KR20180098239A - Organic EL display device - Google Patents

Abstract

The organic EL display device of the present invention is an organic EL display device including an optical laminate including a polarizer, a retardation film and at least one layer other than the above, and an organic EL panel. The organic EL display device has a maximum absorption spectrum A dye compound in which the absorption wavelength is in a wavelength range of 380 to 430 nm is blended in a separate layer constituting the optical laminate and a layer having an ultraviolet absorber is present on a viewer side than a layer having a dye compound. The organic EL display device of the present invention has a mechanism capable of suppressing deterioration of the organic EL element.

Description

Organic EL display device

The present invention relates to an organic EL (electroluminescence) display device (OLED).

2. Description of the Related Art In recent years, an organic EL display device on which an organic EL panel is mounted has been widely used in various applications such as a mobile phone, a car navigation device, a personal computer monitor, and a television. In order to suppress the external light from being reflected by the metal electrode (cathode) and to be visually recognized as a mirror surface, the organic EL display device is usually provided with a circular polarizer plate (a laminate of a polarizing plate and a 1/4 wave plate . Further, a decorative panel or the like may be further laminated on the circularly polarizing plate laminated on the viewer-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 with a bonding material such as a pressure-sensitive adhesive layer or an adhesive layer interposed therebetween.

In an image display apparatus such as an organic EL display apparatus, constituent members or the like in an image display apparatus are sometimes deteriorated by incident ultraviolet light. In order to suppress deterioration by the ultraviolet light, a layer containing an ultraviolet absorber . Specifically, for example, a transparent double-faced pressure-sensitive adhesive sheet for an image display apparatus having at least one ultraviolet absorbing layer, a light transmittance at a wavelength of 380 nm of 30% or less and a visible light transmittance at a longer wavelength side of 80% (See, for example, Patent Document 1), and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing an acrylic polymer and a triazine-based ultraviolet absorber (see, for example, Patent Document 2).

Japanese Patent Laid-Open Publication No. 2111515 Japanese Patent Application Laid-Open No. 2013-75978

The pressure-sensitive adhesive sheet described in Patent Documents 1 and 2 can control the transmittance of light having a wavelength of 380 nm. However, when the pressure-sensitive adhesive sheet is used in an organic EL display device, the organic EL device may be deteriorated by prolonged use, It was not enough. This is because the adhesive sheet described in Patent Documents 1 and 2 can absorb light having a wavelength of 380 nm, but it can absorb light having a wavelength range (380 to 430 nm) on the shorter wavelength side than the light emitting region (longer wavelength than 430 nm) Is insufficiently absorbed, and it is considered that deterioration is caused by the transmitted light.

Therefore, in order to suppress deterioration of the organic EL element, it is necessary to suppress transmission of light having a wavelength (380 nm to 430 nm) on the shorter wavelength side than the luminescent region (longer than 430 nm) of the organic EL element, It has been necessary to provide an organic EL display device having a mechanism capable of sufficiently securing the transmittance of visible light.

It is therefore an object of the present invention to provide an organic EL display device having a mechanism capable of suppressing deterioration of the organic EL element.

As a result of intensive investigations to solve the above problems, the present inventors have found the following organic EL display device, and have completed the present invention.

That is, the present invention is an organic EL display device including an optical laminate including a polarizer, a retardation film and at least one other layer, and an organic EL panel,

A dye compound in which a maximum absorption wavelength of an ultraviolet absorber and absorption spectrum is in a wavelength region of 380 to 430 nm is compounded in a separate layer constituting the optical laminate,

Wherein the layer having an ultraviolet absorber is present on the viewer side of the layer having the dye compound.

Wherein the optical laminate comprises at least a viscous adhesive layer, a transparent protective film, a polarizer, a retardation film and a pressure-sensitive adhesive layer in this order from the visual side,

Wherein the ultraviolet absorber is blended in a visible side layer of the polarizer,

It is preferable that the dye compound is incorporated in the layer on the side of the organic EL panel rather than the polarizer.

It is preferable that the ultraviolet absorber is blended in at least one layer selected from the group consisting of the point adhesive layer, the transparent protective film and the retardation film, and the dye compound is blended in the pressure-sensitive adhesive layer.

It is preferable that the dye compound is an organic dye compound.

It is preferable that the maximum absorption wavelength of the absorption spectrum of the ultraviolet absorbent is in a wavelength range of 300 to 400 nm.

Since the organic EL display device of the present invention has a layer containing a dye compound having a maximum absorption wavelength of 380 to 430 nm and absorption spectrum with the ultraviolet absorber in a specific order, (380 nm to 430 nm) on the shorter wavelength side than that of the organic EL element (the longer wavelength side) can be sufficiently absorbed, and deterioration of the organic EL element can be suppressed. In particular, in the present invention, since the layer containing the ultraviolet absorber is present on the viewer side more than the layer containing the dye compound, it is possible to prevent the dye compound from being exposed to ultraviolet rays to deteriorate, It is possible to suppress deterioration.

1 is a cross-sectional view schematically showing an embodiment of an optical laminate used in the present invention.
2 is a cross-sectional view schematically showing an embodiment of the organic EL display device of the present invention.

An organic EL display device of the present invention includes an optical laminate including a polarizer, a retardation film, and at least one other layer, and an organic EL panel,

A dye compound in which a maximum absorption wavelength of an ultraviolet absorber and absorption spectrum is in a wavelength region of 380 to 430 nm is compounded in a separate layer constituting the optical laminate,

Characterized in that the layer having an ultraviolet absorber is present on the viewer side of the layer having the dye compound.

The optical laminate should have at least one layer other than a polarizer, a retardation film, and other layers, and the other layers are not particularly limited. A preferred embodiment of the optical laminate is shown in Fig. 1, but the present invention is not limited thereto.

1, the optical laminate 1 includes at least a viscous adhesive layer 2, a transparent protective film 3, a polarizer 4, a retardation film 5, and a pressure-sensitive adhesive layer 6 The transparent protective film 3 / the polarizer 4 / the transparent protective film on the organic EL panel side / the first pressure-sensitive adhesive layer on the organic EL panel side (Or the adhesive layer) / the retardation film 5 / (the second side on the organic EL panel) and the pressure-sensitive adhesive layer 6 may be laminated in this order. In addition to these, other functional layers such as a hard coat layer, an antiglare layer and an antireflection layer, a sensor layer, and a pressure-sensitive adhesive layer or an adhesive layer for laminating them may be included. The transparent protective film 4 / polarizer 5 may be referred to as a polarizing film.

In the present invention, the ultraviolet absorber and the dye compound are compounded in a separate layer constituting the optical laminate, and the layer containing the ultraviolet absorber is disposed closer to the viewer side than the layer containing the dye compound Is closer to the organic EL panel than the layer containing the ultraviolet absorber), and the compounding layer is not particularly limited. Further, in the optical laminate, it is more preferable that the layer containing the ultraviolet absorber is disposed closer to the viewing side than the polarizer, and the layer containing the dye compound is closer to the organic EL panel than the polarizer. With this configuration, ultraviolet rays are cut by the layer containing the ultraviolet absorber in the light incident on the layer containing the dye compound, and since the amount of light is reduced by the polarizer, the dye compound is prevented from being deteriorated And it is possible to suppress deterioration of the organic EL element to a higher degree.

Concretely, the layer containing the ultraviolet absorber is preferably at least one layer selected from the group consisting of the above-mentioned point-adhesive layer 2, the above-mentioned transparent protective film 3 and the retardation film 5, (2) or a transparent protective film (3), and it is particularly preferable to be a point-adhesive layer (2). The ultraviolet absorber may be blended in two or more layers. For example, the ultraviolet absorber may be blended in both the adhesive layer 2 and the transparent protective film 3. The layer containing the dye compound is preferably a retardation film (5) or a pressure-sensitive adhesive layer (6), more preferably a pressure-sensitive adhesive layer (6). The dye compound may be blended in two or more layers and may be blended in both the retardation film 5 and the pressure-sensitive adhesive layer 6, and in the case where the pressure-sensitive adhesive layer 6 has two or more layers The pressure sensitive adhesive layer 6 may be blended with a plurality of pressure sensitive adhesive layers 6. When the polarizing film is both protective polarizing films, a dye compound may be added to the transparent protective film on the organic EL panel side.

Hereinafter, various materials used in the present invention and various layers of the optical laminate will be described in detail.

(1) Ultraviolet absorber

Examples of the ultraviolet absorber include, but are not limited to, triazine-based ultraviolet absorbers, benzotriazole based ultraviolet absorbers, benzophenone based ultraviolet absorbers, oxybenzophenone based ultraviolet absorbers, salicylate ester based ultraviolet absorbers, cyanoacrylate based ultraviolet absorbers These may be used alone or in combination of two or more. Of these, a triazine-based ultraviolet absorber and a benzotriazole-based ultraviolet absorber are preferred, and a triazine-based ultraviolet absorber having two or less hydroxyl groups in one molecule and a benzotriazole-based ultraviolet absorber having one benzothiazole skeleton in one molecule Is preferable because it has good solubility in the monomer used for forming the acrylic pressure sensitive adhesive composition and high ultraviolet absorbing ability at a wavelength of around 380 nm.

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} (4-methoxyphenyl) -1,3,5-triazine (Tinosorb S, manufactured by BASF), 2,4-bis [2-hydroxy-4-butoxyphenyl] (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) - 1, 3,5-triazine (TINUVIN460, (2,4-dimethylphenyl) propionate, a reaction product of 5-hydroxyphenyl and [(C10-C16 (mainly C12-C13) alkyloxy) methyl] oxirane (TINUVIN400, (2,4-dihydroxyphenyl) -4, 5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol) (TINUVIN405, manufactured by BASF), 2- (4,6-dimethylphenyl) -1,3,5-triazine and the reaction product of (2-ethylhexyl) Diphenyl-1,3,5-triazin-2-yl) -5 - [(hexyl) oxy] -phenol (TINUVIN 1577, Triazin-2-yl) -5- [2- (2-ethylhexanoyloxy ) Ethoxy] -phenol (ADK STAB LA46, manufactured by ADEKA), 2- (2-hydroxy-4- [ Phenyl) -1,3,5-triazine (TINUVIN479, manufactured by BASF), 6,6 ', 6 "- (1,3,5-triazine-2,4,6-triyl) tris 2-methyl phenol) (LA-F70, manufactured by ADEKA Co., Ltd.).

Examples of the benzotriazole ultraviolet absorber having a benzotriazole skeleton in one molecule include 2- (2H-benzotriazol-2-yl) -6- (1-methyl- Benzyltriazole (manufactured by TINUVIN PS, BASF), benzene (manufactured by BASF), 2- (2-hydroxy- Ester compounds (TINUVIN 384-2, BASF) of propanoic acid and 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl- Methyl-3- (3H-imidazol-1-yl) -propyl] -4- (1,1,3,3- tetramethylbutyl) phenol (TINUVIN 928, (TINUVIN 1130, manufactured by BASF), 2- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 ) -p-cresol (manufactured by TINUVIN P, BASF), 2 (2H-benzotriazol-2-yl) -4,6- 2-yl] -4-methyl-6- (tert-butyl) phenol (TINUVIN 326, produced by BASF), 2 - (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (TINUVIN 328, , 3,3-tetramethylbutyl) phenol (TINUVIN 329, manufactured by BASF), methyl 3- (2H- benzotriazol-2-yl) -5-tert- butyl-4-hydroxyphenyl) propionate (Manufactured by BASF), 2- (2H-benzotriazole-2-yl) -6-dodecyl-4-methylphenol (TINUVIN571, manufactured by BASF) 3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole (Sumisorb 250, manufactured by Sumitomo Chemical Co., 5-methylphenyl) -5-chlorobenzotriazole (SeeSorb 703, manufactured by Cipro Kasei Co., Ltd. or KEMISORB 73, manufactured by Sipro Gaseous Co., Ltd.).

Examples of the benzophenone ultraviolet absorber (benzophenone compound) and oxybenzophenone ultraviolet absorber (oxybenzophenone compound) include 2,4-dihydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone-5-sulfonic acid (anhydride and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzo Phenol, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4-dimethoxybenzophenone, 2 ', 4,4'-tetrahydroxybenzophenone (SeeSorb 106, manufactured by Sipro Kasei Corporation), 2,2'-dihydroxy-4-methoxybenzophenone (KEMISORB 111, ), And the like.

Examples of the salicylic acid ester-based ultraviolet absorber (salicylic ester compound) include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-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- 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (TINUVIN 120, manufactured by BASF).

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

The maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in a wavelength range of 300 to 400 nm, more preferably in a wavelength range of 300 to 380 nm. Here, the maximum absorption wavelength means the absorption maximum wavelength showing the maximum absorbance in the case where a plurality of absorption maximums exist in the spectral absorption spectrum in the wavelength range of 300 to 460 nm.

The ultraviolet absorber may be used alone or in admixture of two or more. The content of the ultraviolet absorber is preferably about 0.1 to 10% by weight, more preferably about 0.1 to 10% by weight based on the total weight of the layer to which the ultraviolet absorber is added , And more preferably about 0.1 to 8 wt%. When the addition amount of the ultraviolet absorber is in the above range, it is preferable because the ultraviolet absorber added layer can sufficiently exhibit the ultraviolet absorptive function. When the ultraviolet absorber is added to two or more layers, it is preferable that the amount of the ultraviolet absorber in all the layers falls within the above range.

When the ultraviolet absorber is added to the pressure-sensitive adhesive layer (2), the ultraviolet absorber may be used alone or in admixture of two or more. ) Is preferably about 0.1 to 8 parts by weight, more preferably about 0.5 to 5 parts by weight, based on 100 parts by weight of the monofunctional monomer component forming the base polymer forming the base polymer. When the addition amount of the ultraviolet absorber is in the above range, the ultraviolet ray absorbing function of the pressure-sensitive adhesive layer can be sufficiently exerted, and when ultraviolet ray polymerization is carried out, it is preferable because it does not interfere with the polymerization. When the ultraviolet absorber is added to two or more layers, it is preferable that the amount of the ultraviolet absorber in all the layers falls within the above range.

(2) Dye compounds

The dye compound used in the present invention is not particularly limited as long as the compound has a maximum absorption wavelength of the absorption spectrum in a wavelength region of 380 to 430 nm. It is more preferable that the maximum absorption wavelength of the absorption spectrum of the dye compound is in the wavelength region of 380 to 420 nm. Here, the maximum absorption wavelength means the absorption maximum wavelength showing the maximum absorbance in the case where a plurality of absorption maximums exist in the spectral absorption spectrum in the wavelength range of 300 to 460 nm. The dye compound is not particularly limited as long as it has the above wavelength characteristics, but a material which does not inhibit the display property of the organic EL element and does not have fluorescence and phosphorescence performance (photo luminescence) is preferable.

The half-value width of the dye compound is not particularly limited, but is preferably 80 nm or less, more preferably 5 to 70 nm, and further preferably 10 to 60 nm. When the half width of the dye compound is in the above range, it is preferable that the light having a wavelength longer than 430 nm can be sufficiently transmitted while sufficiently absorbing light in the region not affecting the emission of the organic EL element. The half width width measurement method is based on the method described below.

≪ Measurement method of half width &

The half width of the dye compound was measured from the transmission absorption spectrum of a 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 spectral spectrum measured by adjusting the concentration so that the absorbance at the maximum absorption wavelength is 1.0, the interval (full width at half maximum) of the wavelength between two points which is 50% of the peak value is defined as the half value width of the dye compound.

(Measuring conditions)

Solvent: Toluene or chloroform

Cell: Quartz cell

Optical path length: 10mm

The dye compound may be any compound having a maximum absorption wavelength of the absorption spectrum in a wavelength range of 380 to 430 nm, and the structure and the like are not particularly limited. Examples of the dye compound include an organic dye compound and an inorganic dye compound. Among them, an organic dye compound is preferable from the viewpoint of maintaining dispersibility and transparency with respect to a resin component such as a base polymer. The organic dye compound is preferably a material having no fluorescence and phosphorescence performance (photoluminescence).

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

Specific examples of the above-mentioned indole compound include BONASORB UA3911 (trade name, absorption spectrum maximum absorption wavelength: 398 nm, half width: 48 nm, Orient Kagaku Kogyo Co., ), BONASORB UA3912 (trade name, maximum absorption wavelength of absorption spectrum: 386 nm, half width: 53 nm, manufactured by Orient Kagaku Kogyo K.K.), SOM-5-0106 (Maximum absorption wavelength of absorption spectrum: 420 nm, full width at half maximum: 14 nm, trade name: Yamada Kagaku Co., Ltd.) as a porphyrin compound, FDB- Ltd.) and the like.

The dye compound may be used alone or in admixture of two or more. The content of the dye compound is preferably 0.01 to 10% by weight, more preferably 0.01 to 10% by weight based on the total weight of the layer to which the dye compound is added (100% , And more preferably about 0.02 to 7% by weight. When the addition amount of the dye compound is within the above range, light in a region that does not affect the luminescence of the organic EL element can be sufficiently absorbed, and deterioration of the organic EL element can be suppressed.

When the dye compound is added to the pressure-sensitive adhesive layer (6), the dye compound may be used singly or in combination of two or more species. However, the total content of the dye compound Is preferably about 0.01 to 10 parts by weight, more preferably about 0.02 to 5 parts by weight, based on 100 parts by weight of the monofunctional monomer component forming the polymer. When the addition amount of the dye compound is within the above range, light in a region that does not affect the luminescence of the organic EL element can be sufficiently absorbed, and deterioration of the organic EL element can be suppressed. When the dye compound is added to two or more layers, it is preferable that the amount of the dye compound in all the layers falls within the above range.

(3) Optical laminate

The optical laminate used in the present invention is a laminate comprising at least the viscous adhesive layer 2, the transparent protective film 3, the polarizer 4, the retardation film 5, and the pressure-sensitive adhesive layer 6 from the viewing side, The transparent protective film 3 / the polarizer 4 / the transparent protective film on the side of the organic EL panel / the side of the organic EL panel (the side on the viewer side) are preferably laminated in this order 1 adhesive layer (or adhesive layer) / retardation film 5 / (second organic EL panel side) adhesive layer 6) may be laminated in this order. In addition to these, for example, functional layers such as a hard coat layer, an antiglare layer, and an antireflection layer, a sensor layer, and a pressure-sensitive adhesive layer or an adhesive layer for laminating them may be included.

(3-1) The point adhesive layer (2)

In the present invention, the term "adhesive layer" refers to a pressure-sensitive adhesive layer or an adhesive layer.

(3-1-1) Adhesive layer

As the adhesive layer, a layer containing any suitable adhesive may be employed. Examples of such adhesives include natural rubber adhesives,? -Olefin adhesives, urethane resin adhesives, ethylene-vinyl acetate resin emulsion adhesives, ethylene-vinyl acetate resin hot melt adhesives, epoxy resin adhesives, vinyl chloride resin solvent adhesives, chloroprene Butadiene rubber adhesive, nitrile rubber adhesive, nitrocellulose adhesive, reactive hot melt adhesive, phenol resin adhesive, modified silicone adhesive, polyester hot melt adhesive, silicone adhesive, silicone adhesive, silicone adhesives, styrene- Polyamide resin hot melt adhesive, polyimide adhesive, polyurethane resin hot melt adhesive, polyolefin resin hot melt adhesive, polyvinyl acetate resin solvent adhesive, polystyrene resin solvent adhesive, polyvinyl alcohol adhesive, polyvinylpyrrolidoneBoundary may be an adhesive, a polyvinyl butyral adhesive, polybenzimidazole adhesive, polymethacrylate resin solution-based adhesive, melamine resin adhesives, urea resin adhesives, resorcinolic adhesive. These adhesives may be used alone or in combination of two or more.

As the adhesive, there can be mentioned, for example, a thermosetting adhesive agent, a hot melt adhesive agent and the like, classified into an adhesive form. These adhesives may be of one kind alone, or two or more kinds.

The thermosetting adhesive is thermally cured by heating to solidify to develop an adhesive force. As the thermosetting adhesive, for example, an epoxy thermosetting adhesive, a urethane thermosetting adhesive, an acrylic thermosetting adhesive and the like can be given. The curing temperature of the thermosetting adhesive is, for example, 100 to 200 占 폚.

The hot-melt adhesive is melted or softened by heating, is thermally fused to the adherend, and is then solidified by the subsequent cooling to be adhered to the adherend. As the hot melt adhesive, for example, hot melt adhesive such as a rubber hot melt adhesive, a polyester hot melt adhesive, a polyolefin hot melt adhesive, an ethylene-vinyl acetate resin hot melt adhesive, a polyamide resin hot melt adhesive, a polyurethane resin hot melt adhesive, . The softening temperature (ring method) of the hot melt adhesive is, for example, 100 to 200 占 폚. The melt viscosity of the hot melt adhesive is 180 DEG C, for example, 100 to 30,000 mPa.s.

The thickness of the adhesive layer is not particularly limited, but is preferably about 0.01 to 10 탆, and more preferably about 0.05 to 8 탆.

(3-1-2) Pressure-sensitive adhesive layer

Examples of the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer include, but are not limited to, a rubber pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, a vinyl alkyl ether pressure-sensitive adhesive, a polyvinyl alcohol pressure- , Polyacrylamide-based pressure-sensitive adhesives, and cellulose-based pressure-sensitive adhesives. Among these pressure-sensitive adhesives, an acrylic pressure-sensitive adhesive is preferably used because of its excellent optical transparency, appropriate adhesiveness, cohesiveness and adhesive property, and excellent weather resistance and heat resistance. In the present invention, the acrylic pressure sensitive adhesive composition is preferably an acrylic pressure sensitive adhesive composition containing a (meth) acrylic polymer as a base polymer.

The acrylic pressure sensitive adhesive composition preferably 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. The acrylic pressure sensitive adhesive composition may contain an ultraviolet absorber Or a dye compound may be added.

(Partial polymer of monomer component and (meth) acrylic polymer)

The acrylic pressure sensitive adhesive composition includes a partial polymer of a monomer component containing an alkyl (meth) acrylate and / or a (meth) acrylic polymer obtained from the monomer component.

Examples of the alkyl (meth) acrylate include straight chain or branched chain alkyl groups having 1 to 24 carbon atoms at the terminal of the ester. The alkyl (meth) acrylates may be used singly or in combination of two or more. The term " alkyl (meth) acrylate " refers to alkyl acrylate and / or alkyl methacrylate, and has the same meaning as in the (meth) acrylate of the present invention.

Examples of the alkyl (meth) acrylate include linear or branched alkyl (meth) acrylates having 1 to 24 carbon atoms. Of these, alkyl (meth) acrylates having 1 to 9 carbon atoms are preferred , And alkyl (meth) acrylates having a branch having 4 to 9 carbon atoms can be preferably exemplified. The alkyl (meth) acrylate is preferable in view of easy balance of the adhesive property. Specific examples of the alkyl (meth) acrylate having a branched group of 4 to 9 carbon atoms include n-butyl (meth) acrylate, s-butyl (meth) acrylate, (Meth) acrylate, isopentyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, 2-ethylhexyl Acrylate, isononyl (meth) acrylate, isononyl (meth) acrylate, etc. These may be used singly or in combination of two or more.

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

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

As the copolymerizable monomer, for example, a cyclic nitrogen-containing monomer may be contained. As the cyclic nitrogen-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 cyclic nitrogen structure can be used without particular limitation. The cyclic nitrogen structure preferably has a nitrogen atom in the cyclic structure. Examples of the cyclic nitrogen-containing monomer include lactam-based vinyl monomers such as N-vinyl pyrrolidone, N-vinyl-epsilon -caprolactam and methyl vinyl pyrrolidone; Vinyl-based monomers having a nitrogen-containing heterocycle such as vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole and vinylmorpholine. Further, (meth) acrylic monomers containing a heterocyclic ring such as morpholine ring, piperidine ring, pyrrolidine ring and piperazine ring can be mentioned. Specific examples thereof include N-acryloyl morpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like. Of the cyclic nitrogen-containing monomers, lactam-based vinyl monomers are preferred.

In the present invention, the cyclic nitrogen-containing monomer is preferably used in an amount of 0.5 to 50% by weight, more preferably 0.5 to 40% by weight, and most preferably 0.5 to 40% by weight, based on the total amount of the monofunctional monomer component forming the (meth) More preferably 30% by weight.

The monomer component used in the present invention may contain a hydroxyl group-containing monomer as the monofunctional monomer component. As the hydroxyl 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 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 (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8- Hydroxyalkyl (meth) acrylates such as hydroxy lauryl (meth) acrylate; (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, and other hydroxyalkylcycloalkane (meth) acrylates. In addition, examples include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. These may be used alone or in combination. Of these, hydroxyalkyl (meth) acrylates are suitable.

In the present invention, the hydroxyl group-containing monomer is preferably 1% by weight or more, more preferably 2% by weight or more based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer, More 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 may become hard and the adhesive force may be lowered, and the viscosity of the pressure-sensitive adhesive may become excessively high or gelation may occur. Is preferably 30% by weight or less, more preferably 27% by weight or less, and even more preferably 25% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer.

The monomer component forming the (meth) acryl-based polymer may contain, as the monofunctional monomer, other functional group-containing monomers, for example, a monomer having a carboxyl group-containing monomer or a cyclic ether group.

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, isocrotonic acid, May be used alone or in combination. Itaconic acid and maleic acid may be used as anhydrides thereof. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable. In addition, a carboxyl group-containing monomer may be optionally used as the monomer component used in the production of the (meth) acrylic polymer of the present invention, and the carboxyl group-containing monomer may not be used on the other hand.

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

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

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, R ² is a substituent having 1 to 3 carbon atoms (Meth) acrylate represented by the following general formula (1).

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 a phenyl group is preferable.

Examples of the monomer represented by CH ₂ ═C (R ¹ ) COOR ² include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclo Hexyl (meth) acrylate, isobornyl (meth) acrylate, and the like. These may be used alone or in combination.

In the present invention, the (meth) acrylate represented by CH ₂ ═C (R ¹ ) COOR ² can be used in an amount of 50% by weight or less based on the total amount of the monofunctional monomer component forming the (meth) acrylic polymer , Preferably 45 wt% or less, more preferably 40 wt% or less, and even more preferably 35 wt% or less.

Other copolymerizable monomers include vinyl acetate, vinyl propionate, styrene,? -Methyl styrene; Glycol type acrylic ester monomers such as (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol and (meth) acrylic acid methoxypolypropylene glycol; Acrylate monomers such as (meth) acrylate tetrahydrofurfuryl, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate; Amide group-containing monomers, amino group-containing monomers, imide group-containing monomers, N-acryloylmorpholine, vinyl ether monomers and the like. As the copolymerizable monomer, a monomer having a cyclic structure such as terpene (meth) acrylate or dicyclopentanyl (meth) acrylate can be used.

Silane-based monomers containing silicon atoms, and the like. Examples of the silane-based monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8- Vinyl octyltrimethoxysilane, 8-vinyl octyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyl tri Ethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.

The monomer component for forming the (meth) acrylic polymer of the present invention may contain, in addition to the monofunctional monomers described above, a multifunctional monomer as necessary in order to adjust the cohesive force of the pressure sensitive adhesive.

The polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and examples thereof include (poly) ethylene glycol di (meth) acrylate, Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri Ester compounds of (meth) acrylic acid with polyhydric alcohols such as methylol methane tri (meth) acrylate; (Meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyldi (meth) acrylate and hexyl have. Among them, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate and dipentaerythritol hexa (meth) acrylate can be suitably used. The polyfunctional monomers may be used singly or in combination of two or more.

The amount of the polyfunctional monomer to be used varies depending on the molecular weight or the number of functional groups, and is preferably 3 parts by weight or less, more preferably 2 parts by weight or less, and more preferably 1 part by weight per 100 parts by weight of the total amount of monofunctional monomers Or less. The lower limit is not particularly limited, but is preferably 0 part by weight or more, more preferably 0.001 part by weight or more. When the usage amount of the polyfunctional monomer is within the above range, the adhesive force can be improved.

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

Further, in the present invention, a partial polymer of the monomer component may be suitably used.

When the (meth) acrylic polymer is produced by radical polymerization, polymerization can be carried out by suitably 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, and emulsifier used in the radical polymerization are not particularly limited and may be appropriately selected and used. The weight average molecular weight of the (meth) acryl-based polymer can be controlled depending on the amount of the polymerization initiator, the amount of the chain transfer agent used, and the reaction conditions.

For example, in solution polymerization or the like, as the polymerization solvent, ethyl acetate, toluene, or the like is used, for example. As concrete solution polymerization, the reaction is carried out under a reaction condition of usually about 50 to 70 ° C for about 5 to 30 hours by adding a polymerization initiator under an inert gas stream such as nitrogen.

Examples of the thermal polymerization initiator used for solution polymerization include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2- Azobisisobalenoic acid, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobisisobalenoic acid, 2,2'- Azo bis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis Bis (N, N'-dimethyleneisobutylamidine), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057, Wako Pure Chemical Industries, Azo type initiators such as a); (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate T-butyl peroxyneodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauryl peroxide, di-n-octanoyl peroxide, 1,1,3,3- (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butyl peroxyisobutyrate, 1,1-di (t-hexylperoxy) A peroxide initiator such as cyclohexane, t-butyl hydroperoxide and hydrogen peroxide, a combination of persulfate and sodium hydrogen sulfite, a combination of peroxide and sodium ascorbate, and a redox initiator in combination with a reducing agent However, the present invention is not limited thereto.

The polymerization initiator may be used singly or in admixture of two or more, but it is preferably about 1 part by weight or less, preferably about 0.005 to 1 part by weight, based on 100 parts by weight of the total amount of the monomer components And 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 to be used is preferably about 0.2 parts by weight or less, more preferably about 0.06 parts by weight or less, More preferably about 0.2 part by weight.

Examples of the chain transfer agent include lauryl mercaptan, glycidylmercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto- . The chain transfer agent may be used singly or in admixture of two or more, but the total content is about 0.3 part by weight or less based on 100 parts by weight of the monomer component.

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

Examples of the emulsifier to which a radically polymerizable functional group such as a propenyl group or an allyl ether group is introduced as the reactive emulsifier include acaralone HS-10, HS-20, KH-10, BC- 10, and BC-20 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and ADEKARIA SOAP SE10N (manufactured by ADEKA). The amount of the emulsifier used is preferably 5 parts by weight or less based on 100 parts by weight of the total amount of the monomer components.

When the (meth) acryl-based polymer is produced by radiation polymerization, the monomer component can be produced by polymerizing by irradiation with radiation such as electron beam or ultraviolet (UV) radiation. Among them, ultraviolet polymerization is preferred. Hereinafter, the ultraviolet polymerization, which is a preferred embodiment of the radiation polymerization, will be described.

When the ultraviolet polymerization is carried out, it is preferable to add a photopolymerization initiator to the monomer component because of the advantage that the polymerization time can be shortened.

Examples of the photopolymerization initiator include a photopolymerization initiator (B) having a absorption band at a wavelength of less than 400 nm. The photopolymerization initiator (B) preferably has no absorption band at a wavelength of 400 nm or more. As the photopolymerization initiator (B), radicals are generated by ultraviolet rays to initiate photopolymerization, and any type of photopolymerization initiator that is usually used can be suitably used as long as it has an absorption band at a wavelength of less than 400 nm and is not particularly limited. Examples of the photopolymerization initiator include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators,? -Ketol photopolymerization initiators, photoactive oxime photopolymerization initiators, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, An initiator, a thioxanthone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator.

Specific 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-diphenylethan-1-one, anisole methyl ether, and the like.

Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4 -t-butyldichloroacetophenone, and the like.

Examples of the? -ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2- And the like.

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

Examples of the benzoin-based photopolymerization initiator include benzoin and the like.

Examples of the benzyl-based photopolymerization initiator include benzyl and the like.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone,? -Hydroxycyclohexylphenylketone and the like.

The ketal group photopolymerization initiator includes benzyl dimethyl ketal and the like.

The thioxanthene photopolymerization initiator includes, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4- Oxanthanone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

The acylphosphine oxide-based photopolymerization initiator includes, for example, 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 may 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 effect of the present invention. The amount of the photopolymerization initiator (B) , Preferably about 0.005 to 0.5 part by weight, and more preferably about 0.02 to 0.1 part by weight.

In the case where the pressure-sensitive adhesive layer contains an ultraviolet absorber (or a dye compound), and when ultraviolet polymerization is carried out, for example, the monomer component containing the alkyl (meth) acrylate and / or the partial polymer , An ultraviolet absorber (or a dye compound), and a photopolymerization initiator. The UV-curable acrylic pressure-sensitive adhesive composition is preferably formed by ultraviolet ray polymerization. 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 not less than 150 탆, which is preferable because a pressure-sensitive adhesive layer having a wide thickness can be formed.

As the photopolymerization initiator at that time, it is preferable to include a photopolymerization initiator (A) having a absorption band at a wavelength of 400 nm or more. When the ultraviolet absorber (or dye compound) is contained in the pressure-sensitive adhesive composition, ultraviolet radiation is absorbed by the ultraviolet absorber (or dye compound) when the ultraviolet radiation polymerization is carried out. However, a photopolymerization initiator (A) having a absorption band at a wavelength of 400 nm or more is preferable because it can sufficiently polymerize even if it contains an ultraviolet absorber (or a dye compound).

Examples of the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, manufactured by BASF), 2,4,6- trimethylbenzoyl- Pin oxide (LUCIRIN TPO, manufactured by BASF), and the like.

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

The addition amount of the photopolymerization initiator (A) having a absorption band at the wavelength of 400 nm or more is not particularly limited, but it is preferably smaller than the addition amount of the ultraviolet absorber (or dye compound), and the monofunctional But it is preferably about 0.005 to 1 part by weight, more preferably about 0.02 to 0.8 part by weight based on 100 parts by weight of the monomer component. When the addition amount of the photopolymerization initiator (A) is in the above range, it is preferable because the ultraviolet polymerization can proceed sufficiently.

When the ultraviolet ray polymerization is carried out, the 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 It is preferable to add a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more and an ultraviolet absorber (or a dye compound) to a partial polymerized monomer component (prepolymer composition) of a partially polymerized monomer component. When the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is added to a partial polymer (a prepolymer composition) of a partially polymerized monomer component by ultraviolet irradiation, the photopolymerization initiator is preferably added after being dissolved in the monomer .

(Silane coupling agent)

In addition, the pressure-sensitive adhesive composition of the present invention may contain a silane coupling agent. The blending amount of the silane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, and still more preferably 0.02 to 0.6 part by weight based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxy Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl- Amino group-containing silane coupling agents such as N- (1,3-dimethylbutylidene) propylamine and N-phenyl- -aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxy (Meth) acrylic group-containing silane coupling agents such as propyltriethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane.

(Crosslinking agent)

The pressure-sensitive adhesive composition of the present invention may contain a crosslinking agent. Examples of the crosslinking agent include crosslinking agents such as isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelating crosslinking agents and peroxides. The crosslinking agent may be used alone or in combination of two or more. Of these, isocyanate-based crosslinking agents are preferably used.

The crosslinking agent may be used alone or in admixture of two or more, but the total content is preferably 5 parts by weight or less based on 100 parts by weight of the monofunctional monomer component forming the (meth) acrylic polymer More preferably 0.01 to 5 parts by weight, still more preferably 0.01 to 4 parts by weight, still more preferably 0.02 to 3 parts by weight.

The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including an isocyanate regenerated functional group temporarily protected by an isocyanate group as a blocking agent or a quantification) in one molecule. Examples of the isocyanate crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, examples thereof include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, alicyclic isocyanates such as 2,4- Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate and polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer addition product (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 diisocyanate Trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) , Trimethylol propane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals), trimethylol propane adduct of hexamethylene diisocyanate (trade name: D160N, Mitsui Gagaku Co., Ltd. )My); Polyether polyisocyanates, polyester polyisocyanates, polyisocyanates that are multifunctionalized by adducts of these with various polyols, isocyanurate bonds, biuret bonds, allophanate bonds, and the like.

(Other additives)

The pressure-sensitive adhesive composition of the present invention may contain, in addition to the above components, appropriate additives depending on the use. For example, a tackifier (for example, a solid, semi-solid or liquid at room temperature including a rosin derivative resin, a polyterpene resin, a petroleum resin, an oil-soluble phenol resin, etc.); Fillers such as hollow glass balloons; Plasticizers; Antioxidants; Antioxidants and the like.

In the present invention, it is preferable that the pressure-sensitive adhesive composition is adjusted to a viscosity suitable for an operation of applying a coating or the like on a substrate. The viscosity of the pressure-sensitive adhesive composition may be adjusted, for example, by adding various polymers such as a thick-viscous additive or a multi-functional monomer, or by partially polymerizing a monomer component in the pressure-sensitive adhesive composition. The partial polymerization may be carried out before or after the addition of various polymers such as a thickening additive and a multifunctional monomer or the like. Since the viscosity of the pressure-sensitive adhesive composition varies depending on the amount of the additives and the like, the polymerization rate when the monomer component in the pressure-sensitive adhesive composition is partially polymerized can not be determined uniquely but is preferably 20% , More preferably about 20%, and even more preferably about 5 to 15%. If it exceeds 20%, the viscosity becomes excessively high, so that it becomes difficult to apply it to the substrate.

(Method of forming pressure-sensitive adhesive layer)

The method of forming the pressure-sensitive adhesive layer is not particularly limited, and can be generally formed by a method used in this field. Specifically, the pressure-sensitive adhesive composition may be applied to at least one surface of a substrate, dried by forming a coating film formed from the pressure-sensitive adhesive composition, or irradiated with active energy rays such as ultraviolet rays. Further, the pressure-sensitive adhesive layer formed on the substrate may be transferred to a polarizing film or the like.

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

Examples of the constituent material of the release film include a resin film such as polyethylene, polypropylene, polyethylene terephthalate and polyester film, a porous material such as paper, cloth and nonwoven fabric, a net, a foamed sheet, a metal foil, And the like, but resin films are preferably used because they have excellent surface smoothness.

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

The thickness of the release film is usually 5 to 200 占 퐉, and preferably 5 to 100 占 퐉. If necessary, the releasing film may be subjected to antistatic treatment such as release, antifouling, coating, kneading, and vapor deposition with silicone, fluorine, long chain alkyl or fatty acid amide releasing agent, silica powder or the like . Particularly, the releasability from the pressure-sensitive adhesive layer can be further improved by appropriately performing the peeling treatment such as the silicone treatment, the long-chain alkyl treatment, and the fluorine treatment on the surface of the release film.

The transparent resin film base material is not particularly limited, but various resin films having transparency are used. The resin film is formed of a single-layer film. For example, as the material thereof, a polyester resin such as polyethylene terephthalate and polyethylene naphthalate, an acetate resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin (Meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, and polyphenylene sulfide resin. Of these, particularly preferred are polyester resins, polyimide resins and polyether sulfone resins.

The thickness of the film base material is preferably 15 to 200 mu m, more preferably 25 to 188 mu m.

The method of applying the pressure-sensitive adhesive composition onto the substrate may be carried out by a method such as roll coating, kiss roll coating, gravure coating, reverse coating, roll brush, spray coating, dip roll coating, bar coating, knife coating, air knife coating, Coat, die coater, and the like, and is not particularly limited.

The drying conditions (temperature and time) of the pressure-sensitive adhesive layer are not particularly limited and may be appropriately set according to the composition, concentration, etc. of the pressure-sensitive adhesive composition, For example, about 60 to 170 DEG C, preferably 60 to 150 DEG C, for 1 to 60 minutes, preferably 2 to 30 minutes.

When the pressure-sensitive adhesive composition is an ultraviolet curable pressure-sensitive adhesive composition and ultraviolet rays are applied to a coating film formed from the ultraviolet curable pressure-sensitive adhesive composition, the illuminance of the ultraviolet light to be irradiated is preferably 5 mW / cm 2 or more. If the illuminance of the ultraviolet ray is less than 5 mW / cm 2, the polymerization reaction time becomes longer and the productivity may be lowered. The intensity of the ultraviolet ray is preferably 200 mW / cm 2 or less. When the intensity of the ultraviolet ray is more than 200 mW / cm 2, the photopolymerization initiator is consumed abruptly, so that the polymer may be lowered in molecular weight, and the holding power may be lowered particularly at high temperatures. It is also preferable that the accumulated amount of ultraviolet light is 100 mJ / cm 2 to 5000 mJ / 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 the polymerization of the pressure-sensitive adhesive layer can be suppressed. Therefore, it is possible to prevent the polymer from lowering in molecular weight, to prevent the cohesive force of the pressure-sensitive adhesive layer from lowering, and to increase the holding force at high temperature when the pressure-sensitive adhesive sheet is used. It is also possible to combine a plurality of ultraviolet lamps. In addition, it is also possible to intermittently irradiate ultraviolet rays and provide a memorizing period for irradiating ultraviolet rays and a memorizing period for not irradiating ultraviolet rays.

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

In the present invention, the peak wavelength of ultraviolet light to be irradiated on the ultraviolet-curing pressure-sensitive adhesive composition is preferably in the range of 200 to 500 nm, more preferably in the range of 300 to 450 nm. When the ultraviolet peak wavelength exceeds 500 nm, the photopolymerization initiator is not decomposed and the polymerization reaction may not be started. If the peak wavelength of the ultraviolet ray is less than 200 nm, the polymer chain may be cut off and the adhesive property may be lowered.

Since the reaction is inhibited by oxygen in the air, it is preferable to form a release film or the like on the coating film formed of the ultraviolet curing type acrylic pressure-sensitive adhesive composition or to perform the photopolymerization reaction under a nitrogen atmosphere in order to block oxygen. Examples of the release film include those described above. When a release film is used, the release film can be used as a separator of a polarizing film having a pressure-sensitive adhesive layer as it is.

When the ultraviolet curable pressure sensitive adhesive composition used in the present invention contains an ultraviolet absorber (or a dye compound), the amount of the monomer component containing alkyl (meth) acrylate and the content of the photopolymerization initiator (B) (Or a dye compound) in a partial polymer of the monomer component, and an ultraviolet absorber (or a dye compound) having an absorption band at a wavelength of 400 nm or more It is preferable to add a photopolymerization initiator (A) (sometimes referred to as " post polymerization addition initiator ") to prepare an ultraviolet (UV) curable pressure sensitive adhesive composition. The polymerization degree of the partial polymer is preferably about 20% or less, more preferably about 3 to 20%, and even more preferably about 5 to 15%. Irradiation conditions of ultraviolet rays are as described above.

As described above, when the pressure-sensitive adhesive layer is formed using an ultraviolet curable pressure-sensitive adhesive composition containing an ultraviolet absorber (or a dye compound), polymerization in the two steps as described above can increase the polymerization rate of the monomer component, The ultraviolet absorbing function of the produced pressure-sensitive adhesive layer can be improved.

The thickness of the pressure-sensitive adhesive layer is preferably 12 占 퐉 or more, more preferably 50 占 퐉 or more, further preferably 100 占 퐉 or more, and particularly preferably 150 占 퐉 or more. The upper limit value of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 mm or less. If the thickness of the pressure-sensitive adhesive layer exceeds 1 mm, it is difficult to transmit the ultraviolet rays, and it takes time to polymerize the monomer component, besides the problem of workability and winding and transportability in the process, not.

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, further preferably 75% or more, particularly preferably 85% or more. In the case where the gel fraction of the pressure-sensitive adhesive layer is small, there are cases where problems in workability and handling property are caused.

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

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

(3-2) polarizing film

The polarizing film may have a transparent protective film on at least one surface of the polarizer.

(3-2-1) Polarizer (4)

The polarizer is not particularly limited, and various polarizers can be used. As the polarizer, for example, a hydrophilic polymer film such as a polyvinyl alcohol film, a partially porous polyvinyl alcohol film, or an ethylene / vinyl acetate copolymerization system partially saponified film may be produced by adsorbing iodine or a dichromatic dye of dichromatic dye to 1 Polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol, and the like. Among them, a polarizer comprising a polyvinyl alcohol-based film and a dichroic substance such as iodine is suitable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 占 퐉.

A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching can be produced by, for example, dying polyvinyl alcohol in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. If necessary, it may be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. If necessary, the polyvinyl alcohol film may be dipped in water and washed with water before dyeing. The polyvinyl alcohol film is washed with water to clean the contaminants and the antiblocking agent on the surface of the polyvinyl alcohol film, and the polyvinyl alcohol film is swollen to prevent unevenness such as uneven dyeing. Stretching may be performed after dyeing with iodine, stretching while dyeing, or dyeing with iodine after stretching. It can be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

In the present invention, a thin polarizer having a thickness of 10 mu m or less can also be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 mu m. Such a thin polarizer is preferable in that it is excellent in durability because thickness irregularity is small, visibility is excellent, and dimensional change is small, and further, thickness as a polarizing film is also thinned.

Typical examples of the thin polarizer include a pamphlet of International Patent Publication Nos. 51-069644 and 2000-338329, a pamphlet of International Publication No. 2010/100917, a pamphlet of International Publication No. 2010/100917, A thin polarizing film described in Japanese Patent No. 4751481 or Japanese Patent Laid-Open Publication No. 2012-073563. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a polyvinyl alcohol resin (hereinafter also referred to as a PVA resin) layer and a lead resin substrate in a laminated state and a step of dyeing. With this method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching because it is supported on the resin base material for drawing.

As the thin polarizing film, from the viewpoint of being capable of stretching at a high magnification and improving the polarization performance even in a process including a step of stretching in the state of a laminate and a step of dyeing, the pamphlet of International Publication No. 2010/100917, In a pamphlet of Japanese Patent Application Laid-Open No. 2010/100917, or in a boric acid aqueous solution as described in Japanese Patent No. 4751481 or Japanese Patent Application Laid-Open No. 2012-073563, It is preferably obtained by a process comprising a step of auxiliary drawing publicly before drawing in an aqueous boric acid solution described in Japanese Patent No. 4751481 or in Japanese Patent Laid-Open Publication No. 2012-073563.

(3-2-2) Transparent protective film (3)

The transparent protective film 3 used in the present invention is disposed on the visible side of the polarizer 4, but a transparent protective film may be disposed on the side of the organic EL panel of the polarizer 4 as well.

As the transparent protective film, those conventionally used can be suitably used. Specifically, a transparent protective film formed of a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. is preferable, and for example, a polyester polymer such as polyethylene terephthalate or polyethylene naphthalate, Cellulose polymers such as cellulose and triacetylcellulose, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin), polycarbonate polymers, etc. have. Examples of the polymer include polyolefin polymers such as polyethylene, polypropylene, polyolefin having a cyclo or norbornene structure, ethylene / propylene copolymer, amide polymers such as vinyl chloride polymers, nylon and aromatic polyamides, imide polymers, Based polymers, polyether sulfone-based polymers, polyether sulfone-based polymers, polyether ether ketone-based polymers, polyphenylene sulfide-based polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, Epoxy-based polymer, or a blend of the above-mentioned polymer may be mentioned as an example of the polymer forming the transparent protective film. The transparent protective film may be formed as a cured layer of a thermosetting or ultraviolet curing resin such as acrylic, urethane, acrylic urethane, epoxy or silicone.

Though the thickness of the transparent protective film can be appropriately determined, it generally ranges from 1 to 500 占 퐉 in view of workability such as strength and handling properties and thin film properties.

The polarizer and the transparent protective film are preferably brought into 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-based, a water-based polyurethane, and a water-based polyester. In addition to the above, examples of the adhesive for the polarizer and the transparent protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The adhesive for an electron beam curing type polarizing film exhibits suitable adhesiveness to the various visible side transparent protective films. Further, the adhesive used in the present invention may contain a metal compound filler.

The surface of the transparent protective film on which the polarizer is not adhered may be a functional layer such as a hard coat layer, an antireflection layer and an anti-sticking layer, or may be a layer subjected to a treatment for diffusing or anti-glare.

As the hard coat layer, for example, a cured film containing a curable resin such as a melamine resin, a urethane resin, an alkyd resin, an acrylic resin or a silicone resin is preferably used. The thickness of the hard coat layer is preferably 0.1 to 30 mu m.

An ultraviolet absorber, a light stabilizer (HALS), an antioxidant, and a dye compound may be added to the functional layer.

(3-3) retardation film (5)

Ny> nz, nx> ny> nz, and nx> ny = nz when the refractive index in the retardation film direction is nx, the refractive index in the fast axis direction in the plane is ny, and the refractive index in the thickness direction is nz, nz, nx> nz> ny, nz = nx> ny, nz> nx> ny, and nz> nx = ny are selected and used according to various applications. Further, nx = ny includes not only the case where nx and ny are completely equal but also the case where nx and ny are substantially equal to each other. Also, ny = nz includes not only the case where ny and nz are completely equal but also the case where ny and nz are substantially equal.

In the present invention, for use in an organic EL display device, the retardation film is preferably a 1/4 wavelength plate having a front retardation of 1/4 wavelength (about 100 to 170 nm). It is preferable that the polarizing film and the 1/4 wavelength plate are laminated so as to function as a circular polarization film for antireflection of the organic EL display device.

That is, only the linearly polarized light component transmits the external light incident on the organic EL display device by the polarizing film. This linearly polarized light is generally elliptically polarized by the retardation film. In particular, when the retardation plate is a quarter wave plate and the angle formed by the direction of polarization with the retardation film is π / 4, the linearly polarized light is circularly polarized.

This circularly polarized light is transmitted through the transparent substrate, the transparent electrode and the organic thin film in the organic EL panel, reflected by the metal electrode, again transmitted through the organic thin film, the transparent electrode and the transparent substrate, and becomes linearly polarized again in the retardation film. Since the linearly polarized light is perpendicular to the polarization direction of the polarizing film, it can not transmit through the polarizing plate. As a result, the mirror surface of the metal electrode can be completely shielded.

(3-4) Pressure-sensitive adhesive layer (6)

Examples of the pressure-sensitive adhesive layer (6) (pressure-sensitive adhesive layer on the side of the organic EL panel) used in the present invention include the same ones as the pressure-sensitive adhesive layer of the above-mentioned pressure-sensitive adhesive layer. Among them, the (meth) acryl- ) Acrylic pressure-sensitive adhesive composition. The same can be said for the production method of the pressure-sensitive adhesive layer and the preferable embodiment.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably about 10 to 75 占 퐉, more preferably about 12 to 50 占 퐉.

(3-5) Other layers

Examples of the transparent protective film (on the side of the organic EL panel) include the same ones as the transparent protective film 3. As the first pressure sensitive adhesive layer (or adhesive layer) on the organic EL panel side, An adhesive layer may also be suitably used.

(4) Transmittance of the layer containing the ultraviolet absorber

The transmittance of the layer containing the ultraviolet absorber at a wavelength of 380 nm is preferably 9% or less, more preferably 7% or less, further preferably 5% or less, and particularly preferably 3% or less. When the transmittance at a wavelength of 380 nm is in the above range, the incident ultraviolet light can be blocked at a higher degree, and deterioration of the organic EL element can be remarkably suppressed.

The transmittance of the layer containing the ultraviolet absorber at a wavelength of 450 nm is preferably 60% or more, more preferably 70% or more, and still more preferably 75% or more. Since the transmittance at a wavelength of 450 nm is in the above range, it is possible to sufficiently transmit the light emitted from the organic EL element, and sufficient display performance can be ensured in the organic EL display device.

(5) Transmittance of the layer containing the dye compound

When the pressure-sensitive adhesive layer contains a dye compound, the transmittance at 400 nm is preferably 50% or less, more preferably 35% or less, and even more preferably 20% or less. When the transmittance at a wavelength of 400 nm is in the above range, the incident ultraviolet light can be blocked at a higher degree, and deterioration of the organic EL element can be remarkably suppressed.

The transmittance of the layer containing the dye compound at a wavelength of 450 nm is preferably at least 60%, more preferably at least 70%, and even more preferably at least 75%. When the transmittance at a wavelength of 450 nm is in the above range, it is possible to sufficiently transmit the light emission of the organic EL element, and sufficient display performance can be ensured in the organic EL display device.

(6) Transmittance of the optical laminate

The transmittance of the optical laminate at a wavelength of 380 nm is preferably 9% or less, more preferably 7% or less, further preferably 5% or less, and particularly preferably 3% or less. When the transmittance at a wavelength of 380 nm is in the above range, the incident ultraviolet rays can be blocked at a higher level, which is preferable because deterioration of the organic EL element can be remarkably suppressed.

The transmittance of the optical laminate at a wavelength of 400 nm is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. When the transmittance at a wavelength of 400 nm is in the above range, the incident ultraviolet light can be blocked at a higher level, and deterioration of the organic EL device can be remarkably suppressed.

In addition, the transmittance of the optical laminate at a wavelength of 450 nm is preferably 25% or more, more preferably 30% or more, and still more preferably 33% or more. When the transmittance at a wavelength of 450 nm is in the above range, it is possible to sufficiently transmit the light emission of the organic EL element, and sufficient display performance can be ensured in the organic EL display device.

(7) Organic EL display device

The organic EL display device of the present invention includes the optical laminate 1 and an organic EL panel, and may include other layers. 2, the cover member 7, the point adhesive layer 2, the protective film 3, the polarizer 4, the retardation film 5, and the pressure-sensitive adhesive layer 6 ) / Organic EL panel 8 are laminated in this order, and the cover member 7 / the viscous adhesive layer 2 / the visual side protective film 3 / Sensitive adhesive layer (6) / organic EL panel (8) on the organic EL panel side / protective film on the organic EL panel / first adhesive layer (or adhesive layer) / retardation film (5) And an organic EL display device laminated in this order. In addition to these, a structure including a functional layer such as a hard coat layer, an antiglare layer, an antireflection layer, a sensor layer, and a pressure-sensitive adhesive layer or an adhesive layer for laminating them may be used.

The cover member is not particularly limited, and those generally used in this field can be suitably used, and cover glass, cover plastic and the like can be mentioned. The organic EL panel is not particularly limited and can be suitably used as is commonly used in this field. For example, the organic EL panel includes a substrate, a plurality of organic EL elements formed side by side on the substrate, A protective layer formed on the protective layer, and a panel having a sealing film formed on the protective layer.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. In the examples, all parts and% are based on weight.

Production Example 1 (Production of acrylic pressure-sensitive adhesive composition (a)) [

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 a photopolymerization initiator , 0.035 part by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, having a absorption band at a wavelength of 200 to 370 nm, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethane- , 0.035 part by weight of an acrylic copolymer (trade name: Irgacure 651, having an absorption band at a wavelength of 200 to 380 nm, manufactured by BASF), and then the viscosity (measurement conditions: BH viscometer No. 5 rotor, 10 rpm, To give a prepolymer composition (polymerization degree: 8%) in which a part of the monomer component was polymerized. 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.) were added to the prepolymer composition and mixed to prepare an acrylic pressure- (a).

Production Example 2 (Production of pressure-sensitive adhesive layer (B1)) [

95 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 0.2 part by weight of azobisisobutyronitrile as a polymerization initiator, and 233 parts by weight of ethyl acetate were added to a separable flask equipped with a thermometer, a stirrer, a reflux condenser tube and a nitrogen gas- After the addition, nitrogen gas was poured, and nitrogen was substituted for about 1 hour while stirring. Thereafter, the flask was heated to 60 占 폚 and reacted for 7 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1,100,000.

0.8 part by weight of trimethylolpropane tollylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as an isocyanate-based crosslinking agent, 0.8 part by weight of a silane coupling agent (trade name: (Trade name: KBM-403, Shin-Etsu Chemical Co., Ltd.) was added to prepare a pressure-sensitive adhesive composition (solution).

The resulting pressure-sensitive adhesive composition solution was coated on a separator (polyethylene terephthalate film whose surface was peeled off) having a thickness of 38 탆 so that the thickness after drying was 12 탆 and dried at 100 캜 for 3 minutes to remove the solvent, Layer. Thereafter, crosslinking treatment was carried out by heating at 50 DEG C for 48 hours. Hereinafter, this pressure-sensitive adhesive layer is referred to as &quot; pressure-sensitive adhesive layer (B1) &quot;.

Production Example 3 (Production of dye compound-containing pressure-sensitive adhesive layer (B1-1)

In the same manner as in Production Example 2 except that BONASORB UA3911 (trade name, Indole (registered trademark)) was used in place of the isocyanate-based crosslinking agent and the silane coupling agent in the acrylic polymer solution (Solid content weight) of the dye compound (c1) in Table 1, the maximum absorption wavelength of the absorption spectrum: 398 nm, the half width of 48 nm, and Orient Kagaku Kogyo Co., Solution) was prepared.

The resulting pressure-sensitive adhesive composition solution was applied on a separator (polyethylene terephthalate film whose surface was peeled off treatment) having a thickness of 38 탆 so that the thickness after drying became 15 탆 and dried at 100 캜 for 3 minutes to remove the solvent, Layer. Thereafter, crosslinking treatment was carried out by heating at 50 DEG C for 48 hours. Hereinafter, this pressure-sensitive adhesive layer is referred to as &quot; pressure-sensitive adhesive layer (B1-1) &quot;. The addition amount of the dye compound was 1.5% by weight based on the total weight (100% by weight) of the pressure-sensitive adhesive layer (B1-1).

Production Example 4 (Production of dye compound-containing pressure-sensitive adhesive layer (B1-2)

A pressure-sensitive adhesive layer was formed in the same manner as in Production Example 3 except that the amount of the dye compound (c) added was changed to 2.5 parts by weight (solid content weight). Hereinafter, this pressure-sensitive adhesive layer is referred to as &quot; pressure-sensitive adhesive layer (B1-2) &quot;. The amount of the dye compound added was 2.5% by weight based on the total weight (100% by weight) of the pressure-sensitive adhesive layer (B1-2).

Production Example 5 (Production of dye-containing pressure-sensitive adhesive layer (B1-3)

The coloring matter compound (c) was dissolved in a mixture of a cinnamic acid compound (trade name: SOM-5-0106, "ultraviolet absorber (c3)" in Table 1, absorption spectrum maximum absorption wavelength: 416 nm, half width: 50 nm, ) Was used in an amount of 1.0 part by weight, a pressure-sensitive adhesive layer was formed. Hereinafter, this pressure-sensitive adhesive layer is referred to as &quot; pressure-sensitive adhesive layer (B1-3) &quot;. The addition amount of the dye compound was 1.0% by weight based on the total weight (100% by weight) of the pressure-sensitive adhesive layer (B1-3).

Production Example 6 (Production of pressure-sensitive adhesive layer (B2)) [

The pressure-sensitive adhesive composition solution obtained in Preparation Example 2 was coated on a separator having a thickness of 38 탆 (polyethylene terephthalate film whose surface was subjected to release treatment) so as to have a thickness after drying of 23 탆 and dried at 100 캜 for 3 minutes, To thereby obtain a pressure-sensitive adhesive layer. Thereafter, crosslinking treatment was carried out by heating at 50 DEG C for 48 hours. Hereinafter, this pressure-sensitive adhesive layer is referred to as &quot; pressure-sensitive adhesive layer (B2) &quot;.

Production Example 7 (Production of dye compound-containing pressure-sensitive adhesive layer (B2-1)) [

BONASORB UA3912 (trade name, indole compound, "dye compound (c2)" in Table 1) dissolved in toluene so as to have a solid content of 5% was added to the acrylic polymer solution (solid content is 100 parts by weight) 1.0 part by weight (solids content weight) of the absorption spectrum: maximum absorption wavelength: 386 nm, half width: 53 nm, manufactured by Orient Kagaku Kogyo Co., Ltd.), trimethylolpropane tolylene diisocyanate (trade name: Coronate L (Manufactured by Nippon Polyurethane Industry Co., Ltd.), and 0.1 part by weight of a silane coupling agent (trade name: KBM-403, Shin-Etsu Chemical Co., Ltd.) were added to prepare a pressure-sensitive adhesive composition (solution).

The pressure-sensitive adhesive composition solution was coated on a separator (polyethylene terephthalate film whose surface was subjected to release treatment) having a thickness of 38 탆 so that the thickness after drying was 23 탆 and dried at 100 캜 for 3 minutes to remove the solvent, Layer. Thereafter, crosslinking treatment was carried out by heating at 50 DEG C for 48 hours. Hereinafter, this pressure-sensitive adhesive layer is referred to as &quot; pressure-sensitive adhesive layer (B2-1) &quot;. The addition amount of the dye compound was 1.0% by weight based on the total weight (100% by weight) of the pressure-sensitive adhesive layer (B2-1).

Production Example 8 (Production of protective film (C1)) [

100 parts by weight of the imidized MS resin described in Production Example 1 of JP-A-2010-284840 and 10 parts by weight of 6,6 ', 6 "- (1,3,5-triazine-2,4,6-tri ) And 0.65 part by weight of tris (3-hexyloxy-2-methylphenol) (trade name: LA-F70, "ultraviolet absorber (b1)" in Table 1, absorption spectrum maximum absorption wavelength: 357 nm, manufactured by ADEKA Corporation) The resultant resin pellets were dried at 100.5 kPa at 100 DEG C for 12 hours and extruded from a T-die at a die temperature of 270 DEG C with a single-screw extruder to give a film-like The film was stretched (thickness: 80 mu m) in an atmosphere at 150 DEG C in the carrying direction thereof, and then stretched in an atmosphere at 150 DEG C in a direction orthogonal to the film carrying direction to form a film having a thickness of 40 ((Meth) acrylic resin film) was obtained in the same manner as in Example 1. The obtained base film A had a light transmittance of 7% at a wavelength of 380 nm, The light transmittance of the sheet 400nm was 68%.

An ultraviolet curable resin (trade name: Unidick 17-P) containing 13 parts of isocyanuric acid triacrylate, 16 parts of pentaerythritol triacrylate, 62 parts of dipentaerythritol hexaacrylate, and 9 parts of isophorone diisocyanate polyurethane, (4-ethylhexyloxy) -4-hydroxyphenyl] -phenyl] - (4-hydroxyphenyl) (Maximum absorbed wavelength of absorption spectrum: 346 nm, manufactured by BASF Japan) 1.5 weight% of 6- (4-methoxyphenyl) -1,3,5-triazine (trade name: Tinosorb S, , 5 parts of a leveling agent (trade name: GRANDIC PC-4100, manufactured by DIC Corporation), 5 parts of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, 3 parts by weight, having an absorption band at a wavelength of 200 to 450 nm, manufactured by BASF Japan) were mixed and diluted with methyl isobutyl ketone so as to have a solid content concentration of 50% Thereby preparing a composition for forming a coat layer. The composition for forming a hard coat layer was applied onto the obtained base film A to form a coated layer, and the coated layer was heated at 120 DEG C for 1 minute. Ultraviolet rays of 500 mJ / cm &lt; 2 &gt; of cumulative light intensity were irradiated to the coated layer after heating with a high-pressure mercury lamp to cure the coating layer to form a hard coat layer of 7 mu m. Hereinafter, the protective film layer having this surface treatment layer is referred to as &quot; protective film layer (C1) &quot;. The addition amount of the ultraviolet absorber was 0.77% by weight based on the total weight (100% by weight) of the protective film (C1).

Production Example 9 (Preparation of protective film (C2-1)) [

100 parts by weight of the imidized MS resin described in Production Example 1 of JP-A-2010-284840 was dissolved in methylene chloride to prepare a 12 wt% dope solution. 0.3 part by weight of a synnamic acid compound (trade name: SOM-5-0106, "ultraviolet absorber (c3)" in Table 1, maximum absorption wavelength of absorption spectrum: 416 nm, half width: 50 nm, manufactured by Orient Kagaku Kogyo Co., Ltd.) Then, the pressure-sensitive adhesive composition solution was coated on the glass plate subjected to the releasing treatment so that the thickness after drying became 40 占 퐉 and dried at 100 占 폚 for 3 minutes to remove the solvent to obtain a protective film C2-1 ). The transmittance of the obtained protective film (C2-1) at a wavelength of 380 nm was 14%, and the transmittance of light at a wavelength of 400 nm was 2.6%. The addition amount of the dye compound was 0.3% by weight based on the total weight (100% by weight) of the protective film (C2-1).

Production Example 10 (Production of protective film (C2-2)) [

As the dye compound (c), BONASORB UA3912 (trade name, indole compound, "dye compound (c2)" in Table 1, maximum absorption wavelength of absorption spectrum: 386 nm, half width: 53 nm, manufactured by Orient Kagaku Kogyo Co., Was used in an amount of 1.3 parts by weight, a protective film (C2-2) was obtained. The transmittance of the obtained protective film (C2-2) at a wavelength of 380 nm was 0.3%, and the transmittance of light at a wavelength of 400 nm was 0.8%. The addition amount of the dye compound was 1.3% by weight based on the total weight (100% by weight) of the protective film (C2-2).

Example 1

(Production of pressure-sensitive adhesive composition (A1)) [

Bis [(4-hydroxyphenyl) acrylic acid], which is obtained by dissolving butyl acrylate so as to have a solid content of 15% with respect to the acrylic pressure sensitive adhesive composition (a) obtained in Production Example 1 (the monomer component forming the acrylic polymer is referred to as 100 parts by weight) (Trade name: Tinosorb S, &quot; ultraviolet absorber b2 &quot; in Table 1) was used in place of 4-hydroxybenzoic acid (4-ethylhexyloxy) , 1.4 parts by weight (solid content weight)) of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, wavelength: 200 to 400 nm, absorption spectrum maximum absorption wavelength: 346 nm, 0.2 part by weight, having an absorption band at 450 nm, manufactured by BASF Japan) was added and stirred to obtain a pressure-sensitive adhesive composition (A1).

(Production of pressure-sensitive adhesive layer (A1)) [

The pressure-sensitive adhesive composition (A1) was applied onto the release film of the release film so that the thickness after formation of the pressure-sensitive adhesive layer became 150 占 퐉, and then the release film was bonded to the surface of the pressure-sensitive adhesive composition layer. Thereafter, ultraviolet irradiation was performed under the conditions of an illuminance of 6.5 mW / cm 2, a light quantity of 1500 mJ / cm 2 and a peak wavelength of 350 nm, and the pressure-sensitive adhesive composition layer was photo-cured to form a pressure-sensitive adhesive layer (A1). The added amount of the ultraviolet absorber was 1.4 wt% with respect to the total weight (100 wt%) of the pressure-sensitive adhesive layer (A1).

(Production of polarizing film P1)

A cycloolefin polymer film having a thickness of 25 占 퐉 was bonded to the viewer side of a polarizer including a stretched polyvinyl alcohol film having a thickness of 5 占 퐉 in which iodine was impregnated using a polyvinyl alcohol adhesive, , And an acrylic film having a thickness of 20 mu m was laminated using a polyvinyl alcohol-based adhesive to obtain a polarizing film (P1). The polarizing film had a Y transmittance Y value of 42.4% and a polarization degree of 99.995.

(Production of polarizing film having pressure-sensitive adhesive layer)

A pressure-sensitive adhesive layer (A1) was laminated on the viewing side of the polarizing film (P1) (i.e., the surface of the cycloolefin polymer film having a thickness of 25 mu m). The pressure-sensitive adhesive layer (B1-1) obtained in Production Example 3 was laminated on the surface of the polarizing film (P) on the side of the organic EL panel (i.e., the surface of the acrylic film having a thickness of 20 m) 탆, material: polycarbonate) and the pressure-sensitive adhesive layer (B2-1) obtained in Production Example 7 were laminated to form a polarizing film having a pressure-sensitive adhesive layer. The resulting polarizing film having the pressure-sensitive adhesive layer had the constitution of the pressure-sensitive adhesive layer (A1) / cycloolefin polymer film / polarizer / acrylic film / pressure-sensitive adhesive layer (B1-1) / retardation film / pressure-sensitive adhesive layer (B2-1).

Example 2

(Production of pressure-sensitive adhesive composition (A2)) [

(1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylpiperazin-1-yl) 1.5 parts by weight (solid content weight) of bis (2,4,6-tetramethylbutyl) phenol (trade name: TINUVIN 928, "ultraviolet absorber b3" in Table 1, absorption spectrum maximum absorption wavelength: 349 nm, Trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, having an absorption band at a wavelength of 200 to 450 nm, manufactured by BASF Japan) was added and stirred to obtain a pressure-sensitive adhesive composition (A2).

(Production of pressure-sensitive adhesive layer (A2)) [

The obtained pressure-sensitive adhesive composition (A2) was coated on the release film of the release film so that the thickness after formation of the pressure-sensitive adhesive layer became 150 占 퐉, and then the release film was bonded to the surface of the pressure-sensitive adhesive composition layer. Thereafter, ultraviolet light irradiation was performed under the conditions of an illuminance of 6.5 mW / cm 2, a light quantity of 1500 mJ / cm 2 and a peak wavelength of 350 nm, and the pressure-sensitive adhesive composition layer was photo-cured to form a pressure-sensitive adhesive layer (A2). The added amount of the ultraviolet absorber was 1.5% by weight with respect to the total weight (100% by weight) of the pressure-sensitive adhesive layer (A2).

(Production of polarizing film P2)

A cycloolefin polymer film having a thickness of 25 占 퐉 was bonded to the viewer side of a polarizer including a stretched polyvinyl alcohol film having a thickness of 5 占 퐉 in which iodine was impregnated using a polyvinyl alcohol adhesive, , The protective film (C2-1) obtained in Production Example 9 was laminated using a polyvinyl alcohol-based adhesive to obtain a polarizing film (P2). The polarizing film had a Y transmittance of 42.5% and a polarization degree of 99.995.

(Production of polarizing film having pressure-sensitive adhesive layer)

The prepared pressure-sensitive adhesive layer (A2) was laminated on the viewing side of the polarizing film (P2) (i.e., the surface of the cycloolefin polymer film having a thickness of 25 mu m). The pressure-sensitive adhesive layer (B1) obtained in Production Example 2 was laminated on the surface of the polarizing film (P) on the side of the organic EL panel (that is, the surface of the protective film (C2-1) , Material: polycarbonate) and the pressure-sensitive adhesive layer (B2) obtained in Production Example 6 were laminated to form a polarizing film having a pressure-sensitive adhesive layer. The resulting polarizing film having the pressure-sensitive adhesive layer had the constitution of the pressure-sensitive adhesive layer (A2) / cycloolefin polymer film / polarizer / protective film (C2-1) / pressure- sensitive adhesive layer (B1) / retardation film / pressure-

Example 3

(Preparation of pressure-sensitive adhesive composition (A3)) [

({4- (4-ethylhexyloxy) -4-hydroxy} -phenyl) -phenol obtained by dissolving butyl acrylate in 15% solids in the acrylic pressure- (Maximum absorption wavelength of absorption spectrum: 346 nm, manufactured by BASF Japan Co., Ltd.) 0.7 weight (trade name: Tinosorb S, ultraviolet absorber b2 in Table 1) (Solid content weight) and 0.2 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, having an absorption band at a wavelength of 200 to 450 nm, manufactured by BASF Japan) Followed by stirring to obtain a pressure-sensitive adhesive composition (A3).

(Production of pressure-sensitive adhesive layer (A3)) [

The pressure-sensitive adhesive composition (A3) was coated on the release film of the release film so that the thickness after formation of the pressure-sensitive adhesive layer became 150 占 퐉, and then the release film was bonded to the surface of the pressure-sensitive adhesive composition layer. Thereafter, ultraviolet irradiation was performed under the conditions of an illuminance of 6.5 mW / cm 2, a light quantity of 1500 mJ / cm 2 and a peak wavelength of 350 nm, and the pressure-sensitive adhesive composition layer was photo-cured to form a pressure-sensitive adhesive layer (A3). The amount of the ultraviolet absorber added was 0.7% by weight with respect to the total weight (100% by weight) of the pressure-sensitive adhesive layer (A3).

(Production of polarizing film P3)

The protective film (C1) obtained in Production Example 8 was contacted with the polarizer on the viewer side of the polarizer including the stretched polyvinyl alcohol film having a thickness of 5 탆 impregnated with iodine using a polyvinyl alcohol adhesive And the protective film (C2-2) of the organic EL side obtained in Production Example 10 was laminated on the surface of the polarizer on the side of the organic EL panel using a polyvinyl alcohol adhesive to obtain a polarizing film (P3). The polarizing film had a Y transmittance Y value of 42.4% and a polarization degree of 99.995.

(Production of polarizing film having pressure-sensitive adhesive layer)

The prepared pressure-sensitive adhesive layer (A3) was laminated on the viewing side of the polarizing film (P3) (that is, the surface of the protective film (C1)). The pressure-sensitive adhesive layer (B1-2) obtained in Production Example 4 was laminated on the surface of the polarizing film (P) on the side of the organic EL panel (that is, the surface of the protective film C2-2) 56 탆, material: polycarbonate) and the pressure-sensitive adhesive layer (B2) obtained in Production Example 6 were laminated to form a polarizing film having a pressure-sensitive adhesive layer. The resulting polarizing film having a pressure-sensitive adhesive layer was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive layer (A3) / protective film (C1) / polarizer / protective film (C2-2) / pressure- B2).

Comparative Example 1

The pressure-sensitive adhesive layer (A3) obtained in Example 3 was laminated on the viewing side of the polarizing film (P1) obtained in Example 1 (that is, the surface of the cycloolefin polymer film having a thickness of 25 탆). The pressure-sensitive adhesive layer (B1) obtained in Production Example 2 was laminated on the surface of the polarizing film (P) on the side of the organic EL panel (i.e., the surface of the acrylic film having a thickness of 20 m) Material: polycarbonate) and the pressure-sensitive adhesive layer (B2) obtained in Production Example 6 were laminated to form a polarizing film having a pressure-sensitive adhesive layer. The resulting polarizing film having the pressure-sensitive adhesive layer had the constitution of the pressure-sensitive adhesive layer (A3) / cycloolefin polymer film / polarizer / acrylic film / pressure-sensitive adhesive layer (B1) / retardation film / organic EL display panel side pressure-

Comparative Example 2

(Production of pressure-sensitive adhesive layer)

A pressure-sensitive adhesive composition (A4) was obtained in the same manner as in Example 1, except that the ultraviolet absorber (b2) was not included in Example 1 (production of pressure-sensitive adhesive composition (A1) A pressure-sensitive adhesive layer (A4) having a thickness of 150 占 퐉 was formed in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (A4) was used in the pressure-sensitive adhesive layer (A1) .

(Production of polarizing film having pressure-sensitive adhesive layer)

The pressure-sensitive adhesive layer (A4) was laminated on the viewing side of the polarizing film (P1) obtained in Example 1 (i.e., the surface of the cycloolefin polymer film having a thickness of 25 占 퐉). The pressure-sensitive adhesive layer (B1-3) obtained in Production Example 5 was laminated on the surface of the polarizing film (P) on the side of the organic EL panel (i.e., the surface of the acrylic film having a thickness of 20 m) 탆, material: polycarbonate) and the pressure-sensitive adhesive layer (B2) obtained in Production Example 6 were laminated to form a polarizing film having a pressure-sensitive adhesive layer. The resulting polarizing film having a pressure-sensitive adhesive layer had the constitution of a pressure-sensitive adhesive layer (A4) / cycloolefin polymer film / polarizer / acrylic film / pressure-sensitive adhesive layer (B1-3) / retardation film / pressure-sensitive adhesive layer (B2).

Each of the obtained layers and the optical laminate (polarizing film having a pressure-sensitive adhesive layer) was subjected to the following evaluations.

&Lt; Measurement of transmittance of layer having ultraviolet absorber >

The releasing film of the layer (pressure-sensitive adhesive layer) containing the ultraviolet absorber obtained in Examples and Comparative Examples was peeled off and placed on the measuring jig and measured by a spectrophotometer (product name: U4100, Hitachi High Technologies). The transmittance was measured as the transmittance in the wavelength range of 350 nm to 780 nm. In addition, in the case of the protective film containing the ultraviolet absorber of Example 3, the transmittance was measured as in the case of the pressure-sensitive adhesive layer, except that the protective film was provided on the measuring jig through the film holder.

<Measurement of Transmittance of Layer Having a Colorant Absorbent>

The releasing film of the layer (pressure-sensitive adhesive layer) containing the dye absorbing agent obtained in Examples and Comparative Examples was peeled off and placed on a measuring jig and measured by a spectrophotometer (product name: U4100, Hitachi High Technologies). The transmittance was measured as the transmittance in the wavelength range of 350 nm to 780 nm. In the case of the protective film containing the dye compounds of Examples 2 and 3, the transmittance was measured as in the case of the pressure-sensitive adhesive layer, except that the protective film was provided on the measuring jig through the film holder.

&Lt; Measurement of transmittance of polarizing film having pressure-sensitive adhesive layer >

The release film of the polarizing film having the pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was peeled off and placed on a measuring jig and measured with a spectrophotometer (product name: U4100, Hitachi High Technologies). The transmittance was measured as the transmittance in the wavelength range of 350 nm to 780 nm.

1: Optical laminate
2: Point adhesive layer
3: Transparent protective film
4: Polarizer
5: retardation film
6: Pressure-sensitive adhesive layer
7: Cover member
8: Organic EL panel
10: organic EL display device

Claims (5)

An optical laminate including at least one layer of a polarizer, a retardation film, and other layers, and an organic EL panel,
A dye compound in which a maximum absorption wavelength of an ultraviolet absorber and absorption spectrum is in a wavelength region of 380 to 430 nm is compounded in a separate layer constituting the optical laminate,
Wherein the layer having an ultraviolet absorber is present on the visible side of the layer having the dye compound. The optical laminate according to claim 1, wherein the optical laminate comprises at least a viscous adhesive layer, a transparent protective film, a polarizer, a retardation film, and a pressure-
Wherein the ultraviolet absorber is blended in a visible side layer of the polarizer,
Wherein the dye compound is blended in a layer on the side of the organic EL panel with respect to the polarizer. The ultraviolet absorber according to claim 2, wherein the ultraviolet absorber is incorporated in at least one layer selected from the group consisting of the point adhesive layer, the transparent protective film, and the retardation film,
Wherein the dye compound is compounded in the pressure-sensitive adhesive layer. The organic EL display device according to any one of claims 1 to 3, wherein the dye compound is an organic dye compound. The organic EL display device according to any one of claims 1 to 4, wherein a maximum absorption wavelength of an absorption spectrum of the ultraviolet absorbent is in a wavelength range of 300 to 400 nm.

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