JP2017165941A - 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

PROBLEM TO BE SOLVED: To provide an adhesive composition for organic EL display device capable of forming an adhesive layer for organic EL display device which is used in an organic EL display device and thereby can suppress deterioration of an organic EL element and has high transparency, and to provide an adhesive layer for organic EL display device formed from the adhesive composition, a polarizing film with an adhesive layer having a polarizing film and the adhesive layer for organic EL display device, and an organic EL display device containing the adhesive layer and/or the polarizing film with an adhesive layer.SOLUTION: An adhesive composition for organic EL display device contains a base polymer, an ultraviolet absorber, and a dye compound of which a maximum absorption wavelength of an absorption spectrum exists in a wavelength region of 380-430 nm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an adhesive composition for an organic EL (electroluminescence) display device (OLED). Moreover, this invention relates to the polarizing film with an adhesive layer which has the adhesive layer for organic EL display devices formed from the said adhesive composition for organic EL display devices, and the said adhesive layer. Furthermore, the present invention relates to an organic EL display device using the pressure-sensitive adhesive layer and / or the 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 monitors, and televisions. In general, an organic EL display device has a circularly polarizing plate (polarizing plate 1 and a polarizing plate 1) on a surface on the viewing side of an organic EL panel in order to prevent external light from being reflected by a metal electrode (cathode) and viewed like a mirror surface. / 4 wavelength plate laminate or the like) is disposed. Moreover, a decorative panel etc. may be further laminated | stacked on the circularly-polarizing plate laminated | stacked on the visual recognition side surface of the organic EL panel. The constituent members of the organic EL display device such as the circularly polarizing plate and the decorative panel are usually laminated via a bonding material such as an adhesive layer and an adhesive layer.

  In an image display device such as an organic EL display device, a component or the like in the image display device may be deteriorated by incident ultraviolet light, and a layer containing an ultraviolet absorber in order to suppress deterioration due to the ultraviolet light. It is known to provide Specifically, for example, it has at least one ultraviolet absorbing layer, the light transmittance at a wavelength of 380 nm is 30% or less, and the visible light transmittance at a wavelength longer than the wavelength of 430 nm is 80% or more. Transparent double-sided pressure-sensitive adhesive sheets for image display devices (for example, see Patent Document 1) and pressure-sensitive adhesive sheets having a pressure-sensitive adhesive layer containing an acrylic polymer and a triazine-based ultraviolet absorber are known (for example, see Patent Document 2). .

JP 2012-211305 A JP 2013-75978 A

  The pressure-sensitive adhesive sheets described in Patent Documents 1 and 2 can control the transmittance of light having a wavelength of 380 nm. When the pressure-sensitive adhesive sheet is used in an organic EL display device, the organic EL element can be used over a long period of time. May deteriorate and was not sufficient. This is because the pressure-sensitive adhesive sheets described in Patent Documents 1 and 2 can absorb light having a wavelength of 380 nm, but the wavelength region on the shorter wavelength side (380 nm) than the light emitting region of the organic EL element (longer wavelength side than 430 nm). (˜430 nm) is not sufficiently absorbed, and it is considered that the transmitted light deteriorates.

  Therefore, in order to suppress deterioration of the organic EL element, transmission of light having a wavelength (380 nm to 430 nm) shorter than the light emitting region (longer wavelength side than 430 nm) of the organic EL element is suppressed. Therefore, it is necessary to use a layer having a high transparency that can sufficiently ensure the transmittance of visible light in the light emitting region of the organic EL display device.

  Therefore, the present invention can be used for an organic EL display device, can suppress deterioration of the organic EL element, and can form a highly transparent pressure-sensitive adhesive layer for an organic EL display device. It aims at providing the adhesive composition for display apparatuses. Moreover, the polarizing film with an adhesive layer which has an adhesive layer for organic EL display devices formed from the said adhesive composition, a polarizing film, and an adhesive layer for organic EL display devices, the said adhesive layer, and / or the said adhesive An object is to provide an organic EL display device including a polarizing film with a layer.

  As a result of intensive studies to solve the above problems, the present inventors have found the following pressure-sensitive adhesive composition for organic EL display devices, and have completed the present invention.

  That is, the present invention relates to a pressure-sensitive adhesive composition for an organic EL display device comprising a base polymer, an ultraviolet absorber, and a pigment compound having a maximum absorption wavelength of an absorption spectrum in a wavelength region of 380 to 430 nm. .

  The base polymer is preferably a (meth) acrylic polymer.

  It is preferable that the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber exists in a wavelength region of 300 to 400 nm.

  Moreover, this invention relates to the adhesive layer for organic EL display apparatuses formed from the said adhesive composition for organic EL display apparatuses.

  In the pressure-sensitive adhesive layer for an organic EL display device, the average transmittance at a wavelength of 300 to 400 nm is 5% or less, the average transmittance at a wavelength of 450 to 500 nm is 70% or more, and the average transmittance at a wavelength of 500 to 780 nm is It is preferable that it is 80% or more.

  Furthermore, the average transmittance at a wavelength of 300 to 400 nm is 5% or less, the average transmittance at a wavelength of 400 nm to 430 nm is 30% or less, and the average transmittance at a wavelength of 450 to 500 nm is 70%. As described above, an embodiment having an average transmittance of 80% or more at a wavelength of 500 to 780 nm can be used.

  Furthermore, the average transmittance at a wavelength of 300 to 400 nm is 5% or less, the average transmittance at a wavelength of 400 nm to 430 nm is more than 30% and 75% or less, and the average transmittance at a wavelength of 450 to 500 nm. It is possible to use an embodiment in which the rate is 80% or more and the average transmittance at a wavelength of 500 to 780 nm is 80% or more.

  Moreover, this invention relates to the polarizing film with an adhesive layer for organic EL display apparatuses characterized by having a polarizing film and the said adhesive layer for organic EL display apparatuses.

  The polarizing film has a transparent protective film on one surface of a polarizer and a retardation film on the other surface, and the pressure-sensitive adhesive layer for an organic EL display device is a polarizing film of the retardation film. It is preferable to be provided on the surface opposite to the surface in contact with the child and / or on the surface opposite to the surface in contact with the polarizer of the transparent protective film.

The polarizing film with a pressure-sensitive adhesive layer for an organic EL display device has a first pressure-sensitive adhesive layer, a transparent protective film, a polarizer, a second pressure-sensitive adhesive layer, a retardation film, and a third pressure-sensitive adhesive layer in this order.
Of the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer, it is preferable that at least one pressure-sensitive adhesive layer is the pressure-sensitive adhesive layer for an organic EL display device.

  It is preferable that the retardation film is a quarter wavelength plate and the polarizing film is a circularly polarizing film.

  The present invention also relates to an organic EL display device characterized by using at least one of the pressure-sensitive adhesive layer for organic EL display devices or the polarizing film with the pressure-sensitive adhesive layer for organic EL display devices.

  The pressure-sensitive adhesive composition for an organic EL display device of the present invention can suppress deterioration of the organic EL element when used in an organic EL display device, and forms a highly transparent pressure-sensitive adhesive layer for an organic EL display device. can do. Therefore, the organic EL display device using the polarizing film with the pressure-sensitive adhesive layer including the pressure-sensitive adhesive layer for the organic EL display device and / or the pressure-sensitive adhesive layer for the organic EL display device of the present invention has excellent weather resistance degradation, The life can be extended.

(A)-(c) It is sectional drawing which shows typically one Embodiment of the polarizing film with an adhesive layer for organic EL display apparatuses of this invention. It is sectional drawing which shows typically one Embodiment of the organic electroluminescent display apparatus of this invention. It is sectional drawing which shows typically one Embodiment of the organic electroluminescent display apparatus of this invention. It is sectional drawing which shows typically one Embodiment of the organic electroluminescent display apparatus of this invention.

1. Adhesive composition for organic EL display device The adhesive composition for organic EL display device of the present invention comprises a base polymer, an ultraviolet absorber, and a dye compound having a maximum absorption wavelength of an absorption spectrum in a wavelength region of 380 to 430 nm. It is characterized by including. Here, the maximum absorption wavelength means an absorption maximum wavelength exhibiting the maximum absorbance among the plurality of absorption maximums in the spectral absorption spectrum in the wavelength region of 300 to 460 nm. .

  The base polymer used in the present invention is not particularly limited. Examples of the pressure-sensitive adhesive composition include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, and vinyl alkyls. Examples thereof include ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate adhesiveness, cohesiveness, and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance, heat resistance, and the like. . In the present invention, an acrylic pressure-sensitive adhesive composition containing a (meth) acrylic polymer as a base polymer is preferable.

  The acrylic pressure-sensitive adhesive composition includes, for example, a partial polymer of a monomer component containing an alkyl (meth) acrylate and / or a (meth) acrylic polymer obtained from the monomer component, an ultraviolet absorber and a dye compound. It is preferable.

(1) Partially polymerized monomer component and (meth) acrylic polymer The acrylic pressure-sensitive adhesive composition is obtained from a partially polymerized monomer component containing alkyl (meth) acrylate and / or the monomer component ( Contains a (meth) acrylic polymer.

  Examples of the alkyl (meth) acrylate include those having a linear or branched alkyl group having 1 to 24 carbon atoms at the ester terminal. Alkyl (meth) acrylate can be used individually by 1 type or in combination of 2 or more types. “Alkyl (meth) acrylate” refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.

  Examples of the alkyl (meth) acrylate include the aforementioned linear or branched alkyl (meth) acrylate having 1 to 24 carbon atoms. Among these, a C1-C9 alkyl (meth) acrylate is preferable, a C4-C9 alkyl (meth) acrylate is more preferable, and a C4-C9 branched alkyl (meth) acrylate is further more preferable. . The alkyl (meth) acrylate is preferable in terms of easily balancing the adhesive properties. For example, as an alkyl (meth) acrylate having 4 to 9 carbon atoms, specifically, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate , N-pentyl (meth) acrylate, isopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and the like. These can be used singly or in combination of two or more.

  In the present invention, the alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms at the ester terminal is 40% by weight or more based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. It is preferably 50% by weight or more, more preferably 60% by weight or more.

  The monomer component may contain a copolymerization monomer other than the alkyl (meth) acrylate as a monofunctional monomer component. A copolymerization monomer can be used as the remainder of the said alkyl (meth) acrylate in a monomer component.

  As the copolymerization monomer, for example, a cyclic nitrogen-containing monomer can be included. As said cyclic nitrogen containing monomer, what has a polymerizable functional group which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, and has a cyclic nitrogen structure can be especially used without a restriction | limiting. The cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure. Examples of cyclic nitrogen-containing monomers include lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinyl Examples thereof include vinyl monomers having a nitrogen-containing heterocyclic ring such as imidazole, vinyl oxazole and vinyl morpholine. Moreover, the (meth) acryl monomer containing heterocyclic rings, such as a morpholine ring, a piperidine ring, a pyrrolidine ring, a piperazine ring, is mentioned. Specific examples include N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like. Among the cyclic nitrogen-containing monomers, lactam vinyl monomers are preferable.

  In the present invention, the cyclic nitrogen-containing monomer is preferably 0.5 to 50% by weight, and preferably 0.5 to 40% by weight, based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. Is more preferable, and 0.5 to 30% by weight is further preferable.

  The monomer component used in the present invention can contain a hydroxyl group-containing monomer as a monofunctional monomer component. As the hydroxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate; -Hydroxyalkylcycloalkane (meth) acrylates such as -hydroxymethylcyclohexyl) methyl (meth) acrylate. Other examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like. These can be used alone or in combination. Of these, hydroxyalkyl (meth) acrylate is preferred.

  In the present invention, the hydroxyl group-containing monomer is preferably 1% by weight or more from the viewpoint of enhancing adhesive force and cohesive force with respect to the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, It is more preferably 2% by weight or more, and further preferably 3% by weight or more. On the other hand, if the amount of the hydroxyl group-containing monomer is too large, the pressure-sensitive adhesive layer becomes hard and the adhesive strength may decrease, and the viscosity of the pressure-sensitive adhesive may become too high or gel. The hydroxyl group-containing monomer is preferably 30% by weight or less, more preferably 27% by weight or less, and more preferably 25% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. Is more preferable.

  In addition, the monomer component that forms the (meth) acrylic polymer can contain other functional group-containing monomers as monofunctional monomers, such as carboxyl group-containing monomers and monomers having a cyclic ether group. It is done.

  As the carboxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Can be used alone or in combination. These anhydrides can be used for itaconic acid and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable. In addition, a carboxyl group-containing monomer can be arbitrarily used for the monomer component used for manufacture of the (meth) acrylic-type polymer of this invention, On the other hand, it is not necessary to use a carboxyl group-containing monomer.

  As a monomer having a cyclic ether group, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and a cyclic ether group such as an epoxy group or an oxetane group. It can be used without particular limitation. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Examples of the oxetane group-containing monomer include 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, and 3-butyl-oxetanylmethyl (meth) acrylate. , 3-hexyl-oxetanylmethyl (meth) acrylate and the like. These can be used alone or in combination.

  In the present invention, the carboxyl group-containing monomer and the monomer having a cyclic ether group are preferably 30% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, and 27% by weight. % Or less is more preferable, and 25% by weight or less is more preferable.

The monomer component forming the (meth) acrylic polymer of the present invention includes, for example, CH ₂ ═C (R ¹ ) COOR ² (wherein R ¹ is hydrogen or a methyl group, and R ² is the number of carbon atoms). An alkyl (meth) acrylate represented by 1 to 3 substituted alkyl groups and a cyclic cycloalkyl group.

Here, the substituent of the substituted alkyl group having 1 to 3 carbon atoms as R ² is preferably an aryl group having 3 to 8 carbon atoms or an aryloxy group having 3 to 8 carbon atoms. . The aryl group is not limited, but is preferably a phenyl group.

Examples of such a monomer represented by CH ₂ ═C (R ¹ ) COOR ² include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl. (Meth) acrylate, isobornyl (meth) acrylate, etc. are mentioned. These can be used alone or in combination.

In the present invention, the (meth) acrylate represented by CH ₂ ═C (R ¹ ) COOR ² is 50% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer. 45% by weight or less is preferable, 40% by weight or less is more preferable, and 35% by weight or less is more preferable.

  Other copolymer monomers include vinyl acetate, vinyl propionate, styrene, α-methylstyrene; (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, (meth) Glycol acrylic ester monomers such as methoxypolypropylene glycol acrylate; Acrylic ester monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; Monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers, and the like can also be used. Moreover, as a copolymerization monomer, the monomer which has cyclic structures, such as terpene (meth) acrylate and dicyclopentanyl (meth) acrylate, can be used.

  Furthermore, the silane type monomer etc. which contain a silicon atom are mentioned. Examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane. , 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.

  The monomer component that forms the (meth) acrylic polymer of the present invention contains a polyfunctional monomer as necessary in order to adjust the cohesive strength of the pressure-sensitive adhesive, in addition to the monofunctional monomer exemplified above. be able to.

  The polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as (poly) ethylene glycol di (meth) acrylate, (Poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate Ester compounds of polyhydric alcohols such as (meth) acrylic acid; allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di (meth) acrylate, hexyl di (meth) ) Acrylate and the like. Among these, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

  The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but it is preferably used at 3 parts by weight or less, more preferably 2 parts by weight or less, with respect to a total of 100 parts by weight of the monofunctional monomer. 1 part by weight or less is more preferable. Moreover, it does not specifically limit as a lower limit, However It is preferable that it is 0 weight part or more, and it is more preferable that it is 0.001 weight part or more. Adhesive force can be improved when the usage-amount of a polyfunctional monomer exists in the said range.

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

  In the present invention, a partial polymer of the monomer component can also be suitably used.

  When the (meth) acrylic polymer is produced by radical polymerization, polymerization can be carried out by appropriately adding a polymerization initiator, a chain transfer agent, an emulsifier and the like used for radical polymerization to the monomer component. The polymerization initiator, chain transfer agent, emulsifier and the like used for the radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, and the usage-amount is suitably adjusted according to these kinds.

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

  Examples of the thermal polymerization initiator used for solution polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis (2 -Methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (N, N′-dimethyleneisobutyl) Amidine), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, Wako Pure Chemical Industries, Ltd.) Azo-based initiators such as potassium persulfate and ammonium persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec -Butyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1 , 3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-hexyl) Peroxy) cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, etc. Compound initiators, combinations of persulfates and sodium bisulfite, redox initiators combining peroxides and reducing agents such as combinations of peroxides and sodium ascorbate, etc. It is not limited.

  The polymerization initiator may be used alone or in combination of two or more, but is preferably about 1 part by weight or less with respect to 100 parts by weight of the total amount of monomer components. The amount is more preferably about 0.005 to 1 part by weight, and still more preferably about 0.02 to 0.5 part by weight.

  When 2,2′-azobisisobutyronitrile is used as the polymerization initiator, the amount of the polymerization initiator used is about 0.2 parts by weight or less with respect to 100 parts by weight of the total amount of monomer components. The amount is preferably about 0.06 to 0.2 parts by weight.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be used alone or in combination of two or more, but the total content is 0.3 parts by weight relative to 100 parts by weight of the total amount of monomer components. Less than or equal to

  Examples of the emulsifier used in emulsion polymerization include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxy Nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer are listed. These emulsifiers may be used alone or in combination of two or more.

  Furthermore, as reactive emulsifiers, as emulsifiers into which radical polymerizable functional groups such as propenyl groups and allyl ether groups are introduced, specifically, for example, Aqualon HS-10, HS-20, KH-10, BC-05 BC-10, BC-20 (all of which are manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Soap SE10N (manufactured by ADEKA), and the like. The amount of the emulsifier used is preferably 5 parts by weight or less with respect to 100 parts by weight of the total amount of the monomer components.

  Moreover, when manufacturing the said (meth) acrylic-type polymer by radiation polymerization, it can superpose | polymerize and manufacture by irradiating radiation, such as an electron beam and an ultraviolet-ray (UV), to the said monomer component. Among these, ultraviolet polymerization is preferable. Hereinafter, ultraviolet polymerization which is a preferable embodiment in radiation polymerization will be described.

  When performing the ultraviolet polymerization, it is preferable to contain a photopolymerization initiator in the monomer component because of the advantage that the polymerization time can be shortened. Accordingly, when performing ultraviolet polymerization, for example, an ultraviolet curable acrylic containing a monomer component containing the alkyl (meth) acrylate and / or a partial polymer of the monomer component, an ultraviolet absorber, a dye compound, and a photopolymerization initiator. It is preferably formed by ultraviolet polymerization of the pressure-sensitive adhesive composition. Since the pressure-sensitive adhesive layer formed by ultraviolet polymerization of the ultraviolet curable acrylic pressure-sensitive adhesive composition can be formed to have a thickness of 150 μm or more, and a pressure-sensitive adhesive layer having a wide thickness can be formed. preferable.

  Although it does not specifically limit as said photoinitiator, It is preferable that the photoinitiator (A) which has an absorption band in wavelength 400nm or more is included. In the case where the pressure-sensitive adhesive composition contains an ultraviolet absorber or a dye compound, when ultraviolet polymerization is performed, the ultraviolet ray is absorbed by the ultraviolet absorber or the dye compound, and thus the polymerization cannot be sufficiently performed. However, the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is preferable because it can be sufficiently polymerized even though it contains an ultraviolet absorber and a dye compound.

  As a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by BASF), 2,4,6-trimethylbenzoyl- And diphenyl-phosphine oxide (LUCIRIN TPO, manufactured by BASF).

  The photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more may be used alone or in combination of two or more.

  Further, the amount of addition of the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is not particularly limited, but is preferably less than the addition amount of an ultraviolet absorber or a dye compound described later, The amount is preferably about 0.005 to 1 part by weight and more preferably about 0.02 to 0.8 part by weight with respect to 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer. preferable. It is preferable that the amount of the photopolymerization initiator (A) added is in the above range because ultraviolet polymerization can sufficiently proceed.

  The photopolymerization initiator may contain a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm. The photopolymerization initiator (B) is not particularly limited as long as it generates radicals by ultraviolet rays and starts photopolymerization and has an absorption band at a wavelength of less than 400 nm. Any initiator can be suitably used. For example, benzoin ether photopolymerization initiator, acetophenone photopolymerization initiator, α-ketol photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone A photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or the like can be used.

  Specifically, examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- Examples include 1-one and anisole methyl ether.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4-t-butyldichloroacetophenone. Etc.

  Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-hydroxy-2-methylpropan-1-one, and the like. Is mentioned.

  Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.

  Examples of the benzoin photopolymerization initiator include benzoin.

  Examples of the benzyl photopolymerization initiator include benzyl.

  Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like.

  Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.

  Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4. -Diisopropylthioxanthone, dodecylthioxanthone and the like are included.

  Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  The photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be used alone or in combination of two or more. The photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be added within a range that does not impair the effects of the present invention, and the addition amount is a monofunctional that forms a (meth) acrylic polymer. The amount is preferably about 0.005 to 0.5 parts by weight and more preferably about 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the monomeric monomer component.

  In the present invention, when the monomer component is subjected to ultraviolet polymerization, a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm is first added to the monomer component, and ultraviolet rays are irradiated to partially polymerize. It is preferable to perform ultraviolet polymerization by adding a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more, an ultraviolet absorber, and a dye compound to a partial polymerization product (prepolymer composition) of the monomer component. When the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is added to the partial polymerization product (prepolymer composition) of the monomer component partially polymerized by ultraviolet irradiation, the photopolymerization is started. It is preferable to add the agent after dissolving it in the monomer.

(2) Ultraviolet absorber The ultraviolet absorber is not particularly limited. For example, a triazine ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, an oxybenzophenone ultraviolet absorber, or a salicylic acid ester ultraviolet ray. An absorber, a cyanoacrylate type ultraviolet absorber, etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types. Among these, triazine-based UV absorbers and benzotriazole-based UV absorbers are preferable, triazine-based UV absorbers having 2 or less hydroxyl groups in one molecule, and benzones having one benzotriazole skeleton in one molecule. It is at least one ultraviolet absorber selected from the group consisting of triazole-based ultraviolet absorbers, has good solubility in monomers used for forming an acrylic pressure-sensitive adhesive composition, and has a wavelength of around 380 nm This is preferable because of its high ultraviolet absorption ability.

  Specific examples of the triazine-based ultraviolet absorber having two or less hydroxyl groups in one molecule include 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6. -(4-Methoxyphenyl) -1,3,5-triazine (Tinosorb S, manufactured by BASF), 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine (TINUVIN 460, manufactured by BASF), 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl And [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxirane reaction product (TINUVIN400, manufactured by BASF), 2- [4,6-bis (2, -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) -4,6 -Reaction product of bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester (TINUVIN405, manufactured by BASF), 2- (4,6-diphenyl-1 , 3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (TINUVIN 1577, manufactured by BASF), 2- (4,6-diphenyl-1,3,5-triazin-2-yl)- 5- [2- (2-Ethylhexanoyloxy) ethoxy] -phenol (ADK STAB LA46, manufactured by ADEKA), 2- (2-hydroxy-4- [ - octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine (TINUVIN 479, manufactured by BASF), and the like.

  Moreover, as a benzotriazole ultraviolet absorber having one benzotriazole skeleton in one molecule, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 928, manufactured by BASF), 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole (TINUVIN PS, manufactured by BASF), benzene Propanoic acid and ester compounds of 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy (C7-9 side chain and linear alkyl) (TINUVIN 384-2, BASF) Manufactured), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenyl) Ethyl) phenol (TINUVIN900, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) ) Phenol (TINUVIN 928, manufactured by BASF), methyl-3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product (TINUVIN 1130, 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- (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol (TINUVIN 326, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4,6-di -Tert-pentylphenol (TINUVIN 328, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (TINUVIN 329, manufactured by BASF), methyl 3 -(3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 reaction product (TINUVIN 213, manufactured by BASF), 2- (2H-benzotriazole -2-yl) -6-dodecyl-4-methylphenol (TI NUVIN571, manufactured by BASF), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole (Sumsorb 250, manufactured by Sumitomo Chemical Co., Ltd.), etc. Can be mentioned.

  Examples of the benzophenone ultraviolet absorber (benzophenone compound) and oxybenzophenone ultraviolet absorber (oxybenzophenone compound) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy. -4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2, Examples include 2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4-dimethoxybenzophenone.

  Examples of the salicylic acid ester-based ultraviolet absorber (salicylic acid ester-based compound) include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, and phenyl-2-acryloyloxy. -4-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, phenyl-2-hydroxy -3-methylbenzoate, phenyl-2-hydroxy-4 methylbenzoate, phenyl-2-hydroxy-5-methylbenzoate, phenyl 2-hydroxy-3-methoxybenzoate, 2,4-di-tert -Butylphenyl-3,5-di-tert-butyl And the like-4-hydroxybenzoate (TINUVIN120, manufactured by BASF).

  Examples of the cyanoacrylate ultraviolet absorber (cyanoacrylate compound) include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl- Examples include 2-cyanoacrylate.

  The maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in the wavelength region of 300 to 400 nm, and more preferably in the wavelength region of 320 to 380 nm. The measuring method of the maximum absorption wavelength is the same as the measuring method of the dye-based compound described later.

  The ultraviolet absorber may be used alone or in combination of two or more, but the total content is a monofunctional monomer component that forms a (meth) acrylic polymer. The amount is preferably about 0.1 to 5 parts by weight and more preferably about 0.5 to 3 parts by weight with respect to 100 parts by weight. By making the addition amount of the ultraviolet absorber within the above range, it is preferable that the ultraviolet ray absorbing function of the pressure-sensitive adhesive layer can be sufficiently exhibited, and when the ultraviolet polymerization is performed, the polymerization is not hindered.

(3) Dye Compound The dye compound used in the present invention is not particularly limited as long as it is a compound having a maximum absorption wavelength of an absorption spectrum in a wavelength region of 380 to 430 nm. The maximum absorption wavelength of the absorption spectrum of the dye compound is more preferably in the wavelength region of 380 to 420 nm. In the present invention, by using a combination of such a dye compound and the ultraviolet absorber, light in a region (wavelength 380 nm to 430 nm) that does not affect the light emission of the organic EL element can be sufficiently absorbed, and The light emitting region of the organic EL element (longer wavelength side than 430 nm) can be sufficiently transmitted, and as a result, deterioration of the organic EL element due to external light can be suppressed. The dye compound is not particularly limited as long as it has the above-mentioned wavelength characteristics, but a material that does not have fluorescence and phosphorescence performance (photoluminescence) so as not to hinder the display properties of the organic EL element is preferable.

The half width of the dye compound 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. When the half-value width of the dye compound is in the above range, it is possible to control to sufficiently transmit light having a wavelength longer than 430 nm while sufficiently absorbing light in a region that does not affect light emission of the organic EL element. Therefore, it is preferable. In addition, the measuring method of a half value width is based on the method as described below.
<Measurement method of half width>
The full width at half maximum of the dye compound was measured from the transmission absorption spectrum of the solution of the dye compound under the following conditions using an ultraviolet-visible spectrophotometer (U-4100, manufactured by Hitachi High-Tech Science Co., Ltd.). From the spectrum measured by adjusting the concentration so that the absorbance at the maximum absorption wavelength is 1.0, the wavelength interval (full width at half maximum) between two points at 50% of the peak value is defined as the half width of the dye compound. .
(Measurement condition)
Solvent: Toluene or chloroform Cell: Quartz cell Optical path length: 10 mm

  The dye compound is not particularly limited as long as it is a compound having a maximum absorption wavelength of an absorption spectrum in a wavelength region of 380 to 430 nm. Examples of the dye compound include an organic dye compound and an inorganic dye compound. Among these, an organic dye is used from the viewpoint of maintaining dispersibility in a resin component such as a base polymer and transparency. Compounds are preferred.

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

  As the organic dye compound, a commercially available product can be suitably used. Specifically, as the indole compound, BONASORB UA3911 (trade name, maximum absorption wavelength of absorption spectrum: 398 nm, half-value width: 48 nm, manufactured by Orient Chemical Industry Co., Ltd.), BONASORB UA3912 (trade name, maximum absorption wavelength of absorption spectrum: 386 nm, half width: 53 nm, manufactured by Orient Chemical Industry Co., Ltd.), and cinnamate compounds as SOM -5-0106 (trade name, absorption spectrum maximum absorption wavelength: 416 nm, full width at half maximum: 50 nm, manufactured by Orient Chemical Industry Co., Ltd.), porphyrin compounds, FDB-001 (trade name, absorption spectrum maximum absorption wavelength : 420 nm, half width: 14 nm, manufactured by Yamada Chemical Co., Ltd.) Can.

  The dye compound may be used alone or in combination of two or more, but the total content is a monofunctional monomer component 100 that forms a (meth) acrylic polymer. The amount is preferably about 0.01 to 10 parts by weight and more preferably about 0.02 to 5 parts by weight with respect to parts by weight. By making the addition amount of the dye compound in the above range, it is possible to sufficiently absorb light in a region that does not affect the light emission of the organic EL element, and by using the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, Since deterioration of an organic EL element can be suppressed, it is preferable.

(4) Silane coupling agent Furthermore, the pressure-sensitive adhesive composition of the present invention can contain a silane coupling agent. The amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer. More preferred is 0.02 to 0.6 parts by weight.

  Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclohexyl). Epoxy group-containing silane coupling agents such as ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, (3-dimethylbutylidene) propylamine, amino group-containing silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane ( (Meth) acrylic group-containing silane Coupling agent, 3-isocyanate propyltriethoxysilane isocyanate group-containing silane coupling agents such as and the like.

(5) Crosslinking agent The adhesive composition of this invention can contain a crosslinking agent. Examples of crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents, Crosslinkers such as oxides are included. A crosslinking agent can be used alone or in combination of two or more. Among these, an isocyanate type crosslinking agent is preferably used.

  The crosslinking agent may be used alone or in combination of two or more, but the total content is a monofunctional monomer that forms a (meth) acrylic polymer. The amount is preferably 5 parts by weight or less, more preferably 0.01 to 5 parts by weight, further preferably 0.01 to 4 parts by weight, and 0.02 to 3 parts by weight with respect to 100 parts by weight of the component. Particularly preferred.

  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 quantification) in one molecule. Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

  More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cycloaliphatic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexamethylene Isocyanurate of isocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like, trimethylolpropane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals, Inc.), hexa Trimethylolpropane adduct of methylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals); polyether polyisocyanate, polyester polyisocyanate, and adducts of these with various polyols, isocyanurate bond, burette bond, Examples thereof include polyisocyanates polyfunctionalized with allophanate bonds.

(6) Other additives The pressure-sensitive adhesive composition of the present invention may contain appropriate additives in addition to the above components, depending on the application. For example, tackifiers (for example, rosin derivative resins, polyterpene resins, petroleum resins, oil-soluble phenol resins, etc., solid, semi-solid, or liquid at room temperature); fillers such as hollow glass balloons; plasticizers; aging An antioxidant; a light stabilizer (HALS); and an antioxidant.

  In the present invention, the pressure-sensitive adhesive composition is preferably adjusted to have a viscosity suitable for work such as coating on a substrate. Adjustment of the viscosity of the pressure-sensitive adhesive composition is performed, for example, by adding various polymers such as thickening additives, polyfunctional monomers, or the like, or by partially polymerizing the monomer components in the pressure-sensitive adhesive composition. The partial polymerization may be performed before or after adding various polymers such as thickening additives, polyfunctional monomers, and the like. Since the viscosity of the pressure-sensitive adhesive composition varies depending on the amount of the additive and the like, the polymerization rate when the monomer component in the pressure-sensitive adhesive composition is partially polymerized cannot be uniquely determined, but as a guideline, it is about 20% or less. Preferably, it is about 3 to 20%, more preferably about 5 to 15%. If it exceeds 20%, the viscosity becomes too high, so that it is difficult to apply to the substrate.

2. The pressure-sensitive adhesive layer for organic EL display devices The pressure-sensitive adhesive layer for organic EL display devices of the present invention is formed from the pressure-sensitive adhesive composition for organic EL display devices.

  The method for forming the pressure-sensitive adhesive layer is not particularly limited, and can be formed by a method usually used in this field. Specifically, the pressure-sensitive adhesive composition is applied to at least one surface of the substrate, and a coating film formed from the pressure-sensitive adhesive composition is formed by drying, or irradiated with active energy rays such as ultraviolet rays. Can be formed.

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

  Examples of the constituent material of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. Suitable thin leaf bodies and the like can be mentioned, but a resin film is suitably used from the viewpoint of excellent surface smoothness.

  Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene. -A vinyl acetate copolymer film etc. are mentioned.

  The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. For the release film, if necessary, release agent and antifouling treatment with silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, silica powder, etc., coating type, kneading type, An antistatic treatment such as a vapor deposition type can also be performed. In particular, the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the release film.

  The transparent resin film substrate is not particularly limited, and various resin films having transparency are used. The resin film is formed of a single layer film. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

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

  The pressure-sensitive adhesive composition is applied onto the substrate by roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain. A known and appropriate method such as a coat, a lip coat, or a die coater can be used and is not particularly limited.

  When the pressure-sensitive adhesive layer is formed by drying a coating film formed from the pressure-sensitive adhesive composition, the drying conditions (temperature, time) are not particularly limited, and the composition of the pressure-sensitive adhesive composition, Although it can set suitably by a density | concentration etc., it is about 60-170 degreeC, for example, Preferably it is 60-150 degreeC, for 1 to 60 minutes, Preferably it is 2 to 30 minutes.

When the pressure-sensitive adhesive composition is an ultraviolet curable pressure-sensitive adhesive composition and is formed by irradiating a coating film formed from the ultraviolet-curable pressure-sensitive adhesive composition with ultraviolet rays, the illuminance of the irradiated ultraviolet rays is 5 mW / cm ² or more is preferable. When the illuminance of the ultraviolet light is less than 5 mW / cm ² , the polymerization reaction time becomes long and the productivity may be inferior. The illuminance of the ultraviolet light is preferably 200 mW / cm ² or less. When the illuminance of the ultraviolet rays exceeds 200 mW / cm ² , the photopolymerization initiator is consumed rapidly, so that the polymer has a low molecular weight, and the holding power particularly at high temperatures may be reduced. Further, the integrated quantity of ultraviolet light ^is preferably ^{100mJ / cm 2 ~5000mJ / cm 2} .

  The ultraviolet lamp used in the present invention is not particularly limited, but an LED lamp is preferable. Since the LED lamp has a lower emission heat than other ultraviolet lamps, the temperature during polymerization of the pressure-sensitive adhesive layer can be suppressed. Therefore, the molecular weight reduction of the polymer can be prevented, the cohesive strength of the pressure-sensitive adhesive layer can be prevented from being lowered, and the holding power at a high temperature when the pressure-sensitive adhesive sheet is used can be increased. It is also possible to combine a plurality of ultraviolet lamps. Further, it is possible to intermittently irradiate ultraviolet rays, and to provide a light period in which ultraviolet rays are irradiated and a dark period in which ultraviolet rays are not irradiated.

  In the present invention, the final polymerization rate of the monomer component in the ultraviolet curable pressure-sensitive adhesive composition is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.

  In this invention, it is preferable that the peak wavelength of the ultraviolet-ray irradiated to the said ultraviolet curable adhesive composition exists in the range of 200-500 nm, and it is more preferable that it exists in the range of 300-450 nm. When the peak wavelength of ultraviolet rays exceeds 500 nm, the photopolymerization initiator may not be decomposed and the polymerization reaction may not start. On the other hand, if the peak wavelength of the ultraviolet light is less than 200 nm, the polymer chain may be cut and the adhesive properties may be deteriorated.

  Since the reaction is inhibited by oxygen in the air, a release film or the like is formed on the coating film formed from the ultraviolet curable acrylic pressure-sensitive adhesive composition to block oxygen, or the photopolymerization reaction is performed by nitrogen. It is preferable to carry out in an atmosphere. The above-mentioned thing can be mentioned as a release film. In addition, when a release film is used, the said release film can be used as a separator of a polarizing film with an adhesive layer as it is.

  Moreover, when the ultraviolet curable adhesive composition used by this invention contains a photoinitiator (B), the monomer component containing an alkyl (meth) acrylate and the said photoinitiator (B) ("Previous The composition including the “addition polymerization initiator” may be irradiated with ultraviolet rays to form a partial polymer of the monomer component, and the partial polymerization product of the monomer component may include an ultraviolet absorber, a dye compound, and a wavelength. It is preferable to add a photopolymerization initiator (A) having an absorption band at 400 nm or more (sometimes referred to as “post-addition polymerization initiator”) to prepare an ultraviolet curable pressure-sensitive adhesive composition. The polymerization rate of the partially polymerized product is preferably about 20% or less, more preferably about 3 to 20%, and still more preferably about 5 to 15%. The ultraviolet irradiation conditions are as described above.

  As described above, when the pressure-sensitive adhesive layer is formed from the ultraviolet curable pressure-sensitive adhesive composition containing the photopolymerization initiator (B), the polymerization rate of the monomer component is increased by polymerization in the two steps as described above. And the ultraviolet absorbing function of the finally produced pressure-sensitive adhesive layer can be improved.

  The thickness of the pressure-sensitive adhesive layer is preferably 12 μm or more, more preferably 50 μm or more, further preferably 100 μm or more, and 150 μm from the viewpoint of ensuring the function of absorbing light having a wavelength of less than 430 nm. The above is particularly preferable. Although the upper limit of the thickness of an adhesive layer is not specifically limited, It is preferable that it is 1 mm or less. When the thickness of the pressure-sensitive adhesive layer exceeds 1 mm, it becomes difficult to transmit ultraviolet rays, and it takes time to polymerize the monomer component, and causes problems in workability, winding in the process, and transportability, resulting in poor productivity. This is not preferable.

  The gel fraction of the pressure-sensitive adhesive layer of the present invention is not particularly limited, but is preferably 35% or more, more preferably 50% or more, and further preferably 75% or more, It is particularly preferably 85% or more. When the gel fraction of the pressure-sensitive adhesive layer is small, the cohesive force is inferior and there may be a problem in workability and handling properties.

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

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

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

  The average transmittance of the pressure-sensitive adhesive layer having a wavelength of 400 to 430 nm or less can be designed according to characteristics required for the organic EL display device. For example, from the viewpoint of sufficiently absorbing light in a region that does not affect the light emission of the organic EL element to suppress and protect the deterioration of the organic EL element, the average transmittance of the adhesive layer having a wavelength of 400 to 430 nm or less is It is preferably 30% or less, and more preferably 20% or less. On the other hand, from the viewpoint of suppressing the coloring of the organic EL element while protecting the organic EL element from ultraviolet light, the average transmittance of the pressure-sensitive adhesive layer at a wavelength of 400 to 430 nm is more than 30% and 75% or less. Is more preferable, and more preferably more than 30% and 65% or less.

  Here, the “average transmittance at a wavelength of 300 to 400 nm” refers to an average value of the measured transmittances obtained by measuring the transmittance at a 1 nm pitch in a wavelength range of 300 to 400 nm. The same applies to the average transmittance in other wavelength regions.

  The pressure-sensitive adhesive layer of the present invention has the above transmittance, so that it can sufficiently absorb light in a region that does not affect the light emission of the organic EL device, and the light emitting region of the organic EL device (wavelength longer than 430 nm). Side) can be sufficiently transmitted, and deterioration of the organic EL element due to external light can be suppressed.

  When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release film until practical use.

3. Polarizing film with pressure-sensitive adhesive layer for organic EL display device The polarizing film with a pressure-sensitive adhesive layer for organic EL display device of the present invention comprises a polarizing film and the pressure-sensitive adhesive layer for organic EL display device.

  As the pressure-sensitive adhesive layer for an organic EL display device, those described above can be suitably used. When the pressure-sensitive adhesive layer is formed on a substrate other than the polarizing film, the pressure-sensitive adhesive layer can be attached to the polarizing film and transferred. Moreover, the said release film can be used as a separator of a polarizing film with an adhesive layer as it is, and can simplify in a process surface.

  Although it does not specifically limit as said polarizing film, What has a transparent protective film in the at least single side | surface of a polarizer and the said polarizer can be mentioned.

(1) Polarizer The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.

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

  As the thin polarizer, typically, Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or a patent. The thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this production method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

  As the thin polarizing film, International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing. , WO 2010/100917 pamphlet, or patent 4751481 specification or JP 2012-073563 A is obtained by a manufacturing method including a step of stretching in a boric acid aqueous solution, particularly patents What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric-acid aqueous solution which is described in the specification of 4751481 or Unexamined-Japanese-Patent No. 2012-073563 is preferable.

(2) Transparent protective film About a transparent protective film, what is used conventionally can be used suitably. Specifically, a transparent protective film formed from a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable. For example, a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate , Cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin), and polycarbonate polymers. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include polymer blends. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.

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

  The polarizer and the transparent protective film are preferably in close contact with each other through an aqueous adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The electron beam curable polarizing film adhesive exhibits suitable adhesiveness with respect to the various viewing-side transparent protective films. The adhesive used in the present invention can contain a metal compound filler.

  The surface of the transparent protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.

  Moreover, as the transparent protective film, any one having a retardation and capable of functioning as an optical compensation layer can be used. When using the transparent protective film which has phase difference, the phase difference characteristic can be suitably adjusted to the value required for optical compensation. As such a retardation film, a stretched film can be suitably used. When the refractive index in the slow axis direction is nx, the in-plane fast axis direction refractive index is ny, and the thickness direction refractive index is nz, nx = ny> nz, nx> ny. > Nz, nx> ny = nz, nx> nz> ny, nz = nx> ny, nz> nx> ny, nz> nx = ny, satisfying the relationship of various types are selected and used. It is done. Note that 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. Moreover, ny = nz includes not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.

  When the polarizing film used in the present invention is used as a circularly polarizing plate for preventing reflection of an organic EL display device, the retardation film has a front retardation of the transparent protective film of ¼ wavelength (about 100 to 170 nm). A quarter-wave plate is preferable.

  When using a retardation film as the transparent protective film, a film having a transparent protective film on one surface of the polarizer and a retardation film on the other surface can be suitably used. Further, in that case, the installation location of the pressure-sensitive adhesive layer is not particularly limited, and may be provided on the surface of the transparent protective film opposite to the surface in contact with the polarizer. However, from the viewpoint of suppressing deterioration of the organic EL element, it is preferably provided on at least one surface or both surfaces.

  An example of the specific structure of the polarizing film with an adhesive layer for organic electroluminescent display devices of this invention is shown to Fig.1 (a)-(c). As shown in FIG. 1A, the pressure-sensitive adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5, as shown in FIG. 1B, transparent protective film 3 / polarizer 4 / retardation. As shown in film 5 / adhesive layer 2 and adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive layer 2 as shown in FIG. The laminated polarizing film 1 with the adhesive layer for organic EL display apparatuses can be mentioned. 1 (a) and 1 (b), the pressure-sensitive adhesive layer 2 is the pressure-sensitive adhesive layer for an organic EL display device of the present invention. In FIG. 1 (c), at least one of the two pressure-sensitive adhesive layers 2 is present. One may be the pressure-sensitive adhesive layer for the organic EL display device of the present invention, and both may be the pressure-sensitive adhesive layer for the organic EL display device of the present invention. In FIG. 1, the polarizing film 6 is a piece protective polarizing film composed of the polarizer 4 and the transparent protective film 3, but is not limited to this, and the polarizer 4 and the retardation film 5 are not limited thereto. Both protective polarizing films having a transparent protective film between them may also be used. As described above, various functional layers such as a hard coat layer can be formed on the surface of the transparent protective film 3 that is not in contact with the polarizer 4.

Moreover, when the said phase difference film is laminated | stacked on a polarizer through an adhesive layer, the said adhesive layer may be the adhesive layer for organic EL display apparatuses of this invention. That is, the polarizing film with an adhesive layer for an organic EL display device has a first adhesive layer, a transparent protective film, a polarizer, a second adhesive layer, a retardation film, and a third adhesive layer in this order.
Of the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer, at least one pressure-sensitive adhesive layer may be the pressure-sensitive adhesive layer for organic EL display devices.

4). Organic EL display device The organic EL display device of the present invention uses at least one of the pressure-sensitive adhesive layer for the organic EL display device of the present invention and / or the polarizing film with the pressure-sensitive adhesive layer for the organic EL display device of the present invention. Features.

  As an example of a specific configuration of the organic EL display device, for example, as shown in FIGS. 2 to 4, a cover glass or cover plastic 7 / adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive layer 2 / organic EL display panel (OLED element panel) 8 (FIG. 2); cover glass or cover plastic 7 / adhesive layer 9 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive Layer 2 / organic EL display panel 8 (FIG. 3); cover glass or cover plastic 7 / adhesive layer 2 / sensor layer 10 / adhesive layer 2 / transparent protective film 3 / polarizer 4 / retardation film 5 / adhesive As the layer 2 / organic EL display panel 8 (FIG. 4), an organic EL display device in which the respective layers are stacked in this order can be given. Of the pressure-sensitive adhesive layers 2 in each configuration, at least one pressure-sensitive adhesive layer of the present invention may be used, and all pressure-sensitive adhesive layers 2 may be pressure-sensitive adhesive layers of the present invention. In addition to the above, the organic EL display device of the present invention may include various functional layers such as a protective film and a hard coat layer. Moreover, in lamination | stacking of each layer, an adhesive layer and / or an adhesive layer can be used suitably. As the pressure-sensitive adhesive layer other than the pressure-sensitive adhesive layer of the present invention, a normal pressure-sensitive adhesive layer used in this field can be appropriately used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, all the parts and% in each example are based on weight.

Production Example 1 (Production of acrylic pressure-sensitive adhesive composition (a))
Photopolymerization started on a monomer mixture composed of 78 parts by weight of 2-ethylhexyl acrylate (2EHA), 18 parts by weight of N-vinyl-2-pyrrolidone (NVP), and 15 parts by weight of 2-hydroxyethyl acrylate (HEA). As an agent, 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, having an absorption band at a wavelength of 200 to 370 nm, manufactured by BASF) 0.035 parts by weight, 2,2-dimethoxy-1,2-diphenylethane-1 -ON (trade name: Irgacure 651, having an absorption band at a wavelength of 200 to 380 nm, manufactured by BASF) 0.035 parts by weight, and then viscosity (measurement conditions: BH viscometer No. 5 rotor, 10 rpm, measurement temperature) (30 ° C) is irradiated with ultraviolet rays until it reaches about 20 Pa · s, and a part of the monomer component is polymerized. A repolymer composition (polymerization rate: 8%) was obtained. Next, 0.15 part by weight of hexanediol diacrylate (HDDA) and 0.3 part by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) are added to the prepolymer composition. And mixed to obtain an acrylic pressure-sensitive adhesive composition (a).

Production Example 2 (Production of acrylic pressure-sensitive adhesive composition (b))
In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, 95 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.2 part by weight of azobisisobutyronitrile as a polymerization initiator, and After 233 parts by weight of ethyl acetate was added, nitrogen gas was passed, 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.
To the acrylic polymer solution (with a solid content of 100 parts by weight), 0.8 parts by weight of trimethylolpropane tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate crosslinking agent, A pressure-sensitive adhesive composition (b) solution was prepared by adding 0.1 part by weight of a silane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.).

Production Example 3 (Production of pressure-sensitive adhesive layer (B1-1))
On the 38 μm thick separator (polyethylene terephthalate film whose surface was peeled), the adhesive composition (b) solution obtained in Production Example 2 was applied so that the thickness after drying was 12 μm. The layer was dried at 100 ° C. for 3 minutes to remove the solvent, and an adhesive layer was obtained. Then, the crosslinking process was performed by heating at 50 degreeC for 48 hours. Hereinafter, this pressure-sensitive adhesive layer is referred to as “organic EL display panel-side pressure-sensitive adhesive layer (B1-1)”.

Production Example 4 (Production of pressure-sensitive adhesive layer (B1-2))
The pressure-sensitive adhesive composition (b) solution obtained in Production Example 2 was applied onto a 38 μm-thick separator (polyethylene terephthalate film whose surface was release-treated) so that the thickness after drying was 23 μm. The layer was dried at 100 ° C. for 3 minutes to remove the solvent, and an adhesive layer was obtained. Then, the crosslinking process was performed by heating at 50 degreeC for 48 hours. Hereinafter, this pressure-sensitive adhesive layer is referred to as “organic EL display panel-side pressure-sensitive adhesive layer (B1-2)”.

Example 1
(Production of pressure-sensitive adhesive composition (A))
With respect to the acrylic pressure-sensitive adhesive composition (a) obtained in Production Example 1 (the monomer component forming the acrylic polymer is 100 parts by weight), it was dissolved in butyl acrylate so as to have a solid content of 15%. 2,4-bis-[{4- (4-ethylhexyloxy) -4-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, Table 1) 2, “UV absorber (b1)”, absorption spectrum maximum absorption wavelength: 346 nm, manufactured by BASF Japan Ltd.) 0.7 parts by weight (solid content weight) and bis (2,4,6-trimethylbenzoyl) -0.3 part by weight of phenylphosphine oxide (trade name: Irgacure 819, having an absorption band at a wavelength of 200 to 450 nm, manufactured by BASF Japan Ltd.) and N-vinyl-2-pyro BONASORB UA3911 (trade name, indole compound, “dye compound (c1)” in Tables 1 and 2, dissolved in Don (NVP) so as to have a solid content of 5%, maximum absorption wavelength of absorption spectrum: 398 nm, half A pressure-sensitive adhesive composition (A) was obtained by adding and stirring 0.5 parts by weight (solid content weight) of a value range: 48 nm, manufactured by Orient Chemical Industry Co., Ltd.

The pressure-sensitive adhesive composition (A) is applied on the release-treated film so that the thickness after forming the pressure-sensitive adhesive layer is 150 μm, and then on the surface of the pressure-sensitive adhesive composition layer. The release film was bonded together. Then, the pressure-sensitive adhesive composition layer is photocured by irradiating with ultraviolet rays under the conditions of illuminance: 6.5 mW / cm ² , light quantity: 1500 mJ / cm ² and peak wavelength: 350 nm, and the pressure-sensitive adhesive layer (A-1) is formed. Formed.

Example 2
BONASORB UA3912 (trade name, indole compound, “Dye Compound (c2) in Tables 1 and 2”, in which the dye compound (c) was dissolved in N-vinyl-2-pyrrolidone (NVP) so as to have a solid content of 10%. ) ", Absorption spectrum maximum absorption wavelength: 386 nm, half-value width: 53 nm, manufactured by Orient Chemical Industry Co., Ltd.) 2.5 parts by weight (solid content weight) so that the thickness after forming the pressure-sensitive adhesive layer is 100 μm A pressure-sensitive adhesive layer (A-2) was formed in the same manner as in Example 1 except that it was applied.

Example 3
2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) prepared by dissolving the type of the ultraviolet absorber of Example 1 in butyl acrylate so as to have a solid content of 15%. -4- (1,1,3,3-tetramethylbutyl) phenol (trade name: Tinuvin 928, “UV absorber (b2)” in Tables 1 and 2, absorption spectrum maximum absorption wavelength: 349 nm, BASF Japan The amount of addition was 1.5 parts by weight (solid content weight). Furthermore, the type of the dye compound was selected from cinnamic acid compounds (sample name: SOM-5-0103, “Dye Compound (c3)” in Tables 1 and 2, maximum absorption wavelength of absorption spectrum: 416 nm, half width: 50 nm. Example 1 except that 0.2 parts by weight (solid content weight) was directly added and applied so that the thickness after forming the pressure-sensitive adhesive layer was 100 μm. In the same manner as described above, an adhesive layer (A-3) was formed.

Example 4
The addition amount of the ultraviolet absorber (b1) of Example 1 was changed to 3.0 parts by weight (solid content weight), and the type of the dye compound was changed to 1% solid content in N-vinyl-2-pyrrolidone (NVP). Porphyrin compound (sample name: FDB-001, “Dye compound (c4)” in Tables 1 and 2), absorption spectrum maximum absorption wavelength: 420 nm, half width: 14 nm, Yamada Chemical Co., Ltd. ) Made) A pressure-sensitive adhesive layer (A-4) was formed in the same manner as in Example 1 except that 0.1 part by weight (solid content weight) was applied so that the thickness after forming the pressure-sensitive adhesive layer was 100 μm. did.

Example 5
(Production of pressure-sensitive adhesive composition (B))
2,4-bis-[{4- (4-ethylhexyloxy) with respect to the solution of the pressure-sensitive adhesive composition (b) obtained in Production Example 2 (with the monomer component forming the acrylic polymer as 100 parts by weight). ) -4-Hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, “UV absorber (b1)” in Tables 1 and 2, absorption spectrum Maximum absorption wavelength: 346 nm, manufactured by BASF Japan Ltd.) 3 parts by weight (solid content weight), BONASORB UA3912 (trade name, indole compound, “dye compound (c2)” in Tables 1 and 2, maximum absorption spectrum Absorption wavelength: 386 nm, half width: 53 nm, manufactured by Orient Chemical Co., Ltd.) 0.8 part by weight (solid content weight) was directly added and stirred to obtain a pressure-sensitive adhesive composition (B) solution. .

  The obtained pressure-sensitive adhesive composition (B) solution was applied onto a separator having a thickness of 38 μm (a polyethylene terephthalate film having a surface peel-treated) so that the thickness after drying was 25 μm, at 120 ° C. The solvent was removed by drying for 3 minutes to obtain an adhesive layer. Then, the crosslinking process was performed by heating at 50 degreeC for 48 hours. An adhesive layer (B) was formed.

Comparative Example 1
A pressure-sensitive adhesive layer (A1-1) was obtained in the same manner as in Example 1 except that only the acrylic pressure-sensitive adhesive composition (a) containing neither the ultraviolet absorber (b1) nor the dye compound (c1) of Example 1 was used. ) Was formed.

Comparative Example 2
The organic EL display panel side pressure-sensitive adhesive layer (B1-2) of Production Example 3 was used.

Comparative Example 3
A pressure-sensitive adhesive layer (A1-2) was formed in the same manner as in Example 1 except that the dye compound (c1) of Example 1 was not included and the thickness after forming the pressure-sensitive adhesive layer was 100 μm.

Comparative Example 4
A pressure-sensitive adhesive layer (A1-3) was formed in the same manner as in Example 3 except that the pigment compound (c3) was not included and the thickness after forming the pressure-sensitive adhesive layer was 150 μm.

Comparative Example 5
The UV absorber (b1) of Example 1 was not included, the amount of the dye compound (c1) added was 0.3 parts by weight (solid content weight), and the thickness after the pressure-sensitive adhesive layer was formed was 100 μm. Except for this, the pressure-sensitive adhesive layer (A1-4) was formed in the same manner as in Example 1.

Comparative Example 6
The pressure-sensitive adhesive layer (A1) was obtained in the same manner as in Example 2 except that the ultraviolet absorber (b1) of Example 2 was not included and the addition amount of the dye compound (c2) was 0.5 parts by weight (solid content weight). -5) was formed.

Comparative Example 7
A pressure-sensitive adhesive layer (A1-6) was formed in the same manner as in Example 3 except that the ultraviolet absorber (b2) of Example 3 was not included.

Comparative Example 8
An adhesive layer (A1-7) was formed in the same manner as in Example 4 except that the ultraviolet absorber (b1) of Example 4 was not included.

Example 6
(Production of pressure-sensitive adhesive layer (A-5))
The same procedure as in Example 1 was conducted, except that the amount of the dye compound (c1) added in Example 1 was 0.7 parts by weight (solid content weight) and the thickness after forming the pressure-sensitive adhesive layer was 100 μm. An adhesive layer (A-5) was formed.

(Manufacture of polarizing film (P))
A 25 μm thick cycloolefin polymer (COP) film is bonded to the viewing side of a polarizer composed of a stretched polyvinyl alcohol film 5 μm thick impregnated with iodine using a polyvinyl alcohol-based adhesive, and the organic EL of the polarizer An acrylic film having a thickness of 20 μm was laminated on the display panel side surface using a polyvinyl alcohol-based adhesive to obtain a polarizing film (P). The polarization degree of the polarizing film was 99.995.

(Manufacture of polarizing film with adhesive layer)
The produced pressure-sensitive adhesive layer (A-5) was laminated on the viewing side of the polarizing film (P) (that is, the surface of a cycloolefin polymer (COP) film having a thickness of 25 μm). An image display unit-side pressure-sensitive adhesive layer (B1-1) is laminated on the surface of the polarizing film (P) on the side of the organic EL display panel (that is, the surface of the acrylic film having a thickness of 20 μm). : 56 μm, material: polycarbonate) and the image display part side pressure-sensitive adhesive layer (B1-2) were laminated to form a polarizing film with a pressure-sensitive adhesive layer. The obtained polarizing film with the pressure-sensitive adhesive layer is pressure-sensitive adhesive layer (A-5) / polarizing film (P) / organic EL display panel side pressure-sensitive adhesive layer (B1-1) / retardation film / organic EL display panel-side pressure-sensitive adhesive. It had the structure of an agent layer (B1-2).

Example 7
A pressure-sensitive adhesive layer (A-6) was formed in the same manner as in Example 2 except that the amount of the dye compound (c2) added in Example 2 was 0.5 part by weight (solid content weight). Moreover, the polarizing film with an adhesive layer was formed like Example 6 except having used the said adhesive layer (A-6).

Comparative Example 9
An adhesive layer (A1-8) was formed in the same manner as in Example 6 except that the adhesive layer (A-5) of Example 6 did not contain the dye compound (c1). Moreover, the polarizing film with an adhesive layer was formed like Example 6 except having used the said adhesive layer (A1-8).

  The following evaluation was performed about the obtained adhesive layer and a polarizing film with an adhesive layer.

<Measurement of transmittance of adhesive layer>
The release film of the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off, the pressure-sensitive adhesive layer was attached to a measurement jig, and a spectrophotometer (product name: U4100, manufactured by Hitachi High-Technologies Corporation) It was measured. For the transmittance, the transmittance in a wavelength range of 300 nm to 780 nm was measured.

<Measurement of transmittance of polarizing film with adhesive layer>
The release film of the polarizing film with the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off and measured with a spectrophotometer (product name: U4100, manufactured by Hitachi High-Technologies Corporation). For the transmittance, the transmittance in a wavelength range of 350 nm to 780 nm was measured.

<Adhesiveness>
A sheet piece having a length of 100 mm and a width of 20 mm was cut out from the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples. Subsequently, one release film of the pressure-sensitive adhesive layer was peeled off, and a PET film (trade name: Lumirror S-10, thickness: 25 μm, manufactured by Toray Industries, Inc.) was attached (backed). Next, the other release film is peeled off, and is bonded to a glass plate (trade name: Soda Lime Glass # 0050, manufactured by Matsunami Glass Industry Co., Ltd.) as a test plate under the conditions of a 2 kg roller and one reciprocating pressure. A sample composed of a test plate / adhesive layer (A) / PET film was prepared. The obtained sample was autoclaved (50 ° C., 0.5 MPa, 15 minutes), and then 23 ° C., 50% R.D. H. And allowed to cool for 30 minutes. After allowing to cool, a tensile tester (device name: Autograph AG-IS, manufactured by Shimadzu Corporation) was used, and in accordance with JIS Z0237, 23 ° C., 50% R.D. H. Under the above conditions, the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer / PET film) was peeled off from the test plate under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 °, and the 180 ° peel-off adhesive strength (N / 20 mm) was measured.

<Total light transmittance, haze>
One release film was peeled off from the pressure-sensitive adhesive layers obtained in Examples and Comparative Examples, and a slide glass (trade name: white polishing No. 1, thickness: 0.8 to 1.0 mm, total light transmission) Rate: 92%, haze: 0.2%, manufactured by Matsunami Glass Industrial Co., Ltd.). Furthermore, the other release film was peeled off to prepare a test piece having a layer structure of pressure-sensitive adhesive layer / slide glass. The total light transmittance and haze value in the visible light region of the test piece were measured using a haze meter (device name: HM-150, manufactured by Murakami Color Research Laboratory).

DESCRIPTION OF SYMBOLS 1 Polarizing film with an adhesive layer for organic EL display devices 2 Adhesive layer 3 Transparent protective film 4 Polarizer 5 Phase difference film 6 Polarizing film 7 Cover glass or cover plastic 8 Organic EL panel 9 Adhesive layer 10 Sensor layer

Claims (12)

  A pressure-sensitive adhesive composition for an organic EL display device, comprising a base polymer, an ultraviolet absorber, and a dye compound present in a wavelength region having a maximum absorption wavelength of an absorption spectrum of 380 to 430 nm.   The pressure-sensitive adhesive composition for an organic EL display device according to claim 1, wherein the base polymer is a (meth) acrylic polymer.   The pressure-sensitive adhesive composition for an organic EL display device according to claim 1 or 2, wherein a maximum absorption wavelength of an absorption spectrum of the ultraviolet absorber is in a wavelength region of 300 to 400 nm.   It forms from the adhesive composition for organic EL display apparatuses in any one of Claims 1-3, The adhesive layer for organic EL display apparatuses characterized by the above-mentioned.   The average transmittance at a wavelength of 300 to 400 nm is 5% or less, the average transmittance at a wavelength of 450 to 500 nm is 70% or more, and the average transmittance at a wavelength of 500 to 780 nm is 80% or more. Item 5. An adhesive layer for an organic EL display device according to Item 4.   The average transmittance at a wavelength of 300 to 400 nm is 5% or less, the average transmittance at a wavelength of 400 nm to 430 nm is 30% or less, the average transmittance at a wavelength of 450 to 500 nm is 70% or more, and a wavelength of 500 to 780 nm 6. The pressure-sensitive adhesive layer for organic EL display devices according to claim 5, wherein the average transmittance is 80% or more.   The average transmittance at a wavelength of 300 to 400 nm is 5% or less, the average transmittance at a wavelength of 400 nm to 430 nm is more than 30% and 75% or less, the average transmittance at a wavelength of 450 to 500 nm is 80% or more, The pressure-sensitive adhesive layer for an organic EL display device according to claim 5, wherein an average transmittance at 500 to 780 nm is 80% or more.   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 4 to 7.   The polarizing film has a transparent protective film on one surface of a polarizer and a retardation film on the other surface, and the pressure-sensitive adhesive layer for an organic EL display device is a polarizing film of the retardation film. The pressure-sensitive adhesive for an organic EL display device according to claim 8, wherein the pressure-sensitive adhesive is provided on a surface opposite to a surface in contact with the child and / or on a surface opposite to the surface in contact with the polarizer of the transparent protective film. Layered polarizing film. A polarizing film with a pressure-sensitive adhesive layer for an organic EL display device having a first pressure-sensitive adhesive layer, a transparent protective film, a polarizer, a second pressure-sensitive adhesive layer, a retardation film, and a third pressure-sensitive adhesive layer in this order,
9. The organic EL display device pressure-sensitive adhesive layer according to claim 8, wherein at least one of the first pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer, and the third pressure-sensitive adhesive layer is the pressure-sensitive adhesive layer for the organic EL display device. The polarizing film with an adhesive layer for organic electroluminescent display devices of description.   11. The polarizing film with an adhesive layer for an organic EL display device according to claim 9, wherein the retardation film is a ¼ wavelength plate, and the polarizing film is a circular polarizing film. The pressure-sensitive adhesive layer for an organic EL display device according to any one of claims 4 to 7 or at least one polarizing film with the pressure-sensitive adhesive layer for an organic EL display device according to any one of claims 8 to 11 is used. An organic EL display device.

Images