydroxyl groups in the molecular structure and a wavelength of 380 to 430 nm where the maximum absorption wavelength of the absorption spectrum exists At least one compound (A) of the pigment compound (b) of the region. Regarding the above-mentioned ultraviolet absorber (a), as described above, the number of 0 to 3 hydroxyl groups in the molecular structure is effective in reducing the hydrogen-donating group that causes radical inactivation and inhibiting the crosslinking inhibition of the radical generator. . Moreover, it is also preferable at the point which suppresses the crosslinking hindrance of this crosslinking agent in the case where the isocyanate type crosslinking agent which is reactive with a hydroxyl group etc. is mix|blended, for example, when a hydroxyl group is 0-3. Moreover, it is preferable that the said ultraviolet absorber (a) is a compound which does not have a phenyl group in a molecular structure as a hydrogen-donating group which deactivates a radical other than a hydroxyl group. In addition, the phenyl group which does not have in a molecular structure means the phenyl group which does not have a substituent (-C ₆ H ₅ ), and the phenyl group which has a substituent, a phenylene group, etc. are not excluded. In addition, as for the above-mentioned dye compound (b), similarly to the above-mentioned ultraviolet absorber (a), from the viewpoint of preventing the crosslinking inhibition of the radical generator, it is preferable that a hydrogen donor such as a hydroxyl group or a phenyl group in the molecular structure is used. Compounds with few reactive groups (0 to 3 hydroxyl groups) or without hydrogen-donating groups such as hydroxyl groups or phenyl groups.

The compounding amount of the ultraviolet absorber (a) and/or the pigment compound (b) as the compound (A) is preferably 0.1 with respect to 100 parts by weight of the base polymer (for example, a (meth)acrylic polymer) ~25 parts by weight, preferably about 0.5 to 20 parts by weight, more preferably about 2 to 10 parts by weight.

The above-mentioned ultraviolet absorbers (a) may be used alone or in combination of two or more. In the case where only the above-mentioned ultraviolet absorber (a) is used as the above-mentioned compound (A), the content of the above-mentioned ultraviolet absorber (a) as a whole relative to the base polymer (for example, (meth)acrylic polymer) 100 parts by weight, preferably 0.1-20 parts by weight, preferably 0.1-10 parts by weight, preferably 0.1-5 parts by weight, more preferably 0.5-3 parts by weight. By making the addition amount of the ultraviolet absorber (a) into the above-mentioned range, the ultraviolet absorption function of the adhesive layer can be fully exhibited, and when ultraviolet polymerization is performed, the polymerization is not hindered, which is preferable.

The above-mentioned dye compound (b) may be used alone or in combination of two or more. In the case where only the above-mentioned dye compound (b) is used as the above-mentioned compound (A), the content of the above-mentioned dye compound (b) as a whole is based on 100 weight of the base polymer (for example, (meth)acrylic polymer) parts, preferably 0.1-20 parts by weight, preferably 0.1-10 parts by weight, preferably 0.1-5 parts by weight, more preferably 0.5-3 parts by weight. By setting the addition amount of the dye compound (b) to the above-mentioned range, light in a region that does not affect the light emission of the organic EL element can be sufficiently absorbed, and by using the adhesive layer formed of the adhesive composition, Since the deterioration of an organic EL element can be suppressed, it is preferable.

Any of the above-mentioned ultraviolet absorber (a) and the dye compound (b) may be used, but it is preferable to use the above-mentioned ultraviolet absorber (a) and the dye compound (b) in combination. The ultraviolet absorber (a) can absorb, for example, light with a wavelength of 380 nm, but there is a wavelength region (380 nm) on the shorter wavelength side than the light-emitting region (wavelength side longer than 430 nm) of the organic EL element that is not sufficiently absorbed. ~430 nm) light, and the transmitted light causes deterioration. The above-mentioned dye compound (b) can suppress the transmission of light of a wavelength side (380 nm to 430 nm) shorter than the light-emitting region (wavelength side longer than 430 nm) of the organic EL element, by using the above-mentioned ultraviolet absorber ( a) and the dye compound (b) can sufficiently secure the transmittance of visible light in the light-emitting region of the organic EL element. In the present invention, by using such a dye compound (b) in combination with the above-mentioned ultraviolet absorber (a2), the region (wavelength 380 nm to 430 nm) that does not affect the light emission of the organic EL element can be sufficiently absorbed The light emitting region (wavelength side longer than 430 nm) of the organic EL element is sufficiently permeable, and as a result, deterioration of the organic EL element caused by external light can be suppressed. When the above-mentioned ultraviolet absorber (a) and the dye compound (b) are used in combination, it is preferable that the total amount of the above-mentioned ultraviolet absorber (a) and the dye compound (b) is set as the compounding amount of the above-mentioned compound (A). controlled in a range of ways. The above-mentioned ultraviolet absorber (a) is preferably 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 parts by weight relative to 100 parts by weight of the base polymer (for example, (meth)acrylic polymer) ~3 parts by weight. The above-mentioned pigment compound (b) is preferably about 0.1 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight, more preferably about 0.1 to 5 parts by weight relative to 100 parts by weight of the base polymer (for example, a (meth)acrylic polymer) 0.5 to 3 parts by weight.

<Ultraviolet absorber (a)> The ultraviolet absorber (a) is not particularly limited as long as the number of hydroxyl groups in the molecular structure is 0 to 3, and examples thereof include trisulfur-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers , benzophenone-based ultraviolet absorbers, benzophenone oxide-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, etc., which can be used alone or in combination Use 2 or more. Among these, tris-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are preferred because they have good solubility in monomers used to form the acrylic adhesive composition, and have a wavelength around 380 nm. Since the ultraviolet absorbing ability is high, it is preferably selected from the group consisting of three (3)-based ultraviolet absorbers having two or less hydroxyl groups in one molecule, and benzotriazole-based ultraviolet absorbers having one benzotriazole skeleton in one molecule. At least one ultraviolet absorber in the group formed.

As a tertiary UV absorber having two or less hydroxyl groups in one molecule, specifically, 2,4-bis-[{4-(4-ethylhexyloxy)-4-hydroxyl}- Phenyl]-6-(4-methoxyphenyl)-1,3,5-tris(Tinosorb S, manufactured by BASF), 2,4-bis[2-hydroxy-4-butoxyphenyl ]-6-(2,4-dibutoxyphenyl)-1,3,5-tris(TINUVIN 460, manufactured by BASF), 2-(4,6-bis(2,4-dimethyl) Reaction product of phenyl)-1,3,5-tri(2-yl)-5-hydroxyphenyl and [(C10-C16(mainly C12-C13)alkoxy)methyl]oxirane (TINUVIN400, manufactured by BASF Corporation), 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl]-5-[3-(dodecylphenyl) alkoxy)-2-hydroxypropoxy]phenol), 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3, Reaction product of 5-tris(2-ethylhexyl) glyceride (TINUVIN405, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-tris-2- yl)-5-[(hexyl)oxy]-phenol (TINUVIN1577, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-tris-2-yl)-5-[ 2-(2-ethylhexyloxy)ethoxy]-phenol (ADK STAB LA46, manufactured by ADEKA), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl) -4,6-bis(4-phenylphenyl)-1,3,5-tris(TINUVIN479, manufactured by BASF) and the like.

Moreover, 2-(2H-benzotriazol-2-yl)-6-(1-methyl- 1-Phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVIN 928, manufactured by BASF), 2-(2-hydroxy-5-tert-butylphenyl) )-2H-benzotriazole (TINUVIN PS, manufactured by BASF Corporation), phenylpropionic acid, and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)- 4-Hydroxy (C7-9 side chain and straight-chain alkyl) ester compound (TINUVIN384-2, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1 -Methyl-1-phenylethyl)phenol (TINUVIN900, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl) -4-(1,1,3,3-Tetramethylbutyl)phenol (TINUVIN928, manufactured by BASF), 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl The reaction product of methyl-4-hydroxyphenyl) propionate/polyethylene glycol 300 (TINUVIN1130, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-p-cresol (TINUVIN P , manufactured by BASF Corporation), 2(2H-benzotriazol-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN234, manufactured by BASF Corporation), 2-[ 5-Chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (TINUVIN326, manufactured by BASF), 2-(2H-benzotriazole-2 -yl)-4,6-di-tert-pentylphenol (TINUVIN328, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethyl) butyl)phenol (TINUVIN329, manufactured by BASF Corporation), methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and polymethyl methacrylate The reaction product of ethylene glycol 300 (TINUVIN213, manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (TINUVIN571, manufactured by BASF Corporation), 2-[2-Hydroxy-3-(3,4,5,6-tetrahydrophthalimide-methyl)-5-methylphenyl]benzotriazole (Sumisorb250, Sumitomo Chemical Industry Co., Ltd. Co., Ltd.), etc.

Moreover, as said benzophenone type ultraviolet absorber (benzophenone type compound), benzophenone oxide type ultraviolet absorber (oxybenzophenone type compound), for example: 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4- Dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4-dimethoxybenzophenone, etc.

Moreover, as said salicylate type ultraviolet absorber (salicylate type compound), 3, 5- di-tert-butyl-4-hydroxybenzoic acid 2, 4- di-tert-butyl phenyl ester is mentioned, for example (TINUVIN120, manufactured by BASF Corporation) and the like.

Examples of the cyanoacrylate-based ultraviolet absorber (cyanoacrylate-based compound) include 2-cyanoacrylate alkyl ester, 2-cyanoacrylate cycloalkyl ester, and 2-cyanoacrylate alkoxy group. Alkyl ester, alkenyl 2-cyanoacrylate, alkynyl 2-cyanoacrylate, etc.

It is preferable that the maximum absorption wavelength of the absorption spectrum of the said ultraviolet absorber (a) exists in the wavelength region of 300-400 nm, More preferably, it exists in the wavelength region of 320-380 nm. The measurement method of the maximum absorption wavelength is the same as the measurement method of the pigment-based compound described below.

<Dye compound (b)> The dye compound (b) is not particularly limited as long as the maximum absorption wavelength of the absorption spectrum exists in the wavelength region of 380 to 430 nm, and it is the same as the above-mentioned ultraviolet absorber (a), Preferably, it is a compound having few hydrogen-donating groups such as hydroxyl or phenyl in its molecular structure, or having no hydrogen-donating groups such as hydroxyl or phenyl. Furthermore, when there are plural absorption maxima in the spectral absorption spectrum in the wavelength region of 300 to 460 nm, the so-called maximum absorption wavelength means the absorption maximum wavelength in which the maximum absorbance is exhibited.

More preferably, the maximum absorption wavelength of the absorption spectrum of the dye compound (b) exists in the wavelength region of 380 to 420 nm. Further, the dye compound (b) is not particularly limited as long as it has the above-mentioned wavelength characteristics, but is preferably a material that does not have fluorescence and phosphorescence properties (photoluminescence) as long as it does not inhibit the display properties of the organic EL element.

Moreover, the half-value width of the said dye compound (b) is not specifically limited, Preferably it is 80 nm or less, More preferably, it is 5-70 nm, More preferably, it is 10-60 nm. When the half-value width of the dye compound is in the above-mentioned range, light in a region that does not affect the light emission of the organic EL element can be sufficiently absorbed, and light on the wavelength side longer than 430 nm can be controlled to transmit sufficiently, so it is preferable. . In addition, the method described below is used for the measurement method of the half value width. <Measurement method of half-value width> The half-value width of the dye compound (b) is determined by using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi High-Tech Science Co., Ltd.) under the following conditions according to the solution of the dye compound It was measured by absorbance spectroscopy. According to the spectral spectrum measured by adjusting the concentration so that the absorbance at the maximum absorption wavelength becomes 1.0, the interval between two wavelengths (full width at half maximum) which becomes 50% of the peak value is used as the half width of the dye compound. (Measurement conditions) Solvent: Toluene or chloroform Cell: Quartz cell Optical path length: 10 mm

Examples of the dye compound (b) include organic dye compounds and inorganic dye compounds, and among these, organic dye compounds are preferred from the viewpoint of maintaining dispersibility and transparency in resin components such as base polymers. Pigment compounds.

As said organic-type coloring matter compound, an azomethine type compound, an indole type compound, a cinnamic acid type compound, a pyrimidine type compound, a porphyrin type compound, a cyanine type compound, etc. are mentioned.

As the above-mentioned organic dye compound, a commercially available one can be suitably used. Specifically, as the above-mentioned indole-based compound, BONASORB UA3911 (trade name, maximum absorption wavelength of absorption spectrum: 398 nm, half-value width: 48 nm, Orient Chemical Industries Co., Ltd.), as the cinnamic acid-based compound, SOM-5-0106 (trade name, maximum absorption wavelength of absorption spectrum: 416 nm, half width: 50 nm, manufactured by Orient Chemical Industries Co., Ltd.) ), FDB-001 (trade name, maximum absorption wavelength of absorption spectrum: 420 nm, half width: 14 nm, manufactured by Yamada Chemical Industry Co., Ltd.) as a porphyrin-based compound, and a cyanine-based compound, part of Cyanine compound (trade name: FDB-009, maximum absorption wavelength of absorption spectrum: 394 nm, half-value width: 43 nm, manufactured by Yamada Chemical Industry Co., Ltd.), polymethine compound (trade name: DAA-247, The maximum absorption wavelength of the absorption spectrum: 389 nm, the half-value width: 49.5 nm, manufactured by Yamada Chemical Industry Co., Ltd.), etc., among them, the above-mentioned cyanine series are preferred from the viewpoint of suppression of crosslinking inhibition and optical reliability compounds, especially polymethine compounds.

<Antioxidant> The antioxidant can be formulated in the adhesive composition of the present invention. Antioxidants can prevent obstruction caused by oxygen of free radicals generated by free radical generators, ensure a stable gel fraction (crosslinking degree), and can inhibit the release film (separation film) applied to the adhesive layer. The peeling force increases, and the gel fraction increases.

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

Specific examples of phenolic antioxidants include monocyclic phenol compounds: 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-ethylphenol, -Dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-tert-pentyl-4-methylphenol, 2,6-di-tert-octyl yl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl- 4-ethyl-6-tert-octylphenol, 2-isobutyl-4-ethyl-6-tert-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, benzene Vinylized mixed cresol, DL-α-tocopherol, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid stearyl ester, etc. As the bicyclic phenol compound, 2, 2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 4,4'- Thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2,2'-ethylenebis(4 , 6-di-tert-butylphenol), 2,2'-butylene bis(2-tert-butyl-4-methylphenol), 3,6-dioxa octamethylenebis[3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-thiodieneethylbis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] etc. As the tricyclic phenol compound, 1,1,3-tris(2-methyl-4- Hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, isocyanurate 1,3,5-Tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] urate, tris(4-tert-butyl-2,6 isocyanurate) -Dimethyl-3-hydroxybenzyl) ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, etc., Examples of the tetracyclic phenol compound include tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and examples of the phosphorus-containing phenol compound include: Bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate) calcium, bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate) nickel, etc.

Specific examples of phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tri(tridecyl) phosphite, triisodecyl phosphite, and diisooctyl phenyl phosphite. , Diisodecyl phenyl phosphite, bis(tridecyl) phenyl phosphite, isooctyl diphenyl phosphite, isodecyl diphenyl phosphite, tridecyl diphenyl phosphite ester, triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tertbutylphenyl) phosphite, tris(butoxyethyl) phosphite, tetrakis (Tridecyl)-4,4'-butylene bis(3-methyl-6-tert-butylphenol) diphosphite, 4,4'-isopropylidene biphenol alkyl phosphite (The alkyl group is about 12 to 15 carbon atoms), 4,4'-isopropylidene bis(2-tert-butylphenol), bis(nonylphenyl) phosphite, tris(biphenyl) phosphite base) ester, tetrakis(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tris(3-phosphite) ,5-di-tert-butyl-4-hydroxyphenyl) ester, hydrogenated-4,4'-isopropylidene biphenol polyphosphite, bis(octylphenyl)-bis[4,4'- Butylene bis(3-methyl-6-tert-butylphenol)]-1,6-hexanediol diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl) yl-4-hydroxy-5-tert-butylphenol) diphosphite, tris[4,4'-isopropylidene bis(2-tert-butylphenol)]phosphite, tris(1) phosphite , 3-distearyloxyisopropyl) ester, 9,10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis(2,4-di-tert-butylphenyl)-4, 4'-Biphenylene diphosphite, distearyl pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidene biphenol - Pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Ester and phenyl bisphenol A-pentaerythritol diphosphite, etc.

As the sulfur-based antioxidant, dialkyl thiodipropionate and polyol ester of alkylthiopropionic acid are preferably used. The dialkyl thiodipropionate used here is preferably a dialkyl thiodipropionate having an alkyl group having 6 to 20 carbon atoms, and a polyol which is an alkyl thiopropionic acid The ester is preferably a polyhydric alcohol ester of an alkylthiopropionic acid having an alkyl group having 4 to 20 carbon atoms. In this case, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, trihydroxyethyl isocyanurate, etc. are mentioned as an example of the polyhydric alcohol which comprises a polyhydric alcohol ester. As such a dialkyl thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, etc. are mentioned, for example. On the other hand, examples of polyhydric alcohol esters of alkyl thiopropionic acid include glycerol tributyl thiopropionate, glycerol trioctyl thiopropionate, glycerol trilauryl thiopropionate, Glycerol tristearyl thiopropionate, trimethylolethane tributyl thiopropionate, trimethylolethane trioctyl thiopropionate, trimethylolethane trilauryl Thiopropionate, Trimethylolethane Tristearylthiopropionate, Pentaerythritol Tetrabutylthiopropionate, Pentaerythritol Tetraoctylthiopropionate, Pentaerythritol Tetralaurylthiopropionate ester, pentaerythritol tetrastearyl thiopropionate, etc.

Specific examples of amine-based antioxidants include bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, dimethyl succinate, and 1-(2-hydroxyl Ethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine ethanol polycondensate, N,N',N'',N'''-tetra(4,6-bis-( Butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-tris-2-yl)-4,7-diazadecane-1 ,10-Diamine, dibutylamine-1,3,5-tris𠯤-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexa) Polycondensate of methylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, poly[{6-(1,1,3,3-tetra Methylbutyl)amino-1,3,5-tris-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene Methyl{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1 , 2,3,4-butane tetracarboxylate, 2,2,6,6-tetramethyl-4-piperidinylbenzoate, bis(1,2,6,6-pentamethyl- 4-Piperidinyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate, bis(N-methyl-2,2,6, 6-Tetramethyl-4-piperidinyl)sebacate, 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperidinone), (Mixed 2,2,6,6-Tetramethyl-4-piperidinyl/tridecyl)-1,2,3,4-butanetetracarboxylate, (Mixed 1,2,2,6 ,6-Pentamethyl-4-piperidinyl/tridecyl)-1,2,3,4-butanetetracarboxylate, mixed [2,2,6,6-tetramethyl-4- Piperidinyl/β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl]-1 ,2,3,4-Butane tetracarboxylate, mixed [1,2,2,6,6-pentamethyl-4-piperidinyl/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-piperidinyl) Amino]-6-chloro-1,3,5-tris𠯤 condensate, poly[6-N-𠰌olinyl-1,3,5-tris𠯤-2,4-diyl][(2,2 ,6,6-Tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imide], N, The condensate of N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 1,2-dibromoethane, [N-(2,2, 6,6-Tetramethyl-4-piperidinyl)-2-methyl-2-(2,2,6,6 -Tetramethyl-4-piperidinyl)imino]propionamide, etc.

The content of the antioxidant in the adhesive composition of the present invention is determined from the viewpoint of preventing the discoloration of the coloring matter caused by the above-mentioned radical generator. Usually, it is preferable to make content of antioxidant in 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 the content of the above-mentioned antioxidant increases, the ratio of capturing the radicals generated by the radical generator increases. As a result, the crosslinking inhibition of the adhesive layer formed from the above-mentioned adhesive composition tends to be easily caused, and the gel fraction of the adhesive layer is lowered, which tends to cause poor appearance. From this viewpoint, the content of the antioxidant is preferably within a range of 5 parts by weight or less, more preferably within a range of 1.5 parts by weight or less, relative to 100 parts by weight of the (meth)acrylic polymer. From the viewpoint of both securing the above-mentioned gel fraction and preventing the discoloration of the pigment, the content of the above-mentioned antioxidant is preferably 0.05 to 1.5 parts by weight relative to 100 parts by weight of the base polymer (for example, a (meth)acrylic polymer). Part by weight, more preferably 0.1 to 1.0 part by weight, still more preferably 0.3 to 0.8 part by weight.

<Crosslinking agent> Furthermore, the adhesive composition of this invention may contain a crosslinking agent (except the said radical generator). In the present invention, when an isocyanate-based cross-linking agent is used in combination as a cross-linking agent, the antioxidant can effectively suppress the hindrance of free radical cross-linking caused by oxygen, and the isocyanate-based cross-linking agent can efficiently form adhesion. The three-dimensional cross-linked network structure of the agent layer. As a result, it is possible to further effectively prevent the occurrence of abnormal appearance at the ends of the polarizing film.

As cross-linking agents, there are isocyanate-based cross-linking agents, epoxy-based cross-linking agents, polysiloxane-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, silane-based cross-linking agents, and alkane-based cross-linking agents. It is a cross-linking agent of etherified melamine-based cross-linking agent and metal chelate-based cross-linking agent. A crosslinking agent may be used individually by 1 type, or may be used in combination of 2 or more types. Among these, an isocyanate-based crosslinking agent can be preferably used.

The above-mentioned cross-linking agent may be used alone or in combination of two or more, and the content as a whole is preferably 5 parts by weight relative to 100 parts by weight of the base polymer (for example, (meth)acrylic polymer) part or less, more preferably 0.01 to 5 parts by weight, still more preferably 0.01 to 4 parts by weight, particularly preferably 0.02 to 3 parts by weight.

The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups in one molecule (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by blocking agents, multimerization, or the like). Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, etc. Family of isocyanates; 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate and other aromatic diisocyanates; trimethylol Propane/toluene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), isocyanurate body of hexamethylene diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and other isocyanate adducts; xylylene diisocyanate Trimethylolpropane adduct of isocyanate (trade name: D110N, manufactured by Mitsui Chemicals Co., Ltd.), trimethylolpropane adduct of hexamethylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals Co., Ltd.) manufacture); polyether polyisocyanates, polyester polyisocyanates, and adducts of these with various polyols; multifunctionalization by isocyanurate linkages, biuret linkages, allophanate linkages, etc. of polyisocyanates, etc.

Furthermore, a silane coupling agent may be contained in the adhesive composition of this invention. The compounding amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, and still more preferably 0.02 with respect to 100 parts by weight of the monofunctional monomer component that forms the (meth)acrylic polymer. ~0.6 parts by weight.

As said silane coupling agent, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldisilane, for example Ethoxysilane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane and other epoxy-containing silane coupling agents; 3-aminopropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N -Phenyl-γ-aminopropyltrimethoxysilane and other amine-containing silane coupling agents; 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethyl Silane coupling agents containing (meth)acrylic groups such as oxysilyl; silane coupling agents containing isocyanate groups such as 3-isocyanatopropyltriethoxysilyl, etc.

In addition to the above-mentioned components, appropriate additives may be contained in the adhesive composition of the present invention according to the application. Examples include: adhesion-imparting agents (for example, those containing rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenolic resins, and the like that are solid, semi-solid, or liquid at room temperature); filling of hollow glass balloons, etc. plasticizer; anti-aging agent; light stabilizer (HALS (Hindered Amine Light Stabilizer, hindered amine light stabilizer)); antioxidant, etc.

2. Adhesive layer for organic EL display device The adhesive layer for organic EL display device of the present invention is characterized in that it is formed from the above-mentioned adhesive composition for organic EL display device.

It does not specifically limit as a formation method of an adhesive bond layer, It can form by the method normally used in this field. Specifically, the above-mentioned adhesive composition can be applied to at least one side of the substrate, and the coating film formed of the adhesive composition can be dried to form, or can be formed by irradiating active energy rays such as ultraviolet rays.

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

Examples of the constituent material of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films; porous materials such as paper, cloth, and non-woven fabrics; A resin film can be suitably used at the point which is excellent in surface smoothness as a foam sheet, a metal foil, and suitable sheet bodies, such as a laminated body of these, etc..

Examples of the resin film include polyethylene films, polypropylene films, polybutene films, polybutadiene films, polymethylpentene films, polyvinyl chloride films, vinyl chloride copolymer films, and polyterephthalene Ethylene formate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

The thickness of the above-mentioned mold release film is usually 5 to 200 μm, preferably about 5 to 100 μm. The above-mentioned mold release film can also be subjected to mold release and antifouling treatment or coating type using polysiloxane-based, fluorine-based, long-chain alkyl-based or aliphatic amide-based mold release agents, silica powder, etc. Antistatic treatment such as kneading type and vapor deposition type. In particular, the peelability from the adhesive layer can be further improved by appropriately performing peeling treatments such as polysiloxane treatment, long-chain alkyl treatment, and fluorine treatment on the surface of the mold release film.

It does not specifically limit as said transparent resin film base material, Various resin films which have transparency can be used. The resin film is formed of one layer of film. For example, examples of the material include polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate; acetate-based resins, polyether-based resins, polycarbonate-based resins, and polyester-based resins. Amide resin, polyimide resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin , Polyarylate resin, polyphenylene sulfide resin, etc. Among these, polyester-based resins, polyimide-based resins, and polyether-based resins are particularly preferred.

The thickness of the film substrate is preferably 15-200 μm, more preferably 25-188 μm.

The method of coating the above-mentioned adhesive composition on the above-mentioned substrate may use roll coating, contact roll coating, gravure coating, reverse coating, roll brush coating, spray coating, dip roll coating, bar coating There are no particular limitations on known appropriate methods such as cloth coating, blade coating, air knife coating, curtain coating, die lip coating, and die nozzle coating.

When the above-mentioned adhesive layer is formed by drying the coating film formed from the above-mentioned adhesive composition, the drying conditions (temperature, time) are not particularly limited, and may be appropriately selected according to the composition, concentration, etc. of the adhesive composition. The setting is, for example, about 60 to 170° C., preferably 60 to 150° C. for 1 to 60 minutes, preferably 2 to 30 minutes. In addition, when the said adhesive composition is an ultraviolet curable adhesive composition, an ultraviolet-ray can be irradiated to a coating film, and an adhesive layer can be formed.

The thickness of the adhesive layer is preferably 5 μm or more, more preferably 50 μm or more, more preferably 100 μm or more, and particularly preferably 150 μm or more, from the viewpoint of securing the function of absorbing light with a wavelength of less than 430 nm. . The upper limit of the thickness of the adhesive layer is not particularly limited, but is preferably 1 mm or less. If the thickness of the adhesive layer exceeds 1 mm, it will be difficult to transmit ultraviolet rays, and the polymerization of the monomer components will take time, and there will be problems in processability, coiling and conveying in steps, and productivity will deteriorate. The situation is therefore not good.

The gel fraction of the adhesive layer of the present invention is not particularly limited, but is preferably 40% or more, more preferably 60% or more, still more preferably 75% or more, particularly preferably 85% or more. When the gel fraction of the adhesive layer is small, the cohesive force may be poor, and there may be problems in processability or workability. In addition, the gel fraction immediately after the adhesive layer is formed by heating and drying the coating film of the adhesive composition or irradiating ultraviolet rays is preferably 60% or more from the viewpoint of preventing abnormal appearance such as paste dents , more preferably 63% or more, still more preferably 66% or more, particularly preferably 70% or more.

The above-mentioned adhesive layer preferably has a haze value measured at a thickness of 25 μm below 2%, more preferably 0-1.5%, and still more preferably 0-1%. When the haze is in the above range, the adhesive layer has high transparency, which is preferable.

The average transmittance of the above-mentioned adhesive layer at a wavelength of 300 to 400 nm is preferably 12% or less, more preferably 5% or less, and more preferably 2% or less. If the transmittance of the adhesive layer is in the above-mentioned range, light in a region that does not affect the light emission of the organic EL element can be sufficiently absorbed, and the deterioration of the organic EL element can be suppressed.

The average transmittance of the above-mentioned adhesive layer with a wavelength of 430 to 450 nm is preferably 70% or more, more preferably 75% or more, and the average transmittance of a wavelength of 500 to 780 nm is preferably 80% or more, more preferably 85% or more . If the transmittance of the adhesive layer is in the above range, light can be sufficiently transmitted in the light-emitting region of the organic EL element (the wavelength side longer than 430 nm), and the organic EL display device using the adhesive layer can sufficiently emit light.

In addition, the average transmittance of the above-mentioned adhesive layer having a wavelength of 400 to 430 nm or less can be designed according to the characteristics required for the organic EL display device. 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 deterioration of the organic EL element and protecting it, the average transmittance of the above-mentioned adhesive layer at a wavelength of 400 to 430 nm or less Preferably it is 30% or less, More preferably, it is 20% or less. On the other hand, from the viewpoint of protecting the organic EL element from damage by ultraviolet light and suppressing the coloring of the organic EL element, the average transmittance of the above-mentioned adhesive layer having a wavelength of 400 to 430 nm or less is preferably more than 30% and 95%. % or less, more preferably more than 50% and 90% or less.

Here, the above-mentioned "average transmittance at a wavelength of 300 to 400 nm" refers to the mean value of the transmittance obtained by measuring the transmittance at a 1 nm pitch in the region with a wavelength of 300 to 400 nm. The average transmittance in other wavelength regions is also the same.

By having the above-mentioned transmittance, the adhesive layer of the present invention can sufficiently absorb light in a region that does not affect the light emission of the organic EL element, and the light emitting region (the wavelength side longer than 430 nm) of the organic EL element is It is possible to sufficiently transmit and suppress the deterioration of the organic EL element due to external light.

When the above-mentioned adhesive layer is exposed, the adhesive layer can be protected by a release film before being put into practical use.

3. Polarizing film with adhesive layer for organic EL display devices The polarizing film with adhesive layer for organic EL display devices of the present invention is characterized by having a polarizing film and the above-mentioned adhesive layer for organic EL display devices.

As the adhesive layer for an organic EL display device, the ones described above can be suitably used. Moreover, when the adhesive layer is formed on a base material other than the polarizing film, the adhesive layer can be attached to the polarizing film and transferred. In addition, the above-mentioned mold release film can be directly used as a release film of the polarizing film with the adhesive layer, which can be simplified in terms of steps.

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

(1) Polarizing element The polarizing element is not particularly limited, and various ones can be used. Examples of polarizers include a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, an ethylene-vinyl acetate copolymer-based partially saponified film, etc. The hydrophilic polymer film is uniaxially stretched; polyene-based alignment films such as dehydration-treated products of polyvinyl alcohol or dehydrochlorination-treated products of polyvinyl chloride, etc. Among these, a polarizing element containing a dichroic substance such as a polyvinyl alcohol-based film and iodine is suitable. The thickness of these polarizers is not particularly limited, and is usually about 5 to 80 μm.

A polarizing element obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially extending it can be produced by, for example, immersing polyvinyl alcohol in an aqueous solution of iodine for dyeing and extending to 3 to 7 times its original length. It can also be immersed in an aqueous solution such as potassium iodide, etc., which may contain boric acid, zinc sulfate, zinc chloride, etc., as required. Furthermore, the polyvinyl alcohol-type film may be immersed in water and washed with water before dyeing as needed. By washing the polyvinyl alcohol-based film with water, the dirt and anti-blocking agent on the surface of the polyvinyl alcohol-based film can be washed away. Even effect. The stretching can be carried out after dyeing with iodine, or it can be stretched while dyeing, or it can be dyed with iodine after stretching. The extension can also be performed in an aqueous solution or a water bath of boric acid or potassium iodide.

In addition, in the present invention, a thin polarizer having a thickness of 10 μm or less can also be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizing element has less thickness unevenness, excellent visibility, and less dimensional change, so it is excellent in durability, and the thickness of the polarizing film can be reduced in thickness, which is preferable.

Typical examples of thin polarizers include Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, and International Publication No. 2010/100917 The thin polarizing film described in the specification, or the specification of Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563. These thin polarizing films can be obtained by a production method including a step of stretching a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a resin substrate for stretching in a laminate state and a step of dyeing. According to this production method, even if the PVA-based resin layer is thin, it can be stretched by being supported by the resin base material for stretching, and there is no abnormality such as fracture caused by stretching.

As the above-mentioned thin polarizing film, in the production method including the step of stretching in the state of a laminate and the step of dyeing, in terms of being able to stretch at a high magnification and improving the polarizing performance, it is preferably as described in International Publication No. 2010/100917 No. , International Publication No. 2010/100917, or Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563, which are obtained by the production method including the step of extending in a boric acid aqueous solution, preferably It is obtained by the production method including the step of performing auxiliary in-air stretching before stretching in a boric acid aqueous solution as described in the specification of Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563.

(2) Transparent protective film As for the transparent protective film, those that have been used from the past can be appropriately used. Specifically, it is preferably a transparent protective film formed of a material excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc., for example, polyethylene terephthalate or Polyester polymers such as polyethylene naphthalate; cellulose polymers such as diacetyl cellulose or triacetate cellulose; acrylic polymers such as polymethyl methacrylate; polystyrene or acrylonitrile - Styrene-based polymers such as styrene copolymers (AS resins); polycarbonate-based polymers and the like. In addition, examples of the polymer forming the above-mentioned transparent protective film include polyethylene, polypropylene, cyclic or polyolefin having a norethylene structure, polyolefin-based polymers such as ethylene-propylene copolymers, vinyl chloride amide-based polymers, amide-based polymers such as nylon and aromatic polyamides, amide-based polymers, sulfite-series polymers, polyether-series polymers, polyether ether ketone-series polymers, polyphenylene sulfide-series polymers polymers, vinyl alcohol-based polymers, vinylidene chloride-based polymers, vinyl butyral-based polymers, arylate-based polymers, polyoxymethylene-based polymers, epoxy-based polymers, or blends of the foregoing polymers Wait. The transparent protective film can also be formed as a cured layer of thermosetting and ultraviolet curing resins such as acrylic, urethane, acrylic urethane, epoxy, and polysiloxane.

The thickness of the transparent protective film can be appropriately determined, but is usually about 1 to 500 μm in terms of strength, workability such as handling properties, and film properties.

It is preferable that the said polarizing element and a transparent protective film are closely_contact|adhered via an aqueous adhesive agent etc.. Examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based adhesives, water-based polyurethanes, and water-based polyesters. In addition to the above, as the adhesive between the polarizing element and the transparent protective film, an ultraviolet curable adhesive, an electron beam curable adhesive, and the like are exemplified. The adhesive for electron beam curable polarizing films exhibits suitable adhesiveness to the above-mentioned various types of transparent protective films on the viewing side. Moreover, a metal compound filler may be contained in the adhesive agent used for this invention.

The surface of the above-mentioned transparent protective film that is not attached to the polarizing element may be subjected to a hard coat layer, anti-reflection treatment, anti-sticking, or treatment for the purpose of diffusion or anti-glare.

Moreover, as the said transparent protective film, any one which has a retardation and can function as an optical compensation layer can be used. In the case of using a transparent protective film with retardation, the retardation characteristic can be appropriately adjusted to a value necessary for optical compensation. As this retardation film, a stretched film can be suitably used. The above retardation film can be selected and used in the case where the refractive index in the slow axis direction is nx, the refractive index in the in-plane advancing axis direction is ny, and the refractive index in the thickness direction is nz, depending on various applications. , which satisfies the relationships of nx=ny>nz, nx>ny>nz, nx>ny=nz, nx>nz>ny, nz=nx>ny, nz>nx>ny, and nz>nx=ny. Furthermore, the so-called nx=ny includes not only the case where nx and ny are completely the same, but also the case where nx and ny are substantially the same. Furthermore, the so-called ny=nz includes not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.

When the polarizing film used in the present invention is used as a circular polarizing plate for anti-reflection of an organic EL display device, the retardation film is preferably set so that the front retardation of the transparent protective film is set to 1/4 wavelength (about 100 ~170 nm) 1/4 wavelength plate.

In the case of using a retardation film as a transparent protective film, a transparent protective film provided on one side of the polarizing element and a retardation film on the other side can be suitably used. Also, in this case, the location where the adhesive layer is provided is not particularly limited, and it can be provided on the opposite side of the transparent protective film and the surface in contact with the polarizer, or on the surface of the retardation film and the polarizer. The surface in contact with the polarizing element is the surface on the opposite side, and from the viewpoint of suppressing deterioration of the organic EL element, it is preferably provided on at least one surface or on both surfaces.

An example of the specific structure of the polarizing film with the adhesive layer for organic EL display devices of this invention is shown in FIG.1(a)-(c). The polarizing film 1 with the adhesive layer for organic EL display devices, which is formed by laminating each layer in sequence as follows: As shown in FIG. 1( a ), adhesive layer 2 / transparent protective film 3 / polarizing element 4 / phase Difference film 5; as shown in Figure 1(b), transparent protective film 3/polarizing element 4/retardation film 5/adhesive layer 2; as shown in Figure 1(c), adhesive layer 2/transparent protective film 3 /polarizing element 4 /retardation film 5 /adhesive layer 2 . In the above-mentioned FIGS. 1( a ) and ( b ), the adhesive layer 2 is the adhesive layer for an organic EL display device of the present invention, and in FIG. 1( c ), at least one of the two adhesive layers 2 exists. The layer may be the adhesive layer for the organic EL display device of the present invention, and both layers may be the adhesive layer for the organic EL display device of the present invention. In addition, in FIG. 1 , the polarizing film 6 is a one-side protective polarizing film including the polarizing element 4 and the transparent protective film 3 , but it is not limited to this, and there may be a transparent film between the polarizing element 4 and the retardation film 5 . The double-sided protective polarizing film of the protective film. Moreover, as mentioned above, various functional layers, such as a hard-coat layer, etc. may be formed in the surface of the transparent protective film 3 which is not in contact with the polarizing element 4.

Moreover, when the said retardation film is laminated|stacked on a polarizing element via an adhesive layer, this adhesive layer can be the adhesive layer for organic EL display devices of this invention. That is, the polarizing film with the adhesive layer for an organic EL display device has a first adhesive layer, a transparent protective film, a polarizing element, a second adhesive layer, a retardation film, and a third adhesive layer in this order, and the above-mentioned At least one of the adhesive layer, the second adhesive layer, and the third adhesive layer may be the above-mentioned adhesive layer for an organic EL display device.

4. Organic EL Display Device The organic EL display device of the present invention is characterized by using at least one of the adhesive layer for an organic EL display device of the present invention and/or the polarizing film with the adhesive layer for an organic EL display device of the present invention By.

As an example of a specific structure of an organic EL display device, for example, an organic EL display device in which each layer is sequentially laminated as follows: As shown in FIGS. 2 to 4 , a cover glass or a cover plastic 7 / an adhesive layer 2 / transparent protective film 3 / polarizing element 4 / retardation film 5 / adhesive layer 2 / organic EL display panel (OLED element panel) 8 (Figure 2); cover glass or cover plastic 7 / adhesive layer 9 / transparent protective film 3/polarizing element 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/polarizing element 4/retardation film 5/adhesive layer 2/organic EL display panel 8 (FIG. 4). At least one of the adhesive layers 2 in the above-mentioned structures may be the adhesive layer of the present invention, and all the adhesive layers 2 may be the adhesive layers of the present invention. Moreover, the organic EL display device of this invention may contain various functional layers, such as a protective film and a hard-coat layer, in addition to the above. Moreover, in the lamination|stacking of each layer, an adhesive layer and/or an adhesive layer can be used suitably. As the adhesive layer other than the adhesive layer of the present invention, an ordinary adhesive layer used in the art can be appropriately used. [Example]

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the parts and % in each example are based on 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). Mw/Mn is also measured in the same manner.・Analysis device: HLC-8120GPC manufactured by Tosoh Corporation ・Column: G7000HXL+GMHXL+GMHXL manufactured by Tosoh Corporation ・Column size: 7.8 mmf x 30 cm each, 90 cm in total ・Column temperature: 40°C ・Flow rate: 0.8 mL/min ・Injection volume: 100 μL ・Eluent: Tetrahydrofuran ・Detector: Differential refractometer (RI (Refractive Index)) ・Standard sample: Polystyrene

<Preparation of (meth)acrylic polymer (1)> Into a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device, 99 parts of butyl acrylate (BA) and 4-hydroxybutyl acrylate were charged (HBA) 1 part monomer mixture. Furthermore, 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator and 100 parts of ethyl acetate were added together with respect to 100 parts of the above-mentioned monomer mixture, and nitrogen gas was introduced while stirring slowly for nitrogen replacement. Then, the liquid temperature in the flask was maintained at around 55°C, and a polymerization reaction was carried out for 8 hours to prepare a solution of an acrylic polymer with a weight average molecular weight (Mw) of 1.8 million and Mw/Mn=4.1 (solid content concentration: 30 wt. %).

<Preparation of (meth)acrylic polymer (2)> Into a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirring device, 94.8 parts of butyl acrylate (BA), 5 parts of acrylic acid (AA), And the monomer mixture of 2-hydroxyethyl acrylate (HEA) 0.2 part. Furthermore, with respect to 100 parts of the above-mentioned monomer mixture, 0.3 part of benzyl peroxide (trade name Nyper BMT, manufactured by NOF Corporation) as a polymerization initiator was added together with 100 parts of ethyl acetate, while stirring slowly After nitrogen replacement was carried out by introducing nitrogen, the liquid temperature in the flask was maintained at around 55°C and a polymerization reaction was carried out for 8 hours to prepare a solution (solid state) of acrylic polymer with a weight average molecular weight (Mw) of 2.2 million and Mw/Mn=4.1. material component concentration 30% by weight).

<Preparation of (meth)acrylic polymer (3)> Into a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device, 73.3 parts of butyl acrylate (BA) and phenoxyethyl acrylate ( A monomer mixture of 21 parts of PEA), 5 parts of N-vinylpyrrolidone (NVP), 0.3 part of acrylic acid (AA) and 0.4 part of 4-hydroxybutyl acrylate (HBA). Furthermore, 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator and 100 parts of ethyl acetate were added together with respect to 100 parts of the above-mentioned monomer mixture (solid content), and the mixture was slowly stirred. After nitrogen replacement was carried out by introducing nitrogen, the liquid temperature in the flask was maintained at around 55°C and a polymerization reaction was carried out for 8 hours to prepare a solution (solid state) of an acrylic polymer with a weight average molecular weight (Mw) of 1.6 million and Mw/Mn=3.8. material component concentration 28% by weight).

Example 1 (Preparation of adhesive composition) With respect to 100 parts of solid content of the solution of the acrylic polymer (1) produced above, a radical generator (benzyl peroxide, manufactured by NOF Corporation) was prepared. 0.3 part of trade name Nyper BMT), 0.1 part of isocyanate-based crosslinking agent (trade name Takenate D110N manufactured by Mitsui Chemicals), 2,4-bis-[{4-(4-ethyl) as ultraviolet absorber (a) Hexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-tris(trade name: Tinosorb S, manufactured by BASF Corporation) 2 parts, and silane 0.1 part of a coupling agent (KBM403 by Shin-Etsu Chemical Co., Ltd.) was used to obtain an adhesive composition.

(Fabrication of the adhesive layer) The above-mentioned adhesive composition was coated on a release film with a thickness of 38 μm (polyethylene terephthalate-based film with surface peeling treatment: peeling off) so that the thickness after drying was 20 μm On the mold film), the solvent was removed by drying at 155° C. for 1 minute to obtain an adhesive layer (A).

Immediately after the above-mentioned adhesive layer (A) is formed, the release film formed with the above-mentioned adhesive layer (A) is transferred to a film having a cycloolefin polymer film/polarizer/acrylic resin film/adhesive layer (B)/retardation The composition of the film is the polarizing film of the retardation film, and the polarizing film of the adhesive layer is produced. The obtained polarizing film with an adhesive layer was composed of a cycloolefin polymer film/polarizing element/acrylic resin film/adhesive layer (B)/retardation film/adhesive layer (A).

Furthermore, the cycloolefin polymer film and the acrylic resin film on both sides of the polarizing element are bonded together using a polyvinyl alcohol-based adhesive to obtain a polarizing film. When producing the polarizing film with the adhesive layer of the retardation film, the polarizing film and the retardation film are bonded together through the adhesive layer (B).

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

(Cycloolefin polymer film) A cycloolefin polymer film (trade name ZEONOR film, manufactured by Zeon Co., Ltd.) having a thickness of 25 μm was used.

(Manufacture of polarizing element) A polarizing element including a 5 μm-thick stretched polyvinyl alcohol film impregnated with iodine was used. The single transmittance Y value of the polarizing element (or the polarizing film attached with the protective film) is 42.4%, and the polarization degree is 99.995.

(Acrylic resin film) 100 weight of resin containing imide MS (Methyl Methacrylate-Styrene Copolymer, methyl methacrylate-styrene copolymer) described in Production Example 1 of Japanese Patent Laid-Open No. 2010-284840 Part of the resin pellets were dried at 100.5 kPa and 100°C for 12 hours, and extruded from a T die by a uniaxial extruder at a die temperature of 270°C to form a film (thickness 80 μm). Further, the film was stretched (thickness: 40 μm) in an environment of 150° C. along its conveying direction, and then stretched in an environment of 150° C. in a direction orthogonal to the film conveying direction to obtain an acrylic resin film having a thickness of 20 μm .

(Retardation film) A polycarbonate film with a thickness of 56 μm (“NRF” manufactured by Nitto Denko Co., Ltd., in-plane retardation Re(550): 135 nm) was used.

(Preparation of the adhesive composition for forming the adhesive layer (B)) Into a separable flask equipped with a thermometer, a stirrer, a reflux cooling tube, and a nitrogen gas introduction tube, 95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were added as polymerization After 0.2 parts by weight of azobisisobutyronitrile and 233 parts by weight of ethyl acetate as the starting agent, nitrogen gas was circulated, and nitrogen substitution was performed for about 1 hour while stirring. Then, the flask was heated at 60 degreeC, and it was made to react for 7 hours, and the acrylic polymer of the weight average molecular weight (Mw) 1,100,000 was obtained. Trimethylolpropane toluene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent was added to the above-mentioned acrylic polymer solution (solid content was 100 parts by weight). 0.8 parts by weight and 0.1 part by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) were used to prepare an adhesive composition (solution).

(Manufacture of the adhesive layer (B)) The above-mentioned adhesive composition (solution) was coated on a release film (polyethylene terephthalate with peeling-treated surface) having a thickness of 38 μm so that the thickness after drying was 15 μm. On the diester-based film: release film), the solvent was removed by drying at 100° C. for 3 minutes to obtain an adhesive layer (B).

Examples 2 to 13, Comparative Examples 1 to 3 In Example 1, when preparing the adhesive composition, the type of (meth)acrylic polymer, the type of cross-linking agent or the preparation were changed as shown in Table 1. An adhesive layer was formed in the same manner as in Example 1, except for the amount, the type or compounding amount of the ultraviolet absorber, the type or compounding amount of the pigment compound, and the compounding amount of the antioxidant. Moreover, it carried out similarly to Example 1, and produced the polarizing film with an adhesive bond layer.

The following evaluations were performed on the adhesive layer (A) and the polarizing film to which the adhesive layer was adhered obtained in the above-mentioned Examples and Comparative Examples. The evaluation results are shown in Table 1.

<Measurement of the transmittance of the adhesive layer> The separator was peeled off from the adhesive layer (A) obtained in the Examples and Comparative Examples, and the adhesive layer (A) was mounted on a measuring jig. Product name: U4100, manufactured by Hitachi High-Technologies Co., Ltd.) for measurement. The transmittance is the transmittance within the wavelength range of 300 nm to 450 nm. The average transmittances of wavelengths 300 nm to 400 nm, wavelengths 400 nm to 430 nm, and wavelengths 430 nm to 450 nm are shown in Table 1.

<Measurement of gel fraction> As for the gel fraction, 0.2 g of the above-mentioned adhesive layer (A) was taken and wrapped in a fluororesin (TEMISH NTF-1122 manufactured by Nitto Denko Co., Ltd.) (Wa) whose weight was measured in advance. , bind it so that no adhesive leaks out, measure the weight (Wb), and put it into a sample bottle. Ethyl acetate 40 cc was added and left for 7 days. Then, the fluororesin was taken out, dried on an aluminum cup at 130° C. for 2 hours, the weight (Wc) of the fluororesin including the sample was measured, and the gel fraction was determined according to the following formula (I). Formula (I): gel fraction=(Wc-Wa)/(Wb-Wa)×100(wt%) The gel fraction is measured immediately after the adhesive layer (A) is formed (within 4 hours), After forming the adhesive layer (A), it was left to stand at room temperature (23° C.) for 1 week.

<Appearance Yield> The obtained polarizing film with the adhesive layer was punched out into a square with a length of 270 mm on one side, and the paste dents and edge dents of the adhesive layer (A) were evaluated according to the following criteria. Paste defects, paste stains on the ends. ○・・・No problem. Δ・・・There are local defects in appearance caused by paste defects, paste stains, and paste dents. ×・・・Defects in appearance caused by paste defects, paste stains, and paste dents are conspicuous.

<Durability> The separator was peeled from the obtained polarizing film with the adhesive layer (290 mm in length x 220 mm in width), and the adhesive layer (A) side was attached to a thickness of 0.7 mm so as to be in a crossed polarized state. Both sides of an alkali-free glass plate of mm. Next, the autoclave treatment was performed at 50° C. and 5 atm for 15 minutes to completely adhere to each other, and a sample was prepared. After each of the samples was treated under the condition of 85 for 500 hours, the states of foaming, peeling, and swelling were visually observed according to the following criteria. ○・・・No foaming, peeling, swelling, etc. Δ・・・ is a grade that has no practical problems, but the grade is slightly worse visually. ×・・・There are practical problems.

<Peeling force> A film piece having a length of 100 mm and a width of 50 mm was cut out from the obtained polarizing film with the adhesive layer, and used as a sample. The obtained sample was subjected to a tensile test in an environment of 23°C and 50% R.H. in accordance with JIS Z0237 using a tensile tester (device name: Auto Stereograph AG-IS, manufactured by Shimadzu Corporation). The release film was peeled off from the sample under the conditions of a speed of 300 mm/min and a peeling angle of 180°, and the 180° peeling force (N/50 mm) was measured.

The peeling force of the above-mentioned separator is preferably 0.02 to 1.0 (N/50 mm). It is preferable that the peeling force of the separator is 0.02 (N/50 mm) or more in order to suppress abnormal appearance caused by the bulge of the separator during processing or handling. On the other hand, it is preferable that the peeling force of the separator is 1.0 (N/50 mm) or less in order to suppress the peeling defect of the separator. The peeling force of the separator is more preferably 0.04 to 0.5 (N/50 mm), more preferably 0.06 to 0.2 (N/50 mm), and still more preferably 0.08 to 0.15 (N/50 mm).

[Table 1]

In Table 1, the radical generator means benzyl peroxide (trade name Nyper BMT manufactured by NOF Corporation); D110N means an isocyanate-based crosslinking agent (trade name Takenate D110N manufactured by Mitsui Chemicals); C/L means isocyanate It is a cross-linking agent (trade name Coronate L, manufactured by Tosoh Corporation); a1 of the ultraviolet absorber represents 2,4-bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]- 6-(4-Methoxyphenyl)-1,3,5-tris(trade name: Tinosorb S, manufactured by BASF); a2 of the ultraviolet absorber represents 2,2',4,4'-tetrahydroxyl Benzophenone (trade name: SeeSorb106, manufactured by Shipro Kasei Co., Ltd.); b1 of the pigment compound represents a merocyanine-based compound (trade name: FDB-009, maximum absorption wavelength of absorption spectrum: 394 nm, half-value width: 43 nm) , manufactured by Yamada Chemical Industry Co., Ltd.); b2 of the pigment compound represents a polymethine compound (trade name: DAA-247, maximum absorption wavelength of absorption spectrum: 389 nm, half-value width: 49.5 nm, Yamada Chemical Industry Co., Ltd. B3 of the pigment compound represents an alkyl phenyl indole cyanoacrylate derivative (indole compound) (trade name: BONASORB UA3912, the maximum absorption wavelength of the absorption spectrum: 386 nm, the half-value width: 53 nm, manufactured by Orient Chemical Industries Co., Ltd.); Antioxidant means a phenolic antioxidant (trade name IRGANOX 1010 manufactured by BASF Japan).

1‧‧‧Polarizing Film with Adhesive Layer for Organic EL Display Device 2‧‧‧Adhesive Layer 3‧‧‧Transparent Protective Film 4‧‧‧Polarizing Element 5‧‧‧Retardation Film 6‧‧‧Polarizing Film 7 ‧‧‧Cover glass or cover plastic 8‧‧‧Organic EL panel 9‧‧‧Adhesive layer 10‧‧‧Sensor layer

FIGS. 1( a ) to ( c ) are cross-sectional views schematically showing one embodiment of the polarizing film with the adhesive layer for organic EL display devices of the present invention. FIG. 2 is a cross-sectional view schematically showing an 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. FIG. 4 is a cross-sectional view schematically showing an embodiment of the organic EL display device of the present invention.

1‧‧‧Polarizing film with adhesive layer for organic EL display device

2‧‧‧Adhesive layer

3‧‧‧Transparent protective film

4‧‧‧Polarizing element

5‧‧‧Retardation film

6‧‧‧Polarizing film

Claims (15)

An adhesive composition for an organic EL display device, characterized in that it contains: a base polymer, a free radical generator, and a compound (A), wherein the compound (A) is selected from 0 to 3 hydroxyl groups in the molecular structure At least one of the ultraviolet absorber (a) and the pigment compound (b) whose maximum absorption wavelength of the absorption spectrum exists in the wavelength region of 380 to 430 nm, the above-mentioned base polymer is a (meth)acrylic polymer, and the above-mentioned ultraviolet absorber (a) is selected from three

UV absorbers, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, benzophenone oxide-based UV absorbers, salicylate-based UV absorbers, and cyanoacrylate-based UV absorbers One or more kinds of ultraviolet absorbers in the group consisting of the above-mentioned pigment compounds (b) are selected from the group consisting of methimine-based compounds, indole-based compounds, cinnamic acid-based compounds, pyrimidine-based compounds, porphyrin-based compounds, and 0.01-2 weight part of the said radical generator is contained in the said adhesive agent composition with respect to 100 weight part of said base polymers with respect to 1 or more types of pigment compounds in the group consisting of cyanine compounds. The adhesive composition for organic EL display devices according to claim 1, wherein the compound (A) contains both the ultraviolet absorber (a) and the dye compound (b). The adhesive composition for an organic EL display device according to claim 1, wherein the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) exists in a wavelength region of 300 to 400 nm. The adhesive composition for organic EL display devices according to claim 1, wherein the radical generator is a peroxide. The adhesive composition for organic EL display devices according to claim 1, which contains 0.1 to 25 parts by weight of the above-mentioned compound (A) with respect to 100 parts by weight of the above-mentioned base polymer. The adhesive composition for organic EL display devices according to any one of claims 1 to 5, which further contains an antioxidant. The adhesive composition for organic EL display devices according to any one of claims 1 to 5, which further contains a crosslinking agent. An adhesive layer for an organic EL display device, characterized in that it is formed from the adhesive composition for an organic EL display device according to any one of claims 1 to 7. The adhesive layer for an organic EL display device according to claim 8, wherein the average transmittance at wavelengths of 300 to 400 nm is below 12%, the average transmittance at wavelengths of 400 nm to 430 nm is below 30%, and the average transmittance at wavelengths of 430 to 450 nm is below 30%. more than 70%. The adhesive layer for an organic EL display device of claim 8, wherein the average transmittance at wavelengths of 300 to 400 nm is 12% or less, the average transmittance at wavelengths of 400 nm to 430 nm exceeds 30% and is below 95%, and the average transmittance at wavelengths of 430 to 450 nm is below 95%. The average transmittance is more than 80%. A polarizing film with an adhesive layer for an organic EL display device, characterized by comprising: a polarizing film and the adhesive layer for an organic EL display device according to any one of claims 8 to 10. The polarizing film with an adhesive layer for an organic EL display device according to claim 11, wherein the polarizing film is provided with a transparent protective film on one side of the polarizing element and a retardation film on the other side, and the adhesive layer for an organic EL display device is provided. It is provided on the surface on the opposite side of the retardation film and the surface in contact with the polarizer, and/or the surface on the opposite side of the transparent protective film on the surface in contact with the polarizer. As claimed in claim 11, the polarizing film with an adhesive layer for an organic EL display device has a first adhesive layer, a transparent protective film, a polarizing element, a second adhesive layer, a retardation film, and a third adhesive in this order. adhesive layer, and at least one adhesive layer among the first adhesive layer, the second adhesive layer, and the third adhesive layer is the adhesive layer for the organic EL display device. The polarizing film with an adhesive layer for an organic EL display device according to claim 12 or 13, wherein the retardation film is a quarter-wave plate, and the polarizing film is a circular polarizing film. An organic EL display device, characterized in that: it uses the adhesive layer for an organic EL display device as claimed in any one of claims 8 to 10, or an attached organic EL display device as claimed in any one of claims 11 to 14 At least one of the polarizing films with the adhesive layer.

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