JP2009070814A - Organic electroluminescent display device which has dispersing member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent display device having high light extraction efficiency and less image blurring. <P>SOLUTION: This is the organic electroluminescent display device which includes the lower part electrode formed on a substrate, the organic electroluminescent layer formed on the lower part electrode, and the upper electrode formed on the organic electroluminescent layer, and which has a dispersing member on the upper electrode. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic electroluminescence display device using a scattering member to increase luminous efficiency.

  An organic electroluminescence display device (organic EL display device) is a self-luminous display device and is used for displays and illumination. The organic EL display has advantages in display performance such as higher visibility than conventional CRTs and LCDs and no viewing angle dependency. There is also an advantage that the display can be made lighter and thinner. On the other hand, in addition to the advantages of reducing the weight and the thickness of organic EL lighting, there is a possibility of realizing illumination in a shape that could not be realized so far by using a flexible substrate.

  An organic EL display device and an inorganic EL display device have excellent characteristics as described above, but generally, the refractive index of each layer constituting the display device including the light emitting layer is higher than that of air. For example, in an organic EL display device, the refractive index of an organic thin film layer such as a light emitting layer is 1.6 to 2.1. For this reason, the emitted light is easily totally reflected at the interface, and its light extraction efficiency is less than 20%, and most of the light is lost.

The optical loss in this organic EL display device will be outlined with reference to FIG.
As shown in FIG. 1, the organic EL display device basically has a back electrode 2, an organic layer 3 including two or three layers including a light emitting layer, a transparent electrode 4, and a transparent substrate on the TFT substrate 1. 5 is laminated, and the holes injected from the back electrode 2 and the electrons injected from the transparent electrode 4 recombine in the organic layer 3 to emit light by exciting a fluorescent substance or the like. is there. Then, the light emitted from the organic layer 3 is reflected directly or by the back electrode 2 formed of aluminum or the like and is emitted from the transparent substrate 5.
However, as shown in FIG. 1, the light generated inside the display device may be totally reflected depending on the angle of incidence on the adjacent layer interface having a different refractive index, and may be guided out of the display device and taken out to the outside. Not possible (lights Lb and Lc in FIG. 1). The ratio of the guided light is determined by the relative refractive index with the adjacent layer, and is a general organic EL display device (air (n = 1.0) / transparent substrate (n = 1.5) / transparent electrode (n = 2.0) / organic layer (n = 1.7) / back electrode), the proportion of light that is not emitted into the atmosphere (air) but is guided inside the display device is about 81%. That is, only about 19% of the total light emission amount can be effectively used.

Therefore, in order to improve the light extraction efficiency, (a) the light (Lb in FIG. 1) that is totally reflected at the transparent substrate / air interface and guided through the “organic layer + transparent electrode + transparent substrate” is extracted (b) ) It is essential to take out light (Lc in FIG. 1) that is totally reflected at the transparent electrode / transparent substrate interface and guided through the “organic layer + transparent electrode”.
Among these, regarding (a), a method has been proposed in which irregularities are formed on the surface of the transparent substrate to prevent total reflection at the transparent substrate / air interface (see, for example, Patent Document 1).
Regarding (b), a method of processing a transparent electrode / transparent substrate interface or a light emitting layer / adjacent layer interface into a diffraction grating (for example, see Patent Document 2 and Patent Document 3) has been proposed. Furthermore, a method of increasing the luminous efficiency by processing the interface between the stacked organic layers into irregularities has been proposed (see, for example, Patent Document 4). Of these, the method of forming a diffraction grating at the light emitting layer / adjacent layer interface described above is that the adjacent layer is made of a conductive medium, and the depth of the unevenness of the diffraction grating is about 40% of the film thickness of the light emitting layer. By taking a specific relationship between the pitch and the depth, the guided light is extracted. Further, in the method of forming irregularities at the interface between organic layers, the layer adjacent to the irregularities is made of a conductive medium, the depth of the light emitting layer is about 20% deep, and the inclination angle of the interface is about 30 °. The unevenness is formed at the interface between the organic layers, and the light emission efficiency is increased by increasing the bonding interface between the organic layers.
However, the above-described method is difficult to process and has a problem that dielectric breakdown is likely to occur during energization, and further development of a useful light extraction method is desired for increasing the efficiency of the display device.

As one means for solving these problems, for example, means for improving the extraction efficiency by providing a light scattering layer on the surface of the organic EL surface light emitter has been proposed (for example, Patent Document 5 and Patent Document 6). See). However, when light scattering occurs on the surface, there is a problem that light blur increases and resolution deteriorates.
On the other hand, there has been proposed a method of reducing blurring of an image while improving light extraction efficiency by disposing a light diffusion layer immediately above the upper electrode (see, for example, Patent Document 7).
However, this method uses 1.5 to 1.6 as the base material of the light diffusing layer, and is not suitable as a refractive index for efficiently extracting the light guided through the organic layer and the transparent electrode. .

US Pat. No. 4,774,435 Japanese Patent Laid-Open No. 11-283951 JP 2002-31554 A JP 2002-31567 A JP 2003-109747 A JP 2003-173877 A JP 2006-107744 A

  Accordingly, an object of the present invention is to provide a light-emitting display device having high light extraction efficiency and less image blur in a self-luminous light-emitting display device in which the refractive index of the light-emitting portion is higher than the refractive index of air. It is in. In particular, it is to provide an organic electroluminescence display device in which the extraction efficiency of light guided through “organic layer + transparent electrode” is enhanced.

  The object of the present invention has been achieved by the organic electroluminescence display device described in the following (1) to (22).

(1) An organic electroluminescence display device including a lower electrode formed on a substrate, an organic electroluminescence layer formed on the lower electrode, and an upper electrode formed on the organic electroluminescence layer, An organic electroluminescence display device comprising a scattering member on an electrode.
(2) The organic electroluminescence display device according to (1), wherein the scattering member is a light diffusion film.
(3) The light diffusion film is a film including a transparent substrate film and a light diffusion layer formed on the transparent substrate film, and the light diffusion layer has a refractive index different from that of the transparent resin composition. The organic electroluminescence display device according to (2), wherein the transparent resin composition containing light scattering particles and contained in the light diffusion layer has a refractive index of 1.6 or more.
(4) The resin composition of the light diffusing layer contains at least one inorganic fine particle selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO. Organic electroluminescence display device.
(5) The organic electroluminescence display device according to (3) or (4), wherein a refractive index of the light scattering particles contained in the light diffusion layer is 1.55 or less.
(6) The organic material according to any one of (3) to (5), wherein an average diameter of the light scattering particles dispersed in the light diffusion layer is 0.1 μm or more and 2.0 μm or less. Electroluminescence display device.
(7) The light diffusing film is a film including a transparent base film and a light diffusing layer formed on the transparent base film, and the light diffusing layer has an average particle diameter in the transparent resin composition. The organic electroluminescence display device according to (2), comprising at least one fine particle selected from 50 nm to 300 nm of ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO.
(8) The organic electroluminescence display device according to any one of (3) to (7), wherein the diffusion film has a low refractive index layer between the transparent base film and the light diffusion layer. .
(9) The organic electroluminescence display device according to (8), wherein a refractive index of the low refractive index layer is 1.45 or less.
(10) The organic electroluminescence display device according to any one of (8) to (9), wherein the low refractive index layer contains hollow silica.
(11) The organic electroluminescence display device according to (1), wherein the scattering member is a color filter.
(12) The organic electroluminescence display device according to (11), wherein the color filter is obtained by curing a curable composition containing a colorant and light scattering particles.
(13) The organic electroluminescence display device according to (12), wherein the curable composition has a refractive index of 1.6 or more during the curing.
(14) The curable composition contains at least one inorganic fine particle selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO, according to (12) to (13), Organic electroluminescence display device.
(15) The organic electroluminescence display device according to any one of (12) to (14), wherein the light scattering particles have a refractive index of 1.55 or less.
(16) The organic electroluminescence display device according to any one of (12) to (15), wherein an average diameter of the light scattering particles is 0.5 μm or more and 2.0 μm or less.
(17) The organic electroluminescence display according to (12), wherein the light scattering particles are at least one fine particle selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO having an average particle diameter of 50 nm to 300 nm. apparatus.
(18) The organic electroluminescence display device according to any one of (1) to (17), wherein the scattering member is directly attached to the upper electrode.
(19) The organic electroluminescence display device according to any one of (1) to (17), wherein the scattering member is directly attached to the barrier layer via the barrier layer on the upper electrode.
(20) The light diffusing film is attached to the upper electrode or a barrier layer provided on the upper electrode through an adhesive layer, (2) to (10) The organic electroluminescence display device according to any one of the above.
(21) The organic electroluminescence display device according to (20), wherein the adhesive layer has a refractive index of 1.6 or more.
(22) The organic material according to (20) or (21), wherein the adhesive layer contains at least one inorganic fine particle selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO. Electroluminescence display device.

As described in the background art, the reason for the low light extraction efficiency of the self-luminous display device is that the light generated inside the display device causes total reflection when the angle of incidence on the adjacent layer interface having a different refractive index is large, This is because the inside of the display device is guided and cannot be taken out.
In contrast, by introducing a scattering member having a transparent resin composition and a light scattering layer composed of light scattering particles having a refractive index different from that of the resin composition into the organic EL display device, the light is emitted. It can be taken out to the outside. This is realized by bending the traveling direction of light guided in the layer by total reflection by the action of light scattering.
At this time, by making the refractive index of the transparent resin composition equal to or greater than the refractive index of the organic light emitting layer, it is possible to extract light guided in the high refractive index layer including the organic light emitting layer. Become.
Furthermore, by introducing a scattering member so that a light scattering layer is formed immediately above the upper electrode, the distance between the light emitting point and the scattering layer can be reduced, and deterioration of image resolution due to light scattering can be suppressed. it can. In order to further increase the light extraction efficiency, it is preferable to increase the number of times light scattering occurs. For this purpose, it is preferable to increase the number of total reflections in the high refractive index layer including the organic light emitting layer, and this point is realized by thinning the high refractive index layer including the organic light emitting layer. It becomes possible.

  Moreover, the light extraction efficiency can be further improved by setting the refractive index of the layer in contact with the high refractive index layer including the organic light emitting layer to be a low refractive index.

Then, by forming a scattering member having a light scattering layer in advance, it becomes easy to incorporate the light scattering layer into the organic EL display device. Furthermore, by forming a scattering member having a light scattering layer in advance, it becomes easy to impart arbitrary scattering characteristics to the scattering layer.
This makes it possible to obtain a scattering member optimal for the organic EL according to the present invention. Therefore, it can be said that the scattering member, the light diffusing film or the color filter, and the method for attaching them according to the present invention are useful from the viewpoints of both processability and optical characteristics.

An organic electroluminescence display device of the present invention includes a lower electrode formed on a substrate, an organic electroluminescence layer formed on the lower electrode, and an upper electrode formed on the organic electroluminescence layer. It has a scattering member on it.
Hereinafter, the scattering member, the organic electroluminescence display device, and the adhesive in the present invention will be described in detail.

<< scattering member >>
A light diffusing film and a color filter can be selected as the scattering member. Hereinafter, the light diffusion film and the color filter in the present invention will be described in detail.

<Light diffusion film>
FIG. 2 is a schematic cross-sectional view showing the basic structure of the light diffusion film. The light diffusion film (10) shown in FIG. 2 is formed by laminating a transparent base film (20) and a light diffusion layer (30). The light diffusion layer (30) includes light scattering particles (41) in the translucent resin (31). The light diffusion layer (30) may be composed of a plurality of layers. Two or more kinds of light scattering particles may be used. In addition, the light diffusion film (11) shown in FIG. 3 in which the low refractive index layer (50) is inserted between the transparent base film (20) and the light diffusion layer (30) also improves the light extraction efficiency. Can do.

<Light diffusion layer>
The light diffusion layer (30) is composed of light scattering particles (41) and a translucent resin (31). The scattered light profile and haze value are adjusted according to the refractive index and particle size of each of the light scattering particles (41) and the translucent resin (31).

  The refractive index of the light scattering particles (41) of the light diffusion layer (30) is 1.55 because the difference in refractive index from the translucent resin layer is 0.05 or more and a sufficient amount of scattering is obtained. Or less, more preferably 1.36 to 1.50. The refractive index of the low refractive index layer (50) is preferably 1.45 or less because the difference in refractive index from air is 0.45 or less, and total reflection can be suppressed. More preferably, it is 45. The refractive index of triacetyl cellulose preferably used as the transparent substrate film (20) is 1.48. By increasing the refractive index of the light diffusion layer (30), an excellent effect of improving the light extraction efficiency can be obtained.

<Light scattering particles>
The light scattering particles (41) preferably have a refractive index difference of 0.02 or more with respect to the translucent resin (31) constituting the entire light diffusion layer (30). When the refractive index difference is less than 0.02, the difference in refractive index between the two is too small to obtain a light diffusion effect. In the present invention, in order to increase the light extraction efficiency, it is necessary to diffuse the light totally reflected at the interface. The greater the diffusion effect, the better the light extraction efficiency.

  Only one type of light scattering particles (41) may be used, or a plurality of types of particles may be used in combination.

The type of the light scattering particles (41) is not limited, and may be organic fine particles or inorganic fine particles. As the organic fine particles, polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, styrene beads, crosslinked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde beads and the like are used. As the inorganic fine particles, SiO ₂ (for example, amorphous silica-based beads), ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , etc. are used.
The average diameter (particle diameter) of the light scattering particles (41) is 0.1 μm or more and 2.0 μm or less because the scattering amount can be sufficiently obtained and the directivity of light scattering is almost isotropic scattering. Preferably there is. By making the scattering directivity close to isotropic scattering, more light can be extracted.

  In the case of the light scattering particles (41) as described above, since the light scattering particles easily settle in the translucent resin (31), an inorganic filler such as silica may be added to prevent sedimentation. As the amount of the inorganic filler added increases, it is more effective in preventing the precipitation of the light scattering particles, but adversely affects the transparency of the coating film. Therefore, preferably, an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of less than 0.1% by mass so as not to impair the transparency of the coating film with respect to the translucent resin (31).

<Translucent resin>
As the translucent resin (31), there are mainly used three types of resins that are cured by ultraviolet rays, electron beams, or heat, that is, photocurable resins, ionizing radiation curable resins, and thermosetting resins. Also, a mixture of these curable resins with a thermoplastic resin and a solvent may be used. The thickness of the light diffusion layer (30) is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 2 μm to 10 μm, and most preferably 3 μm to 7 μm.

  The binder used for the translucent resin (31) is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder, it is preferable to use a monomer having two or more ethylenically unsaturated groups.

  Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, penta Erythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, 1,3,5-cyclohexanetriol trimethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene derivatives Examples include 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. included. Among these, acrylate or methacrylate monomers having at least three functional groups, and further acrylate monomers having at least five functional groups are preferable from the viewpoint of film hardness, that is, scratch resistance. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is commercially available and is particularly preferably used.

  These monomers having an ethylenically unsaturated group can be cured by a polymerization reaction by light, ionizing radiation or heat after being dissolved in a solvent together with various polymerization initiators and other additives, applied and dried.

  Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder by the reaction of a crosslinkable group. Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition. The binder having these crosslinkable functional groups can form a crosslinked structure by heating after coating.

The translucent resin (31) is preferably formed from a monomer having a high refractive index and / or metal oxide ultrafine particles having a high refractive index in addition to the binder polymer. Examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether and the like. Examples of the metal oxide ultrafine particles having a high refractive index include a particle diameter of 100 nm or less, preferably 50 nm or less, made of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony. It is preferable to contain fine particles. The metal oxide ultrafine particles having a high refractive index are preferably oxide ultrafine particles of at least one metal selected from Al, Zr, Zn, Ti, In and Sn. Specific examples include ZrO ₂ , TiO ₂ , _{al 2 O 3, In 2 O} 3, ZnO, SnO 2, Sb 2 O 3, ITO , and the like. Among these, ZrO ₂ is particularly preferably used. The addition amount of the high refractive index monomer and the metal oxide ultrafine particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the translucent resin (31).

  When the translucent resin (31) and the transparent substrate film (20) are in contact with each other, the solvent of the coating solution for forming the translucent resin (31) is expressed as antiglare property and the support and the antiglare layer. In order to achieve both cohesiveness, at least one solvent that dissolves the transparent substrate film (20) (for example, triacetyl cellulose support) and at least one solvent that does not dissolve the transparent substrate film (20). It consists of a solvent. More preferably, at least one of the solvents that do not dissolve the transparent substrate film (20) has a higher boiling point than at least one of the solvents that dissolve the transparent substrate film (20). More preferably, the boiling point temperature difference between the solvent having the highest boiling point among the solvents that do not dissolve the transparent substrate film (20) and the solvent having the highest boiling point among the solvents that dissolve the transparent substrate film (20) is 30. It is more than 50 degreeC, Most preferably, it is 50 degreeC or more.

  As a solvent for dissolving the transparent substrate film (20), ethers having 3 to 12 charcoal display devices: specifically, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4- Ketones having 3 to 12 carbon atoms such as dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole and phenetole: specifically, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl Esters having 3 to 12 carbon atoms such as ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone: specifically, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, propionic acid Methyl, propion brewing Organic solvent having two or more types of functional groups such as methyl, n-pentyl acetate, and γ-ptyrolactone: specifically, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, 2-ethoxy Examples include ethyl propionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate. These can be used alone or in combination of two or more. The solvent for dissolving the transparent substrate is preferably a ketone solvent.

  As a solvent that does not dissolve the transparent substrate film (20), methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl-2-butanol, Examples include cyclohexanol, isobutyl acetate, methyl isobutyl ketone, 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone, and 4-heptanone. These can be used alone or in combination of two or more.

  The mass ratio (A / B) of the total amount (A) of the solvent that dissolves the transparent substrate film and the total amount (B) of the solvent that does not dissolve the transparent substrate film is preferably 5/95 to 50/50, more preferably. It is 10 / 90-40 / 60, More preferably, it is 15 / 85-30 / 70.

  As a curing method of the photocurable resin composition as described above, it can be cured by a normal curing method of the photocurable resin composition, that is, by irradiation with ultraviolet rays. Moreover, as a curing method of the ionizing radiation curable resin composition, the ionizing radiation curable resin composition can be cured by a normal curing method of the ionizing radiation curable resin composition, that is, by irradiation with an electron beam.

  For example, in the case of electron beam curing, 50 to 1000 keV emitted from various electron beam accelerators such as a Cockrowalton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type. Preferably, an electron beam having an energy of 100 to 300 keV is used, and in the case of ultraviolet curing, ultraviolet rays emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. are used. it can.

<Low refractive index layer>
The low refractive index layer (50) is provided between the transparent base film (20) and the light diffusion layer (30) for the purpose of imparting a further light extraction efficiency improving function (see FIG. 3). The effect of improving the light extraction efficiency by the low refractive index layer (50) can be obtained by combining with the light diffusion layer (30). The refractive index of the low refractive index layer is preferably 1.30 to 1.45 as described above. The thickness of the low refractive index layer is preferably larger than about λ / 4, and is 100 nm or more.

  For the low refractive index layer (50) of the present invention, a fluorine-containing resin obtained by curing a thermosetting or photo-curable crosslinkable fluorine-containing compound is used. Thereby, compared with the low refractive index layer using magnesium fluoride or calcium fluoride, it is excellent in scratch resistance even when used as the outermost layer. The refractive index of the thermosetting or photocurable crosslinkable fluorine-containing compound is preferably 1.30 or more and 1.45 or less. The dynamic friction coefficient of the cured fluororesin is preferably 0.03 to 0.15, and the contact angle with water is preferably 90 to 120 degrees. Examples of such crosslinkable fluorine-containing compounds include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane), fluorine-containing monomers and crosslinkable groups. Examples thereof include a fluorine-containing copolymer having a monomer for imparting as a structural unit.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like.

  As a monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule like glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.). JP-A-10-25388 and JP-A-10-147739 disclose that the latter can introduce a crosslinked structure after copolymerization.

  Further, in the low refractive index layer, not only a copolymer of the above-mentioned fluorine-containing monomer and a monomer for imparting a crosslinkable group, but also a polymer obtained by copolymerizing other monomers may be used. Other monomers that may be copolymerized are not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate) , 2-ethylhexyl acrylate), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), Vinyl ethers (methyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tert-butylacrylamide, N-cyclohexylacrylamide, etc.), methacrylate Amides, and acrylonitrile derivatives.

  In order to give scratch resistance to the fluorine-containing resin used for the low refractive index layer (50), the average particle diameter is preferably 0.1 μm or less, more preferably 0.001 to 0.05 μm. It is preferable to add and use fine particles. From the viewpoint of improving the light extraction efficiency, the lower the refractive index, the better. However, as the refractive index of the fluorine-containing resin is lowered, the fastness deteriorates. Therefore, by optimizing the refractive index of the fluorine-containing resin and the addition amount of Si oxide ultrafine particles, it is possible to find the best point of the balance between scratch resistance and low refractive index. As the ultrafine particles of Si, silica sol dispersed in a commercially available organic solvent may be added to the coating solution as it is, or various commercially available silica powders may be dispersed in an organic solvent. Further, by using hollow silica particles containing bubbles in the Si fine particles, it is possible to further reduce the refractive index.

A preferred embodiment of the light diffusion film described above is a film having a transparent base film (20) and a light diffusion layer formed on the transparent base film, and the light diffusion layer is a transparent resin. A light scattering particle having a refractive index different from that of the resin composition is dispersed in the composition, and the refractive index of the resin composition of the light diffusion layer is 1.6 or more, whereby total reflection in the organic EL light emitting layer is achieved. Is less than half. In this embodiment, the resin composition of the light diffusion layer preferably contains at least one inorganic fine particle selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO. The resin layer has a high refractive index.

In another preferred embodiment of the light diffusing film, the light diffusing film includes a transparent base film and a light diffusing layer formed on the transparent base film, and the light diffusing layer Is formed by dispersing at least one kind of fine particles selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO having an average particle diameter of 50 nm to 300 nm in a transparent resin composition. A high refractive index layer having

<Transparent substrate film>
Examples of the material for the transparent substrate film (20) include a transparent resin film, a transparent resin plate, and a transparent resin sheet. Transparent resin films include triacetyl cellulose (TAC) film (refractive index 1.48), polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film Polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylonitrile film and the like can be used. The thickness is usually about 25 μm to 1000 μm.

<< Color filter >>
Hereinafter, the color filter of the present invention will be described in detail. The color filter can be obtained by curing a curable composition containing a colorant and light scattering particles. For example, the color filter is applied on a transparent substrate or a barrier layer, and UV-cured using a mask pattern. A pattern of each color of RGB can be formed. It is also possible to form each pixel using an inkjet method.

<Curable composition>
The curable composition of the present invention includes at least an alkali-soluble resin, light scattering particles, a colorant, a photosensitive polymerization component, and a photopolymerization initiator, and generally includes a solvent (hereinafter also referred to as an organic solvent). It will be. The curable composition of the present invention can be formed into a negative type by containing the above-mentioned photosensitive polymerization component and photopolymerization initiator, and further, a crosslinking agent for improving the degree of curing of the film, other It can comprise and comprise a component.

<Colorant>
Colorants that are preferably used in the present invention include, for example, organic pigments, organic dyes, fullerenes, polydiacetylenes, polyimides and other high molecular organic materials, aromatic hydrocarbons or aliphatic hydrocarbons (for example, aromatic hydrocarbons having orientation). Particles composed of hydrogen or aliphatic hydrocarbons, or aromatic hydrocarbons or aliphatic hydrocarbons having sublimability), organic pigments, organic dyes, or polymeric organic materials are preferable, and organic pigments are particularly preferable. Further, the organic particles may be used alone, or a plurality of organic particles may be used in combination.

  The organic agent is not limited in hue, for example perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium , Dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or a mixture thereof.

  More specifically, for example, C.I. I. Pigment red 190 (C.I. No. 71140), C.I. I. Pigment red 224 (C.I. No. 71127), C.I. I. Perylene compound pigments such as C.I. Pigment Violet 29 (C.I. No. 71129); I. Pigment orange 43 (C.I. No. 71105), or C.I. I. Perinone compound pigments such as C.I. Pigment Red 194 (C.I. No. 71100); I. Pigment violet 19 (C.I. No. 73900), C.I. I. Pigment violet 42, C.I. I. Pigment red 122 (C.I. No. 73915), C.I. I. Pigment red 192, C.I. I. Pigment red 202 (C.I. No. 73907), C.I. I. Pigment Red 207 (C.I. No. 73900, 73906) or C.I. I. Pigment Red 209 (C.I. No. 73905), a quinacridone compound pigment; I. Pigment red 206 (C.I. No. 73900/73920), C.I. I. Pigment orange 48 (C.I. No. 73900/73920), or C.I. I. Quinacridonequinone compound pigments such as CI Pigment Orange 49 (C.I. No. 73900/73920); I. Anthraquinone compound pigments such as C.I. Pigment Yellow 147 (C.I. No. 60645); I. Anthanthrone compound pigments such as CI Pigment Red 168 (C.I. No. 59300); I. Pigment brown 25 (C.I. No. 12510), C.I. I. Pigment violet 32 (C.I. No. 12517), C.I. I. Pigment yellow 180 (C.I. No. 21290), C.I. I. Pigment yellow 181 (C.I. No. 11777), C.I. I. Pigment orange 62 (C.I. No. 11775), or C.I. I. Benzimidazolone compound pigments such as CI Pigment Red 185 (C.I. No. 12516); I. Pigment yellow 93 (C.I. No. 20710), C.I. I. Pigment yellow 94 (C.I. No. 20038), C.I. I. Pigment yellow 95 (C.I. No. 20034), C.I. I. Pigment yellow 128 (C.I. No. 20037), C.I. I. Pigment yellow 166 (C.I. No. 20035), C.I. I. Pigment orange 34 (C.I. No. 21115), C.I. I. Pigment orange 13 (C.I. No. 21110), C.I. I. Pigment orange 31 (C.I. No. 20050), C.I. I. Pigment red 144 (C.I. No. 20735), C.I. I. Pigment red 166 (C.I. No. 20730), C.I. I. Pigment red 220 (C.I. No. 20055), C.I. I. Pigment red 221 (C.I. No. 20065), C.I. I. Pigment red 242 (C.I. No. 20067), C.I. I. Pigment red 248, C.I. I. Pigment red 262, or C.I. I. Disazo condensed compound pigments such as CI Pigment Brown 23 (C.I. No. 20060); I. Pigment yellow 13 (C.I. No. 21100), C.I. I. Pigment yellow 83 (C.I. No. 21108), or C.I. I. Disazo compound pigments such as CI Pigment Yellow 188 (C.I. No. 21094); I. Pigment red 187 (C.I. No. 12486), C.I. I. Pigment red 170 (C.I. No. 12475), C.I. I. Pigment yellow 74 (C.I. No. 11714), C.I. I. Pigment yellow 150 (C.I. No. 48545), C.I. I. Pigment red 48 (C.I. No. 15865), C.I. I. Pigment red 53 (C.I. No. 15585), C.I. I. Pigment orange 64 (C.I. No. 12760), or C.I. I. Azo compound pigments such as CI Pigment Red 247 (C.I. No. 15915), C.I. I. Indanthrone compound pigments such as C.I. Pigment Blue 60 (C.I. No. 69800); I. Pigment green 7 (C.I. No. 74260), C.I. I. Pigment green 36 (C.I. No. 74265), C.I. I. Pigment green 37 (C.I. No. 74255), C.I. I. Pigment blue 16 (C.I. No. 74100), C.I. I. Pigment blue 75 (C.I. No. 74160: 2), C.I. I. Pigment Blue 15: 6 (C.I. No. 74160), or C.I. I. Phthalocyanine compound pigments such as C.I. Pigment Blue 15: 3 (C.I. No. 74160); I. Pigment blue 56 (C.I. No. 42800), or C.I. I. Pigment Blue 61 (C.I. No. 42765: 1) and the like triarylcarbonium compound pigments, C.I. I. Pigment violet 23 (C.I. No. 51319) or C.I. I. Pigment Violet 37 (C.I. No. 51345) and other dioxazine compound pigments, C.I. I. Aminoanthraquinone compound pigments such as C.I. Pigment Red 177 (C.I. No. 65300); I. Pigment red 254 (C.I. No. 56110), C.I. I. Pigment Red 255 (C.I. No. 561050), C.I. I. Pigment red 264, C.I. I. Pigment red 272 (C.I. No. 561150), C.I. I. Pigment orange 71, or C.I. I. Diketopyrrolopyrrole compound pigments such as C.I. Pigment Orange 73; I. Thioindigo compound pigments such as C.I. Pigment Red 88 (C.I. No. 7313); I. Pigment yellow 139 (C.I. No. 56298), C.I. I. Pigment Orange 66 (C.I. No. 48210), an isoindoline compound pigment such as C.I. I. Pigment yellow 109 (C.I. No. 56284), C.I. I. Pigment yellow 185 (C.I. No. 56290), or C.I. I. Pigment Orange 61 (C.I. No. 11295) and the like, an inindolinone compound pigment such as C.I. I. Pigment Orange 40 (C.I. No. 59700), or C.I. I. Pyranthrone compound pigments such as C.I. Pigment Red 216 (C.I. No. 59710); I. Quinophthalone pigments such as CI Pigment Yellow 138; I. And isoviolanthrone compound pigments such as CI Pigment Violet 31 (60010). Among these, quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments, or azo compound pigments are preferable, and diketopyrrolopyrrole compound pigments, dioxazine compound pigments, and phthalocyanine compound pigments are more preferable.

  As a total amount in the curable composition of the coloring agent based on this invention, 20-60 mass% is preferable with respect to the mass in this composition, More preferably, it is 30-55 mass%, More preferably, it is 35-50. % By mass. In addition, the ratio of the material which comprises a coloring agent can be suitably selected according to purposes, such as a hue.

  The above colorant has good dispersibility and dispersion stability when used as a powdery processed pigment finely dispersed in acrylic resin, maleic acid resin, vinyl chloride-vinyl acetate copolymer, ethyl cellulose resin, etc. It can be.

  Next, a method for treating a pigment will be described. In the present invention, it is preferable to treat the pigment with various resins in advance. In other words, the pigment is generally dried by various methods after synthesis, and is usually dried from an aqueous medium and supplied as a powder, but requires a large latent heat of vaporization to dry the water, resulting in a dry powder. Gives a lot of heat energy. Therefore, pigments usually form aggregates (secondary particles) in which primary particles are aggregated, and it is not easy to disperse pigments forming such aggregates into fine particles. It is desirable to process with. Examples of the resin include an alkali-soluble resin described later.

As a processing method, there are a flushing process, a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, and the like. Among these, a flushing process or a kneading method using two or three roll mills is suitable for fine particle formation.
The flushing treatment is usually a method in which an aqueous dispersion of pigment and a resin solution dissolved in a solvent immiscible with water are mixed, the pigment is extracted from an aqueous medium into an organic medium, and the pigment is treated with a resin. According to this method, since the pigment is not dried, the aggregation of the pigment can be prevented and the dispersion becomes easy. In the above kneading by the two or three roll mill, the pigment and the resin or the resin solution are mixed, and then the pigment and the resin are kneaded while applying a high shear (shearing force) to thereby obtain the resin on the pigment surface. This is a method of treating a pigment by coating. The pigment particles aggregated in this process are dispersed from the lower order aggregates to the primary particles.

  Moreover, it can also be used as a processed pigment previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like. The form of the processed pigment is preferably a powder, paste, pellet, or paste in which the resin and the pigment are uniformly dispersed. Further, a non-uniform lump in which the resin is gelled is not preferable.

  Conventionally known pigment dispersants and surfactants can be used in combination for the purpose of improving the dispersibility of the pigment. Examples of the pigment dispersant and the surfactant include various compounds. For example, phthalocyanine derivatives (EFKA-745 manufactured by Efka), Solsperse 5000 (manufactured by Geneca); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), (Meth) acrylic acid-based (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Nonionic surfactants such as oxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disper Polymer dispersants such as Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sannopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000 , 28000, etc. (manufactured by Zeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, the same P94, the same L101, the same P103, the same F108, the same L121, the same P-123 (manufactured by Asahi Denka Co., Ltd.), and the ISONET S-20 (manufactured by Sanyo Kasei Co., Ltd.).

<Alkali-soluble resin>
The curable composition of the present invention contains at least one alkali-soluble resin. The alkali-soluble resin is not particularly limited, and is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and an acidic cellulose derivative having a carboxylic acid in the side chain. In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful.

  Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable. In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful as the water-soluble polymer. In addition, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful in increasing the strength of the cured film. These polymers can be mixed and used in an arbitrary amount.

  Further, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer described in JP-A-7-140654 / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Can be mentioned.

  Preferred alkali-soluble resins in the present invention are those having a carboxyl group, particularly in the side chain. Moreover, the thing whose acid value is 30-200 is preferable from a viewpoint of maintaining the developability and applicability | paintability after exposure favorably.

  As described above, the alkali-soluble resin is generally an acrylic copolymer using an unsaturated carboxylic acid as a copolymerizable monomer. Among them, an acrylic copolymer having a polyalkylene oxide chain in the side chain improves the liquid characteristics when the curable composition is prepared in a coating liquid state, and there are few problems of liquid remaining in the coating pipe. It is preferable in that it is easy to obtain a coating film having a uniform thickness with a thin film. In particular, a good coating can be obtained with a high yield for slit coating suitable for coating on a wide substrate having a large area.

  The total amount of the alkali-soluble resin in the curable composition is preferably 5 to 80% by mass, more preferably 20 to 60% by mass with respect to the total solid components. When the total amount is 5% by mass or more, sufficient film strength can be obtained, and when it is 80% by mass or less, the acidic content does not increase so much that the solubility can be easily controlled, and the pigment amount is relatively high. Therefore, a sufficient image density can be obtained.

  In order to improve the crosslinking efficiency of the curable composition of the present invention, a polymerizable group may be present in the side chain of the alkali-soluble resin, and includes an allyl group, a (meth) acryl group, an allyloxyalkyl group, and the like. Polymers contained in the side chain are also useful. Examples of the polymer containing these polymerizable groups are shown, but the polymer is not limited to the following as long as it contains an alkali-soluble group such as a COOH group, an OH group, and an ammonium group and an unsaturated bond between carbon atoms.

As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used. As a compound having both an alkali solubilizing group such as a COOH group and a carbon-carbon unsaturated group, for example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyuret)
Hane acrylic oligomer, Diamond Shamrock Co. Ltd .. Biscoat R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel UCB) Etc.).

<Photosensitive polymerization component>
The curable composition of the present invention contains at least one photosensitive polymerization component. As the photosensitive polymerization component, a compound having at least one addition-polymerizable ethylenically unsaturated group and a boiling point of 100 ° C. or higher under normal pressure is preferable, and a tetrafunctional or higher functional acrylate compound is more preferable.

  Examples of the “compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher under normal pressure” include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Monofunctional acrylates and methacrylates such as acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxyp) Pyr) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylated after addition of ethylene oxide or propylene oxide, pentaerythritol or dipentaerythritol Poly (meth) acrylates, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-49-43191 and JP-B-52-30490, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and the like. Can mention . Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  Further, as a compound obtained by adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol and then (meth) acrylated, it is described as a general formula (1) or (2) together with its specific example in JP-A-10-62986. What was made can also be used as a photosensitive polymerization component.

  Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and a structure in which these acryloyl groups are via ethylene glycol or propylene glycol residues are preferable.

  An oligomer type is also suitable, and an acrylic oligomer having a monomer repeating unit of 3 to 20 (preferably 3 to 10) is preferred.

When an acrylic oligomer is used as the photosensitive polymerization component, the exposure sensitivity is high and the polymerization strength is high, so that the pattern is hardly peeled off when developing with a developer, and the suitable time for development is widened. That is, the development latitude can be expanded.
In addition, the above-mentioned photosensitive polymerization component can be used not only individually but also in combination of 2 or more types.

<Photopolymerization initiator>
The curable composition of the present invention contains at least one photopolymerization initiator. Examples of the photopolymerization initiator include active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, 3-aryl-substituted coumarin compounds, and at least one lophine dimer. Particularly preferred are halomethyl-s-triazine compounds. Hereinafter, these compounds will be described in detail.

  Among the active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, examples of the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds. Specific examples include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2- And trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole.

  Examples of the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphth-1-yl)-described in JP-A-53-133428. Examples include 4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

  Specific examples of the vinyl-halomethyl-s-triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1 -P-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.

  Specific examples of the 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound include 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s- Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl ] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [ 4- (2-butoxyethyl) -Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloro Methyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4 , 6-Bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphtho- 1-yl) -4 3,6-Bis - trichloromethyl -s- triazine, and the like.

  Specific examples of the 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound include 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6. -Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [PN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl]- 2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxyca) Bonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6- Di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

  4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [O-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (eth Cycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

  4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN -Ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxy) Carbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine,

  4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m- Chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro- -N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl)- and s-triazine.

  A sensitizer can be used in combination with the photopolymerization initiator. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) ) Benzophenone (or Mihira) Ketone), p- (diethylamino) benzophenone, and benzanthrone, etc., benzothiazole based compounds disclosed in JP-B-51-48516.

  Particularly preferable examples of the above-described 3-aryl-substituted coumarin compounds mentioned as photopolymerization initiators include {(s-triazin-2-yl) amino} -3-arylcoumarin compounds.

  The above-mentioned lophine dimer mentioned as a photopolymerization initiator means a 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and specific examples thereof include 2- (o -Chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer 2-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) ) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, and the like.

  In this invention, other well-known compounds other than the above photoinitiator can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triallylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, And benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516. Adeka optomer SP-150, 151, 170, 171, N-1717, N1414, etc. manufactured by Asahi Denka Co., Ltd. can also be used as the polymerization initiator.

  As content in the curable composition of the said photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-5.0. % By mass. When the content is 0.1% by mass or more, polymerization easily proceeds with certainty, and when it is 10.0% by mass or less, sufficient film strength can be obtained.

<Solvent>
In preparing the curable composition of the present invention, a solvent (also referred to as “organic solvent” in the present specification) is generally contained. The solvent is basically not particularly limited as long as the solubility of each component and the applicability of the curable composition are satisfied, but in particular, the colorant and the solubility of the resin component, applicability, and safety should be selected. Is preferred.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

  3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .;

  Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable. These solvents may be used alone or in combination of two or more.

<Various additives>
In the curable composition of the present invention, various additives, for example, a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, etc., if necessary. Can be blended.

  Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, hydroxyl group A polymer having an acid anhydride added thereto, an alcohol-soluble nylon, an alkali-soluble resin such as a phenoxy resin formed from bisphenol A and epichlorohydrin; a nonionic, a kachin-based, an anionic surfactant, etc. Specifically, phthalocyanine derivatives (EFKA-745 manufactured by Morishita Sangyo); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, the same manufactured by BASF) Nonionic surfactants such as 701, 704, 901, 904, and 150R1; EFTOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F-141, -142, F-143, F-144 (manufactured by Dainippon Ink & Chemicals, Inc.), etc .; anionic surfactants such as W004, W005, W017 (manufactured by Yusho Co., Ltd.); EFKA -46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Polymer dispersing agents such as Disperseide 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Agent (manufactured by Zeneca); Adeka Pluronic L 1, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.);

  Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol) , 2, -Antioxidants such as di-t-butylphenol; ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone; and sodium polyacrylate And the like.

  Further, when the alkali solubility of the non-image area is promoted and the developability of the curable composition of the present invention is further improved, the composition is an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the curable composition of the present invention, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. Useful.

<Light scattering particles>
The kind of light-scattering particle which comprises the curable composition in this invention is not limited, Organic fine particle or inorganic fine particle may be sufficient. As the organic fine particles, polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, styrene beads, crosslinked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde beads and the like are used. As the inorganic fine particles, SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , etc. are used. The light scattering particles are preferably at least one kind of fine particles selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO having an average particle diameter of 50 nm to 300 nm, whereby the translucent resin layer has light scattering properties. It becomes a high refractive index layer.

The cured product of the curable composition according to the present invention described above preferably has a refractive index of 1.6 or more, and this reduces the total reflection amount in the organic EL light emitting layer to half or less.
The curable composition preferably contains at least one inorganic fine particle selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO, thereby increasing the isoluminous resin layer. It becomes a refractive index layer.
Moreover, in the said curable composition, it is preferable that the refractive index of light-scattering particle | grains is 1.55 or less, and this can fully obtain the amount of scattering.
Further, in the curable composition, the average diameter of the light scattering particles is preferably 0.1 μm or more and 2.0 μm or less, whereby a sufficient amount of scattering can be obtained and the directivity of light scattering can be obtained. Almost isotropic scattering. By making the scattering directivity close to isotropic scattering, more light can be extracted.

  The curable composition of the present invention is generally prepared by mixing light scattering particles, a colorant, an alkali-soluble resin, a photosensitive polymerization component, a photopolymerization initiator, and various additives used as necessary, with a solvent. It can be prepared by mixing and dispersing using a mixer and a disperser.

  For example, it can be suitably produced as follows. That is, the curable composition of the present invention is kneaded and dispersed by mixing a color modifier with a surface modifier or dispersant, an alkali-soluble resin, and a solvent. The equipment used for kneading and dispersing is a two-roll, three-roll, ball mill, disper, kneader, homogenizer, blender or the like, and disperses while applying a strong shearing force. Next, a photosensitive polymerization component and a photopolymerization initiator, and, if necessary, a solvent, a dispersant, an alkali-soluble resin, light scattering particles, and other components are added to the obtained kneaded dispersion, and mainly a sand grinder, a pin mill. Using a slit mill, an ultrasonic disperser or the like, beads made of glass having a particle diameter of 0.1 to 10 mm, zirconia or the like are finely dispersed as a dispersion medium. Note that this kneading and dispersing process can be omitted. In that case, fine dispersion treatment is performed with a colorant and a dispersant or a surface treatment agent, an alkali-soluble resin, and a solvent.

  For details of kneading and dispersion, see T.W. C. Also described in “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964).

<How to create a color filter>
The color filter of this invention can form the pattern of each RGB color by apply | coating the said curable composition on a transparent substrate or a barrier layer, and ultraviolet-curing using a mask pattern. It is also possible to form each pixel using an inkjet method. Hereinafter, a method for forming a color filter by applying a curable composition on a substrate, an organic EL upper electrode, or an organic EL barrier layer will be described in detail.

The color filter of the present invention is prepared using at least three kinds of curable compositions each having a different colorant composition. After applying one of the three curable compositions onto the substrate, exposing through a mask and developing to form a first color pixel, and after forming the first color pixel, the coloring Another one having a hue different from that of the first color pixel selected from the curable composition is applied onto the substrate, exposed through a mask, and developed to form a second color pixel, and the second color pixel. After the second color pixel is formed, the first color selected from the colored curable composition and the other one having a different hue from the second color are applied on the substrate, exposed through a mask, developed, and developed. This is obtained by forming a pixel of the third color. In addition to the first color to the third color (for example, green, red, and blue), further pixels may be formed so as to have four or more colors.

  That is, the radiation-sensitive layer is formed by applying at least three kinds of the curable compositions of the present invention in the desired hue order on a substrate by a coating method such as spin coating, cast coating, roll coating, and drying. Further, the step of performing exposure through a predetermined mask pattern and developing with a developing solution after exposure to form a pixel having a desired pattern can be obtained by repeating at least three times in accordance with the number of coloring compositions. it can. At this time, if necessary, a step of curing the formed pixels by heating and / or exposure can be provided. The exposure can be performed by radiation irradiation, and ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used as the radiation.

  Examples of the substrate constituting the color filter include soda glass, Pyrex (registered trademark) (R) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto. It is also possible to form a color filter after forming a low refractive index layer in advance on these substrates. It is also possible to directly form a color filter on the upper electrode or the barrier layer constituting the organic EL element. These substrates may have black stripes that separate pixels.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the curable composition of the present invention but does not dissolve the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the above-described solvents used for preparing the curable composition of the present invention.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. An alkaline aqueous solution in which an alkaline compound such as choline, pyrrole or piperidine is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is suitable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

<< Organic electroluminescence display device >>
The light emitting display device of the present invention is a display device in which a plurality of organic compound thin films including a light emitting layer or a light emitting layer are formed between a pair of electrodes of an anode and a cathode, in addition to the light emitting layer, a hole injection layer, a hole transport layer, An electron injection layer, an electron transport layer, a protective layer, and the like may be included, and each of these layers may have other functions. Various materials can be used for forming each layer.

  The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Is a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, preferably conductive metals It is an oxide, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like. Although the film thickness of the anode can be appropriately selected depending on the material, it is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 500 nm.

  As the anode, a layer formed on a soda-lime glass, non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but when glass is used, a thickness of 0.2 mm or more, preferably 0.7 mm or more is usually used.

  A barrier film can also be used as the transparent resin substrate. The barrier film is a film in which a gas impermeable barrier layer is provided on a plastic support. Examples of the barrier film include those deposited with silicon oxide or aluminum oxide (Japanese Patent Publication No. Sho 53-12953, Japanese Patent Laid-Open Publication No. 58-217344), and those having an organic-inorganic hybrid coating layer (Japanese Patent Laid-Open No. 2000-323273, Japanese Patent Laid-Open Publication No. 2004-25732). ), Those having an inorganic layered compound (Japanese Patent Laid-Open No. 2001-205743), those obtained by laminating inorganic materials (Japanese Patent Laid-Open No. 2003-206361, Japanese Patent Laid-Open No. 2006-263389), those obtained by alternately laminating organic layers and inorganic layers (Japanese Patent Laid-Open No. 2006-263389) 2007-30387, U.S. Pat. No. 6413645, Affinito et al., Thin Solid Films 1996, pages 290-291), and organic layers and inorganic layers laminated continuously (U.S. Patent No. 2004-46497).

  Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), an indium tin oxide dispersion A film is formed by a method such as coating. The anode can be subjected to cleaning or other processing to lower the driving voltage of the display device or to increase the light emission efficiency. For example, in the case of ITO, UV-ozone treatment is effective.

The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, etc., and the adhesion, ionization potential, stability, etc., between the negative electrode and the adjacent layer such as the electron injection layer, electron transport layer, light emitting layer, etc. Selected in consideration of As the material of the cathode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples include alkali metals (for example, Li, Na, K, etc.) or fluorides thereof, alkaline earths. Metals (for example, Mg, Ca, etc.) or fluorides thereof, gold, silver, lead, aluminum, sodium-potassium alloy or mixed metal thereof, lithium-aluminum alloy or mixed metal thereof, magnesium-silver alloy or mixed thereof Examples thereof include metals, rare earth metals such as indium and ytterbium, preferably a material having a work function of 4 eV or less, more preferably aluminum, lithium-aluminum alloy or mixed metal thereof, magnesium-silver alloy or mixed metal thereof Etc. The film thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 1 μm. For production of the cathode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, and a coating method are used, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, a plurality of metals can be vapor-deposited simultaneously to form an alloy electrode, or a previously prepared alloy may be vapor-deposited.
The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

  The barrier film may be bonded onto the cathode to prevent gas from entering, and a protective layer may be formed on the display surface.

The material of the light emitting layer is a function that can inject holes from the anode or hole injection layer, hole transport layer and cathode or electron injection layer, electron transport layer when an electric field is applied, Any layer can be used as long as it can form a layer having a function of moving injected charges and a function of emitting light by providing a recombination field of holes and electrons. Preferably, the light emitting layer contains the compound of the present invention, but other light emitting materials of the compound of the present invention can also be used. For example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives , Pyraziridine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives, metal complexes and rare earth complexes Representative metal complexes, polymer compounds such as polythiophene, polyphenylene, polyphenylene vinylene, etc. And the like. Although the film thickness of a light emitting layer is not specifically limited, Usually, the thing of the range of 1 nm-5 micrometers is preferable, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm.
The method for forming the light emitting layer is not particularly limited, but methods such as resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method (spin coating method, casting method, dip coating method, etc.), LB method, etc. Are preferably used by resistance heating vapor deposition and coating.

The material of the hole injection layer and the hole transport layer has any one of the function of injecting holes from the anode, the function of transporting holes, and the function of blocking electrons injected from the cathode. That's fine. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline compounds Examples thereof include conductive polymer oligomers such as copolymers, thiophene oligomers, and polythiophenes. The film thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 nm. . The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
As a method for forming the hole injection layer and the hole transport layer, a vacuum deposition method, an LB method, a method in which the hole injection / transport agent is dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating method) Etc.) are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and the like.

The material for the electron injection layer and the electron transport layer may be any material having any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyryl. Various metal complexes such as pyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, metal complexes of phthalocyanine derivatives, 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole and benzothiazole as ligands, etc. Is mentioned. Although the film thickness of an electron injection layer and an electron carrying layer is not specifically limited, The thing of the range of 1 nm-5 micrometers is preferable normally, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
As a method for forming the electron injection layer and the electron transport layer, a vacuum deposition method, an LB method, a method in which the electron injection / transport agent is dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating method, etc.), etc. Is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

As a material for the protective layer, any material may be used as long as it has a function of preventing a substance that promotes deterioration of the display device such as moisture or oxygen from entering the display device. Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychloro Trifluoroethylene, polydichlorodifluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, a copolymer obtained by copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer, copolymerization Fluorine-containing copolymer having a cyclic structure in the main chain, water absorption 1% Water absorbing material of the above, water absorption of 0.1% or less of the moisture-proof material, and the like.
There is no particular limitation on the method for forming the protective layer. For example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency excitation ions) Plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method can be applied.

<Light diffusion film pasting method>
As a method of using the light diffusing film or color filter of the present invention in an organic display, it is directly bonded on the light extraction side electrode or barrier layer of the organic EL via an adhesive or pressure-sensitive adhesive. There is a method to use. That is, in one embodiment of the organic electroluminescence display device of the present invention, the scattering member is directly attached on the upper electrode.
In another embodiment of the organic electroluminescence display device of the present invention, the scattering member is directly attached to the barrier layer on the upper electrode via the barrier layer.
When the scattering member is a light diffusing film, as a preferred embodiment of the organic electroluminescence display device of the present invention, an adhesive layer is interposed on the upper electrode or on the barrier layer provided on the upper electrode. Thus, a form in which the light diffusion film is attached can be mentioned.

<Adhesive>
The refractive index of the adhesive layer made of an adhesive is preferably equal to or higher than that of the organic layer. Further, if the refractive index is too large, the efficiency decreases due to reflection at the interface, and therefore the refractive index difference from the organic layer is preferably 0.2 or less. That is, the refractive index of the adhesive layer is preferably 1.6 or more, and preferably 1.60 to 2.00, because the total reflection in the organic EL light emitting layer is less than half. Is more preferable. As another method for suppressing reflection at the interface, it is possible to create a gradation of refractive index in the adhesive layer and connect the adhesive and the material at both ends of the adhesive without jumping the refractive index.

The adhesive is preferably an adhesive that flows by heating or pressurization, and particularly an adhesive that exhibits fluidity by heating at 200 ° C. or less or pressurization by 1 kgf / cm ² or more. By using such an adhesive, the light diffusion film of the present invention can be bonded to a display or a plastic plate as an adherend by flowing the adhesive. Since it can flow, the optical film can be easily adhered to an adherend having a curved surface or a complicated shape by laminating or pressure forming, particularly pressure forming, on the adherend. For this purpose, the softening temperature of the adhesive is preferably 200 ° C. or lower. Since the environment in which the optical film is used is usually lower than 80 ° C., the softening temperature of the adhesive layer is preferably 80 ° C. or higher, and most preferably 80 to 120 ° C. from the viewpoint of workability. The softening temperature is a temperature at which the viscosity is 10 ¹² poise (10 ¹³ Pa · s or less) or less, and usually at that temperature, a flow is recognized in about 1 to 10 seconds.

  Typical examples of the adhesive that flows by heating or pressurization as described above include the following thermoplastic resins. For example, natural rubber (refractive index n = 1.52), polyisoprene (n = 1.521), poly-1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.513), poly- Such as 2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-butadiene (n = 1.506), poly-1,3-butadiene (n = 1.515) ) Polyenes such as ene, polyoxyethylene (n = 1.456), polyoxypropylene (n = 1.450), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.459), polyvinyl butyl ether (n = 1.456) Ethers, polyvinyl acetate (n = 1.467), polyesters such as polyvinyl propionate (n = 1.467), polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.54 to 1.55) ), Polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5 to 1.6), polyethyl acrylate (n = 1.469), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463) , Poly-t-butyl acrylate (n = 1.464), poly-3-ethoxypropyl acrylate (n = 1.465), polyoxycarbonyltetramethylene (n = 1.465), polymethyl acrylate (n = 1.472-1.480), polyisopropyl Methacrylate (n = 1.473), polydodecyl methacrylate (n = 1.474), polytetradecyl methacrylate (n = 1.475), poly-n-propyl methacrylate (n = 1.484), poly-3,3,5-trimethylcyclohexyl methacrylate ( n = 1.484), polyethyl methacrylate (n = 1.485), poly-2-nitro-2-methylpropyl methacrylate (n = 1.487), poly-1,1-diethylpropyl methacrylate (n = 1.485). 489) and poly (meth) acrylic acid esters such as polymethyl methacrylate (n = 1.489) can be used. Two or more kinds of these acrylic polymers may be copolymerized as needed, or two or more kinds may be blended and used. Furthermore, as copolymer resins other than acrylic resin and acrylic, epoxy acrylate (n = 1.48 to 1.60), urethane acrylate (n = 1.5 to 1.6), polyether acrylate (n = 1.48 to 1.49), polyester acrylate (n = 1.48) ~ 1.54) can also be used. In particular, urethane acrylate, epoxy acrylate, and polyether acrylate are excellent from the viewpoint of adhesiveness. Examples of epoxy acrylate include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, and resorcinol. (Meth) acrylic such as diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether An acid adduct is mentioned. A polymer having a hydroxyl group in the molecule such as epoxy acrylate is effective for improving the adhesion. These copolymer resins can be used in combination of two or more as required. The softening temperature of the polymer used as these adhesives is preferably 200 ° C. or less, and more preferably 150 ° C. or less from the viewpoint of handleability. Since the environment in which the light diffusing film is used is usually 80 ° C. or lower, the softening temperature of the adhesive layer is most preferably 80 to 120 ° C. in view of processability. On the other hand, it is preferable to use a polymer having a mass average molecular weight (measured using a standard polystyrene calibration curve by gel permeation chromatography, the same applies hereinafter) of 500 or more. When the molecular weight is 500 or more, the cohesive force of the adhesive composition is sufficiently expressed, so that adhesion to an adherend can be reliably obtained. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, a coloring agent, a ultraviolet absorber, and a tackifier, with the adhesive agent used by this invention as needed. The thickness of the adhesive layer is preferably 5 to 80 μm, and particularly preferably 10 to 50 μm.

  Adhesive materials include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrahydroxyphenylmethane type epoxy resin, novolac type epoxy resin, resorcin type epoxy resin, polyalcohol / polyglycol type epoxy resin, polyolefin type epoxy resin Epoxy resins such as alicyclic and halogenated bisphenol (both having a refractive index of 1.55 to 1.60) can be used. Other than epoxy resin, natural rubber (n = 1.52), polyisoprene (n = 1.521), poly1,2-butadiene (n = 1.50), polyisobutene (n = 1.505 to 1.51), polybutene (n = 1.5125), poly- Such as 2-heptyl-1,3-butadiene (n = 1.50), poly-2-tert-butyl-1,3-butadiene (n = 1.506), poly-1,3-butadiene (n = 1.515) ) Polyenes such as ene, polyoxyethylene (n = 1.4563), polyoxypropylene (n = 1.4495), polyvinyl ethyl ether (n = 1.454), polyvinyl hexyl ether (n = 1.4591), polyvinyl butyl ether (n = 1.4563) Ethers, polyesters such as polyvinyl acetate (n = 1.4665), polyvinyl propionate (n = 1.4665), polyurethane (n = 1.5 to 1.6), ethyl cellulose (n = 1.479), polyvinyl chloride (n = 1.5 4-1.55), polyacrylonitrile (n = 1.52), polymethacrylonitrile (n = 1.52), polysulfone (n = 1.633), polysulfide (n = 1.6), phenoxy resin (n = 1.5-1.6), etc. Can do. These express suitable visible light transmittance.

In addition to the above resins, polyethyl acrylate (n = 1.4685), polybutyl acrylate (n = 1.466), poly-2-ethylhexyl acrylate (n = 1.463), poly-t-butyl acrylate (n = 1.4638), poly -3-Ethoxypropyl acrylate (n = 1.465), polyoxycarbonyltetramethacrylate (n = 1.465), polymethyl acrylate (n = 1.472 to 1.480), polyisopropyl methacrylate (n = 1.4728), polydodecyl methacrylate (n = 1.474) ), Polytetradecyl methacrylate (n = 1.4746), poly-n-propyl methacrylate (n = 1.484), poly-3,3,5-trimethylcyclohexyl methacrylate (n = 1.484), polyethyl methacrylate (n = 1.485), Poly-2-nitro-2-methylpropyl methacrylate (n = 1.4868), polytetra Le vanillic methacrylate (n = 1.4889), poly-1,1-diethyl-propyl methacrylate (n = 1.4889), poly (meth) acrylic acid esters such as polymethyl methacrylate (n = 1.4893) can be used. Two or more kinds of these acrylic polymers may be copolymerized as necessary, or two or more kinds may be blended and used.
Furthermore, epoxy acrylate, urethane acrylate, polyether acrylate, polyester acrylate, or the like can also be used as a copolymer resin of an acrylic resin and other than acrylic. In particular, epoxy acrylate and polyether acrylate are excellent from the viewpoint of adhesiveness. As the epoxy acrylate, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether (Meth) acrylic acid adducts such as adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether Is mentioned. Epoxy acrylate has a hydroxyl group in the molecule and is effective in improving adhesiveness. These copolymer resins can be used in combination of two or more as required. The polymer used as the main component of the adhesive has a mass average molecular weight of 1,000 or more. When the molecular weight is 1,000 or more, the cohesive force of the composition is sufficiently expressed, so that adhesion to an adherend can be reliably obtained.

In addition to the above materials, the adhesive may contain a monomer having a high refractive index and / or metal oxide ultrafine particles having a high refractive index. Examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether and the like. Examples of the metal oxide ultrafine particles having a high refractive index include a particle diameter of 100 nm or less, preferably 50 nm or less, made of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony. It is preferable to contain fine particles. The metal oxide ultrafine particles having a high refractive index are preferably oxide ultrafine particles of at least one metal selected from Al, Zr, Zn, Ti, In and Sn. Specific examples include ZrO ₂ , TiO ₂ , _{al 2 O 3, In 2 O} 3, ZnO, SnO 2, Sb 2 O 3, ITO , and the like. In particular, the adhesive layer preferably contains at least one kind of inorganic fine particles selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO, whereby the adhesive layer becomes a high refractive index layer. Among these, ZrO ₂ is particularly preferably used. The addition amount of the high refractive index monomer and the metal oxide ultrafine particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the translucent resin (31).

  A curing agent (crosslinking agent) may be used for the adhesive. Examples of the crosslinking agent include amines such as triethylenetetramine, xylenediamine and diaminodiphenylmethane, phthalic anhydride, maleic anhydride, dodecyl succinic anhydride, Mellitic acid, acid anhydrides such as benzophenone tetracarboxylic anhydride, diaminodiphenylsulfone, tris (dimethylaminomethyl) phenol, polyamide resin, dicyandiamide, ethylmethylimidazole, and the like can be used. These may be used alone or in combination of two or more. The addition amount of these crosslinking agents is selected in the range of 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the polymer. If the amount added is less than 0.1 parts by mass, curing may be insufficient, and if it exceeds 50 parts by mass, excessive crosslinking may occur, which may adversely affect adhesiveness. You may mix | blend additives, such as a diluent, a plasticizer, antioxidant, a filler, and a tackifier, with the resin composition of the adhesive agent used by this invention as needed. The adhesive resin composition is applied to cover a part or the entire surface of the base material of the constituent material provided with a geometric figure drawn with a conductive material on the surface of the transparent plastic base material, After the solvent drying and heat curing steps, the adhesive film according to the present invention is obtained. The adhesive film having electromagnetic shielding properties and transparency obtained above can be used by directly attaching to an adhesive film adhesive such as a CRT, PDP, liquid crystal, EL display, acrylic plate, glass plate, etc. Affixed to a plate or sheet of a sheet and used for a display.

  The adhesive is preferably transparent. Specifically, the total light transmittance is preferably 70% or more, more preferably 80% or more, and most preferably 85 to 92%. Furthermore, it is preferable that the degree of purity is low. Specifically, 0 to 3% is preferable, and 0 to 1.5% is more preferable. The adhesive used in the present invention is preferably colorless so as not to change the original display color of the display. However, even if the resin itself is colored, it can be considered substantially colorless if the adhesive is thin. Similarly, when intentionally coloring as described later, it is not within this range.

  Examples of the adhesive having the above characteristics include acrylic resins, α-olefin resins, vinyl acetate resins, acrylic copolymer resins, urethane resins, epoxy resins, vinylidene chloride resins, vinyl chloride resins, Examples thereof include ethylene-vinyl acetate resin, polyamide resin, and polyester resin. Of these, acrylic resins are preferred. Even when the same resin is used, the adhesiveness can be improved by reducing the amount of crosslinking agent added, adding a tackifier, or changing the end group of the molecule when synthesizing the adhesive by polymerization. Is also possible. Even if the same adhesive is used, it is possible to improve the adhesion by modifying the surface of the adhesive, that is, the surface of the transparent plastic film or glass plate. Examples of such surface modification methods include physical methods such as corona discharge treatment and plasma glow treatment, and methods such as forming an underlayer for improving adhesion.

  From the viewpoint of transparency, colorlessness, and handling properties, the thickness of the adhesive is preferably about 1 to 50 μm. Specifically, it is about 1 to 20 μm. However, when the display color of the display itself is not changed as described above and the transparency is within the above range, the thickness may exceed the above range.

<< Preparation of light diffusion film >>

(Preparation of coating solution for light diffusion layer (1))
Zirconia ultrafine particle dispersion-containing hard coat coating liquid (Desolite KZ-7114A, manufactured by JSR Corporation) as a translucent resin constituting the light diffusion layer (average particle diameter of zirconia ultrafine particles is 0.05 μm) 100 parts by mass In addition, 57 parts by mass of a polymerizable monomer (polymerizable compound) (DPHA manufactured by Nippon Kayaku Co., Ltd.) is stirred and mixed and dissolved in a methyl ethyl ketone / methyl isobutyl ketone (20/80 mass ratio) solution, and then light scattering particles are added to this solution. As a polymethylmethacrylate bead (MX150, manufactured by Soken Chemical Co., Ltd., particle size 1.5 μm, refractive index 1.49), 17 parts by mass were mixed and methyl ethyl ketone / methyl isobutyl ketone (20/80 mass ratio) was used to obtain a solid content of 50%. It was adjusted to become. Here, in order to measure the refractive index of the translucent resin in a state where particles were not mixed, a coating solution in which particles were not mixed was separately applied and ultraviolet cured to create a coating film. The refractive index of the obtained coating film was 1.61.

(Preparation of coating solutions for light diffusion layer (2) to (4))
Zirconia ultrafine particle dispersion-containing hard coat coating liquid (Desolite KZ-7114A, manufactured by JSR Corporation) as a translucent resin constituting the light diffusion layer (average particle diameter of zirconia ultrafine particles is 0.05 μm) 100 parts by mass In addition, 57 parts by mass of a polymerizable monomer (polymerizable compound) (DPHA manufactured by Nippon Kayaku Co., Ltd.) is stirred and mixed and dissolved in a methyl ethyl ketone / methyl isobutyl ketone (20/80 mass ratio) solution, and then light scattering particles are added to this solution. As described above, 17 parts by mass of amorphous silica beads were mixed and adjusted to a solid content of 50% with methyl ethyl ketone / methyl isobutyl ketone (20/80 mass ratio). Here, three types of coating liquids (2) to (4) for the light diffusion layer were prepared using three types of KE-P10, KE-P30, and KE-P50 manufactured by Nippon Shokubai as amorphous silica-based beads. The particle diameters of the amorphous silica-based beads KE-P10, KE-P30, and KE-P50 were 0.1 μm, 0.3 μm, and 0.5 μm, respectively, and the refractive indexes were all 1.43. Here, in order to measure the refractive index of the translucent resin in a state where particles were not mixed, a coating solution in which particles were not mixed was separately applied and ultraviolet cured to create a coating film. The refractive index of the obtained coating film was 1.61.

(Preparation of coating solution for light diffusion layer (5))
200 parts by mass of a zirconia ultrafine particle dispersion-containing hard coat coating solution (Desolite KZ-7114A, manufactured by JSR Corporation) as a translucent resin constituting the light diffusion layer, and a polymerizable monomer (polymerizable compound) ( 57 parts by mass of Nippon Kayaku DPHA) was stirred and mixed, dissolved in a methyl ethyl ketone / methyl isobutyl ketone (20/80 mass ratio) solution, and adjusted to a solid content of 50%. The average particle diameter of the ultrafine zirconia particles used here was 0.05 μm, and the refractive index was 2.18. Here, in order to measure the refractive index of the translucent resin, this coating solution was applied and cured with ultraviolet rays to form a coating film. The refractive index of the obtained coating film was 1.70.

(Preparation of coating solution for low refractive index layer)
MEK-ST (SiO ₂ sol methyl ethyl ketone having an average particle size of 10 to 20 nm and a solid content concentration of 30 parts by mass) is added to 93 parts by mass of a heat-crosslinkable fluoropolymer having a refractive index of 1.42 (JN-7228, manufactured by JSR Corporation). (MEK) dispersion, manufactured by Nissan Chemical Co., Ltd.) 8 parts by mass and methyl ethyl ketone 100 parts by mass were added, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer. .

<Light diffusion film 1>
On a triacetyl cellulose film (manufactured by FUJIFILM Corporation, TD-80U), the coating solution for the light diffusion layer (1) is applied to a coating amount of 1.5 μm polymethyl methacrylate beads to 0.4 g / m ² . After coating and solvent drying, the coating layer is irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). Was cured to prepare a light diffusion film 1. The dry thickness of the light diffusion layer of this film was 3.0 μm. The haze value of this film was 65%.

<Light diffusion film 2>
The above-mentioned coating solution for low refractive index layer is applied onto a triacetyl cellulose film (manufactured by FUJIFILM Corporation, TD-80U) using a bar coater, dried at 80 ° C., and further heated at 120 ° C. for 10 minutes. Crosslinking was performed to form a low refractive index layer having a thickness of 3.0 μm. Next, the light diffusion layer coating liquid (1) is applied onto the low refractive index layer so that the coating amount of 1.5 μm polymethyl methacrylate beads is 0.4 g / m ^2, and after solvent drying, Using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), an ultraviolet ray having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² was irradiated to cure the coating layer, thereby producing a light diffusion film 2. . The dry thickness of the light diffusion layer of this film was 3.0 μm. The haze value of this film was 65%.

<Light diffusion films a to c>
On the triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., TD-80U), the coating liquids (2) to (4) for the light diffusing layer are each coated with an amorphous silica-based bead of 0.4 g / m ^2. After coating and solvent drying, the film was applied by irradiating with ultraviolet light having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). The layer was cured to produce light diffusing films ac. The dry thickness of the light diffusion layer of this film was 3.0 μm. The haze value of this film was a: 15%, b: 65%, c: 65%.

<Light diffusion film df>
The above-mentioned coating solution for low refractive index layer is applied onto a triacetyl cellulose film (manufactured by FUJIFILM Corporation, TD-80U) using a bar coater, dried at 80 ° C., and further heated at 120 ° C. for 10 minutes. Crosslinking was performed to form a low refractive index layer having a thickness of 3.0 μm. Next, the light diffusion layer coating liquids (2) to (4) are applied onto the low refractive index layer so that the amount of the amorphous silica-based beads applied is 0.4 g / m ^2, and after solvent drying, Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm, the coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to form the light diffusion films d to f. Produced. The dry thickness of the light diffusion layer of this film was 3.0 μm. The haze values of this film were d: 15%, e: 65%, and f: 65%.

<Light diffusion film g>
On the triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., TD-80U), the light diffusion layer coating solution (5) is applied so as to have a thickness of 6 μm, and after drying the solvent, an air-cooled metal halide of 160 W / cm. Using a lamp (made by Eye Graphics Co., Ltd.), an ultraviolet ray having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² was irradiated to cure the coating layer, and a light diffusion film g containing zirconia fine particles was produced. . The dry thickness of the light diffusion layer of this film was 3.0 μm. The haze value of this film was 10%.

<Light diffusion film h>
The above-mentioned coating solution for low refractive index layer is applied onto a triacetyl cellulose film (manufactured by FUJIFILM Corporation, TD-80U) using a bar coater, dried at 80 ° C., and further heated at 120 ° C. for 10 minutes. Crosslinking was performed to form a low refractive index layer having a thickness of 3.0 μm. Next, the light diffusion layer coating solution (5) is applied onto the low refractive index layer so as to have a thickness of 6 μm, and after drying the solvent, a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). Was used to cure the coating layer by irradiating ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to prepare a light diffusing film h containing zirconia fine particles. The dry thickness of the light diffusion layer of this film was 3.0 μm. The haze value of this film was 10%.

<Color filter>
First, the following three curable compositions were dispersed with a sand mill all day and night.
(green)
-Benzyl methacrylate / methacrylic acid copolymer ... 80 parts by mass (weight average molecular weight 30000, acid value 120)
Propylene glycol monomethyl ether acetate: 500 parts by mass Copper phthalocyanine pigment: 33 parts by mass I. Pigment Yellow 185 ... 67 parts by mass (red)
-Benzyl methacrylate / methacrylic acid copolymer ... 80 parts by mass (weight average molecular weight 30000, acid value 120)
Propylene glycol monomethyl ether acetate: 500 parts by mass Pigment Red 254: 50 parts by mass Pigment Red PR177: 50 parts by mass (blue)
-Benzyl methacrylate / methacrylic acid copolymer ... 80 parts by mass (weight average molecular weight 30000, acid value 120)
Propylene glycol monomethyl ether acetate: 500 parts by mass Pigment Blue 15: 6: 95 parts by mass Pigment Violet 23: 5 parts by mass

The following ingredients were then added:
Dipentaerythritol hexaacrylate (DPHA): 80 parts by mass TiO ₂ (titania fine particles, average particle diameter (average diameter) 150 nm, refractive index: 2.54): 100 parts by mass 4- [ o-Bromo-p-N, N-di (ethoxycarbonyl) aminophenyl] 2,6-di (trichloromethyl) -S-triazine 5 mass parts 7-[{4-chloro-6- (diethylamino) ) -S-triazin-2-yl} amino] -3-phenylcoumarin 2 mass parts Hydroquinone monomethyl ether 0.01 mass parts Propylene glycol monomethyl ether acetate 500 mass parts

  Each of the above components was uniformly mixed and then filtered through a filter having a pore size of 5 μm to obtain a three-color curable composition of the present invention. Among these, the green curable composition was applied onto a glass substrate for color filter production using a spin coater so that the dry film thickness was 2.0 μm, and dried at 120 ° C. for 2 minutes to obtain a uniform green color. A coating film was formed.

Next, using an exposure apparatus, the coating film was irradiated with an exposure dose of 300 mJ / cm ² through a 100 μm mask at a wavelength of 365 nm. After irradiation, development was performed at 26 ° C. for 60 seconds using a 10% CD (manufactured by FUJIFILM Arch Corporation) developer. Subsequently, after rinsing with running water for 20 seconds, it was dried with an air knife, and heat-treated at 220 ° C. for 60 minutes to form a green pattern image (green pixel). This operation is similarly performed on the same glass substrate for the red curable composition and the blue curable composition, and a red pattern image (red pixel) and a blue pattern image (blue pixel) are sequentially formed. Thus, the color filter of the present invention was obtained. The refractive indexes of the green pixel, the red pixel, and the blue pixel (cured product of the curable composition) were 1.80, 1.78, and 1.82 at wavelengths of 550 nm, 630 nm, and 450 nm that transmit light, respectively.

<Adhesive>
A transparent adhesive having a refractive index of 1.61 was obtained by containing 10 parts by mass of ultrafine zirconium oxide particles in 90 parts by mass of a transparent adhesive made of an acrylate polymer.

<< Production of Multicolor Organic EL Display Device >>

Next, the top emission type organic EL display device of the present invention will be described.
First, a TFT is formed on an insulating substrate through a buffer layer, and then an interlayer insulating film layer made of a SiN film is deposited on the entire surface, and then reaches a source region and a drain region using a normal photoetching process. Each contact hole is formed.

Next, after depositing an Al / Ti / Al multilayer structure conductive layer on the entire surface, patterning is performed using a normal photoetching process, thereby forming a source electrode so as to extend also on the TFT portion, and a drain. An electrode is formed.
Note that the source electrode branches from the common source line into four branch lines.

  Next, for example, by applying a photosensitive resin to the entire surface by using a spin coating method to form an interlayer insulating film, the interlayer insulating film is exposed using a predetermined mask, and then developed using a predetermined developer. Then, a contact hole for the branch line of the source electrode is formed.

  Next, for example, an Al film is deposited on the entire surface by sputtering, and then patterned into a predetermined shape using a normal photoetching process, so that the divided lower electrode connected to the branch line of the source electrode through the contact hole Form.

  Next, after forming an organic EL layer that covers the divided lower electrode exposed at the bottom of the pixel opening using a mask vapor deposition method, the thickness that covers the organic EL layer again using the mask vapor deposition method is, for example, 10 nm. A common upper electrode is formed by sequentially depositing an ITO film having a thickness of, for example, 30 nm, and a region corresponding to each divided lower electrode is a divided pixel portion.

  Next, a SiN film and a SION film are sequentially deposited on the entire surface by CVD to form a barrier layer having a thickness of 5 μm. Further, a glass plate is attached as a transparent substrate on the barrier layer.

  FIG. 4 shows a basic configuration of the simplified organic EL element 100. A lower electrode 120 is formed on the TFT substrate 110, and an organic EL layer 130, an upper electrode 140, a barrier layer 150, and a transparent substrate 160 are sequentially formed thereon.

<Example 1>
The form 101 of Example 1 is shown in FIG. An adhesive layer 170 obtained by applying the adhesive at a thickness of 10 μm is provided on the barrier layer 150, and the light diffusion film 1 (10 in the figure) is attached thereon so that the light diffusion layer is in contact with the adhesive layer 170. . Further, a transparent substrate 160 is attached thereon.

<Example 2>
The form 102 of Example 2 is shown in FIG. An adhesive layer 170 formed by applying the adhesive at a thickness of 10 μm is provided on the barrier 150 layer, and a light diffusion film 2 (11 in the figure) is attached thereon so that the light diffusion layer is in contact with the adhesive layer 170. . Further, a transparent substrate 160 is attached thereon.

<Example 3>
As Example 3, the color material surface of the color filter formed on the glass substrate was attached to the barrier layer of the organic EL display device through the adhesive layer (thickness 10 μm) containing the ZrO ₂ .

<Example 4-6>
Form 101 of Example 4-6 is shown in FIG. An adhesive layer 170 formed by applying the adhesive at a thickness of 10 μm is provided on the barrier layer 150, and a light diffusion film (10 in the figure) is attached thereon so that the light diffusion layer is in contact with the adhesive layer 170. Further, a transparent substrate 160 is attached thereon. The light diffusion film ac corresponds to each of Examples 4-6.

<Example 7-9>
Form 102 of Examples 7-9 is shown in FIG. An adhesive layer 170 formed by applying the adhesive at a thickness of 10 μm is provided on the barrier 150 layer, and a light diffusion film (11 in the figure) is attached thereon so that the light diffusion layer is in contact with the adhesive layer 170. Further, a transparent substrate 160 is attached thereon. The light diffusion film df corresponds to each of Examples 7-9.

<Example 10>
The form 101 of Example 10 is shown in FIG. An adhesive layer 170 formed by applying the adhesive at a thickness of 10 μm is provided on the barrier layer 150, and a light diffusion film (10 in the figure) is attached thereon so that the light diffusion layer is in contact with the adhesive layer 170. Further, a transparent substrate 160 is attached thereon. Example 10 corresponds to the light diffusion film g.

<Example 11>
FIG. 6 shows the form 102 of the eleventh embodiment. An adhesive layer 170 formed by applying the adhesive at a thickness of 10 μm is provided on the barrier 150 layer, and a light diffusion film (11 in the figure) is attached thereon so that the light diffusion layer is in contact with the adhesive layer 170. Further, a transparent substrate 160 is attached thereon. Example 11 corresponds to the light diffusion film h.

<Comparative Example 1>
The basic configuration of the organic EL element of FIG. The adhesive is applied to the barrier layer 150 with a thickness of 10 μm, and a transparent substrate 160 is attached.

<Comparative example 2>
On the barrier layer 150 in FIG. 4, the adhesive is applied with a thickness of 10 μm, and a transparent substrate 160 with a thickness of 0.7 mm is attached. Further, the adhesive is applied thereon with a thickness of 10 μm, and the light diffusion film 1 is attached so that the light diffusion layer is in contact with the adhesive.

<Comparative Example 3>
100 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate {“DPHA”, manufactured by Nippon Kayaku Co., Ltd.} was diluted with 100 parts by mass of methyl isobutyl ketone. Furthermore, 5 parts by mass of a polymerization initiator {“Irgacure 184”, manufactured by Ciba Specialty Chemicals Co., Ltd.} was added and mixed and stirred. Subsequently, 0.1 part by mass of a fluorine-based surface modifier (FP-149) and 20 parts by mass of a silane coupling agent {“KBM-5103”, manufactured by Shin-Etsu Chemical Co., Ltd.} were added. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.520. A spin coating solution was prepared by adding 25 parts by mass of TiO ₂ having an average particle size of 300 nm as light scattering particles to the solution composition of the light diffusion coating solution. This spin coating solution was spin-coated on the barrier layer 150 in FIG. 4 to a thickness of 1.5 μm, dried with a solvent, and then dried using a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). The light-diffusing layer was formed by irradiating ultraviolet rays at 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² to cure the coating layer. Further, the adhesive was applied to the light diffusion layer with a thickness of 10 μm, and a transparent substrate 160 was attached.

  The embodiments of the present invention have been described above. However, the present invention is not limited to the conditions and configurations described in the embodiments, and various modifications are possible. For example, the embodiments described above are shown. The material and layer structure constituting the organic EL layer are merely examples, and the material of the organic layer is appropriately selected from known organic EL materials according to the emission color.

An image was displayed on the organic EL display device, and the luminance was subjected to sensory evaluation in the following three stages.
Bright: A
Slightly dark: B
Dark: C

In addition, an image was displayed on the organic EL display device, and sensory evaluation of image blur was performed in the following three stages.
I don't understand the image blur at all: A
The image is slightly amazed: B
Can recognize image blur: C

The quality of the completed display was evaluated based on the following two criteria based on the viewpoint that the luminance was improved and there was no image blur.
Luminance A or B and image blur A or B: ○
Either brightness or image blur is C: ×

  Table 1 shows the results of Examples 1 to 3 and Comparative Examples 1 to 3. The results of Examples 4 to 11 are shown in Table 2.

In Examples 10 and 11, the same effect was obtained even when light scattering particles other than ZrO _{2 having} a refractive index of 1.8 or more were used.

It is a figure explaining the cause of the light extraction efficiency fall in a self-light-emitting display device. It is sectional drawing of the light-diffusion film which consists of a transparent base film and a light-diffusion layer in this invention. It is sectional drawing of the light-diffusion film which consists of a transparent base film in this invention, a low refractive index layer, and a light-diffusion layer. It is the schematic of the basic composition of the organic electroluminescence display in this invention. It is a figure which shows the structure of Example 1, 4-6 and 10 of this invention. It is a figure which shows the structure of Example 2, 7-9 and 11 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... TFT substrate 2 ... Back electrode 3 ... Organic layer 4 ... Transparent electrode 5 ... Transparent substrate 10 ... Light diffusion film 1
11: Light diffusion film 2
DESCRIPTION OF SYMBOLS 20 ... Transparent base film 30 ... Light-diffusion layer 31 ... Translucent resin 41 ... Light-scattering particle 50 ... Low-refractive-index layer 100 ... Basic structure of organic electroluminescence display 101 ... Element configuration of Example 1 102 ... Element configuration of Example 2 110 ... TFT substrate 120 ... Lower electrode 130 ... Organic EL layer 140 ... Upper electrode 150 ... Barrier layer 160 ... Transparent substrate 170 ... Adhesive layer

Claims (22)

A lower electrode formed on the substrate;
An organic electroluminescence layer formed on the lower electrode;
An organic electroluminescence display device comprising an upper electrode formed on the organic electroluminescence layer,
An organic electroluminescence display device comprising a scattering member on an upper electrode.   The organic electroluminescence display device according to claim 1, wherein the scattering member is a light diffusion film.   The light diffusing film is a film including a transparent substrate film and a light diffusing layer formed on the transparent substrate film, and the light diffusing layer has a refractive index different from that of the transparent resin composition. The organic electroluminescence display device according to claim 2, wherein the transparent resin composition contained in the light diffusion layer has a refractive index of 1.6 or more. The organic electro according to claim 3, wherein the resin composition of the light diffusion layer contains at least one inorganic fine particle selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO. Luminescence display device.   5. The organic electroluminescence display device according to claim 3, wherein a refractive index of the light scattering particles contained in the light diffusion layer is 1.55 or less.   6. The organic electroluminescence display device according to claim 3, wherein an average diameter of the light scattering particles contained in the light diffusion layer is 0.1 μm or more and 2.0 μm or less. . The light diffusion film is a film including a transparent substrate film and a light diffusion layer formed on the transparent substrate film, and the light diffusion layer has an average particle diameter of 50 nm to 300 nm in a transparent resin composition. The organic electroluminescence display device according to claim 2, comprising at least one kind of fine particles selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO.   The organic light-emitting display device according to claim 3, wherein the light diffusion film has a low refractive index layer between the transparent base film and the light diffusion layer.   The organic electroluminescence display device according to claim 8, wherein a refractive index of the low refractive index layer is 1.45 or less.   The organic electroluminescence display device according to claim 8, wherein the low refractive index layer contains hollow silica.   The organic electroluminescence display device according to claim 1, wherein the scattering member is a color filter.   The organic electroluminescence display device according to claim 11, wherein the color filter is obtained by curing a curable composition containing a colorant and light scattering particles.   The organic electroluminescence display device according to claim 12, wherein a refractive index of the curable composition at the time of curing is 1.6 or more. The curable _composition according to any one of _{ZrO 2, TiO 2, SnO 2} , and claim 12 to 13, characterized in that contains at least one inorganic particulate selected from among ZnO Organic electroluminescence display device.   The organic electroluminescence display device according to any one of claims 12 to 14, wherein a refractive index of the light scattering particles is 1.55 or less.   16. The organic electroluminescence display device according to claim 12, wherein an average diameter of the light scattering particles is 0.1 μm or more and 2.0 μm or less. 13. The organic electroluminescence display device according to claim 12, wherein the light scattering particles are at least one kind of fine particles selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO having an average particle diameter of 50 nm to 300 nm.   The organic electroluminescence display device according to claim 1, wherein the scattering member is directly attached on the upper electrode. 18. The organic electroluminescence display device according to claim 1, wherein the scattering member is directly attached to the barrier layer via the barrier layer on the upper electrode.   The said light-diffusion film is affixed on the said upper electrode or the barrier layer provided on the said upper electrode through the contact bonding layer, The any one of Claim 2 to 10 characterized by the above-mentioned. The organic electroluminescence display device described.   21. The organic electroluminescence display device according to claim 20, wherein a refractive index of the adhesive layer is 1.6 or more. The organic electroluminescence display device according to claim 20 or 21, wherein the adhesive layer contains at least one kind of inorganic fine particles selected from ZrO ₂ , TiO ₂ , SnO ₂ , and ZnO.

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