TW201905143A - 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 organic EL display devices, which is characterized by containing a base polymer, a radical generator and at least one compound (A) that is selected from among ultraviolet absorbents (a), each of which has 0-3 hydroxyl groups in the molecular structure and dye compounds (b), each of which has the maximum absorption wavelength of absorption spectrum within the wavelength range of from 380 nm to 430 nm. An adhesive composition for organic EL display devices according to the present invention is capable of suppressing deterioration of an organic EL element if used for an organic EL display device, and is also capable of suppressing decrease in the appearance yield, the occurrence of foaming in terms of heating durability, and the like.

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 invention relates to an adhesive composition for an organic EL (Electroluminescence) display device (OLED (organic light emitting diode, organic light emitting diode)). The present invention also relates to an adhesive layer for an organic EL display device formed from the adhesive composition for an organic EL display device, and a polarizing film having an adhesive layer with the adhesive layer. Furthermore, this invention relates to the organic EL display device using the said adhesive layer and / or the said polarizing film.

In recent years, organic EL display devices equipped with organic EL panels have been widely used in various applications such as mobile phones, car navigation devices, personal computer displays, and televisions. Organic EL display devices are usually viewed as mirrors in order to suppress external light from being reflected by metal electrodes (cathodes). Circular polarizers (layered bodies of polarizers and 1/4 wavelength plates, etc.) are arranged on the visible side surface of organic EL panels. . In addition, a circular polarizing plate laminated on the visible side surface of the organic EL panel may be further laminated with a decorative panel or the like. The constituent members of the organic EL display device such as the circular polarizing plate or 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, there is a case where the incident ultraviolet light causes deterioration of a constituent member or the like in the image display device. In order to suppress the deterioration caused by the ultraviolet light, it is known to provide an ultraviolet absorber Floor. Specifically, for example, a transparent double-sided adhesive sheet for an image display device is known, which has at least one ultraviolet absorbing layer, a light transmittance of a wavelength of 380 nm is 30% or less, and a wavelength longer than a wavelength of 430 nm. The visible light transmittance on 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 the invention]

Generally, the adhesive composition to which the transparent double-sided adhesive sheet for image display devices is applied contains a base polymer, such as a (meth) acrylic-type polymer. In addition, in the adhesive composition, in addition to the base polymer, a radical generator (for example, a peroxide) may be used as a crosslinking agent to form an adhesive layer for performing radical crosslinking. When a (meth) acrylic polymer is used as the base polymer, in order to prepare a monomer component in the (meth) acrylic polymer by heat or radiation curing, the adhesive is combined with the adhesive. It contains a radical polymerization initiator.

However, when a UV absorbent is contained in the above-mentioned adhesive composition containing a radical generator, the presence of the UV absorber causes the gel fraction (crosslinking degree) of the adhesive layer formed from the adhesive composition. Declining tendency. If the decrease in the gel fraction (crosslinking degree) of the above-mentioned adhesive layer becomes larger, the appearance of the adhesive layer due to paste dents or paste stains during processing is reduced, or it is caused by heating durability. The occurrence of foaming and other abnormalities.

Therefore, an object of the present invention is to provide an adhesive composition for an organic EL display device. The adhesive composition for an organic EL display device can suppress deterioration of an organic EL element, and can suppress a decrease in appearance yield or heating durability. The production of foam and so on.

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

The present inventors have intensively studied in order to solve the above-mentioned problems, and as a result, have found that the following adhesive composition for an organic EL display device completes the present invention.

That is, the present invention relates to an adhesive composition for an organic EL display device, comprising: a base polymer, a radical generator, and a compound (A), wherein the compound (A) is a hydroxyl group selected from a molecular structure There are 0 to 3 ultraviolet absorbers (a) and at least one pigment compound (b) having a maximum absorption wavelength in a wavelength range of 380 to 430 nm.

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

In the above-mentioned adhesive composition for an organic EL display device, it is preferable that the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) exists in a wavelength region of 300 to 400 nm.

In the adhesive composition for an organic EL display device, a peroxide may be used as the radical generator.

In the adhesive composition for an organic EL display device, a (meth) acrylic polymer can be used as the base polymer.

The adhesive composition for an organic EL display device preferably contains 0.01 to 2 parts by weight of the radical generator with respect to 100 parts by weight of the base polymer.

The adhesive composition for an organic EL display device preferably contains the compound (A) in an amount of 0.1 to 25 parts by weight based on 100 parts by weight of the base polymer.

The adhesive composition for an organic EL display device may further contain an antioxidant.

The adhesive composition for an organic EL display device may further contain a crosslinking agent.

The present invention relates to an adhesive layer for an organic EL display device, which is characterized by being formed of 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 less than 12% at a wavelength of 300 to 400 nm, an average transmittance of less than 30% at a wavelength of 400 to 430 nm, and an average transmittance of 430 to 450 nm. More than 70%.

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

The present invention also relates to a polarizing film with an adhesive layer for an organic EL display device, which includes a polarizing film and the adhesive layer for an organic EL display device.

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

The polarizing film with an adhesive layer for an organic EL display device is preferably one having 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, In addition, at least one of the first adhesive layer, the second adhesive layer, and the third adhesive layer is the adhesive layer for an organic EL display device.

In the polarizing film with an adhesive layer for an organic EL display device, the retardation film is preferably a 1/4 wavelength plate, and the polarizing film is a circular polarizing film.

The present invention relates to an organic EL display device using at least one of the adhesive layer for an organic EL display device or the polarizing film with an adhesive layer for an organic EL display device. [Effect of the invention]

The adhesive composition for an organic EL display device of the present invention contains an ultraviolet absorber (a) in addition to the base polymer. The ultraviolet absorber (a) can suppress deterioration caused by ultraviolet light and suppress deterioration of the organic EL element. In addition, the adhesive composition for an organic EL display device of the present invention contains a pigment compound (b) having a maximum absorption wavelength in an absorption spectrum in a wavelength range of 380 to 430 nm instead of the ultraviolet absorber (a), or the ultraviolet absorber. Agent (a) is used in combination. This pigment compound (b) can also suppress deterioration due to ultraviolet light and suppress deterioration of the organic EL element.

The adhesive composition for an organic EL display device of the present invention contains a radical generator such as a peroxide. This radical generator functions as a crosslinking agent for a base polymer such as a (meth) acrylic polymer, and can control the gel fraction of the adhesive layer formed from the above-mentioned adhesive composition to a desired level. Range, a good adhesive layer can be formed.

As described above, since the ultraviolet absorber and / or the pigment compound and the radical generator coexist in the adhesive composition for an organic EL display device of the present invention, there is a concern that the gel fraction of the obtained adhesive layer is lowered. However, in the adhesive composition for an organic EL display device of the present invention, an ultraviolet absorbent (a) having 0 to 3 hydroxyl groups in its molecular structure is selected as the ultraviolet absorbent. 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 cross-linking caused by the inactivation of the radical generated by the radical generator. As the donor group, by using an ultraviolet absorber (a) having 3 or less hydroxyl groups as the donor group, the ultraviolet absorber can inhibit the cross-linking resistance of the radical generator.

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, which can suppress the reduction in appearance yield, the occurrence of foaming due to heating durability, and the like. Therefore, the organic EL display device using the adhesive layer for an organic EL display device of the present invention and / or the polarizing film with an adhesive layer containing the adhesive layer for an organic EL display device has excellent weather resistance and can have a long life. .

1. Adhesive composition for organic EL display device The adhesive composition for organic EL display device of the present invention is characterized by containing a base polymer, a radical generator, and a compound (A), and the compound (A) is selected The ultraviolet absorber (a) having 0 to 3 hydroxyl groups in its molecular structure and the maximum absorption wavelength of the absorption spectrum exist in at least one of the pigment compounds (b) in a wavelength range of 380 to 430 nm.

The adhesive composition for an organic EL display device of the present invention contains a base polymer as a main component. The so-called main component refers to the component having the largest proportion of all solid content components contained in the adhesive composition, for example, refers to a component that accounts for more than 50% by weight of all solid content components contained in the adhesive composition, and further refers to 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, silicone-based adhesives, and urethane-based adhesives. Adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinyl pyrrolidone-based adhesives, polypropylene amidamine-based adhesives, cellulose-based adhesives, and the like. Among these adhesives, acrylic adhesives can be preferably used in terms of excellent optical transparency, exhibiting suitable adhesiveness, cohesiveness, and adhesiveness, and excellent weather resistance or heat resistance. . In the present invention, an acrylic adhesive composition containing a (meth) acrylic polymer as a base polymer is preferred.

<(Meth) acrylic polymer> The (meth) acrylic polymer usually contains an alkyl (meth) acrylate as a main component as a monomer unit. In addition, (meth) acrylate means an acrylate and / or a methacrylate, and what is called (meth) in this invention has the same meaning.

Examples of the (meth) acrylic acid alkyl ester constituting the main skeleton of the (meth) acrylic polymer include those having a linear or branched alkyl group having 1 to 18 carbon atoms. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably from 3 to 9.

In addition, in terms of adhesion characteristics, durability, adjustment of phase difference, adjustment of refractive index, and the like, phenoxyethyl (meth) acrylate and benzyl (meth) acrylate containing aromatic ring can be used Alkyl (meth) acrylate.

In order to improve adhesion or heat resistance, one or more polymerizable functions having unsaturated double bonds such as a (meth) acrylfluorenyl group or a vinyl group may be introduced into the (meth) acrylic polymer by copolymerization. Based comonomer. Specific examples of such a comonomer include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (methyl) ) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) acrylate ) Hydroxy-containing monomers such as methyl esters; (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, Ikonic acid, maleic acid, fumaric acid, butenoic acid, etc. Monomers containing carboxyl groups; Monomers containing anhydride groups such as maleic anhydride, itaconic anhydride; caprolactone adducts of acrylic acid; styrene sulfonic acid or allyl sulfonic acid, 2- (meth) acrylamide Sulfonic acid group-containing monomers such as 2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, and (naphthyl) naphthosulfonic acid; acrylic acid Phosphate-containing monomers such as 2-hydroxyethyl phosphate and the like.

Examples of monomers for modification purposes include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, or (N-substituted) fluorene-based monomers such as N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamine; aminoethyl (meth) acrylate, (formyl) (Meth) acrylic acid, such as N, N-dimethylaminoethyl acrylate, tert-butylaminoethyl (meth) acrylate, and other (meth) acrylic acid alkylaminoalkyl ester-based monomers; (meth) acrylic acid (Meth) acrylic alkoxyalkyl ester-based monomers such as methoxyethyl and ethoxyethyl (meth) acrylate; N- (meth) acryloxymethylene succinimide or N- (meth) acrylfluorenyl-6-oxyhexamethylene succinimide, N- (meth) acrylfluorenyl-8-oxyoctamethylene succinimide, N-acrylfluorene Succinimide-based monomers such as phenylline; N-cyclohexylmaleimide or N-isopropylmaleimide, N-laurylmaleimide or N-phenylmaleimide Maleimide monomers such as amines; N-methyl Ikonimide, N-ethyl Ikonimide, N-butyl Ikonimide, N-octyl Ikonimide , N Ikonimine-based monomers such as 2-ethylhexyl Ikonimide, N-cyclohexyl Ikonimide, and N-Lauryl Ikonimide.

Further, as the modifying monomer, vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, and vinyl pyrimidine can also be used. , Vinylpipe, vinylpyrrole, vinylpyrrole, vinylimidazole, vinyloxazole, vinylline, N-vinylcarboxamides, styrene, α-methylstyrene, N-vinyl Vinyl monomers such as lactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy-based acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (formaldehyde Base) glycol-based acrylate monomers such as acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxy polypropylene glycol (meth) acrylate; (meth) ) Acrylic monomers such as tetrahydrofurfuryl acrylate, fluorine-containing (meth) acrylate, polysiloxane (meth) acrylate or 2-methoxyethyl acrylate. Further examples include isoprene, butadiene, isobutylene, vinyl ether, and the like.

Further, examples of the copolymerizable monomer other than the above include a silane-based monomer containing a silicon atom and the like. Examples of the silane-based monomer include 3-propenyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and 4-vinylbutyltrimethoxy Methylsilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxy Decyltrimethoxysilyl, 10-propenyloxydecyltrimethoxysilane, 10-methacryloxymethoxydecyltriethoxysilyl, 10-propenyloxydecyltriethoxy Methylsilane and so on.

As comonomers, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 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) acrylic acid esters, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Polyfunctional monomers having two or more unsaturated double bonds such as (meth) acrylfluorene and vinyl groups, such as esterified products, or two added to the backbone of polyester, epoxy, and urethane Polyester (meth) acrylate, epoxy (meth) acrylate, (meth) ) Urethane acrylate and the like.

The (meth) acrylic polymer contains alkyl (meth) acrylate as a main component in the weight ratio of all constituent monomers, and the ratio of the comonomer in the (meth) acrylic polymer is not It is particularly limited that the proportion of the above comonomer is preferably about 0 to 20%, about 0.1 to 15%, and more preferably about 0.1 to 10% of the weight ratio of all constituent monomers.

Among these comonomers, a hydroxyl-containing monomer and a carboxyl-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. When the comonomer contains a crosslinking agent, the comonomer becomes a reaction point with the crosslinking agent. Since hydroxyl-containing monomers and carboxyl-containing monomers are rich in reactivity with intermolecular cross-linking agents, they can be preferably used to improve the cohesiveness or heat resistance of the obtained adhesive layer. A hydroxyl group-containing monomer is preferred in terms of secondary processability, and a carboxyl group-containing monomer is preferred in terms of both durability and secondary processability.

In the case where a hydroxy-containing monomer is contained as the comonomer, the proportion 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 comonomer, the proportion 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 one having a weight average molecular weight in the range of 500,000 to 3 million. In consideration of durability, particularly heat resistance, it is preferable to use a weight average molecular weight of 700,000 to 2.7 million. Furthermore, it is preferably 800,000 to 2.5 million. When the weight average molecular weight is less than 500,000, it is inferior in heat resistance. In addition, if the weight average molecular weight is more than 3 million, in order to adjust the viscosity for coating, a large amount of a diluent solvent is required, and the cost is increased, which is unfavorable. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated by polystyrene conversion.

The production of such a (meth) acrylic polymer may be appropriately selected from known production methods such as solution polymerization, UV (ultraviolet) polymerization, radiation polymerization, block polymerization, emulsion polymerization, and various radical polymerization. The obtained (meth) acrylic polymer may be any of a random copolymer, a block copolymer, and a graft copolymer.

In the solution polymerization, as the polymerization solvent, for example, ethyl acetate, toluene, or the like can be used. As a specific solution polymerization example, the reaction is performed under an inert gas flow such as nitrogen, and a polymerization initiator is added, and the reaction is usually performed under reaction conditions of about 50 to 70 ° C. and about 5 to 30 hours.

The polymerization initiator, chain transfer agent, emulsifier, and the like used in the radical polymerization are not particularly limited, and may be appropriately selected and used. In addition, the weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of the polymerization initiator, the amount of chain transfer agent used, and the reaction conditions, and the amount used can be appropriately adjusted according to the type of these.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-fluorenylpropane) dihydrochloride, and 2,2'-couple Azabis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-Azobis (2-methylpropionamidine) disulfate, 2,2 '-Azobis (N, N'-dimethylmethylene isobutylphosphonium), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropylhydrazone] hydrate ( Made by Wako Pure Chemical Industries, Ltd., VA-057) and other azo initiators; persulfates such as potassium persulfate and ammonium persulfate; bis (2-ethylhexyl) peroxydicarbonate, and di (2-ethylhexyl) peroxydicarbonate 4-tert-butylcyclohexyl) ester, di-second butyl peroxydicarbonate, tertiary butyl peroxydecanoate, tertiary hexyl pervalerate, tertiary butyl pervalerate , Dilauryl Peroxide, Di-n-octyl Peroxide, Di (2-ethylhexanoic acid) 1,1,3,3-tetramethylbutyl Peroxide, Di (4-methylbenzyl Peroxide) Peroxide, such as benzophenone peroxide, tert-butyl isobutyrate, 1,1-bis (tertiary hexylperoxy) cyclohexane, tertiary butyl hydroperoxide, hydrogen peroxide and other peroxides Series initiator; persulfate and sulfurous acid Combination of sodium, of sodium ascorbate in combination with a peroxide or the like with a reducing agent a combination of a peroxide of redox initiator and so forth, but are not limited to such.

The above-mentioned radical polymerization initiators may be used alone or in combination of two or more kinds. The content of the radical polymerization initiator is preferably 0.005 to 1 part by weight relative to 100 parts by weight of the monomer, more preferably 0.02 to 0.5 part by weight. Servings.

Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto- 1-propanol and the like. The chain transfer agent may be used singly, or two or more kinds may be used in combination, and the content thereof as a whole is about 0.1 parts by weight or less based on 100 parts by weight of the total amount of the monomer components.

Examples of the emulsifier used in the case of performing emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyalkylene ether ammonium sulfate, and Anionic emulsifiers such as sodium oxyethyl alkyl phenyl ether sodium sulfate; polyoxyethyl phenyl ether, polyoxy ethyl phenyl alkyl ether, polyoxy ethyl carboxylic acid ester, polyoxyethylene- Nonionic emulsifiers such as polyoxypropylene block polymers. 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 an propylene group or an 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 Pharmaceutical Co., Ltd.), ADEKA REASOAP SE10N (made by Solectron Chemical Co., Ltd.), etc. Since the reactive emulsifier is taken in by the polymer chain after polymerization, the water resistance becomes good and is preferred. The used 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 in terms of polymerization stability or mechanical stability, it is more preferably 0.5 to 1 part by weight.

<Free Radical Generator> As the free radical generator formulated in the adhesive composition of the present invention, a radical polymerization initiator used in the production of the (meth) acrylic polymer can be exemplified. Among the above-mentioned radical polymerization initiators, the radical generator formulated in the adhesive composition is preferably a peroxide.

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

Examples of the peroxide include bis (4-third-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), and disecond butyl peroxydicarbonate (1 minute half-life temperature). : 92.4 ° C), third butyl peroxyneodecanoate (1 minute half-life temperature: 103.5 ° C), third hexyl pervalerate (1 minute half-life temperature: 109.1 ° C), third pervalerate 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 Caproic acid) 1,1,3,3-tetramethylbutyl ester (1 minute half-life temperature: 124.3 ° C), bis (4-methylbenzidine) (1 minute half-life temperature: 128.2 ° C), peroxide Dibenzidine (1 minute half-life temperature: 130.0 ° C), tert-butyl isobutyrate peroxide (1 minute half-life temperature: 136.1 ° C), 1,1-bis (third-hexylperoxy) cyclohexane ( 1 minute half-life temperature: 149.2 ° C) and the like. Among them, especially in terms of excellent crosslinking reaction efficiency, bis (4-third-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), dilauric acid peroxide can be preferably used. Thallium (1 minute half-life temperature: 116.4 ° C), dibenzopyrene peroxide (1 minute half-life temperature: 130.0 ° C), and the like.

The so-called half-life of the peroxide is an index indicating the decomposition rate of the peroxide, and refers to the time until the residual amount of the peroxide becomes half. The decomposition temperature used to obtain the half-life at any time, or the half-life time at any temperature, is described in the manufacturer's catalogue, for example, in the "Organic Peroxide Catalog 9th Edition (2003, May 2003)" Month) "and so on.

The content of the radical generator (especially the peroxide) in the adhesive composition of the present invention is for the workability, secondary processability, cross-linking stability, and peelability of the adhesive layer formed from the above-mentioned adhesive composition. The adjustment is determined in consideration of the gel fraction and the like. If the content of the radical generator (especially the peroxide) is made large, it is better in terms of ensuring the gel fraction (crosslinking degree) of the obtained adhesive layer, but if it is too much, there is The release force of the release film (release film) to which the adhesive layer is applied tends to increase. In general, the content of the radical generator is preferably 0.01 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and more preferably 100 parts by weight of the base polymer (for example, a (meth) acrylic polymer). It is preferably from 0.05 to 0.8 parts by weight, and more preferably from 0.1 to 0.6 parts by weight.

Furthermore, in the (meth) acrylic polymer, there may be a case where a radical polymerization initiator (radical generator) not used in the polymerization reaction during the preparation of the (meth) acrylic polymer remains. This residual radical generator can be used as a radical generator in the above-mentioned adhesive composition. In this case, the amount of the residual radical generating agent can be quantified, and the radical generating agent can be appropriately formulated according to the content of the residual radical generating agent.

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

More specifically, for example, the adhesive composition after the reaction treatment can be taken out at 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. Then, it was left to stand at room temperature for 3 days. Next, add 10 mL of acetonitrile, shake at 120 rpm for 30 minutes at 25 ° C, filter through a membrane filter (0.45 μm), inject about 10 μL of the obtained extract into HPLC for analysis, and set it as the reaction treatment The amount of peroxide.

<Compound (A)> In the adhesive composition of the present invention, the ultraviolet absorber (a) having 0 to 3 hydroxyl groups in the molecular structure is selected and the maximum absorption wavelength of the absorption spectrum exists at a wavelength of 380 to 430 nm. At least one compound (A) of the regional pigment compound (b). Regarding the above-mentioned ultraviolet absorbent (a), as described above, the number of hydroxyl groups in the molecular structure is 0 to 3, which is effective in reducing the hydrogen donor group that causes radical inactivation and inhibiting the cross-linking barrier of the radical generator. . In addition, when the number of hydroxyl groups is 0 to 3, for example, when an isocyanate-based crosslinking agent having reactivity with the hydroxyl group is prepared, it is also preferable in terms of inhibiting the cross-linking hindrance of the crosslinking agent. 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, a phenyl group not having a molecular structure means a phenyl group having no substituent (-C ₆ H ₅ ), and does not exclude a phenyl group having a substituent or a phenylene group. In addition, as for the pigment compound (b), as with the ultraviolet absorber (a), from the viewpoint of preventing the cross-linking inhibition of the radical generator, it is preferred that hydrogen is supplied from a hydroxyl group or a phenyl group in the molecular structure. Compounds that have few sex groups (0 to 3 hydroxyl groups) or do not have hydrogen donor 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 to 100 parts by weight of a base polymer (for example, a (meth) acrylic polymer). It is about 25 parts by weight, preferably about 0.5 to 20 parts by weight, and even more preferably about 2 to 10 parts by weight.

The said ultraviolet absorber (a) can be used individually or in mixture of 2 or more types. When using only the said ultraviolet absorber (a) as said compound (A), the content of the said ultraviolet absorber (a) as a whole with respect to a base polymer (for example, (meth) acrylic-type polymer) 100 parts by weight, preferably 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight. By setting the addition amount of the ultraviolet absorber (a) to the above range, it is possible to sufficiently exert the ultraviolet absorption function of the adhesive layer, and it is preferable that the polymerization is not hindered when the ultraviolet polymerization is performed.

The said pigment compound (b) can be used individually or in mixture of 2 or more types. When using only the said pigment compound (b) as said compound (A), the content of the said pigment compound (b) as a whole with respect to 100 weight of a base polymer (for example, (meth) acrylic-type polymer) Parts, preferably 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight. By setting the addition amount of the pigment compound (b) to the above range, light in a region that does not affect the light emission of the organic EL element can be sufficiently absorbed, and by using an adhesive layer formed from the adhesive composition, It is preferable because deterioration of the organic EL element can be suppressed.

Any one of the ultraviolet absorber (a) and the pigment compound (b) may be used, and it is preferable to use the ultraviolet absorber (a) and the pigment compound (b) together. With the ultraviolet absorber (a), for example, light having a wavelength of 380 nm can be absorbed, but there is a wavelength region (380 nm) that is shorter than the light-emitting region of the organic EL element (the wavelength side longer than 430 nm) than the wavelength side. ~ 430 nm), and the transmitted light causes degradation. The pigment compound (b) can suppress transmission of light having a wavelength (380 nm to 430 nm) shorter than a light emitting region (a wavelength side longer than 430 nm) of the organic EL element, and by using the ultraviolet absorber ( a) and the pigment compound (b) can sufficiently ensure the transmittance of visible light in the light-emitting region of the organic EL element. In the present invention, by using such a pigment compound (b) in combination with the above-mentioned ultraviolet absorber (a2), it is possible to sufficiently absorb a region (wavelength 380 nm to 430 nm) that does not affect the light emission of the organic EL element. Light, and the light-emitting area (wavelength side longer than 430 nm) of the organic EL element is sufficiently transmissive. As a result, degradation of the organic EL element due to external light can be suppressed. When using the said ultraviolet absorber (a) and a pigment compound (b) together, it is preferable that the total amount of the said ultraviolet absorber (a) and a pigment compound (b) becomes the compounding quantity of the said compound (A). Way to control. The ultraviolet absorber (a) is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 100 parts by weight of a base polymer (for example, a (meth) acrylic polymer). ~ 3 parts by weight. The pigment compound (b) is preferably about 0.1 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight, and more preferably 100 parts by weight of the base polymer (for example, a (meth) acrylic polymer). 0.5 ~ 3 parts by weight.

<Ultraviolet absorber (a)> The ultraviolet absorber (a) is not particularly limited as long as it has 0 to 3 hydroxyl groups in the molecular structure, and examples thereof include three-line ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, Benzophenone-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, etc. These can be used alone or in combination of 2 More than one kind of use. Among these, a three-series ultraviolet absorber and a benzotriazole-based ultraviolet absorber are preferred, because of good solubility in a monomer for forming an acrylic adhesive composition, and ultraviolet rays near a wavelength of 380 nm It has a high absorptive capacity, so it is preferably selected from the group consisting of a tri-series ultraviolet absorber having two or less hydroxyl groups in one molecule and a benzotriazole-type ultraviolet absorber having one benzotriazole skeleton in one molecule. At least one ultraviolet absorber in the group.

Specific examples of the three-type ultraviolet absorber having two or less hydroxyl groups in one molecule include 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -benzene Group] -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-dimethylphenyl) Reaction product of -1,3,5-tri-2-yl) -5-hydroxyphenyl and [(C10-C16 (mainly C12-C13) alkoxy) methyl] ethylene oxide (TINUVIN400, BASF (Manufactured by the company), 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-tri-2-yl] -5- [3- (dodecyloxy)- 2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-tri and Reaction product of water glyceric acid (2-ethylhexyl) ester (TINUVIN405, manufactured by BASF), 2- (4,6-diphenyl-1,3,5-tri-2-yl) -5-[( Hexyl) oxy] -phenol (TINUVIN 1577, manufactured by BASF), 2- (4,6-diphenyl-1,3,5-tri-2-yl) -5- [2- (2-ethylhexyl) (Methoxy) ethoxy] -phenol (ADK STAB LA46, manufactured by ADEKA), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6- (4-phenylphenyl) -1,3,5 (TINUVIN479, BASF Co., Ltd.).

Examples of the benzotriazole-based ultraviolet absorber having one benzotriazole skeleton in one molecule include 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-third butylphenyl) ) -2H-benzotriazole (TINUVIN PS, manufactured by BASF), phenylpropionic acid, and 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl)- 4-hydroxy (C7-9 side chain and linear alkyl) ester compounds (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 Reaction product of methyl-4-hydroxyphenyl) propionic acid methyl ester / polyethylene glycol 300 (TINUVIN 1130, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -p-cresol (TINUVIN P , Manufactured by BASF), 2 (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN234, manufactured by BASF), 2- [ 5-chloro (2H) -benzotriazole 2-yl] -4-methyl-6- (third butyl) phenol (TINUVIN326, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4,6-di-third Amylphenol (TINUVIN328, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN329, manufactured by BASF) ), Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 (TINUVIN213, BASF (Manufactured by the company), 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol (TINUVIN571, manufactured by BASF), 2- [2-hydroxy-3- (3 , 4,5,6-tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole (Sumisorb 250, manufactured by Sumitomo Chemical Industry Co., Ltd.) and the like.

Examples of the benzophenone-based ultraviolet absorber (benzophenone-based compound) and the benzophenone-based ultraviolet absorber (benzophenone-based compound) include, for example, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyl oxide benzophenone, 4- Dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4-dimethoxybenzophenone, and the like.

Examples of the salicylate-based ultraviolet absorber (salicylate-based compound) include 3,5-di-tert-butyl-4-hydroxybenzoic acid and 2,4-di-tert-butylphenyl ester. (TINUVIN120, manufactured by BASF).

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

The maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber (a) is preferably in a wavelength region of 300 to 400 nm, and more preferably in a wavelength region of 320 to 380 nm. The measurement method of the maximum absorption wavelength is the same as that of the pigment-based compound described below.

<Pigment compound (b)> The pigment compound (b) is not particularly limited as long as it has a maximum absorption wavelength in the absorption spectrum in a wavelength range of 380 to 430 nm. Similar to the ultraviolet absorber (a), A compound having a small hydrogen donating group such as a hydroxyl group or a phenyl group or having no hydrogen donating group such as a hydroxyl group or a phenyl group in the molecular structure is preferred. In addition, when the so-called maximum absorption wavelength has a plurality of absorption maximums in a spectral absorption spectrum in a wavelength region of 300 to 460 nm, it means an absorption maximum wavelength in which the maximum absorbance is exhibited.

The maximum absorption wavelength of the absorption spectrum of the pigment compound (b) is more preferably in a wavelength range of 380 to 420 nm. The pigment compound (b) is not particularly limited as long as it has the above-mentioned wavelength characteristics, and is preferably a material having no fluorescent and phosphorescent properties (photoluminescence) as long as it does not inhibit the display properties of the organic EL element.

The half-value width of the pigment compound (b) is not particularly limited, but is preferably 80 nm or less, more preferably 5 to 70 nm, and still more preferably 10 to 60 nm. Since the half-value width of the pigment compound is in the above range, light in a region that does not affect the light emission of the organic EL element can be sufficiently absorbed, and light at a wavelength side longer than 430 nm can be controlled to be fully transmitted, which is preferable. . The method of measuring the half-value width uses the method described below. <Measurement method of half-value width> The half-value width of the pigment compound (b) is an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi High-Tech Science Co., Ltd.), and the solution of the pigment compound under the following conditions The absorption spectrum was measured. The spectroscopic spectrum measured by adjusting the concentration so that the absorbance at the maximum absorption wavelength becomes 1.0, and the wavelength interval (full width at half maximum) between 2 points that becomes 50% of the peak value is taken as the half width of the pigment compound. (Measurement conditions) Solvent: Toluene or chloroform Cell: Quartz cell Optical path length: 10 mm

Examples of the pigment compound (b) include organic pigment compounds and inorganic pigment compounds. Among these, organic compounds are preferred from the viewpoint of maintaining dispersibility and transparency in resin components such as a base polymer. Department of pigment compounds.

Examples of the organic pigment compound include a methylimine compound, an indole compound, a cinnamic acid compound, a pyrimidine compound, a porphyrin compound, and a cyanine compound.

As the organic pigment compound, a commercially available one can be suitably used. Specifically, as the 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 a cinnamic acid-based compound, SOM-5-0106 (trade name, maximum absorption wavelength of absorption spectrum: 416 nm, half-value width: 50 nm, manufactured by Orient Chemical Industries Co., Ltd.) ), As the porphyrin-based compound, FDB-001 (trade name, maximum absorption wavelength of the absorption spectrum: 420 nm, half-value width: 14 nm, manufactured by Yamada Chemical Industry Co., Ltd.), as the cyanine-based compound, Cyanine compound (trade name: FDB-009, absorption maximum absorption wavelength: 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, half-value width: 49.5 nm, manufactured by Yamada Chemical Industry Co., Ltd., etc.), among which the inhibition of cross-linking and optical On the viewpoint of the properties, the above-described cyanine compounds preferred, particularly preferably poly-methine compound.

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

Examples of the antioxidant include phenol-based, phosphorus-based, sulfur-based, and amine-based antioxidants, and at least one selected from these is used. Among these, a phenolic antioxidant is preferable.

As specific examples of the phenol-based antioxidant, examples of the monocyclic phenol compound include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, and 2,6 -Dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-tertiarypentyl-4-methylphenol, 2,6-di-tert-octyl Methyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl- 4-ethyl-6-third octylphenol, 2-isobutyl-4-ethyl-6-third hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, benzene Vinyl mixed cresol, DL-α-tocopherol, β- (3,5-di-third-butyl-4-hydroxyphenyl) stearate, etc. Examples of the bicyclic phenol compound include: 2, 2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylenebis (3-methyl-6-tert-butylphenol), 4,4'- Thiobis (3-methyl-6-third butylphenol), 2,2'-thiobis (4-methyl-6-third 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-third butyl-4-methylphenol), 3,6-dioxaoctamethylene bis [3- (3-third butyl-4-hydroxy-5-methyl Phenyl) propionate], triethylene glycol bis [3- (3-third-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylene bis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate] and the like, and examples of the tricyclic phenol compound include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, isopropyl 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) cyanurate, 1,3,5-tris [(3,5-di Tert-butyl-4-hydroxyphenyl) propanyloxyethyl] ester, tris (4-third-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and the like, as the tetracyclic phenol compound, tetra [methylene-3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, etc. Examples of phosphorus-containing phenol compounds include bis (3,5-di-tert-butyl-4-hydroxy Ethyl benzylphosphonate) Calcium, bis (3,5-Di-tertiarybutyl-4-hydroxybenzylphosphonate) E ) Nickel.

Specific examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, triisodecyl phosphite, and phenyl phosphite diisooctyl ester. , Phenyl phosphite diisodecyl, phenyl phosphite di (tridecyl) ester, diphenyl phosphite isooctyl, diphenyl phosphite isodecyl, diphenyl phosphite tridecyl Ester, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (butoxyethyl) phosphite, tetra (Tridecyl) -4,4'-butylene bis (3-methyl-6-third butylphenol) diphosphite, 4,4'-isopropylidene biphenol alkyl phosphite (Wherein the alkyl group is about 12 to 15 carbon atoms), 4,4'-isopropylidene bis (2-third butylphenol), bis (nonylphenyl) phosphite, and tris (biphenyl phosphite) Yl) ester, tetrakis (tridecyl) -1,1,3-tris (2-methyl-5-third butyl-4-hydroxyphenyl) butane diphosphite, and tris (3 , 5-Di-tert-butyl-4-hydroxyphenyl) ester, hydrogenated-4,4'-isopropylidene biphenol polyphosphite, bis (octylphenyl) -bis [4,4'- Butylene bis (3-methyl-6- Butylphenol)]-1,6-hexanediol diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol ) Bisphosphite, tris [4,4'-isopropylidenebis (2-third-butylphenol)] phosphite, tris (1,3-distearyloxyisopropyl) Ester, 9,10-dihydro-9-phosphaphenanthrene-10-oxide, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylphenyl phosphinate, Distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidenebiphenol-pentaerythritol diphosphite, bis (2,4- Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and phenylbisphenol A-pentaerythritol diphosphite Wait.

As the sulfur-based antioxidant, a dialkyl thiodipropionate and a polyol ester of an alkyl thiopropionic acid are preferably used. The dialkyl thiodipropionate used herein is preferably a dialkyl thiodipropionate having an alkyl group having 6 to 20 carbon atoms, and a polyhydric alcohol as an alkyl thiopropionate 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, examples of the polyol constituting the polyol ester include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trihydroxyethyl isocyanurate. Examples of such a dialkyl thiodipropionate include dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate. On the other hand, examples of polyhydric alcohol esters of alkylthiopropionic acid include glycerol tributylthiopropionate, glycerol trioctylthiopropionate, glycerol trilaurylthiopropionate, Glyceryl tristearyl thiopropionate, trimethylolethane tributyl thiopropionate, trimethylolethane trioctyl thiopropionate, trimethylolethane trilauryl Thiopropionate, trimethylolethanetristearylthiopropionate, pentaerythritol tetrabutylthiopropionate, pentaerythritol tetraoctylthiopropionate, pentaerythritol tetralaurylthiopropionate Esters, pentaerythritol tetrastearyl thiopropionate, and the like.

Specific examples of the amine-based antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate, and 1- (2-hydroxy 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) -tri-2-yl) -4,7-diazadecane-1, 10-diamine, dibutylamine-1,3,5-tri-N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylene Polycondensate of N- (2,2,6,6-tetramethyl-4-piperidinyl) butylamine, poly [(6- (1,1,3,3-tetramethyl) Butyl) amino-1,3,5-tri-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) imino} hexamethylene { (2,2,6,6-tetramethyl-4-piperidinyl) imino}), tetra (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-piperidine) Pyridyl) -2- (3,5-di-third-butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (N-methyl-2,2,6,6-tetra Methyl-4-piperidinyl) sebacate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperidone), (mixed 2, 2,6,6-tetramethyl-4-piperidinyl / tridecyl) -1,2,3,4-butane tetracarboxylic acid ester, (mixed 1,2,2,6,6-pentamethyl-4-piperidinyl / tridecyl) -1,2,3, 4-butane tetracarboxylic acid ester, 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 tetracarboxylic acid ester, 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-butane tetracarboxylic acid ester, 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-tricondensate, poly [6-N-line -1,3,5-tri-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] hexamethylene [(2,2 , 6,6-tetramethyl-4-piperidinyl) fluorenimine], N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) hexamethylene di Condensate of amine and 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidinyl) -2-methyl-2- (2,2,6 , 6-tetramethyl-4-piperidinyl) imino] propylamidine and the like.

The content of the antioxidant in the adhesive composition of the present invention is determined from the viewpoint of preventing discoloration of pigments caused by the above-mentioned radical generator. Generally, the content of the antioxidant is preferably in a range of 0.03 parts by weight or more based on 100 parts by weight of the (meth) acrylic polymer. On the other hand, if the content of the antioxidant is increased, the proportion of capturing free radicals generated by the radical generator increases. As a result, the blocking of the cross-linking of the adhesive layer formed from the above-mentioned adhesive composition tends to be easily caused, the gel fraction of the adhesive layer is lowered, and the appearance tends to be poor. From this viewpoint, the content of the antioxidant is preferably in a range of 5 parts by weight or less, and more preferably in a range of 1.5 parts by weight or less, based on 100 parts by weight of the (meth) acrylic polymer. From the viewpoint of ensuring both the gel fraction and the discoloration prevention of the pigment, the content of the antioxidant is preferably 0.05 to 1.5 with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). The weight part is more preferably 0.1 to 1.0 part by weight, and 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 as a cross-linking agent, it is possible to effectively inhibit free radical cross-linking hindrance caused by oxygen with an antioxidant, and to efficiently form adhesion with the isocyanate-based cross-linking agent. The three-dimensional network structure of the agent layer. As a result, it is possible to further effectively prevent the appearance of the polarizing film from being abnormal.

Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a polysiloxane-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, a silane-based crosslinking agent, and an alkane. Cross-linking agent based on melamine-based crosslinking agent and metal chelate-based crosslinking agent. The crosslinking agent may be used alone or in combination of two or more kinds. Among these, an isocyanate-based crosslinking agent can be preferably used.

The above-mentioned cross-linking agents may be used singly or in combination of two or more kinds. The total content is preferably 5 parts by weight relative to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer). It is more preferably 0.01 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and even more preferably 0.02 to 3 parts by weight.

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

More specifically, examples include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; and alicyclic rings such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate. Group isocyanates; 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate and other aromatic diisocyanates; trimethylol Propane / toluene diisocyanate terpolymer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate terpolymer 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; Trimethylolpropane adduct of isocyanate (trade name: D110N, manufactured by Mitsui Chemicals Co., Ltd.), three of hexamethylene diisocyanate Methylpropane adduct (trade name: D160N, manufactured by Mitsui Chemicals Co., Ltd.); polyether polyisocyanate, polyester polyisocyanate, and these adducts with various polyols; via isocyanurate bonds , Polyisocyanate, etc. which are multifunctionalized with biuret bond, urethane bond, etc.

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

Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilyl, and 3-glycidyloxypropylmethyldi Epoxy-containing silane coupling agents such as ethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane; 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-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltriethyl (Meth) acrylic group-containing silane coupling agents such as oxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane.

In addition to the above-mentioned components, appropriate additives may be contained in the adhesive composition of the present invention depending on the application. Examples thereof include adhesion-imparting agents (for example, those containing rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc. that are solid, semi-solid, or liquid at normal temperature); filled with hollow glass balloons, and the like Agents; plasticizers; anti-aging agents; light stabilizers (HALS (Hindered Amine Light Stabilizer)); antioxidants and the like.

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 of the above-mentioned adhesive composition for organic EL display device.

The method for forming the adhesive layer is not particularly limited, and can be formed by a method generally used in the art. Specifically, the adhesive composition may be formed on at least one side of a substrate, a coating film formed from the adhesive composition may be dried and formed, or formed by irradiating active energy rays such as ultraviolet rays.

The substrate is not particularly limited, and for example, various substrates such as a release film and a transparent resin film substrate, or a polarizing film described below can be suitably used as the substrate.

Examples of the constituent materials 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; Suitable sheets such as blister sheets, metal foils, and laminates thereof can be suitably used with a resin film in terms of excellent surface smoothness.

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

The thickness of the release film is usually 5 to 200 μm, and preferably about 5 to 100 μm. If necessary, the above release film may be subjected to mold release, antifouling treatment or coating type using polysiloxane-based, fluorine-based, long-chain alkyl-based or fatty ammonium-based release agents, silicon dioxide, etc. Antistatic treatment such as kneading type and evaporation type. In particular, by appropriately performing a peeling treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the release film, the peelability from the adhesive layer can be further improved.

The transparent resin film substrate is not particularly limited, and various resin films having transparency can be used. This resin film is formed of a single film. Examples of the material include polyester resins such as polyethylene terephthalate and polyethylene naphthalate; acetate resins, polyether fluorene resins, polycarbonate resins, and polyethylene resins. Fluorene 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, a polyester-based resin, a polyfluorene-based resin, and a polyetherfluorene-based resin are particularly preferred.

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

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

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

The thickness of the adhesive layer is preferably 5 μm or more, more preferably 50 μm or more, still more preferably 100 μm or more, and even more preferably 150 μm or more from the viewpoint of ensuring the function of absorbing light having a wavelength of less than 430 nm. . The upper limit of the thickness of the adhesive layer is not particularly limited, but is preferably 1 mm or less. If the thickness of the adhesive layer exceeds 1 mm, it will be difficult to transmit ultraviolet rays. In addition to the polymerization of the monomer components, it will take time, and there will be problems in processability, coiling and transportability in the process, 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, and particularly preferably 85% or more. In the case where the gel fraction of the adhesive layer is small, there are cases where the cohesive force is poor and the workability or operability is problematic. In addition, the gel fraction immediately after heating and drying the coating film of the adhesive composition or irradiating ultraviolet rays to form an adhesive layer is preferably 60% or more from the viewpoint of preventing appearance abnormalities such as paste dents. , More preferably 63% or more, still more preferably 66% or more, and even more preferably 70% or more.

The above-mentioned adhesive layer preferably has a haze value of 2% or less measured at a thickness of 25 μm, more preferably 0 to 1.5%, and still more preferably 0 to 1%. Since the haze is in the above range, the adhesive layer has high transparency, so it is preferable.

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

The average transmittance of the above 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, and 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 (wavelength side longer than 430 nm) of the organic EL element, 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 with 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 an area that does not affect the light emission of the organic EL element, and suppressing and protecting the degradation of the organic EL element, the average transmittance of the adhesive layer above 400 to 430 nm It is preferably 30% or less, and more preferably 20% or less. On the other hand, from the viewpoint of protecting the organic EL element from ultraviolet light and suppressing the coloring of the organic EL element, the average transmittance of the above-mentioned adhesive layer at a wavelength of 400 to 430 nm is preferably more than 30% and 95 % Or less, more preferably 50% or more and 90% or less.

Here, the above-mentioned "average transmittance at a wavelength of 300 to 400 nm" refers to an average value of the transmittance measured by measuring the transmittance at a 1 nm pitch in a region of a wavelength of 300 to 400 nm. The same applies to the average transmittance in other wavelength regions.

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 can sufficiently transmit and suppress deterioration of the organic EL element due to external light.

When the above-mentioned adhesive layer is exposed, the adhesive layer may be protected by a release film before being used in practice.

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

As the adhesive layer for an organic EL display device, those described above can be suitably used. When the adhesive layer is formed on a substrate other than the polarizing film, the adhesive layer can be bonded to the polarizing film and transferred. In addition, the above-mentioned release film can be directly used as an isolation film of a polarizing film with an adhesive layer, and the steps can be simplified.

The polarizing film is not particularly limited, and examples thereof include a polarizing element and a transparent protective film on at least one side of the polarizing element.

(1) Polarizing element The polarizing element is not particularly limited, and various types can be used. Examples of the polarizing element include a dichroic substance that adsorbs iodine or a dichroic dye to a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, an ethylene-vinyl acetate copolymer-based partially saponified film, and the like. A hydrophilic polymer film that is uniaxially stretched; a polyene-based alignment film such as a dehydrated product of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among these, a polarizing element including a polyvinyl alcohol-based film and a dichroic substance such as iodine is suitable. The thickness of these polarizing elements 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 stretching it can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine for dyeing and extending it to 3-7 times the original length. If necessary, it may be immersed in an aqueous solution which may contain boric acid, zinc sulfate, zinc chloride, or the like. Furthermore, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, dirt or an anti-blocking agent on the surface of the polyvinyl alcohol-based film can be washed. In addition, the polyvinyl alcohol-based film can be swollen to prevent uneven dyeing Even effect. The stretching may be performed after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. It can also be extended in an aqueous solution or a water bath such as boric acid or potassium iodide.

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

As the thin polarizing element, representative examples include Japanese Patent Laid-Open No. 51-069644 or 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 Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) layer and a stretching resin substrate in a state of a laminate and a dyeing step. According to this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched by being supported by a stretching resin substrate, and there is no abnormality such as breakage caused by stretching.

As the thin polarizing film described above, in a manufacturing method including a step of stretching in a state of a laminated body and a step of dyeing, in terms of being capable of being stretched at a high magnification and improving polarization performance, it is preferably as disclosed in International Publication No. 2010/100917 Especially preferably obtained by the manufacturing method described in Japanese Patent Publication No. 2010/100917, International Patent Publication No. 2010/100917, or Japanese Patent No. 4751481 or Japanese Patent Laid-Open Publication No. 2012-073563 by including a step of extending in an aqueous boric acid solution. It is obtained by a manufacturing method including a step of performing auxiliary aerial stretching before stretching in an aqueous boric acid solution as described in Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563.

(2) Transparent protective film As for the transparent protective film, it can be suitably used by users from the previous. Specifically, a transparent protective film made of a material excellent in transparency, mechanical strength, thermal stability, moisture blocking property, isotropy, and the like is preferable, and examples thereof include polyethylene terephthalate or Polyester polymers such as polyethylene naphthalate; cellulose polymers such as diacetyl cellulose or triethyl cellulose; acrylic polymers such as polymethyl methacrylate; polystyrene or acrylonitrile -Styrenic polymers such as styrene copolymers (AS resins); polycarbonate polymers and the like. Examples of the polymer forming the transparent protective film include polyethylene, polypropylene, ring-based polyolefins, polyolefins having a olefin-reducing structure, polyolefin-based polymers such as ethylene-propylene copolymers, and vinyl chloride-based polymers. Polymers, fluorene-based polymers such as nylon, aromatic polyamines, fluorene-based polymers, fluorene-based polymers, polyether fluorene-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymerization Polymers, vinyl alcohol polymers, vinylidene chloride polymers, ethylene butyraldehyde polymers, aryl ester polymers, polyoxymethylene polymers, epoxy polymers, or blends of the above polymers, etc. . The transparent protective film can also be formed as a hardened layer of a thermosetting, ultraviolet curing resin such as acrylic, urethane, urethane, epoxy, or silicone.

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

The polarizing element and the transparent protective film are preferably in close contact with each other via an aqueous adhesive or the like. Examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, ethylene-based latexes, water-based polyurethanes, and water-based polyesters. In addition to the above, examples of the adhesive for the polarizing element and the transparent protective film include an ultraviolet curing adhesive, an electron beam curing adhesive, and the like. The adhesive for an electron beam-curable polarizing film exhibits suitable adhesion to the above-mentioned various transparent protective films on the visible side. The adhesive used in the present invention may contain a metal compound filler.

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

As the transparent protective film, any one having a retardation and capable of functioning as an optical compensation layer can be used. When a transparent protective film having a retardation is used, its retardation characteristic can be appropriately adjusted to a value necessary for optical compensation. As this retardation film, a stretch film can be used suitably. The above retardation film can be selected for use in a case where the refractive index in the late phase axis direction is set to nx, the refractive index in the in-plane phase axis direction is set to ny, and the refractive index in the thickness direction is set to nz. , Satisfying the relationship of nx = ny> nz, nx> ny> nz, nx> ny = nz, nx> nz> ny, nz = nx> ny, nz> nx> ny, nz> nx = ny. Furthermore, the term 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. The term ny = nz includes not only a case where ny and nz are completely the same, but also a case where ny and nz are substantially the same.

In the case where the polarizing film used in the present invention is used as a circular polarizing plate for reflection prevention of an organic EL display device, the retardation film is preferably a retardation of the front surface of the transparent protective film to 1/4 wavelength (about 100) ~ 170 nm) 1/4 wavelength plate.

When a retardation film is used as a transparent protective film, a transparent protective film is provided on one side of a polarizing element and a retardation film is provided on the other side. In this case, the location of the adhesive layer is not particularly limited, and it may be provided on the surface of the transparent protective film opposite to the surface where the polarizing element is in contact, or on the phase difference film. The surface that is in contact with the polarizing element is the opposite surface. From the viewpoint of suppressing deterioration of the organic EL element, it is preferably provided on at least one side or on both sides.

An example of a specific configuration of the polarizing film with an adhesive layer for an organic EL display device of the present invention is shown in Figs. 1 (a) to (c). Examples include polarizing film 1 with an adhesive layer for an organic EL display device, which is sequentially laminated as follows: As shown in FIG. 1 (a), the adhesive layer 2 / transparent protective film 3 / polarizing element 4 / phase Differential film 5; as shown in FIG. 1 (b), transparent protective film 3 / polarizing element 4 / phase difference film 5 / adhesive layer 2; as shown in FIG. 1 (c), adhesive layer 2 / transparent protective film 3 / Polarizing element 4 / phase difference film 5 / adhesive layer 2. In FIGS. 1 (a) and (b), the adhesive layer 2 is an adhesive layer for an organic EL display device of the present invention. In FIG. 1 (c), at least one of the two adhesive layers 2 is present. The layer may be an adhesive layer for an organic EL display device of the present invention, and both layers may be the adhesive layer for an organic EL display device of the present invention. Further, in FIG. 1, the polarizing film 6 is a unilateral protective polarizing film including a polarizing element 4 and a transparent protective film 3, but it is not limited thereto, and may be transparent between the polarizing element 4 and the retardation film 5. Both sides of the protective film protect the polarizing film. In addition, as described above, various functional layers such as a hard coat layer may be formed on the surface of the transparent protective film 3 which is not in contact with the polarizing element 4.

When the phase difference film is laminated on a polarizing element via an adhesive layer, the adhesive layer may be an adhesive layer for an organic EL display device of the present invention. That is, a 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 layer in this order. At least one of the 1 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 an adhesive layer for an organic EL display device of the present invention. By.

As an example of a specific structure of the organic EL display device, for example, an organic EL display device in which each layer is sequentially laminated as shown in the following can be listed: as shown in FIG. 2 to FIG. 4, covered with glass or covered with plastic 7 / adhesive layer 2 / Transparent protective film 3 / Polarizing element 4 / Phase retardation film 5 / Adhesive layer 2 / Organic EL display panel (OLED element panel) 8 (Figure 2); Cover glass or plastic 7 / Adhesive layer 9 / Transparent protective film 3 / polarizing element 4 / retardation film 5 / adhesive layer 2 / organic EL display panel 8 (Figure 3); cover glass or plastic 7 / adhesive layer 2 / sensor layer 10 / adhesive layer 2 / transparent The protective film 3 / the polarizing element 4 / the retardation film 5 / the adhesive layer 2 / the organic EL display panel 8 (FIG. 4). At least one of the adhesive layer 2 in each of the above configurations may be the adhesive layer of the present invention, and all of the adhesive layer 2 may be the adhesive layer of the present invention. The organic EL display device of the present invention may include various functional layers such as a protective film and a hard coat layer in addition to the above. Moreover, an adhesive layer and / or an adhesive layer can be suitably used for the buildup of each layer. As the adhesive layer other than the adhesive layer of the present invention, an ordinary adhesive layer used in the field can be appropriately used. [Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by these examples. In addition, parts and% in each case are a basis of weight.

<Measurement of weight average molecular weight of (meth) acrylic polymer> The weight average molecular weight (Mw) of the (meth) acrylic polymer is measured by GPC (gel permeation chromatography). About Mw / Mn, it measured similarly.・ Analytical device: Tosoh Corporation, HLC-8120GPC ・ Tube: Tosoh Corporation, G7000HXL + GMHXL + GMHXL ・ Column size: Each 7.8 mmf × 30 cm, total 90 cm ・ 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)> A reaction vessel including a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device was charged with 99 parts of butyl acrylate (BA) and 4-hydroxybutyl acrylate. (HBA) 1 part of monomer mixture. Furthermore, with respect to 100 parts of the monomer mixture, 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was added together with 100 parts of ethyl acetate, and nitrogen was introduced to perform nitrogen substitution while stirring slowly. Thereafter, the temperature of the liquid in the flask was maintained at around 55 ° C and polymerization was carried out for 8 hours to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1.8 million and Mw / Mn = 4.1 (solid content concentration of 30 weight). %).

<Preparation of (meth) acrylic polymer (2)> A reaction vessel including a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device was charged with 94.8 parts of butyl acrylate (BA), 5 parts of acrylic acid (AA), And a monomer mixture of 0.2 parts of 2-hydroxyethyl acrylate (HEA). Furthermore, with respect to 100 parts of the monomer mixture, 0.3 part of benzamidine peroxide (Nyper BMT manufactured by Nippon Oil & Fats Co., Ltd.) and 100 parts of ethyl acetate were added together as a polymerization initiator, while stirring slowly. After introducing nitrogen for nitrogen substitution, the temperature of the liquid in the flask was maintained at about 55 ° C. and a polymerization reaction was performed for 8 hours to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 2.2 million and Mw / Mn = 4.1 (solid form). Concentration of ingredients (30% by weight).

<Preparation of (meth) acrylic polymer (3)> A reaction vessel including a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device was charged with 73.3 parts containing butyl acrylate (BA) and phenoxyethyl acrylate ( A monomer mixture of 21 parts of PEA, 5 parts of N-vinylpyrrolidone (NVP), 0.3 parts of acrylic acid (AA), and 0.4 parts of 4-hydroxybutyl acrylate (HBA). Furthermore, 0.1 part of 2,2'-azobisisobutyronitrile, which is a polymerization initiator, and 100 parts of ethyl acetate were added to 100 parts of the monomer mixture (solid content component) together, while stirring slowly. After introducing nitrogen for nitrogen substitution, the temperature of the liquid in the flask was maintained at around 55 ° C and polymerization was performed for 8 hours to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1.6 million and Mw / Mn = 3.8 (solid form). Concentration of ingredients (28% by weight).

Example 1 (Preparation of Adhesive Composition) 100 parts of the solid content of the solution of the acrylic polymer (1) produced above was formulated with a radical generator (benzidine peroxide, manufactured by Japan Oil Corporation) Trade name Nyper BMT) 0.3 parts, isocyanate-based crosslinking agent (trade name Takenate D110N manufactured by Mitsui Chemicals Co., Ltd.) 0.1 part, 2,4-bis-[(4- (4-ethyl Hexyloxy) -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-tri (trade name: Tinosorb S, manufactured by BASF) and 2 parts 0.1 part of a mixture (KBM403 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) to obtain an adhesive composition.

(Production of Adhesive Layer) The above adhesive composition was applied to a 38 μm-thick release film so that the thickness of the adhesive layer after drying became 20 μm (polyethylene terephthalate film with a surface peeled off: (Film), dried at 155 ° C for 1 minute to remove the solvent, and an adhesive layer (A) was obtained.

Immediately after the formation of the above-mentioned adhesive layer (A), the release film having the above-mentioned adhesive layer (A) was transferred to a film having a cycloolefin polymer film / polarizing element / acrylic resin film / adhesive layer (B) / phase difference A polarizing film made of a retardation film made of a film, and a polarizing film with an adhesive layer was produced. The structure of the obtained polarizing film with an adhesive layer was a cycloolefin polymer film / polarizing element / acrylic resin film / adhesive layer (B) / phase difference film / adhesive layer (A).

In addition, the cyclic olefin polymer film and the acrylic resin film on both sides of the polarizing element were laminated using a polyvinyl alcohol-based adhesive to obtain a polarizing film. When a polarizing film with an adhesive layer with a retardation film is produced, the polarizing film and the retardation film are bonded together via the adhesive layer (B).

The constituent members of the polarizing film having a retardation film are as follows.

(Cyclic olefin polymer film) A cyclic olefin polymer film (trade name Zeonor film, manufactured by Zeon Corporation) having a thickness of 25 μm was used.

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

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

(Phase retardation film) A polycarbonate film ("NRF" manufactured by Nitto Denko Corporation, in-plane retardation Re (550): 135 nm) was used with a thickness of 56 μm.

(Preparation of the adhesive composition forming the adhesive layer (B)) In a separable flask equipped with a thermometer, a stirrer, a reflux cooling tube, and a nitrogen introduction tube, 95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were charged as polymerization. After 0.2 parts by weight of azobisisobutyronitrile as the initiator and 233 parts by weight of ethyl acetate, nitrogen was allowed to flow, and nitrogen substitution was performed for about 1 hour while stirring. Thereafter, the flask was heated to 60 ° C. and reacted for 7 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million. Trimethylolpropane toluene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent was added to the acrylic polymer solution (with a solid content of 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 Industry Co., Ltd.) to prepare an adhesive composition (solution).

(Production of Adhesive Layer (B)) The above-mentioned adhesive composition (solution) was applied to a 38 μm-thick release film (polyethylene terephthalate with a peeled surface) so that the thickness after drying became 15 μm. The diester film (release film) was dried at 100 ° C for 3 minutes to remove the solvent to obtain an adhesive layer (B).

Examples 2 to 13 and 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 formulation were changed as shown in Table 1. A pressure-sensitive adhesive layer was formed in the same manner as in Example 1 except for the amount, the type or the amount of the ultraviolet absorber, the type or the amount of the pigment compound, and the amount of the antioxidant. A polarizing film with an adhesive layer was produced in the same manner as in Example 1.

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

<Measurement of the transmittance of the adhesive layer> The release film was peeled from the adhesive layer (A) obtained in the examples and comparative examples, and the adhesive layer (A) was mounted on a measuring jig, and a spectrophotometer ( Product name: U4100, manufactured by Hitachi High-Technologies Co., Ltd.). The transmittance is the transmittance in the range of 300 nm to 450 nm. Table 1 shows the average transmittances of the wavelengths from 300 nm to 400 nm, from 400 nm to 430 nm, and from 430 nm to 450 nm.

<Measurement of gel fraction> Regarding 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 Corporation) (Wa) beforehand. After bundling in such a way that the adhesive is not leaked, the weight (Wb) is measured and put into a sample bottle. 40 cc of ethyl acetate was added and left for 7 days. After that, the fluororesin was taken out and dried on an aluminum cup at 130 ° C. for 2 hours. The weight (Wc) of the fluororesin containing 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 (% by weight) The gel fraction is measured immediately after the formation of the adhesive layer (A) (within 4 hours), After formation of the adhesive layer (A), it was left to stand at room temperature (23 ° C) for one week.

<Appearance Yield> For those obtained by punching the obtained polarizing film with an adhesive layer into a square having a length of 270 mm on one side, evaluate the paste dents and end portions of the adhesive layer (A) according to the following criteria. Paste defects, paste stains at the ends. ○ ... No problem. Δ ... There are local appearance defects caused by paste defects, paste stains, and paste dents. × ... The appearance defects caused by paste defects, paste stains, and paste dents are remarkable.

<Durability> Peel off the barrier film from the polarizing film (290 mm in length × 220 mm in width) with the adhesive layer obtained, and attach the adhesive layer (A) side to a thickness of 0.7 so that it is in the orthogonal polarization state. Both sides of mm alkali-free glass plate. Then, an autoclave treatment was performed at 50 ° C. and 5 atm for 15 minutes, and the samples were prepared by completely sealing them. After treating each sample for 500 hours under the condition of 85, the state of foaming, peeling, and bulging was visually observed according to the following criteria. ○ ・ ・ ・ No foaming, peeling, or bulging. Δ ・ ・ ・ It is a grade with no practical problems, but the grade is slightly worse visually. × ... There are practical problems.

<Peeling force> A 100 mm long and 50 mm wide film was cut out of the obtained polarizing film with an adhesive layer and used as a sample. For the obtained samples, a tensile tester (apparatus name: autostereograph AG-IS, manufactured by Shimadzu Corporation) was used in accordance with JIS Z0237 at 23 ° C and 50% RH in a tensile test. The release film was peeled from the sample at 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 separator is preferably 0.02 to 1.0 (N / 50 mm). The peeling force of the separator is 0.02 (N / 50 mm) or more, which is preferable in terms of suppressing the appearance abnormality caused by the bulging of the separator during processing or operation. On the other hand, it is preferable that the peeling force of the separator is 1.0 (N / 50 mm) or less in terms of suppressing poor peeling of the separator. The peeling force of the aforementioned separator is more preferably 0.04 to 0.5 (N / 50 mm), more preferably 0.06 to 0.2 (N / 50 mm), and even more preferably 0.08 to 0.15 (N / 50 mm).

[Table 1]

In Table 1, the radical generator represents benzamidine peroxide (Nyper BMT, trade name manufactured by Nippon Oil & Fats Co., Ltd.); D110N represents an isocyanate-based crosslinking agent (Takenate D110N, trade name manufactured by Mitsui Chemicals Corporation); C / L represents isocyanate 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-tri (trade name: Tinosorb S, manufactured by BASF); a2 of the ultraviolet absorber represents 2,2 ', 4,4'-tetrahydroxydi Benzophenone (trade name: SeeSorb106, manufactured by Shipro Kasei); b1 of the pigment compound represents a merocyanine compound (trade name: FDB-009, the maximum absorption wavelength of the absorption spectrum: 394 nm, half-value width: 43 nm, Yamada Chemical Industry Co., Ltd.); b2 of the pigment compound represents a polymethine compound (trade name: DAA-247, the maximum absorption wavelength of the absorption spectrum: 389 nm, half-value width: 49.5 nm, Yamada Chemical Industry Co., Ltd.) (Manufactured); b3 of the pigment compound represents an alkylphenylindole cyanoacrylate derivative (indolized) Compound) (trade name: BONASORB UA3912, maximum absorption wavelength of absorption spectrum: 386 nm, half-value width: 53 nm, manufactured by Orient Chemical Industries Co., Ltd.); antioxidant means a phenolic antioxidant (a product manufactured by BASF Japan) Name IRGANOX 1010).

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‧‧‧ Covered glass or plastic

8‧‧‧Organic EL Panel

9‧‧‧ Adhesive layer

10‧‧‧Sensor layer

1 (a) to (c) are cross-sectional views schematically showing an embodiment of a polarizing film with an adhesive layer for an organic EL display device according to the present invention. FIG. 2 is a cross-sectional view schematically showing an embodiment of an organic EL display device according to the present invention. 3 is a cross-sectional view schematically showing an embodiment of an organic EL display device according to the present invention. 4 is a cross-sectional view schematically showing an embodiment of an organic EL display device according to the present invention.

Claims (17)

An adhesive composition for an organic EL display device, comprising: a base polymer, a radical generator, and a compound (A), wherein the compound (A) is selected from 0 to 3 hydroxyl groups in a molecular structure. The ultraviolet absorbent (a) and at least one pigment compound (b) having a maximum absorption wavelength in a wavelength range of 380 to 430 nm exist. The adhesive composition for an organic EL display device according to claim 1, wherein the compound (A) contains both the ultraviolet absorber (a) and the pigment compound (b). The adhesive composition for an organic EL display device according to claim 1 or 2, 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 an organic EL display device according to any one of claims 1 to 3, wherein the radical generator is a peroxide. The adhesive composition for an organic EL display device according to any one of claims 1 to 4, wherein the base polymer is a (meth) acrylic polymer. The adhesive composition for an organic EL display device according to any one of claims 1 to 5, comprising 0.01 to 2 parts by weight of the radical generator with respect to 100 parts by weight of the base polymer. The adhesive composition for an organic EL display device according to any one of claims 1 to 6, which contains 0.1 to 25 parts by weight of the compound (A) with respect to 100 parts by weight of the base polymer. The adhesive composition for an organic EL display device according to any one of claims 1 to 7, further comprising an antioxidant. The adhesive composition for an organic EL display device according to any one of claims 1 to 8, further comprising a crosslinking agent. An adhesive layer for an organic EL display device is characterized in that it is formed of the adhesive composition for an organic EL display device according to any one of claims 1 to 9. For example, the adhesive layer for an organic EL display device according to claim 10, wherein the average transmittance of the wavelength of 300 to 400 nm is 12% or less, the average transmittance of the wavelength of 400 to 430 nm is 30% or less, and the wavelength of 430 to 450 nm The average transmittance is above 70%. For example, the adhesive layer for an organic EL display device of claim 10, wherein the average transmittance of the wavelength of 300 to 400 nm is less than 12%, the average transmittance of the wavelength of 400 to 430 nm is more than 30% and less than 95%, and the wavelength is 430. The average transmittance of ~ 450 nm is above 80%. A polarizing film with an adhesive layer for an organic EL display device, comprising: a polarizing film; and the adhesive layer for an organic EL display device according to any one of claims 10 to 12. For example, the polarizing film with an adhesive layer for an organic EL display device according to claim 13, 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 the organic EL display device described above The surface of the retardation film that is in contact with the polarizing element is the surface on the opposite side, and / or the surface of the transparent protective film that is in contact with the polarizing element is the surface on the opposite side. For example, the polarizing film with an adhesive layer for an organic EL display device according to claim 13 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. As the adhesive layer, at least one of the first adhesive layer, the second adhesive layer, and the third adhesive layer is the adhesive layer for the organic EL display device. For example, the polarizing film with an adhesive layer for an organic EL display device according to claim 14 or 15, wherein the retardation film is a 1/4 wavelength plate, and the polarizing film is a circular polarizing film. An organic EL display device characterized in that it uses an adhesive layer for an organic EL display device according to any one of claims 10 to 12 or an organic EL display device with any one of claims 13 to 16 At least one of the polarizing films using an adhesive layer.