WO2010122913A1 - Fine particle dispersion for light extraction member, coating composition, light extraction member, and organic electroluminescence display device - Google Patents

Fine particle dispersion for light extraction member, coating composition, light extraction member, and organic electroluminescence display device Download PDF

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Publication number
WO2010122913A1
WO2010122913A1 PCT/JP2010/056488 JP2010056488W WO2010122913A1 WO 2010122913 A1 WO2010122913 A1 WO 2010122913A1 JP 2010056488 W JP2010056488 W JP 2010056488W WO 2010122913 A1 WO2010122913 A1 WO 2010122913A1
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Prior art keywords
fine particle
light extraction
extraction member
coating composition
layer
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PCT/JP2010/056488
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French (fr)
Inventor
Yohsuke Takeuchi
Hidemasa Hosoda
Masanori Hikita
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Fujifilm Corporation
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Publication of WO2010122913A1 publication Critical patent/WO2010122913A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • H10K59/877—Arrangements for extracting light from the devices comprising scattering means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer

Definitions

  • the present invention relates to a fine particle dispersion for light extraction member, a coating composition, a light extraction member, and an organic electroluminescence display device.
  • an electroluminescence element in which a cathode, an electroluminescence layer, a transparent electrode layer and a light transmitter are disposed in this order, and a leaked-light-diffusion layer is disposed between the transparent electrode layer and the light transmitter, wherein the leaked-light- diffusion layer contains a particle for scattering light in a matrix formed of a low refractive index material (see PTL l) .
  • the transfer film includes an inorganic particle-containing resin layer and a support film, ⁇ wherein the inorganic particle -containing resin layer contains an oxide fine particle having an average particle diameter of 0.001 ⁇ m to 5 ⁇ m, a refractive index of 1.4 to 1.8 and a specific surface area of 0.5 m 2 /g to 300 m 2 /g, a glass powder, an alkali-soluble resin and a radiation-sensitive component, and wherein the oxide fine particle content is 0.01 parts by weight to 20 parts by weight relative to 100 parts by weight of the glass powder (see PTL 2).
  • an inorganic oxide fine particle dispersion in which a surface-treated inorganic oxide fine particle is dispersed in an organic solvent (see PTL 3) .
  • the inorganic oxide fine particle dispersion is, however, for use in surface protective films and reflection preventive films for liquid crystal display devices and the like. Therefore, there has not yet been provided an inorganic oxide fine particle dispersion which is satisfactory for use in light extraction members for improving light extraction efficiency.
  • a light extraction member for use in light emitting devices such as organic electroluminescence display devices
  • a light extraction member made of an organic/inorganic-mixture film is placed near light emitting elements, there is a problem that dissociation occurs at the interface between the organic component and the inorganic component in each of the light emitting elements due to the local thermal history (heat cycle) based on the ON/OFF switch operation.
  • the present invention is made to solve the above-mentioned conventional problems and to achieve the following object. That is, the present invention aims to provide a fine particle dispersion for light extraction member which is capable of improving light extraction efficiency and suppressing deterioration of a light extraction member due to the heat cycle, a coating composition, a light extraction member and an organic electroluminescence display device .
  • the present inventors have found that a mixture of a binder resin with a matrix containing an inorganic fine particle degrades its durability, in particular, heat resistance thereof, and then have tried to prevent dissociation between the inorganic fine particle and the matrix due to heat and to improve the durability thereof by improving the adhesion between the inorganic fine particle and the binder resin.
  • a functional group capable of reacting an inorganic fine particle with a binder resin is introduced into the inorganic fine particle to form a surface-modified fine particle in which the surface of the inorganic fine particle is modified and to form a bond between the surface -modified fine particle and the binder resin during formation of a layer of a light extraction member, whereby preventing dissociation between the surface-modified fine particle and the matrix material due to heat and improving the durability.
  • a fine particle dispersion for light extraction member including: a surface-modified fine particle, and a dispersion medium, the surface-modified fine particle being dispersed in the dispersion medium, wherein the surface-modified fine particle contains an inorganic oxide fine particle having a mass average particle diameter greater than 100 nm and a surface modifier containing one of a hydrolysate obtained by hydrolysis of an organosilane compound represented by General Formula (l) below and a partial condensate obtained by partial condensation of the organosilane compound, and the surface of the inorganic oxide fine particle is covered with the surface modifier,
  • a surface-modified fine particle contains an inorganic oxide fine particle having a mass average particle diameter greater than 100 nm and a surface modifier containing one of a hydrolysate obtained by hydrolysis of an organosilane compound represented by General Formula (l) below and a partial condensate obtained by partial condensation of the organosilane compound, and the surface of the inorganic oxide fine particle is covered with the surface
  • R 1 represents any one of an oxygen-containing 3- or
  • ⁇ 3 > The fine particle dispersion according to one of ⁇ 1 > and ⁇ 2 >, wherein the inorganic oxide fine particle contains at least one selected from Zr ⁇ 2, Ti ⁇ 2 and ZnO .
  • R 1 is the oxygen-containing 3- or 4-membered condensed ring compound.
  • a coating composition including: the fine particle dispersion for light extraction member according to any one of ⁇ 1 > to ⁇ 5 >, an organic polymer, and a binder resin.
  • ⁇ 7 > The coating composition according to ⁇ 6 >, wherein the organic polymer has an acid value of 120 mgKOH/g to 200 mgKOH/g.
  • ⁇ 8 > The coating composition according to one of ⁇ 6 > and ⁇ 7 >, wherein the inorganic oxide fine particle is contained in an amount of 5% by mass to 25% by mass relative to the total solid content of the coating composition.
  • a light extraction member including: the coating composition according to any one of ⁇ 6 > to ⁇ 8 >.
  • ⁇ 10 > The light extraction member according to ⁇ 9 >, wherein the light extraction member is used as a color filter.
  • An organic electroluminescence display device including: the light extraction member according to one of ⁇ 9 > and ⁇ 10 >.
  • ⁇ 12 > The organic electroluminescence display device according to ⁇ 11 >, further including an adhesion layer, wherein the adhesion layer has a refractive index of 1.5 to 1.9.
  • the adhesion layer has a thickness of 10 ⁇ m to 100 ⁇ m.
  • the present invention it is possible to solve the above-mentioned problems, to achieve the above-mentioned object, and to provide a fine particle dispersion for light extraction member capable of improving light extraction efficiency and suppressing deterioration of a light extraction member due to the heat cycle, a coating composition, a light extraction member and an organic electroluminescence display device .
  • FIG. 1 is a schematic diagram illustrating the basic structure of a light extraction member according to the present invention.
  • FIG. 2 is a partial cross-sectional diagram schematically illustration the layer structure of an organic electroluminescence display device 100 according to a first embodiment of the present invention. Description of Embodiments
  • a fine particle dispersion for light extraction member of the present invention includes a surface-modified fine particle, and a dispersion medium, the surface-modified fine particle being dispersed in the dispersion medium, wherein the surface modified fine particle contains an inorganic oxide fine particle and a surface modifier, and the surface of the inorganic oxide fine particle is covered with a surface modifier.
  • the fine particle dispersion for light extraction member includes other components as required.
  • the inorganic oxide fine particle is a fine particle having a mass average particle diameter greater than 100 nm.
  • the mass average particle diameter is preferably 200 nm or greater, particularly preferably 300 nm or greater.
  • the upper limit of the mass average particle diameter is not particularly limited. It is, however, preferably 1,000 nm, more preferably 800 nm or smaller. When the upper limit of the mass average particle diameter is greater than 1,000 nm, it may be difficult to obtain a thin layer when the particle is applied onto a light extraction member, leading to a degradation in physical strength of the light extraction member.
  • the inorganic oxide fine particle is not particularly limited and may be suitably selected in accordance with the intended use. From the viewpoint that a colorless film can be obtained without limiting the choice of color, it is, however, preferably an oxide fine particle of at least one element selected, for example, from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium.
  • These inorganic oxide fine particles are not particularly limited. Examples thereof include particles made, for example, of silica, alumina, zirconia (Zr ⁇ 2), titanium oxide (Ti ⁇ 2), zinc oxide (ZnO), germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide or the like. Among these, from the viewpoint of obtaining high heat cycle durability, preferred are a zirconia (Zr ⁇ 2) particle, a titanium oxide (Ti ⁇ 2) particle, and a zinc oxide (ZnO) particle. These inorganic oxide fine particles may be used alone or in combination.
  • the refractive index of the inorganic oxide fine particle is not particularly limited. However, from the viewpoint of obtaining high light extraction efficiency, the inorganic oxide fine particle preferably has a high refractive index.
  • the refractive index is preferably 2.1 to 4.0, more preferably 2.2 to 3.5, particularly preferably 2.2 to 2.8.
  • the surface -modified fine particle contains one of a hydrolysate obtained by hydrolysis of an organosilane compound represented by the following General Formula (l) and a partial condensate obtained by partial condensation of the organosilane compound.
  • R 1 represents any one of an oxygen-containing 3- or 4-membered condensed ring compound, an alkyl group substituted with a substituent containing an unsaturated bond, and an aryl group substituted with a substituent containing an unsaturated bond;
  • X represents one of a hydroxyl group and a hydrolyzable group," and m represents an integer of 1 to 3.
  • the number of carbon atoms contained in the alkyl group is not particularly limited.
  • the number of carbon atoms is, however, preferably 1 to 30, more preferably 1 to 16, particularly preferably 1 to 6.
  • alkyl group examples include a methyl group, ethyl group, propyl group, isopropyl group, hexyl group, t-butyl group, sec-butyl group, decyl group, and hexadecyl group.
  • the aryl group is not particularly limited. However, preferred examples thereof are a phenyl group, and naphthyl group. Of these, phenyl group is preferable.
  • the hydrolyzable group is not particularly limited. Specific examples thereof include an alkoxy group an alkoxy group (preferred is an alkoxy group having 1 to 5 carbon atoms; examples thereof include a methoxy group, and an ethoxy group), a halogen atom (e.g., Cl, Br, I, etc.), and R 2 COO (R 2 is preferably an hydrogen atom or an alkyl group having 1 to 5 carbon atoms,' examples thereof include CH3COO, and C2H5COO).
  • R 2 is preferably an hydrogen atom or an alkyl group having 1 to 5 carbon atoms,' examples thereof include CH3COO, and C2H5COO.
  • the alkoxy group is preferable.
  • Preferred examples of the alkoxy group are a methoxy group, and an ethoxy group .
  • each R 1 or each X may be identical or different.
  • the integer m is not particularly limited, however, it is preferably 1 or 2, particularly preferably 1.
  • the substituent containing an unsaturated bond is not particularly limited.
  • examples thereof include a vinyl polymerizable substituent, an allene substituent, and an isocyanate substituent.
  • a vinyl polymerizable substituent is preferred.
  • an organosilane compound represented by the following General Formula (2) is preferred.
  • R 10 represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom.
  • alkoxycarbonyl group examples include a methoxy carbonyl group, and an ethoxy carbonyl group .
  • a hydrogen atom, a methyl group, methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable.
  • a hydrogen atom, methyl group, methoxycarbonyl group, fluorine atom, and chlorine atom are more preferred, with hydrogen atom and methyl group being particularly preferred.
  • Y represents any one of a single bond, an ester group, an amide group, an ether group, and a urea group.
  • preferred are a single bond, an ester group, and an amide group ; more preferred are a single bond and an ester group, with an ester group being particularly preferred.
  • L represents a divalent linking chain. More specifically, L is a substituted or unsubstituted alkylene group, a substituted or unsubstituted allylene group, a substituted or unsubstituted alkylene group having in the inside thereof a linking group (e.g., ether group, ester group, an amide group) or a substituted or unsubstituted allylene group having in the inside thereof a linking group.
  • a linking group e.g., ether group, ester group, an amide group
  • a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms preferred are a substituted or unsubstituted allylene group having 6 to 20 carbon atoms, and an alkylene group having 3 to 10 carbon atoms and having in the inside thereof a linking group. More preferred are an unsubstituted alkylene group, an unsubstituted allylene group, and an alkylene group having in the inside thereof an ether or ester linking group, with an unsubstituted alkylene group, and an alkylene group having in the inside thereof an ether or ester linking group being particularly preferred.
  • a halogen atom As the substituent, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group and an aryl group are exemplified. These substituents may be further substituted.
  • n represents an integer of zero or 1.
  • each X may be identical or different.
  • the integer n is preferably zero.
  • R 1 has the same meaning as that defined for R 1 in General
  • Specific examples of the compound represented by General Formula (2) include acryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, and methacryloyloxypropyltrimethoxysilane.
  • R 1 is not particularly limited as long as it is any one of an oxygen-containing 3- or 4-membered condensed ring compound, an alkyl group substituted with a substituent containing an unsaturated bond, and an aryl group substituted with a substituent containing an unsaturated bond.
  • an oxygen-containing 3- or 4-membered condensed ring compound is preferred.
  • the oxygen-containing 3- or 4-membered condensed ring compound is not particularly limited and may be suitably selected in accordance with the intended use. Specific examples thereof include 3-glycidylpropyltrimethoxysilane, 3- glycidylpropyltriethoxysilane, and 2, 3-epoxycyclohexylpropyltrimethoxysilane.
  • - Surface -Modified Fine Particle -
  • the surface-modified fine particle is formed by surface treatment of the surface of an inorganic oxide fine particle so as to be covered with a surface modifier.
  • the surface treatment is preferably performed in the presence of at least one of a catalyst and a metal chelate compound.
  • the catalyst is not particularly limited and may be suitably selected in accordance with the intended use.
  • examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methansulfonic acid, and toluene sulfonic acid; inorganic basic catalysts such as sodium hydroxide, potassium hydroxide, and ammonium, " organic basic catalysts such as triethylamine, and pyridine, ' and metal alkoxides such as triisopropoxy aluminum, and tetrabutoxy zirconium.
  • inorganic oxide fine particle dispersion In terms of the production stability and storage stability of the , inorganic oxide fine particle dispersion, acid catalysts (inorganic acids and organic acids) are preferred.
  • the use amount of the acid catalyst is 0.01 mole% to 10 mole%, preferably 0.1 mole% to 5 mole% relative to the amount of the hydrolyzable group .
  • the acid catalyst is an organic acid, the most appropriate use amount of the acid catalyst varies depending on the addition amount of water, but, if water is added, it is 0.01 mole% to 10 mole%, preferably 0.1 mole% to 5 mole% relative to the amount of the hydrolyzable group.
  • metal chelate compound those having, as a ligand, an alcohol represented by the general formula R 3 OH (where R 3 represents an alkyl group having 1 to 10 carbon atoms) and/or a compound represented by the general formula R 4 COCH2COR 5 (where R 4 represents an alkyl group having 1 to 10 carbon atoms, R 5 represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) and including, as a center metal, a metal selected from Zr, Ti or Al are suitably used without particular limitation. These metal chelate compounds may be used alone or in combination.
  • the metal chelate compound is preferably selected from compounds each represented by any one of the following general formulae, and functions to accelerate condensation reaction of the organosilane compound.
  • R 3 and R 4 may be identical to or different from each other, and each represent an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include an ethyl group, n-propyl group, i-propyl group, n-butyl group, secbutyl group, t-butyl group, n-pentyl group , and phenyl group .
  • R 5 represents the same alkyl group having 1 to 10 carbon atoms as that described above or an alkoxy group having 1 to 10 carbon atoms.
  • p i, p2, ql, q2, rl and r2 each represent an integer which is determined so that the ligand is tetradentate or hexadentate.
  • the metal chelate compound include zirconium chelate compounds such as tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis(ethyl acetoacetate)zirconium, n-butoxy -trisCethyl acetoacetate) zirconium, tetrakis(n-p ropy lace to acetate) zirconium, tetrakis(acetylacetoacetate)zirconium, and tetrakisCethyl acetoacetate)zirconium; titanium chelate compounds such as diisopropoxybis (ethyl ace to acetate) titanium, diisopropoxybis(acetylacetate)titanium, and diisopropoxybis(acetylacetone)titaniumJ and aluminum chelate compounds such as diisopropoxy ethyl acetoacetate aluminum, diisopropoxy acetylace
  • the dispersion medium is not particularly limited, and water and/or an organic solvent may be used alone or in combination.
  • the organic solvent include ketones such as methylethylketone, and acetone; alcohols such as ethyl alcohol, propyl alcohol, butanol, butyl cellosolve, and propylene glycol monomethyl ether,' esters such as propylene glycol monomethyl ether acetate, and butyl acetate,' amides such as dimethylformamide, dimethylacetoamide, and N-methylpyrrolidoneJ and ethers such as tetrahydrofuran, and dioxane .
  • the other components are not particularly limited and may be suitably selected in accordance with the intended use. For example, stabilizing additives for dispersion liquid are exemplified.
  • the stabilizing additive for dispersion liquid functions as a stabilization improver of the fine particle dispersion for light extraction member and the coating composition of the present invention.
  • the stabilizing additive for dispersion liquid is not particularly limited.
  • R 4 COCH2COR 5 are exemplified. Each of these compounds is considered to be coordinated to a metal atom in the metal chelate compound (zirconium, titanium and/or aluminum compound) thereby to have an effect in suppressing the accelerating action, by the metal chelate compound, of condensation reaction between the organosilane compound and metal chelate components and improving the storage stability of the resulting composition.
  • R 4 and R 5 constituting the compound are same as R 4 and R 5 constituting the metal chelate compound.
  • ⁇ -diketone compound and/or ⁇ -ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate, 2,4-hexane-dione, 2, 4-heptane-dione, 3, 5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, and 5-methyl-hexane -dione.
  • ethyl acetoacetate, and acetyl acetone are preferred, with acetyl acetone being particularly preferred.
  • the coating composition of the present invention contains a fine particle dispersion for light extraction member, an organic polymer and a binder resin.
  • the above-mentioned fine particle dispersion for light extraction member of the present invention can be used.
  • the amount of an inorganic oxide fine particle contained in the fine particle dispersion for light extraction member is preferably 5% by mass to 25% by mass, more preferably 10% by mass to 25% by mass, particularly preferably 15% by mass to 25% by mass relative to the total solid content of the coating composition.
  • the amount of the inorganic oxide fine particle is less than 5% by mass, the light extraction efficiency may degrade.
  • it is more than 25% by mass the resulting film may become brittle, leading to degradation in durability.
  • the organic polymer is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, polymers having a carboxylic acid on the side chain thereof such as a partially esterified maleic acid copolymer," and acidic cellulose derivatives having a carboxylic acid group on the side chain thereof. In addition to the above, compounds obtained by addition of an acid anhydride to a polymer having a hydroxyl group are also effectively used.
  • a benzyl(meth)acrylate/(meth)acrylic acid copolymer and a multi-component copolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/other monomer are preferred.
  • water-soluble polymers 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also effectively used.
  • alcohol-soluble nylon, 2,2-bis-(4-hydroxyphenyl)-propane, and polyether such as epichlorohydrin are also effectively used.
  • These polymers may be used in combination in a predetermined amount. Furthermore, there may be exemplified those described in
  • JP-A Japanese Patent Application Laid-Open (JP-A) No. 07- 140654, such as 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, and 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer.
  • organic polymer those having a carboxyl group on the side chain thereof are preferred.
  • the acid value of the organic polymer is not particularly limited. It is, however, preferably 120 mgKOH/g to 200 mgKOH/g, more preferably 120 mgKOH/g to 180 mgKOH/g, particularly preferably 120 mgKOH/g to 150 mgKOH/g.
  • the acid value is less than 120 mgKOH/g, the durability may degrade.
  • it is more than 200 mgKOH/g the formability of pattern may degrade.
  • the mass average molecular weight of the organic polymer is not particularly limited. It is, however, preferably 1,000 to 100,000, more preferably 30,000 to 35,000.
  • the binder resin is not particularly limited and may be suitably selected in accordance with the intended use.
  • acrylic copolymers are exemplified.
  • a polymer having saturated hydrocarbon or polyether in the main chain is preferred, with a polymer having saturated hydrocarbon in the main chain being more preferred.
  • binder resin be crosslinked.
  • the polymer having saturated hydrocarbon in the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer.
  • a crosslinked binder resin it is preferred to use a monomer having two or more ethylenically unsaturated groups.
  • the monomer having two or more ethylenically unsaturated groups is not particularly limited and may be suitably selected in accordance with the intended use.
  • Specific examples thereof include esters of polyhydric alcohol with a (meth)acrylic acid (e. g. , ethylene glycol di(meth)acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol 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, pentaerythritol hexa(meth)acrylate, 1,2,3-cyclohexane tetrame
  • an acrylate or a methacrylate monomer each having at least three functional groups, and an acrylate monomer having at least five functional groups are preferable in terms of film hardness, i.e., scratch resistance, with a mixture of dipentaerythritol pentaacrylate with dipentaerythritol hexaacrylate (commercial products) being more preferable. These monomers may be used in combination.
  • the term "(meth)acrylate" means "acrylate or methacrylate".
  • These monomers having an ethylenically unsaturated group can be cured by dissolving each of these monomers along with various polymerization initiators and other additives in a solvent to prepare a coating solution, applying the coating solution onto an object, followed by drying and subjecting to a polymerization reaction under application of light, ionizing radiation or heat.
  • Other Components -
  • the other components are not particularly limited.
  • a photosensitive polymerizable component for example, a photosensitive polymerizable component, a photopolymerizable initiator, and solvents may be selected.
  • the photosensitive polymerizable component is not particularly limited and may be suitably selected in accordance with the intended use . It is, however, preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 0 C or higher under normal pressure . Among such compounds, more preferred are tetrafunctional or higher functional acrylate compounds.
  • compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100°C or higher under normal pressure is not particularly limited and may be suitably selected in accordance with the intended use.
  • examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl(meth)acrylate; compounds obtained by adding an ethylene oxide or a propylene oxide to a polyfunctional alcohol, and then subjecting to (meth)acrylation (e.g.
  • JP-B Japanese Patent Application Publication
  • dipentaerythritol penta(meth)acrylate dipentaerythritol hexa(meth)acrylate, and compounds having a structure where these acryloyl groups are attached via an ethylene glycol residue or a propylene glycol residue.
  • oligomer type compounds are also favorably used.
  • Acrylic oligomers with monomer repeating units of 3 to 20 are preferred.
  • the photopolymerization initiator is not particularly limited and may be suitably selected in accordance with the intended use .
  • the photopolymerization initiator include active halogen compounds, such as halomethyl oxadiazole and halomethyl-s-triazine,' 3-aryl-substituted coumarine compounds, and at least one lophine dimer.
  • active halogen compounds such as halomethyl oxadiazole and halomethyl-s-triazine,' 3-aryl-substituted coumarine compounds, and at least one lophine dimer.
  • halomethyl-s-triazine compounds are preferred.
  • these compounds will be described in detail.
  • the halomethyl oxadiazole is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include 2-halomethyl- 5-vinyl- l, 3,4-oxadiazole compounds. Specific examples of the 2-halomethyl- 5-vinyl- l, 3, 4-oxadiazole compounds include 2-trichloromethyl- 5-styryl- l,3,4-oxadiazole, 2 -trichloromethyl- 5 -(p -cyanostyryl)- 1, 3, 4- oxadiazole, and 2 - trichloromethyl- 5 -(p - me thoxy sty ry I) - 1, 3, 4 -oxadiazole.
  • halomethyl-s-triazine compound is not particularly limited and may be suitably selected in accordance with the intended use.
  • vinyl-halomethyl-s-triazine compound described in Japanese Patent Application Publication (JP-B) No. 59- 1281, and
  • the vinyl-halomethyl-s-triazine compound is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl) -6- (l-p -dimethylaminophenyl- l, 3-butadienyl) -s-triazine, and
  • a sensitizer may be used in combination with the photopolymerization initiator.
  • the sensitizer is not particularly limited and may be suitably selected in accordance with the intended use.
  • Examples thereof include benzoin, benzoin methyl ether, 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, dibenzal acetone, p- (dimethylamino)phenyl styryl ketone, p -(dimethylamino)phenyl-p -methyl styryl ketone, benzophenone, p -(dimethylamino)
  • the coating composition In preparation of the coating composition, the coating composition generally contains a solvent (otherwise, referred to as "organic solvent” in the present invention).
  • the solvent is not particularly limited as long as the solubility of each component and the coatability of the curable composition are satisfied.
  • the solvent is, however, preferably selected in consideration of especially, the solubility, coatability and safety of colorants used and the resin components.
  • the solvent is not particularly limited and may be suitably selected in accordance with the intended use.
  • 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, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl oxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, methyl 3-ethoxypropionat
  • ethyl 3-methoxy propionate ethyl 3-ethoxypropionate, etc.
  • 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate (e.g., methyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2" ⁇ xy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate), ethyl 2-oxypropionate (e.g., ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-oxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), propyl 2-methoxypropionate, and propyl 2-oxypropionate, etc.
  • methyl 2-oxypropionate e.g., methyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2" ⁇ xy-2-methyl propionate, methyl 2-meth
  • 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, and propylene glycol propyl ether acetate; ketones such as methylethylketone, cyclohexanone, 2-heptan
  • the light extraction member of the present invention includes a coating composition.
  • the above-mentioned coating composition of the present invention can be used.
  • the light extraction member preferably has a structure composed of at least a transparent substrate provided with a barrier layer; a low- refractive-index layer! and a light diffusion layer.
  • the light diffusion layer is preferably formed to contain the coating composition.
  • FIG. 1 is a schematic diagram illustrating the basic structure of a light extraction member according to the present invention.
  • a light extraction member 1 includes a transparent substrate 20 provided with a barrier layer, and a light diffusion layer 30, with the light diffusion layer 30 being provided over the transparent substrate 20.
  • - Transparent Substrate Provided With Barrier Layer -
  • the transparent substrate 20 provided with a barrier layer includes at least a transparent base film and a barrier layer, and further includes other layers as required.
  • the other layers include a matting agent layer, a protective layer, a solvent resistant layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light shielding layer, a reflection preventing layer, a hard coat layer, a stress relaxation layer, an antifogging layer, an antifouling layer, a printed layer, and an easy-adhesion layer.
  • the transparent base film is not particularly limited and may be suitably selected in accordance with the intended use.
  • a transparent resin film, a transparent resin plate, and a transparent resin sheet are exemplified.
  • the transparent resin film is not particularly limited and may be suitably selected in accordance with the intended use. Specific examples of include a triacetylcellulose (TAC) film (refractive index- 1.48), a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a diacethylene cellulose film, a cellulose acetate butylate film, a polyether sulfone film, a polyacrylic resin film, a polyurethane resin film, a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethyl pentene film, a polyether ketone film, and a (meth)acrylonitrile film.
  • TAC triacetylcellulose
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • diacethylene cellulose film a cellulose acetate butylate film
  • a polyether sulfone film a polyacrylic resin
  • the refractive index of triacetylcellulose which is preferably used as the transparent base film is 1.48.
  • the barrier layer is not particularly limited as long as it has a function to prevent transmission of oxygen, moisture, nitrogen oxides, sulfur oxides and ozone in air, and may be suitably selected in accordance with the intended use.
  • the material of the barrier layer may be a material having a function to prevent substances that accelerate degradation of the element, such as moisture and oxygen, from entering the element.
  • Specific examples of the barrier layer include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni; metal oxides such as MgO, SiO, Si ⁇ 2, Al 2 O 3 , GeO, NiO, CaO, BaO, Fe 2 O 3 , Y2O3, and TiO 2 , metal nitrides such as SiN; metal oxynitrides such as SiON, ' metal fluorides such as MgF 2 , LiF, AlF 3 , and CaF 2 ,' copolymers of a dichlorodifluoroethylene with polyethylene, polypropylene, polymethylmethacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, or chlorotrifluoroethylene, " cop
  • the thickness of the barrier layer is not particularly limited and may be suitably selected in accordance with the intended use. It is, however, preferably 5 nm to 1, 000 nm, more preferably 7 nm to 750 nm, particularly preferably 10 nm to 500 nm. When the thickness of the barrier layer is less than 5 nm, the barrier function for preventing transmission of oxygen and moisture in air may be insufficient. When the thickness is more than 1,000 nm, the light transmittance may decrease, which may impair the transparency of the transparent substrate. The light transmittance of the barrier layer is usually 80% or higher, preferably 85% or higher, more preferably 90% or higher.
  • the forming method of the barrier layer is not particularly limited and may be suitably selected in accordance with the intended use.
  • Examples of the forming method include a vacuum evaporation method, sputtering method, reactive sputtering method, MBE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high-frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas-source CVD method, and coating method.
  • the light diffusion layer contains at least a binder resin, and a surface-modified fine particle .
  • the light diffusion layer When the light diffusion layer is used to function as the after-mentioned color filter, the light diffusion layer contains a colorant.
  • the binder resin the binder resins described above in the coating composition of the present invention can be used.
  • a surface-modified fine particle 41 is dispersed in a matrix material 31 (portions of constituents of the light diffusion layer 30 from which the surface-modified fine particle 41 is excluded), which contains a binder resin and a colorant 42.
  • the light diffusion layer 30 may be composed of a plurality of layers. Further, as the surface -modified fine particle 41, two or more types of particles may be used.
  • the light scattering profile and the haze value of the light diffusion layer 30 are controlled by controlling each refractive index of the matrix material 31 and the surface-modified fine particle 41 and the particle size of the surface -modified fine particle 41.
  • a light extraction member 1 having the light diffusion layer is controlled by controlling each refractive index of the matrix material 31 and the surface-modified fine particle 41 and the particle size of the surface -modified fine particle 41.
  • a bond is formed between the surface-modified fine particle 41, into which a functional group (a surface-modifier) of the binder resin (including an organic polymer) reacting with an inorganic fine particle is introduced, and the binder resin (including the organic polymer) constituting the matrix material 31 of the light diffusion layer, thereby preventing dissociation between the surface-modified fine particle 41 and the matrix material 31 due to heat and improving the durability.
  • high light extraction efficiency can be obtained at the light diffusion layer 30 owing to light scattering of the surface-modified fine particle 41.
  • the refractive index of the surface-modified fine particle 41 in the light diffusion layer 30 is not particularly limited and may be suitably selected in accordance with the intended use.
  • the refractive index of the surface-modified fine particle 41 is, however, preferably 2.1 or higher, more preferably 2.15 or higher, particularly preferably 2.2 or higher, in terms that a difference in refractive index from the matrix material 31 is 0.05 or more and a sufficient amount of light scattering can be obtained.
  • the thickness of the light diffusion layer 30 is not particularly limited as long as it is about 0.5 ⁇ m to about 50 ⁇ m in dry film thickness, and may be suitably selected in accordance with the intended use.
  • the optical member is a film having a transparent substrate 20 provided with a barrier layer, and a light diffusion layer 30 formed on the transparent substrate 20 provided with a barrier layer, wherein in a matrix material 31 of the light diffusion layer 30, a surface-modified fine particle 41 having a refractive index different from that of the matrix material 31 is dispersed; and the refractive index of the matrix material 31 is 1.6 or lower.
  • the total reflection amount in the organic light emitting layer is reduced to one-half or less.
  • the surface -modified fine particle 41 which is formed by surface treatment of the surface of at least one type inorganic fine particle selected from Zr ⁇ 2, Ti ⁇ 2, Sn ⁇ 2, and ZnO, is preferably contained in the matrix material 31 of the light diffusion layer 30.
  • the light diffusion layer 30 will be a high refractive layer having light scattering property.
  • the application of the light extraction member is not particularly limited, and there may be exemplified all optical members for which high light extraction efficiency and high heat cycle durability are required.
  • the light extraction member is suitably used as a color filter. i o - ⁇ Colorant - -
  • the colorant is not particularly limited and may be suitably selected in accordance with the intended use.
  • examples of the colorant include high-molecular weight organic materials such as organic pigments, organic dyes, fullerene, polydiacetylene, and
  • organic particles composed of an aromatic hydrocarbon or an aliphatic hydrocarbon (e.g. , aromatic hydrocarbons or aliphatic hydrocarbons having orientation property, or aromatic hydrocarbons or aliphatic hydrocarbons having sublimation property) .
  • aromatic hydrocarbons or aliphatic hydrocarbons having orientation property e.g., aromatic hydrocarbons or aliphatic hydrocarbons having orientation property, or aromatic hydrocarbons or aliphatic hydrocarbons having sublimation property
  • organic materials are preferable, with the organic pigments being more preferable. These organic particles may be used alone or in combination.
  • the organic pigments are not limited in terms of color phase.
  • examples of the organic pigments include perylene, perinone,
  • quinacridone quinacridonequinone, anthraquinone, anthanthorone, benzimidazolone, disazo condensates, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone, cyanine or isoviolanthrone compound pigments, and mixtures thereof.
  • organic pigments include perylene compound pigments such as C.I. Pigment Red 190 (CI. No. 71140), C.I. Pigment Red 224 (CI. No.
  • Pigment Violet 29 (CI. No. 71129) ; perinone compound pigments such as CI. Pigment Orange 43 (CI. No. 71105) and CI. Pigment Red 194 (CI. No. 71100); quinacridone compound pigments such as C.I. Pigment Violet 19 (CI. No. 73900), CI. Pigment Violet 42, CI. Pigment Red 122 (CI. No. 73915), CI. Pigment Red 192, CI. Pigment Red 202 (CI. No. 73907), C.I. Pigment Red 207 (CI. No. 73900, 73906) and CI. Pigment Red 209 (CI. No.
  • quinacridonequinone compound pigments such as CI. Pigment Red 206 (CI. No. 73900/73920), CI. Pigment Orange 48 (CI. No. 73900/73920) and CI. Pigment Orange 49 (CI. No. 73900/73920); anthraquinone compound pigments such as CL Pigment Yellow 147 (CI. No. 60645); anthanthorone compound pigments such as CI. Pigment Red 168 (CI. No. 59300); benzimidazolone compound pigments such as CI. Pigment Brown 25 (CI. No. 12510) , CI. Pigment Violet 32 (CI. No. 12517), CI. Pigment Yellow 180 (CI. No. 21290), CI.
  • Pigment Yellow 181 (CI. No. 11777), CI. Pigment Orange 62 (CI. No. 11775) and CI. Pigment Red 185 (CI. No. 12516); disazo condensate compound pigments such as CI. Pigment Yellow 93 (CI. No. 20710) , CI. Pigment Yellow 94 (CI. No. 20038), CI. Pigment Yellow 95 (CI. No. 20034), CI. Pigment Yellow 128 (CI. No. 20037) , C.I. Pigment Yellow 166 (CI. No. 20035), C.I. Pigment Orange 34 (CI. No. 21115), C.I. Pigment Orange 13 (CI. No. 21110), C.I. Pigment Orange 31 (CI. No.
  • C.I. Pigment Red 144 (CI. No. 20735), C.I. Pigment Red 166 (CI. No. 20730), C.I. Pigment Red 220 (CI. No. 20055), C.I. Pigment Red 221 (CI. No. 20065), C.I. Pigment Red 242 (CI. No. 20067), C.I. Pigment Red 248, C.I. Pigment Red 262 and C.I. Pigment Brown 23 (CI. No. 20060); disazo compound pigments such as C.I. Pigment Yellow 13 (CI. No. 21100), C.I. Pigment Yellow 83 (CI. No. 21108) and C.I. Pigment Yellow 188 (CI. No.
  • azo compound pigments such as C.I. Pigment Red 187 (CI. No. 12486), C.I. Pigment Red 170 (CI. No. 12475), C.I. Pigment Yellow 74 (CI. No. 11714), C.I. Pigment Yellow 150 (CI. No. 48545), C.I. Pigment Red 48 (CI. No. 15865), C.I. Pigment Red 53 (CI. No. 15585), C.I. Pigment Orange 64 (CI. No. 12760) and C.I. Pigment Red 247 (CI. No. 15915) ; indanthrone compound pigments such as C.I.
  • dioxazine compound pigments such as C.I. Pigment Violet 23 (CI. No. 51319) and C.I. Pigment Violet 37 (CI. No. 51345) ; aminoanthraquinone compound pigments such as C.I. Pigment Red 177 (CI. No. 65300) ; diketopyrrolopyrrole compound pigments such as C.I. Pigment Red 254 (CI. No. 56110), C.I. Pigment Red 255 (CI.
  • Pigment Orange 61 (CI. No. 11295); pyranthrone compound pigments such as CI. Pigment Orange 40 (CI. No. 59700) and CI. Pigment Red
  • Pigment Violet 31 60010.
  • the dispersibility and the dispersion stability of the colorant can be improved by using the colorant as a powdery processed pigment in which the colorant is finely dispersed in an acrylic resin, maleic resin, vinyl chloride-vinyl acetate copolymer, ethylcellulose resin or the like.
  • the pigment be preliminarily treated with various types of resins.
  • the resulting pigment is generally died by various drying methods.
  • a pigment is dispersed in an aqueous medium, dried and supplied in the form of a powder. Drying water requires a large amount of evaporation latent heat, and then a large amount of thermal energy is applied to the aqueous medium so as to be a dry powder. Therefore, it is usual that the pigment is formed of aggregates (secondary particles) in which primary particles aggregate to each other. It is not easy to disperse such a pigment formed of the aggregates in fine particles, and thus it is desired that the pigment be preliminarily treated with resins.
  • the resins used here include the above-mentioned organic polymers.
  • flushing treatments and kneading methods using a kneader, extruder, ball mill, double- or triple roll mill or the like there are flushing treatments and kneading methods using a kneader, extruder, ball mill, double- or triple roll mill or the like .
  • flushing treatment and a kneading method using double - or triple roll mill are favorably used for forming fine particles.
  • the flushing treatment is a method in which a water-dispersion liquid containing a common pigment is mixed with a resin solution in which the resin has been dissolved in a water-immiscible solvent so as to extract the pigment into the organic medium from the aqueous medium, thereby treating the pigment with the resin.
  • a water-dispersion liquid containing a common pigment is mixed with a resin solution in which the resin has been dissolved in a water-immiscible solvent so as to extract the pigment into the organic medium from the aqueous medium, thereby treating the pigment with the resin.
  • the kneading method using a double - or triple roll mill is a method in which a pigment and a resin or a resin solution are mixed, and the pigment and the resin are kneaded under application of a high-shearing force to coat a surface of the pigment with the resin, thereby treating the pigment.
  • aggregated pigment particles are dispersed from low-level aggregates to primary particles.
  • the pigment may also be used as a processed pigment which is preliminarily treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic resin, ethylcellulose resin, nitrocellulose resin or the like.
  • a processed pigment which is preliminarily treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic resin, ethylcellulose resin, nitrocellulose resin or the like.
  • Unfavorable one is an inhomogeneous agglomerate form in which the resin is gelled.
  • pigment dispersants and surfactants are not particularly limited and may be suitably selected in accordance with the intended use.
  • examples thereof include cationic surfactants such as phthalocyanine derivatives (EFKA- 745 produced by EFKA) , SOLSPERSE 5000 (produced by Zeneca Inc.); organosiloxane polymer KP341 (produced by Shin-Etsu Chemical Co. , Ltd.), (meth)acrylic (co)polymers of POLYFLOW No. 75, No. 90 and No. 95 (produced by Kyoeisha Chemical Co.
  • nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and.
  • sorbitan aliphatic acid ester.' anionic surfactants such as W004, W005, W017 (produced by Yusho Co., Ltd.); polymer dispersants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, and EFKA POLYMER 450 (produced by Morishita Sangyo K. K.), and DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, and DISPERSE AID 9100 (produced by San Nopco Co.
  • SOLSPERSE dispersants such as SOLSPERSE series of 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 (Zeneca Inc.); ADEKA PULRONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, LlOl, P103, F108, L121, and P- 123(Asahi Denka Kogyo K. K.) , and ISONET S-20 (produced by Sanyo Chemical Industries, Ltd.) .
  • - - Method for Producing Color Filter - - ⁇ Color Filter > The color filter can be obtained by curing a coating composition.
  • the coating composition is applied onto a transparent substrate or a barrier layer, and curing the coating composition with ultraviolet ray, using a mask pattern, thereby forming a pattern in each of RGB colors.
  • patterns can be formed using an inkjet method for individual pixels.
  • a method for producing a color filter in which a curable composition is applied onto a substrate, an upper electrode in an organic electroluminescence element or a barrier layer in the organic electroluminescence element.
  • the color filter for use in the present invention is prepared using at least three kinds of curable compositions differing in the colorant composition. Out of these three kinds of curable compositions, any one curable composition is applied onto a substrate, exposed through a mask and developed to form pixels in the first color.
  • the color filter may also be constructed to have four or more colors by further forming pixels in addition to the first to third colors (for example, green, red and blue).
  • a process of applying a curable composition onto a substrate by a coating method such as spin coating, cast coating or roll coating, drying the coating to from a radiation-sensitive layer, exposing the layer through a predetermined mask pattern, and subsequently developing the layer with a developer to form pixels in a desired pattern is repeated at least three times according to the number of colored compositions, whereby the color filter can be obtained.
  • a step of curing the formed pixels by means of heating and/or exposure may be provided, if desired. This exposure may be effected by irradiating radiation.
  • the radiation used here is preferably an ultraviolet ray such as g-line, h-line or i-line.
  • the substrate constituting the color filter is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include soda glass used for liquid crystal display devices and the like, Pyrex (registered) glass, quartz glass and those obtained by attaching a transparent electrically conductive film to such a glass. Also, the color filter may be constructed after previously forming a lowrefractive-index layer on such a substrate . Furthermore, the color filter may be constructed directly on the upper electrode or barrier layer constituting an organic electroluminescence device. In some cases, black stripes for isolating individual pixels are formed on the substrate.
  • the developer is not particularly limited and may be suitably selected in accordance with the intended use. Any developer may be used as long as it dissolves the uncured part of the curable composition for use in the present invention and does not dissolve the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution may be used.
  • the organic solvent is not particularly limited and may be suitably selected in accordance with the intended use. Examples of the organic solvent include the above-described solvents which are used in preparing the curable composition.
  • the alkaline aqueous solution is not particularly limited and may be suitably selected in accordance with the intended use.
  • the alkaline aqueous solution is suitably an alkaline aqueous solution where an alkaline compound, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole or piperidine, is dissolved to a concentration of an alkaline compound, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole or piperidine
  • the organic electroluminescence display device of the present invention is a display device where the light extraction member of the present invention is provided, and a light emitting layer or a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, that is, an anode and a cathode.
  • the organic electroluminescence display device is preferably further provided with an adhesion layer for bonding the light extraction member with the construction part of the organic electroluminescence display device .
  • the organic compound thin film may have a hole injection layer, a hole transporting layer, an electron injection layer, an electron transporting layer, a protective layer and the like, and these layers each may have other functions. For the formation of each layer, various materials can be used. - Anode -
  • the anode supplies holes to the hole injection layer, hole transporting layer, light emitting layer or the like.
  • the material of the anode is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include a metal, an alloy, a metal oxide, an electrically conductive compound, and a mixture thereof.
  • the material preferably has a work function of 4 eV or more.
  • an electrically conductive metal oxide such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), a metal such as gold, silver, chromium and nickel, a mixture or laminate of such a metal and such an electrically conductive metal oxide, an inorganic electrically conductive substance such as copper iodide and copper sulfide, an organic electrically conductive material such as polyaniline, polythiophene and polypyrrole, and a laminate of such a material with ITO.
  • An electrically conductive metal oxide is preferred, and ITO is more preferred in view of productivity, high electrical conductivity, transparency and the like.
  • the thickness of the anode is not particularly limited and may be suitably selected in accordance with the intended use, and may be suitably selected in accordance with the intended use.
  • the thickness is, however, preferably from 10 nm to 5 ⁇ m, more preferably from 50 nm to 1 ⁇ m, particularly preferably from 100 nm to 500 nm.
  • the anode is not particularly limited and may be suitably selected in accordance with the intended use.
  • a layer formed on soda lime glass, alkali-free glass, a transparent resin substrate or the like In the case of using glass, the material thereof is preferably alkali-free glass so as to reduce the ion eluted out from the glass. In the case of using soda lime glass, this is preferably used after applying thereto a barrier coat such as silica.
  • the thickness of the substrate is not particularly limited as long as it is sufficiently thick to maintain the mechanical strength. In the case of using glass, the thickness of the glass is not particularly limited as long as it is 0.2 mm or more, and may be suitably selected in accordance with the intended use. A glass having a thickness of 0.7 mm or more is preferred.
  • a barrier film may also be used as the transparent resin substrate.
  • the barrier film is a film produced by providing a gas-impermeable barrier layer on a plastic support.
  • Examples of the barrier film include those where silicon oxide or aluminum oxide is vapor-deposited (see Japanese Patent Application Publication (JP-B) No. 53- 12953 and Japanese Patent Application Laid-Open (JP-A) No. 58-217344), an organic-inorganic hybrid coating layer is provided (see JP-A Nos. 2000- 323273 and 2004-25732), an inorganic layered compound is provided (see JP-A No. 2001 -205743), an inorganic material is stacked (see, JP-A Nos.
  • anode In the production of the anode, various methods are employed according to the material.
  • examples of the film formation method include an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (e.g., sol-gel method), and a method of coating an indium tin oxide dispersion.
  • a UV-ozone treatment or the like is effective.
  • the cathode supplies electrons to the electron injection layer, electron transporting layer, light emitting layer or the like, and the material therefor is selected by taking into consideration the adhesion to a layer adjacent to the negative electrode, such as electron injection layer, electron transporting layer or light-emitting layer, the ionization potential, the stability and the like.
  • the material of the cathode is not particularly limited and may be suitably selected in accordance with the intended use .
  • a metal, an alloy, a metal oxide, an electrically conductive compound or a mixture thereof can be used.
  • Specific examples of the material include an alkali metal (e.g., Li, Na, K) or a fluoride thereof, an alkaline earth metal (e. g.
  • Mg, Ca or a fluoride thereof, gold, silver, lead, aluminum, an alloy or mixed metal of sodium and potassium, an alloy or mixed metal of lithium and aluminum, an alloy or mixed metal of magnesium and silver, and a rare earth metal such as indium and ytterbium.
  • a material having a work function of 4 eV or less is preferred, and more preferred are aluminum, an alloy or mixed metal of lithium and aluminum, and an alloy or mixed metal of magnesium and silver.
  • the thickness of the cathode is not particularly limited and may be suitably selected in accordance with the intended use.
  • the thickness is, however, preferably from 10 nm to 5 ⁇ m, more preferably from 50 nm to 1 ⁇ m, still more preferably from 100 nm to 1 ⁇ m.
  • Examples of the production method of the cathode include an electron beam method, a sputtering method, a resistance heating vapor deposition method and a coating method, and a single metal component may be vapor-deposited or two or more components may be simultaneously vapor-deposited.
  • an alloy electrode may also be formed by simultaneously vapor-depositing a plurality of metals, or an alloy previously prepared may be vapor-deposited.
  • the sheet resistance of the anode and cathode is preferably lower, and is preferably several hundreds of ⁇ /square or less.
  • the material for the light emitting layer is not particularly limited and may be any material as long as it can form a layer having functions to receive, at the time of electric field application, holes from the anode, hole injecting layer or hole transporting layer, and to receive electrons from the cathode, electron injection layer or electron transporting layer, and offer the field of recombination of holes and electrons to emit light.
  • Examples thereof include various metal complexes as typified by a metal complex or rare earth complex of benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perynone derivatives, oxadiazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidine compound or 8-quinolinol derivatives! and a polymer compound such as polythiophene, polyphenylene and polyphenylenevinylene.
  • the thickness of the light emitting layer is not particularly limited and may be suitably selected in accordance with the intended use.
  • the thickness is, however, preferably from 1 nm to 5 ⁇ m, more preferably from 5 nm to 1 ⁇ m, still more preferably from 10 nm to 500 nm.
  • the method of forming the light emitting layer is not particularly limited, and may be suitably selected in accordance with the intended use.
  • the method include a resistance heating vapor deposition method, an electron beam method, a sputtering method, a molecular lamination method, a coating method (e. g. , spin coating, casting, dip coating) and a LB method. Among these, resistance heating vapor deposition method and coating method are preferred.
  • the details on the hole transporting layer, electron transporting layer, hole injection layer, electron injection layer, a charge blocking layer etc. and a driving method of the organic electroluminescence display element composed of these layers are not particularly limited and may be suitably selected in accordance with the intended use. Those described, for example, in Japanese Patent Application Laid-Open (JP-A) Nos. 2009-016184, 2009-016579, and 2009-031750 can be used.
  • JP-A Japanese Patent Application Laid-Open
  • an optical member light diffusion film
  • an adhesion layer on an upper electrode or a barrier layer which has been provided over an upper electrode.
  • the refractive index of the adhesion layer formed of an adhesive is not particularly limited and may be suitably selected in accordance with the intended use . It is, however, preferably equal to or greater than that of the organic layer including the light emitting layer. If the refractive index is excessively large, the efficiency decreases due to reflection at the interface. Therefore, the difference in the refractive index from the organic layer is preferably 0.2 or less.
  • the refractive index of the adhesion layer is preferably 1.5 to 1.9, more preferably from 1.6 to 1.9, particularly preferably from 1.65 to 1.9, in that an amount of total reflection in an organic EL emitting layer is reduced to one half or less.
  • a method for suppressing reflection at the interface there may be used a method of creating a refractive index gradation in the adhesion layer to allow for bonding of the adhesive and the material at both ends of the adhesive without discontinuity in the refractive index.
  • the adhesive is preferably an adhesive which flows under heating or pressure, more preferably an adhesive which exhibits flowability under heating at 200 0 C or lower or under pressure of 1 kgf/cm 2 or more.
  • the light extraction film (color filter) of the present invention can be attached to an adherend, that is, a display or plastic plate, by fluidizing the adhesive.
  • the adhesive can be fluidized, so that the light extraction member (color filter) can be easily attached to an adherend by lamination or pressing, particularly pressing, or even to an adherend having a curved surface or a complicated shape.
  • the softening point of the adhesive is preferably 200 0 C or lower.
  • the softening point of the adhesion layer is preferably 8O 0 C or more, and in view of the processability, it is more preferably 80 0 C to 120 0 C.
  • the softening point indicates a temperature at which the viscosity thereof becomes 10 12 poises or less (l ⁇ 13 Pa s or less), and the adhesive is usually fluidized within a time of from approximately 1 second to approximately 10 seconds at the above-described temperature.
  • thermoplastic resins are exemplified.
  • Two or more of these acrylic polymers may be copolymerized or blended, if desired.
  • urethane acrylate, epoxy acrylate and polyether acrylate are excellent in view of adhesive property.
  • the epoxy acrylate include (meth)acrylic acid adducts of 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol tetraglycidyl ether.
  • a polymer having a hydroxyl group within its molecule such as epoxy acrylate, is effective in enhancing the adhesion property.
  • These copolymerized resins may be used in combination, if desired.
  • the softening point of the polymer becoming an adhesive is, in view of handleability, preferably 200 0 C or lower, more preferably 150 0 C or lower.
  • the use environment is usually at 80 0 C or lower and therefore, the softening point of the adhesion layer is particularly preferably from 80 0 C to 12O 0 C in view of the processability.
  • the mass average molecular weight (a mass average molecular weight measured using a calibration curve of standard polystyrene by gel permeation chromatography; hereinafter the same) of the polymer used is preferably 500 or more.
  • the cohesive force of the adhesive composition is sufficiently brought out and the adhesion to an adherend can be unfailingly obtained.
  • additives such as diluent, plasticizer, antioxidant, filler, colorant, ultraviolet absorbent and tackifier may be blended, if desired.
  • the thickness of the adhesion layer is not particularly limited and may be suitably selected in accordance with the intended use.
  • the thickness is less than 10 ⁇ m, it may result in insufficient adhesion.
  • the adhesive tends to stick out of the outer periphery of the light extraction member, resulting in a troublesome adhesion process.
  • the material of the adhesive is not particularly limited and may be suitably selected in accordance with the intended use.
  • the material of the adhesive bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, tetrahydroxy-phenylmethane-type epoxy resin, novolak'type epoxy resin, resorcin-type epoxy resin, polyalcohol.polyglycol-type epoxy resin, polyolefin-type epoxy resin, and epoxy resin such as alicyclic or halogenated bisphenol, may be used (all have a refractive index of 1.55 to 1.60) .
  • a copolymerized resin of an acrylic resin with a polymer other than acryl such as epoxy acrylate, urethane acrylate, polyether acrylate and polyester acrylate, may also be used.
  • epoxy acrylate and polyether acrylate are excellent in view of adhesion property.
  • the epoxy acrylate is not particularly limited and may be suitably selected in accordance with the intended use.
  • examples of the epoxy acrylate include (meth)acrylic acid adducts of 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol tetraglycidyl ether.
  • the epoxy acrylate has a hydroxyl group within its molecule and therefore, is effective in enhancing the adhesion property.
  • These copolymerized resins may be used in combination, if desired.
  • the mass average molecular weight of the polymer used to become the main component of the adhesive is 1,000 or more. When the molecular weight is 1,000 or more, the cohesive force of the composition is sufficiently brought out and the adhesion to an adherend can be unfailingly obtained.
  • the adhesive may contain, for example, a monomer having a high refractive index and/or a metal oxide ultrafine particle having a high refractive index.
  • the monomer having a high refractive index is not particularly limited and may be suitably selected in accordance with the intended use.
  • examples thereof include bis(4-methacryloylthiophenyl)sulfide, vinylnaphthalene, vinylphenyl sulfide and 4-methacryloxyphenyl-4'-methoxyphenyl thioether.
  • a curing agent may also be used in the adhesive, and examples of the crosslinking agent which can be used include amines such as triethylenetetramine, xylenediamine and diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecylsuccinic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic anhydride, diaminodiphenylsulfone, tris(dimethylaminomethyl)phenol, polyamide resin, dicyandiamide, and ethylmethylimidazole. These crosslinking agents may be used alone or in combination.
  • the amount of the crosslinking agent added is 0.1 parts by mass to 50 parts by mass, preferably 1 part by mass to 30 parts by mass, based on 100 parts by mass of the above-described polymer. If the amount added is less than 0.1 parts by mass, the curing becomes insufficient, whereas if it exceeds 50 parts by mass, excessive crosslinking results adversely affects the adhesion property.
  • additives such as diluent, plasticizer, antioxidant, filler, colorant and tackifier may be blended, if desired.
  • the resin composition of the adhesive is applied to partially or entirely cover the substrate of a constituent material where a geometric pattern drawn with an electrically conductive material is provided on the surface of a transparent plastic substrate, and through drying of the solvent and curing under heating, the adhesive film according to the present invention is obtained.
  • This adhesive film having electromagnetic wave shielding property and transparency is directly attached to a display such as CRT, PDP, liquid crystal and EL by the adhesive of the adhesive film, or attached to a plate or sheet such as acrylic plate or glass plate and then used for a display.
  • the adhesive is preferably transparent.
  • the total light transmittance is preferably 70% or higher, more preferably 80% or higher, and particularly preferably from 85% to 92%.
  • the adhesive preferably has a low haze level. Specifically, the haze level is preferably from 0% to 3%, more preferably from 0% to 1.5%.
  • the adhesive for use in the present invention is preferably colorless so as not to change the display color inherent in the display. However, even if the resin itself is colored, when the thickness of the adhesive is thin, the adhesive can be regarded as being substantially colorless.
  • the adhesive having the above-described properties is not particularly limited and may be suitably selected in accordance with the intended use.
  • examples thereof include acrylic resins, crolefin resins, vinyl acetate-based resins, acrylic copolymer-based resins, urethane-based resins, epoxybased resins, vinylidene chloride-based resins, vinyl chloride-based resins, ethylene-vinyl acetate-based resins, polyamide-based resins and polyester-based resins.
  • acrylic resins are preferred.
  • the self-adhesion property can be enhanced by such a method as that, at the synthesis of the adhesive by a polymerization method, the amount of the crosslinking agent added is decreased, a tackifier is added, or the terminal group of the molecule is changed.
  • the adhesion can be enhanced by modifying the surface to which the adhesive is to be adhered, that is, by applying surface modification to the transparent plastic film or glass plate. Examples of the surface modification method include a physical method such as corona discharge treatment and plasma glow treatment, and a method of forming an underlying layer for enhancing the adhesion.
  • the thickness of the adhesive is not particularly limited and may be suitably selected in accordance with the intended use. In view of transparency, colorlessness and handleability, the thickness of the adhesive is, however, preferably about 1 ⁇ m to about 50 ⁇ m, more preferably about 1 ⁇ m to 20 ⁇ m. In the case where a change in the display color of the display itself is not caused and the transparency is in the range above, the thickness of the adhesive may exceed the above-described range.
  • a titanium oxide fine particle (333 parts by mass) (titania fine particle (Ti ⁇ 2), mass average particle diameter (average diameter) : 280 nm, refractive index: 2.54, R-580: produced by Ishihara Sangyo K. K.) as an inorganic oxide fine particle, 30 parts by mass of
  • Example 1 Components described below were added based on the following composition, and mixed uniformly to prepare a coating composition of Example 1.
  • Example 1 The coating composition of Example 1 was filtrated through a filter with a pore size of 5 ⁇ m, the filtered coating composition was applied onto a glass substrate for use in preparation of a color filter by a spin coater so as to have a dry film thickness of 1.0 ⁇ m, and dried at 220 0 C for 60 minutes, thereby producing a light extraction member of Example 1 on the glass substrate .
  • Example 2 was prepared in the same manner as in Example 1, except that 30 parts by mass of acryloyloxypropyltrimethoxysilane were used as a surface modifier instead of 30 parts by mass of 3-glycidylpropyltrimethoxysilane.
  • Example 3 A coating composition of Example 2 was prepared and a light extraction member of Example 2 was produced in the same manner as in Example 1, except that the fine particle dispersion for light extraction member of Example 2 was used instead of using the fine particle dispersion for light extraction member of Example 1. (Example 3)
  • a fine particle dispersion for light extraction member of Example 3 was prepared in the same manner as in Example 1, except that 30 parts by mass of acryloyloxypropyl trimethoxysilane were used as a surface modifier instead of 30 parts by mass of 3-glycidylpropyltrimethoxysilane; 3 parts by mass of IN nitric acid were used as a catalyst instead of 1.5 parts by mass of diisopropoxy ethyl acetate aluminum; the addition amount of ion exchanged water was changed from 9 parts by mass to 1 part by mass; the reaction condition was changed from 60 0 C for 8 hours to 40 0 C for 8 hours; and 8.3 parts of ion exchanged water were used instead of 1.8 parts by mass of acetylacetone.
  • Example 4 Preparation of Coating Composition and Production of Light Extraction Member - A coating composition of Example 3 was prepared and a light extraction member of Example 3 was produced in the same manner as in Example 1, except that the fine particle dispersion for light extraction member of Example 3 was used instead of using the fine particle dispersion for light extraction member of Example 1. (Example 4)
  • a fine particle dispersion for light extraction member of Example 4 was prepared in the same manner as in Example 1 , except that 333 parts of a zirconium oxide fine particle (Zr ⁇ 2, mass average particle diameter (average diameter) : 440 nm, refractive index: 2.15, UEP zirconia oxide: produced by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) were used as an inorganic oxide fine particle instead of 333 parts by mass of the titanium oxide fine particle.
  • Zr ⁇ 2 mass average particle diameter (average diameter) : 440 nm
  • refractive index 2.15
  • UEP zirconia oxide produced by Daiichi Kigenso Kagaku Kogyo Co., Ltd.
  • Example 4 A coating composition of Example 4 was prepared and a light extraction member of Example 4 was produced in the same manner as in Example 1, except that the fine particle dispersion for light extraction member of Example 4 was used instead of using the fine particle dispersion for light extraction member of Example 1. (Example 5)
  • a fine particle dispersion for light extraction member of Example 5 was prepared in the same manner as in Example 1, except that 333 parts by mass of a zinc oxide fine particle (ZnO, mass average particle diameter- 600 nm, refractive index- 1.9 to 2.0) produced by Sakai Chemical Industry Co., Ltd.) were used as an inorganic oxide fine particle instead of 333 parts by mass of the titanium oxide fine particle.
  • ZnO zinc oxide fine particle
  • SiO mass average particle diameter- 600 nm, refractive index- 1.9 to 2.0
  • Example 5 A coating composition of Example 5 was prepared and a light extraction member of Example 5 was produced in the same manner as in Example 1, except that the fine particle dispersion for light extraction member of Example 5 was used instead of using the fine particle dispersion for light extraction member of Example 1. (Example 6) - Preparation of Coating Composition -
  • Example 6 A coating composition of Example 6 was prepared in the same manner as in Example 1, except that a benzyl methacrylate/methacrylic acid copolymer (molecular weight: 35,000, acid value : 150 mgKOH/g) was used as an organic polymer instead of the benzyl methacrylate/methacrylic acid copolymer (molecular weight: 30,000, acid value : 120 mgKOH/g).
  • a benzyl methacrylate/methacrylic acid copolymer molecular weight: 35,000, acid value : 150 mgKOH/g
  • ⁇ Production of Light Extraction Member -
  • Example 6 A light extraction member of Example 6 was produced in the same manner as in Example 1, except that the coating composition of Example 6 was used instead of the coating composition of Example 1. (Example 7) - Preparation of Coating Composition -
  • a coating composition of Example 7 was prepared in the same manner as in Example 1, except that the addition amount of the fine particle dispersion for light extraction member of Example 1 was changed from 60 parts by mass to 15 parts by mass.
  • Example 7 A light extraction member of Example 7 was produced in the same manner as in Example 1, except that the coating composition of Example 7 was used instead of the coating composition of Example 1. (Example 8)
  • a coating composition of Example 8 was prepared in the same manner as in Example 1, except that the addition amount of the fine particle dispersion for light extraction member of Example 1 was changed from 60 parts by mass to 8 parts by mass.
  • Example 8 A light extraction member of Example 8 was produced in the same manner as in Example 1, except that the coating composition of Example 8 was used instead of the coating composition of Example 1. (Example 9)
  • Example 9 A coating composition of Example 9 was prepared in the same manner as in Example 1, except that the acid value of the benzyl methacrylate/methacrylic acid copolymer was changed from 120 mgKOH/g to 50 mgKOH/g.
  • Example 9 Production of Light Extraction Member - A light extraction member of Example 9 was produced in the same manner as in Example 1, except that the coating composition of Example 9 was used instead of the coating composition of Example 1. (Comparative Example l) - Preparation of Fine Particle Dispersion for Light Extraction Member -
  • a fine particle dispersion for light extraction member of Comparative Example 1 was prepared in the same manner as in Example 1, except that 333 parts by mass of a titanium oxide fine particle (titania fine particle (Ti ⁇ 2), particle diameter (average diameter) : 30 nm, TTO- 51 (A) : produced by Ishihara Sangyo K. K.) were used as an inorganic oxide fine particle, instead of 333 parts by mass of the titanium oxide fine particle (titania fine particle (Ti ⁇ 2), mass average particle diameter (average diameter) : 280 nm, refractive index: 2.54, R- 580: produced by Ishihara Sangyo K. K.) .
  • Comparative Example 2 Comparative Example 2
  • Example 1 Components described below were added based on the following composition, and mixed uniformly to prepare a coating composition of Example 1.
  • the coating composition was filtrated through a filter with a pore size of 5 ⁇ m, the filtered coating composition was applied onto a glass substrate for use in preparation of a color filter by a spin coater so as to have a dry film thickness of 1.0 ⁇ m, and dried at 220 0 C for 60 minutes, thereby producing a light extraction member of Comparative Example 2 on the glass substrate.
  • (Comparative Example 3) Preparation of Coating Composition -
  • a coating composition of Comparative Example 3 was prepared in the same manner as in Example 1, except that the fine particle dispersion for light extraction member was not added.
  • a coating composition of Comparative Example 3 was prepared in the same manner as in Example 1, except that the coating composition of Comparative Example 3 was used instead of the coating composition of Example 1. (Evaluation Method of Light Extraction Efficiency) ⁇ Production of Organic Electroluminescence Display Device ⁇
  • ITO On a fine-particle-containing layer that had been formed on a glass substrate, ITO was deposited by vacuum evaporation so as to form an ITO electrode (anode) having a thickness of 100 nm.
  • organic compound layers (a hole injection layer, a hole transporting layer, a light emitting layer, and an electron injection layer) were formed in this order.
  • the hole injection layer was formed by depositing 2-TNATA [4,4',4"-tris(2-naphthylphenylamino)triphenylamine] so as to have a thickness of 50 nm.
  • the hole transporting layer wad formed by depositing crNPD [N,N'-(dinaphthylphenylamino)pyrene] so as to have a thickness of 50 nm.
  • the light emitting layer was formed by depositing Alq3 [8-quinolinol-aluminum complex] so as to have a thickness of 50 nm.
  • the electron injection layer was formed by depositing a pyridine derivative so as to have a thickness of 25 nm (average refractive index of the organic compound layers: 1.80) .
  • Al was formed by vacuum evaporation so as to have a thickness of 100 nm.
  • the organic electroluminescence display device With each of the light extraction members of Examples 1 to 9 and Comparative Examples 1 to 3 being disposed on the organic electroluminescence display device, the organic electroluminescence display device was caused to emit light. Using an integrating sphere device that had been attached to the organic electroluminescence display device, the overall amount of light emitted outside the integrating sphere device was measured.
  • the light extraction members of Examples 1 to 9 and Comparative Examples 1 to 3 were left standing at a temperature of 80°C for 20 hours, and thereafter, left standing at room temperature for 4 hours. This procedure was taken as one cycle, and the cycle was repeated 3 times.
  • the amount of light extraction of each of the light extraction members that had undergone the durability test was measured according to the method described above in the measurement and evaluation of light extraction efficiency, regarding the amount of light extraction measured by the integrating sphere device as the overall amount of light emitted.
  • the amount of light extraction measured before the durability test was determined by conversion calculation.
  • the amount of light extraction after the durability test i.e, the value changed (decreased) from the amount of light extraction measured before the durability test was used for the evaluation.
  • Table 1 The results are shown in Table 1 below.
  • composition solutions in three colors (green, red, and blue) were prepared based on each of the following compositions, followed by dispersion treatment by a sand mill for 24 hours.
  • composition solutions in three colors were individually, uniformly mixed, and then were individually filtrated through a filter with a pore size of 5 ⁇ m to thereby prepare coating compositions (in green, red and blue colors) of Example 10.
  • the coating composition in green color was applied onto a glass substrate for use in preparation of a color filter by a spin coater so as to have a dry film thickness of 1.0 ⁇ m, dried at 12O 0 C for 2 minutes, and thus a uniform coat film in green color was formed, thereby producing a light extraction member of Example 10 on the glass substrate .
  • the thus formed coat film of the light extraction member was exposed to light having a wavelength of 365 nm via a mask of 100 ⁇ m in thickness by an exposing device at an exposure dose of 300 mJ/cm 2 .
  • the coat film was developed using a 10% CD- I (Fujifilm Electronics Co. , Ltd.) developer at 26°C for 60 seconds.
  • the light extraction member was rinsed under running water for 20 seconds, dried at 220 0 C for 60 minutes to thereby form a green-color pattern image (green pixel).
  • the same procedure was applied for the red-color and blue-color coating compositions, on the above-mentioned glass substrate so as to form a red-color pattern image (red pixel) and a blue-color pattern image (blue pixel) in this order on the glass substrate, thereby obtaining a color filter of Example 10.
  • the refractive indices of the green pixel, red pixel and blue pixel (the surface-modified fine particle in the coating compositions) being transmissive to light were measured at wavelengths 550 nm, 630 nm, and 450 nm respectively, and found to be 1.80 (green pixel), 1.78 (red pixel) and 1.82 (blue pixel).
  • a TFT substrate 110 was formed as follows. Specifically, a TFT was formed, via a buffer layer, on an insulating substrate. Next, an interlayer-insulating-film layer formed of an SiN film was deposited on the entire surface of the TFT, and then contact holes each reaching a source region and a drain region were formed through a common photo-etching process.
  • an Al/Ti/Al multilayer-structured conductive layer was deposited on the entire surface of the TFT, followed by patterning through a common photo-etching process, so that a source electrode and a drain electrode reaching to the TFT section were formed. Note that the source electrode was branched from a common source light into four branched lines.
  • a photosensitive resin was applied over the entire surface of the laminate by spin coating to form an inter-layer-insulating film. The inter-layer-insulating film was exposed to light via a mask, and then developed with a predetermined developer to form contact holes corresponding to each of the branched lines of the source electrode, thereby forming a TFT substrate 110 composed of the above-mentioned layers.
  • an Al film was deposited on the entire surface of the TFT substrate 110 by sputtering, followed by patterning through photo-etching so as to be in a desired shape, thereby forming a divided lower electrodes (lower electrodes 120) each connecting, through each of the contact holes, to the branched lines of the source electrode.
  • an SiN film and an SiON film were deposited over the entire surface of the laminate in this order by a CVD (chemical vapor deposition) method to form a barrier layer 150 of 5 ⁇ m in thickness.
  • the adhesive was applied, in a thickness of 10 ⁇ m, onto the barrier layer 150 to provide an adhesion layer 180 thereon, and the color filter (light diffusion layer 30) of Example 10 was attached on the adhesion layer 180, thereby producing a multi-color organic electroluminescence display device.
  • the fine particle dispersion for light extraction member of the present invention is capable of improving the light extraction efficiency and suppressing deterioration of a light extraction member due to the heat cycle, and thus it is suitably used for light extraction members such as color filters.

Abstract

A fine particle dispersion for light extraction member, the fine particle dispersion including: a surface-modified fine particle, and a dispersion medium, the surface-modified fine particle being dispersed in the dispersion medium, wherein the surface-modified fine particle comprises an inorganic oxide fine particle having a mass average particle diameter greater than 100 nm and a surface modifier containing one of a hydrolysate obtained by hydrolysis of an organosilane compound represented by General Formula (1) below and a partial condensate obtained by partial condensation of the organosilane compound, and the surface of the inorganic oxide fine particle is covered with the surface modifier: General Formula (1).

Description

DESCRIPTION Title of Invention
FINE PARTICLE DISPERSION FOR LIGHT EXTRACTION MEMBER, COATING COMPOSITION, LIGHT EXTRACTION MEMBER, AND ORGANIC ELECTROLUMINESCENCE DISPLAY DEVICE
Technical Field
The present invention relates to a fine particle dispersion for light extraction member, a coating composition, a light extraction member, and an organic electroluminescence display device.
Background Art
In order to improve light extraction efficiency, there have been proposed technologies of using a light extraction member containing a fine particle .
For example, in an electroluminescence element is proposed in which a cathode, an electroluminescence layer, a transparent electrode layer and a light transmitter are disposed in this order, and a leaked-light-diffusion layer is disposed between the transparent electrode layer and the light transmitter, wherein the leaked-light- diffusion layer contains a particle for scattering light in a matrix formed of a low refractive index material (see PTL l) .
Meanwhile, a method of manufacturing a display panel member using a transfer film is proposed wherein the transfer film includes an inorganic particle-containing resin layer and a support film, ■ wherein the inorganic particle -containing resin layer contains an oxide fine particle having an average particle diameter of 0.001 μm to 5 μm, a refractive index of 1.4 to 1.8 and a specific surface area of 0.5 m2/g to 300 m2/g, a glass powder, an alkali-soluble resin and a radiation-sensitive component, and wherein the oxide fine particle content is 0.01 parts by weight to 20 parts by weight relative to 100 parts by weight of the glass powder (see PTL 2).
However, in these electroluminescence elements, film peel-off sometimes occurs at the interface between an organic layer and the inorganic layer, causing a problem that satisfactory durability cannot be achieved for a desired period of time.
As a technique for improving the dispersibility of a fine particle, there has been proposed an inorganic oxide fine particle dispersion in which a surface-treated inorganic oxide fine particle is dispersed in an organic solvent (see PTL 3) . The inorganic oxide fine particle dispersion is, however, for use in surface protective films and reflection preventive films for liquid crystal display devices and the like. Therefore, there has not yet been provided an inorganic oxide fine particle dispersion which is satisfactory for use in light extraction members for improving light extraction efficiency.
In the meanwhile, as a light extraction member for use in light emitting devices such as organic electroluminescence display devices, it is necessary to have heat resistance required for ON/OFF switch operation in the case of displaying an image. More specifically, a light emitting device generates heat during an ON-state, and the light emitting device is left standing to cool during an OFF-state. When a light extraction member made of an organic/inorganic-mixture film is placed near light emitting elements, there is a problem that dissociation occurs at the interface between the organic component and the inorganic component in each of the light emitting elements due to the local thermal history (heat cycle) based on the ON/OFF switch operation.
However, at the present time, there is no technique disclosed for effectively solve this problem.
Citation List
Patent Literature
PTL 1 Japanese Patent Application Laid-Open (JP-A) No. 2004-296437
PTL 2 Japanese Patent Application Laid-Open (JP-A) No. 2007-246568
PTL 3 Japanese Patent Application Laid-Open (JP-A) No. 2005- 307158
Summary of Invention Technical Problem
The present invention is made to solve the above-mentioned conventional problems and to achieve the following object. That is, the present invention aims to provide a fine particle dispersion for light extraction member which is capable of improving light extraction efficiency and suppressing deterioration of a light extraction member due to the heat cycle, a coating composition, a light extraction member and an organic electroluminescence display device .
Solution to Problem As a result of carrying out earnest examinations in an attempt to solve the above -mentioned problems, the present inventors have obtained the following knowledge.
Specifically, the present inventors have found that a mixture of a binder resin with a matrix containing an inorganic fine particle degrades its durability, in particular, heat resistance thereof, and then have tried to prevent dissociation between the inorganic fine particle and the matrix due to heat and to improve the durability thereof by improving the adhesion between the inorganic fine particle and the binder resin. As a result, the present inventors have found that a functional group (surface modifier) capable of reacting an inorganic fine particle with a binder resin is introduced into the inorganic fine particle to form a surface-modified fine particle in which the surface of the inorganic fine particle is modified and to form a bond between the surface -modified fine particle and the binder resin during formation of a layer of a light extraction member, whereby preventing dissociation between the surface-modified fine particle and the matrix material due to heat and improving the durability.
This means that concerning a surface-modified fine particle whose surface is modified with an inorganic fine particle, novel useful properties conventionally unknown were found out, and an extremely useful solution is brought to light extraction members for which high extraction efficiency and high durability are required.
The present invention has been made based on the finding and knowledge. Means for solving the above-mentioned problems are as follows^
< 1 > A fine particle dispersion for light extraction member, the fine particle dispersion including: a surface-modified fine particle, and a dispersion medium, the surface-modified fine particle being dispersed in the dispersion medium, wherein the surface-modified fine particle contains an inorganic oxide fine particle having a mass average particle diameter greater than 100 nm and a surface modifier containing one of a hydrolysate obtained by hydrolysis of an organosilane compound represented by General Formula (l) below and a partial condensate obtained by partial condensation of the organosilane compound, and the surface of the inorganic oxide fine particle is covered with the surface modifier,
(R Si-(X)+1-
General Formula (l) where, R1 represents any one of an oxygen-containing 3- or
4-membered condensed ring compound, an alkyl group substituted with a substituent containing an unsaturated bond, and an aryl group substituted with a substituent containing an unsaturated bond; X represents one of a hydroxyl group and a hydrolyzable group; and m represents an integer of 1 to 3. < 2 > The fine particle dispersion according to < 1 >, wherein the inorganic oxide fine particle has a mass average particle diameter of 1,000 nm or smaller.
< 3 > The fine particle dispersion according to one of < 1 > and < 2 >, wherein the inorganic oxide fine particle contains at least one selected from Zrθ2, Tiθ2 and ZnO .
< 4 > The fine particle dispersion according to any one of < 1 > to
< 3 >, wherein the inorganic oxide fine particle has a refractive index of 2.1 to 4.0. < 5 > The fine particle dispersion according to any one of < 1 > to
< 4 >, wherein R1 is the oxygen-containing 3- or 4-membered condensed ring compound.
< 6 > A coating composition including: the fine particle dispersion for light extraction member according to any one of < 1 > to < 5 >, an organic polymer, and a binder resin.
< 7 > The coating composition according to < 6 >, wherein the organic polymer has an acid value of 120 mgKOH/g to 200 mgKOH/g. < 8 > The coating composition according to one of < 6 > and < 7 >, wherein the inorganic oxide fine particle is contained in an amount of 5% by mass to 25% by mass relative to the total solid content of the coating composition.
< 9 > A light extraction member including: the coating composition according to any one of < 6 > to < 8 >.
< 10 > The light extraction member according to < 9 >, wherein the light extraction member is used as a color filter.
< 11 > An organic electroluminescence display device including: the light extraction member according to one of < 9 > and < 10 >.
< 12 > The organic electroluminescence display device according to < 11 >, further including an adhesion layer, wherein the adhesion layer has a refractive index of 1.5 to 1.9.
< 13 > The organic electroluminescence display device according to
< 12 >, wherein the adhesion layer has a thickness of 10 μm to 100 μm.
Advantageous Effects of Invention
According to the present invention, it is possible to solve the above-mentioned problems, to achieve the above-mentioned object, and to provide a fine particle dispersion for light extraction member capable of improving light extraction efficiency and suppressing deterioration of a light extraction member due to the heat cycle, a coating composition, a light extraction member and an organic electroluminescence display device .
Brief Description of Drawings
FIG. 1 is a schematic diagram illustrating the basic structure of a light extraction member according to the present invention. FIG. 2 is a partial cross-sectional diagram schematically illustration the layer structure of an organic electroluminescence display device 100 according to a first embodiment of the present invention. Description of Embodiments
(Fine Particle Dispersion for Light Extraction Member)
A fine particle dispersion for light extraction member of the present invention includes a surface-modified fine particle, and a dispersion medium, the surface-modified fine particle being dispersed in the dispersion medium, wherein the surface modified fine particle contains an inorganic oxide fine particle and a surface modifier, and the surface of the inorganic oxide fine particle is covered with a surface modifier. The fine particle dispersion for light extraction member includes other components as required. - Inorganic Oxide Fine Particle -
The inorganic oxide fine particle is a fine particle having a mass average particle diameter greater than 100 nm. When the mass average particle diameter is greater than 100 nm, the inorganic fine particle can efficiently scatter visible light. Further, from the above viewpoint, the mass average particle diameter is preferably 200 nm or greater, particularly preferably 300 nm or greater. Meanwhile, the upper limit of the mass average particle diameter is not particularly limited. It is, however, preferably 1,000 nm, more preferably 800 nm or smaller. When the upper limit of the mass average particle diameter is greater than 1,000 nm, it may be difficult to obtain a thin layer when the particle is applied onto a light extraction member, leading to a degradation in physical strength of the light extraction member. The inorganic oxide fine particle is not particularly limited and may be suitably selected in accordance with the intended use. From the viewpoint that a colorless film can be obtained without limiting the choice of color, it is, however, preferably an oxide fine particle of at least one element selected, for example, from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium.
These inorganic oxide fine particles are not particularly limited. Examples thereof include particles made, for example, of silica, alumina, zirconia (Zrθ2), titanium oxide (Tiθ2), zinc oxide (ZnO), germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide or the like. Among these, from the viewpoint of obtaining high heat cycle durability, preferred are a zirconia (Zrθ2) particle, a titanium oxide (Tiθ2) particle, and a zinc oxide (ZnO) particle. These inorganic oxide fine particles may be used alone or in combination.
The refractive index of the inorganic oxide fine particle is not particularly limited. However, from the viewpoint of obtaining high light extraction efficiency, the inorganic oxide fine particle preferably has a high refractive index. The refractive index is preferably 2.1 to 4.0, more preferably 2.2 to 3.5, particularly preferably 2.2 to 2.8. - Surface -Modified Fine Particle -
The surface -modified fine particle contains one of a hydrolysate obtained by hydrolysis of an organosilane compound represented by the following General Formula (l) and a partial condensate obtained by partial condensation of the organosilane compound.
(R )m- Si-(X)4-m
General Formula (l)
In General Formula (l), R1 represents any one of an oxygen-containing 3- or 4-membered condensed ring compound, an alkyl group substituted with a substituent containing an unsaturated bond, and an aryl group substituted with a substituent containing an unsaturated bond; X represents one of a hydroxyl group and a hydrolyzable group," and m represents an integer of 1 to 3.
As to R1 described above, the number of carbon atoms contained in the alkyl group is not particularly limited. The number of carbon atoms is, however, preferably 1 to 30, more preferably 1 to 16, particularly preferably 1 to 6.
Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, hexyl group, t-butyl group, sec-butyl group, decyl group, and hexadecyl group.
The aryl group is not particularly limited. However, preferred examples thereof are a phenyl group, and naphthyl group. Of these, phenyl group is preferable.
As to X described above, the hydrolyzable group is not particularly limited. Specific examples thereof include an alkoxy group an alkoxy group (preferred is an alkoxy group having 1 to 5 carbon atoms; examples thereof include a methoxy group, and an ethoxy group), a halogen atom (e.g., Cl, Br, I, etc.), and R2COO (R2 is preferably an hydrogen atom or an alkyl group having 1 to 5 carbon atoms,' examples thereof include CH3COO, and C2H5COO). However, the alkoxy group is preferable. Preferred examples of the alkoxy group are a methoxy group, and an ethoxy group .
When a plurality of R1S or Xs are present in proportion to the value of m, each R1 or each X may be identical or different. The integer m is not particularly limited, however, it is preferably 1 or 2, particularly preferably 1.
As to R1 described above, the substituent containing an unsaturated bond is not particularly limited. Examples thereof include a vinyl polymerizable substituent, an allene substituent, and an isocyanate substituent. Among these, a vinyl polymerizable substituent is preferred. In this case, an organosilane compound represented by the following General Formula (2) is preferred.
Figure imgf000012_0001
General Formula (2)
In General Formula (2), R10 represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom.
Examples of the alkoxycarbonyl group include a methoxy carbonyl group, and an ethoxy carbonyl group .
As R1 in General Formula (2), a hydrogen atom, a methyl group, methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable. Among these, a hydrogen atom, methyl group, methoxycarbonyl group, fluorine atom, and chlorine atom are more preferred, with hydrogen atom and methyl group being particularly preferred.
In General Formula (2), Y represents any one of a single bond, an ester group, an amide group, an ether group, and a urea group. Among these, preferred are a single bond, an ester group, and an amide group ; more preferred are a single bond and an ester group, with an ester group being particularly preferred.
In General Formula (2), L represents a divalent linking chain. More specifically, L is a substituted or unsubstituted alkylene group, a substituted or unsubstituted allylene group, a substituted or unsubstituted alkylene group having in the inside thereof a linking group (e.g., ether group, ester group, an amide group) or a substituted or unsubstituted allylene group having in the inside thereof a linking group. Among these, preferred are a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted allylene group having 6 to 20 carbon atoms, and an alkylene group having 3 to 10 carbon atoms and having in the inside thereof a linking group. More preferred are an unsubstituted alkylene group, an unsubstituted allylene group, and an alkylene group having in the inside thereof an ether or ester linking group, with an unsubstituted alkylene group, and an alkylene group having in the inside thereof an ether or ester linking group being particularly preferred.
As the substituent, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group and an aryl group are exemplified. These substituents may be further substituted.
In General Formula (2), n represents an integer of zero or 1. When a plurality of Xs are present, each X may be identical or different. The integer n is preferably zero. R1 has the same meaning as that defined for R1 in General
Formula (l) .
Specific examples of the compound represented by General Formula (2) include acryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, and methacryloyloxypropyltrimethoxysilane.
In General Formula (l), R1 is not particularly limited as long as it is any one of an oxygen-containing 3- or 4-membered condensed ring compound, an alkyl group substituted with a substituent containing an unsaturated bond, and an aryl group substituted with a substituent containing an unsaturated bond. However, from the viewpoint of obtaining high heat cycle durability, an oxygen-containing 3- or 4-membered condensed ring compound is preferred.
That is, when the oxygen-containing 3- or 4-membered condensed ring compound is contained in the surface -modified fine particle, high bond forming efficiency is easily obtained through heat, and high durability, in particular, high heat resistance can be easily obtained.
The oxygen-containing 3- or 4-membered condensed ring compound is not particularly limited and may be suitably selected in accordance with the intended use. Specific examples thereof include 3-glycidylpropyltrimethoxysilane, 3- glycidylpropyltriethoxysilane, and 2, 3-epoxycyclohexylpropyltrimethoxysilane. - Surface -Modified Fine Particle -
The surface-modified fine particle is formed by surface treatment of the surface of an inorganic oxide fine particle so as to be covered with a surface modifier.
The surface treatment is preferably performed in the presence of at least one of a catalyst and a metal chelate compound.
The catalyst is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methansulfonic acid, and toluene sulfonic acid; inorganic basic catalysts such as sodium hydroxide, potassium hydroxide, and ammonium," organic basic catalysts such as triethylamine, and pyridine,' and metal alkoxides such as triisopropoxy aluminum, and tetrabutoxy zirconium.
In terms of the production stability and storage stability of the , inorganic oxide fine particle dispersion, acid catalysts (inorganic acids and organic acids) are preferred.
When the acid catalyst is an inorganic acid, the use amount of the acid catalyst is 0.01 mole% to 10 mole%, preferably 0.1 mole% to 5 mole% relative to the amount of the hydrolyzable group . When the acid catalyst is an organic acid, the most appropriate use amount of the acid catalyst varies depending on the addition amount of water, but, if water is added, it is 0.01 mole% to 10 mole%, preferably 0.1 mole% to 5 mole% relative to the amount of the hydrolyzable group.
As the metal chelate compound, those having, as a ligand, an alcohol represented by the general formula R3OH (where R3 represents an alkyl group having 1 to 10 carbon atoms) and/or a compound represented by the general formula R4COCH2COR5 (where R4 represents an alkyl group having 1 to 10 carbon atoms, R5 represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) and including, as a center metal, a metal selected from Zr, Ti or Al are suitably used without particular limitation. These metal chelate compounds may be used alone or in combination.
Among these, the metal chelate compound is preferably selected from compounds each represented by any one of the following general formulae, and functions to accelerate condensation reaction of the organosilane compound. Zr(OR3)p l(R4COCHCOR5)P2, Ti(OR3)qi(R4COCHCOR5)q2, and Al(OR3)r l(R4COCHCOR5)r2
In the metal chelate compound, R3 and R4 may be identical to or different from each other, and each represent an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include an ethyl group, n-propyl group, i-propyl group, n-butyl group, secbutyl group, t-butyl group, n-pentyl group , and phenyl group . In addition, R5 represents the same alkyl group having 1 to 10 carbon atoms as that described above or an alkoxy group having 1 to 10 carbon atoms. Specific examples thereof include a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, and t-butoxy group . Further, in the metal chelate compound, p i, p2, ql, q2, rl and r2 each represent an integer which is determined so that the ligand is tetradentate or hexadentate. Specific examples of the metal chelate compound include zirconium chelate compounds such as tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis(ethyl acetoacetate)zirconium, n-butoxy -trisCethyl acetoacetate) zirconium, tetrakis(n-p ropy lace to acetate) zirconium, tetrakis(acetylacetoacetate)zirconium, and tetrakisCethyl acetoacetate)zirconium; titanium chelate compounds such as diisopropoxybis (ethyl ace to acetate) titanium, diisopropoxybis(acetylacetate)titanium, and diisopropoxybis(acetylacetone)titaniumJ and aluminum chelate compounds such as diisopropoxy ethyl acetoacetate aluminum, diisopropoxy acetylacetonate aluminum, isopropoxybisCethyl acetoacetate) aluminum, isopropoxy bis (acetylacetonate) aluminum, tris(ethyl acetoacetate) aluminum, tris(acetylacetonate)aluminum, and monoacetylacetonate-bis(ethyl acetoacetate)aluminum. Among these compounds, preferred are tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy bis(acetylacetonate) titanium, diisopropoxy ethyl acetoacetate aluminum, and tris(ethyl acetate)aluminum. These may be used alone or in combination. Besides, partial hydrolysates of these metal chelate compounds may also be used. ■ Dispersion Medium -
The dispersion medium is not particularly limited, and water and/or an organic solvent may be used alone or in combination. Examples of the organic solvent include ketones such as methylethylketone, and acetone; alcohols such as ethyl alcohol, propyl alcohol, butanol, butyl cellosolve, and propylene glycol monomethyl ether,' esters such as propylene glycol monomethyl ether acetate, and butyl acetate,' amides such as dimethylformamide, dimethylacetoamide, and N-methylpyrrolidoneJ and ethers such as tetrahydrofuran, and dioxane . - Other Components - The other components are not particularly limited and may be suitably selected in accordance with the intended use. For example, stabilizing additives for dispersion liquid are exemplified.
The stabilizing additive for dispersion liquid functions as a stabilization improver of the fine particle dispersion for light extraction member and the coating composition of the present invention.
The stabilizing additive for dispersion liquid is not particularly limited. For example, a β-diketone compound represented by the general formula R4COCHaCOR5 and/or a β-ketoester compound represented by the general formula
R4COCH2COR5 are exemplified. Each of these compounds is considered to be coordinated to a metal atom in the metal chelate compound (zirconium, titanium and/or aluminum compound) thereby to have an effect in suppressing the accelerating action, by the metal chelate compound, of condensation reaction between the organosilane compound and metal chelate components and improving the storage stability of the resulting composition. In the general formula, R4 and R5 constituting the compound are same as R4 and R5 constituting the metal chelate compound.
Specific examples of the β-diketone compound and/or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate, 2,4-hexane-dione, 2, 4-heptane-dione, 3, 5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, and 5-methyl-hexane -dione. Among these, ethyl acetoacetate, and acetyl acetone are preferred, with acetyl acetone being particularly preferred. (Coating Composition)
The coating composition of the present invention contains a fine particle dispersion for light extraction member, an organic polymer and a binder resin.
- Fine Particle Dispersion for Light Extraction Member -
As the fine particle dispersion for light extraction member, the above-mentioned fine particle dispersion for light extraction member of the present invention can be used. When the fine particle dispersion for light extraction member is used in the coating composition, the amount of an inorganic oxide fine particle contained in the fine particle dispersion for light extraction member is preferably 5% by mass to 25% by mass, more preferably 10% by mass to 25% by mass, particularly preferably 15% by mass to 25% by mass relative to the total solid content of the coating composition. When the amount of the inorganic oxide fine particle is less than 5% by mass, the light extraction efficiency may degrade. When it is more than 25% by mass, the resulting film may become brittle, leading to degradation in durability. - Organic Polymer - The organic polymer is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, polymers having a carboxylic acid on the side chain thereof such as a partially esterified maleic acid copolymer," and acidic cellulose derivatives having a carboxylic acid group on the side chain thereof. In addition to the above, compounds obtained by addition of an acid anhydride to a polymer having a hydroxyl group are also effectively used. Among these, a benzyl(meth)acrylate/(meth)acrylic acid copolymer, and a multi-component copolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/other monomer are preferred. Besides, as water-soluble polymers, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also effectively used. In addition, in terms of increasing the strength of a cured film, alcohol-soluble nylon, 2,2-bis-(4-hydroxyphenyl)-propane, and polyether such as epichlorohydrin are also effectively used. These polymers may be used in combination in a predetermined amount. Furthermore, there may be exemplified those described in
Japanese Patent Application Laid-Open (JP-A) No. 07- 140654, such as 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymer, and 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer.
As the organic polymer, those having a carboxyl group on the side chain thereof are preferred.
The acid value of the organic polymer is not particularly limited. It is, however, preferably 120 mgKOH/g to 200 mgKOH/g, more preferably 120 mgKOH/g to 180 mgKOH/g, particularly preferably 120 mgKOH/g to 150 mgKOH/g. When the acid value is less than 120 mgKOH/g, the durability may degrade. When it is more than 200 mgKOH/g, the formability of pattern may degrade.
The mass average molecular weight of the organic polymer is not particularly limited. It is, however, preferably 1,000 to 100,000, more preferably 30,000 to 35,000.
When the mass average molecular weight is less than 1,000, the curing of the coating film may be insufficient. When it is more than 100,000, the coating of the coating composition may be difficult due to the poor solubility. - Binder Resin -
The binder resin is not particularly limited and may be suitably selected in accordance with the intended use. For example, acrylic copolymers are exemplified. A polymer having saturated hydrocarbon or polyether in the main chain is preferred, with a polymer having saturated hydrocarbon in the main chain being more preferred.
It is preferable that binder resin be crosslinked. The polymer having saturated hydrocarbon in the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder resin, it is preferred to use a monomer having two or more ethylenically unsaturated groups.
The monomer having two or more ethylenically unsaturated groups is not particularly limited and may be suitably selected in accordance with the intended use. Specific examples thereof include esters of polyhydric alcohol with a (meth)acrylic acid (e. g. , ethylene glycol di(meth)acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol 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, pentaerythritol hexa(meth)acrylate, 1,2,3-cyclohexane tetramethacrylate, 1, 3, 5-cyclohexanetriol trimethacrylate, polyurethane polyacrylate, and polyester polyacrylate), derivatives of vinylbenzene (e.g., 1,4-divinylbenzene, 4-vinyl benzoate-2-acryloylethyl ester, and 1,4-divinylcyclohexanone), vinylsulfone (e.g., divinylsulfone), acrylamide (e.g. , methylene bis acrylamide), and methacrylamide . Among these, an acrylate or a methacrylate monomer each having at least three functional groups, and an acrylate monomer having at least five functional groups are preferable in terms of film hardness, i.e., scratch resistance, with a mixture of dipentaerythritol pentaacrylate with dipentaerythritol hexaacrylate (commercial products) being more preferable. These monomers may be used in combination. In the present invention, the term "(meth)acrylate" means "acrylate or methacrylate". These monomers having an ethylenically unsaturated group can be cured by dissolving each of these monomers along with various polymerization initiators and other additives in a solvent to prepare a coating solution, applying the coating solution onto an object, followed by drying and subjecting to a polymerization reaction under application of light, ionizing radiation or heat. - Other Components -
The other components are not particularly limited. For the purpose of forming a light extraction member, for example, a photosensitive polymerizable component, a photopolymerizable initiator, and solvents may be selected.
- ■ Photosensitive Polymerizable Component - ■
The photosensitive polymerizable component is not particularly limited and may be suitably selected in accordance with the intended use . It is, however, preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 1000C or higher under normal pressure . Among such compounds, more preferred are tetrafunctional or higher functional acrylate compounds.
The above-mentioned "compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100°C or higher under normal pressure" is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl(meth)acrylate; compounds obtained by adding an ethylene oxide or a propylene oxide to a polyfunctional alcohol, and then subjecting to (meth)acrylation (e.g. 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, hexane diol (meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, and trimethylolethane); poly(meth)acrylated products of pentaerythritol or dipentaerythritol; urethane acrylates as described in Japanese Patent Application Publication (JP-B) Nos. 48-41708, and 50-6034, and Japanese Patent Application Laid-Open (JP-A) No. 51 -37193; polyester acrylates as described in Japanese Patent Application Laid-Open (JP-A) No. 48-64183, Japanese Patent Application Publication (JP-B) Nos. 49-43191, and 52- 30490; and polyfunctional acrylates and polyfunctional methacrylates as reaction products between an epoxy resin and a (meth)acrylic acid (e. g. , epoxy acrylates) . Further, those disclosed as photocurable monomer and oligomers in Nihon Secchaku Kyokai-shi (Japan Adhesive Association), Vol. 20, No. 7, pp. 300-308 can also be used. As the compounds obtained by adding an ethylene oxide or a 5 propylene oxide to a polyfunctional alcohol, and then subjecting to (meth)acrylation, it is possible to use, as the photosensitive polymerizable component, the specific examples of the compound, and the compounds represented by one of the General Formulae (l) and (2) described in Japanese Patent Application Laid-Open (JP-A) No. i o 10-62986.
Among these, preferred are dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and compounds having a structure where these acryloyl groups are attached via an ethylene glycol residue or a propylene glycol residue.
15 In addition, oligomer type compounds are also favorably used.
Acrylic oligomers with monomer repeating units of 3 to 20 (preferably 3 to 10) are preferred.
When an acrylic oligomer is used as the photosensitive polymerizable component, the light exposure sensitivity is increased
20 and the polymerization strength is increased. Therefore, it is difficult to cause peeling-off of a pattern when developing is performed with a developing liquid containing the acrylic oligomer, and the applicable time span for developing is widened. That is, it is possible to widen the developing latitude.
25 The above photosensitive polymerizable components may be used alone or in combination. - - Photopolymerization Initiator - -
The photopolymerization initiator is not particularly limited and may be suitably selected in accordance with the intended use . Examples of the photopolymerization initiator include active halogen compounds, such as halomethyl oxadiazole and halomethyl-s-triazine,' 3-aryl-substituted coumarine compounds, and at least one lophine dimer. Among these, halomethyl-s-triazine compounds are preferred. Hereinafter, these compounds will be described in detail.
The halomethyl oxadiazole is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include 2-halomethyl- 5-vinyl- l, 3,4-oxadiazole compounds. Specific examples of the 2-halomethyl- 5-vinyl- l, 3, 4-oxadiazole compounds include 2-trichloromethyl- 5-styryl- l,3,4-oxadiazole, 2 -trichloromethyl- 5 -(p -cyanostyryl)- 1, 3, 4- oxadiazole, and 2 - trichloromethyl- 5 -(p - me thoxy sty ry I) - 1, 3, 4 -oxadiazole.
The halomethyl-s-triazine compound is not particularly limited and may be suitably selected in accordance with the intended use. For example, there may be exemplified vinyl-halomethyl-s-triazine compound described in Japanese Patent Application Publication (JP-B) No. 59- 1281, and
2 -(naphtho- 1-yl) - 4, 6 -bis -halomethyl-s-triazine compound,
4- (p -aminopheny I) - 2, 6 -di- halomethyl-s-triazine compound described in Japanese Patent Application Laid-Open (JP-A) No. 53- 133428.
The vinyl-halomethyl-s-triazine compound is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2,4-bis(trichloromethyl) -6- (l-p -dimethylaminophenyl- l, 3-butadienyl) -s-triazine, and
2-trichloromethyl-4-amino-6-p -methoxystyryl-s-triazine. A sensitizer may be used in combination with the photopolymerization initiator. The sensitizer is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include benzoin, benzoin methyl ether, 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, dibenzal acetone, p- (dimethylamino)phenyl styryl ketone, p -(dimethylamino)phenyl-p -methyl styryl ketone, benzophenone, p -(dimethylamino)benzophenone (or Michler's ketone), p -(diethylamino)benzophenone, benzoanthrone, and benzothiazole compounds described in JP-B No. 51-48516. ■ Solvent -
In preparation of the coating composition, the coating composition generally contains a solvent (otherwise, referred to as "organic solvent" in the present invention). Basically, the solvent is not particularly limited as long as the solubility of each component and the coatability of the curable composition are satisfied. The solvent is, however, preferably selected in consideration of especially, the solubility, coatability and safety of colorants used and the resin components.
The solvent is not particularly limited and may be suitably selected in accordance with the intended use. 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, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl oxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.) and ethyl 3-oxypropionate (e. g. ethyl 3-methoxy propionate, ethyl 3-ethoxypropionate, etc.) ; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate (e.g., methyl 2-methoxypropionate, methyl 2-ethoxypropionate, methyl 2"θxy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate), ethyl 2-oxypropionate (e.g., ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-oxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), propyl 2-methoxypropionate, and propyl 2-oxypropionate, etc. ; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2- oxobutanoate, and ethyl 2- oxobutanoate; 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, and propylene glycol propyl ether acetate; ketones such as methylethylketone, cyclohexanone, 2-heptanone, and 3-heptanone; aromatic hydrocarbons such as toluene, and xylene,' ethyl carbitol acetate, and butyl carbitol acetate .
Among these, preferred are 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxy methyl propionate, 2-heptane, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. These solvents may be used alone or in combination. (Light Extraction Member) The light extraction member of the present invention includes a coating composition.
As the coating composition, the above-mentioned coating composition of the present invention can be used.
From the viewpoint of obtaining high light extraction efficiency, the light extraction member preferably has a structure composed of at least a transparent substrate provided with a barrier layer; a low- refractive-index layer! and a light diffusion layer. The light diffusion layer is preferably formed to contain the coating composition. FIG. 1 is a schematic diagram illustrating the basic structure of a light extraction member according to the present invention. In FIG. 1, a light extraction member 1 includes a transparent substrate 20 provided with a barrier layer, and a light diffusion layer 30, with the light diffusion layer 30 being provided over the transparent substrate 20. - Transparent Substrate Provided With Barrier Layer -
The transparent substrate 20 provided with a barrier layer includes at least a transparent base film and a barrier layer, and further includes other layers as required. Examples of the other layers include a matting agent layer, a protective layer, a solvent resistant layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light shielding layer, a reflection preventing layer, a hard coat layer, a stress relaxation layer, an antifogging layer, an antifouling layer, a printed layer, and an easy-adhesion layer.
The transparent base film is not particularly limited and may be suitably selected in accordance with the intended use. For example, a transparent resin film, a transparent resin plate, and a transparent resin sheet are exemplified.
The transparent resin film is not particularly limited and may be suitably selected in accordance with the intended use. Specific examples of include a triacetylcellulose (TAC) film (refractive index- 1.48), a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a diacethylene cellulose film, a cellulose acetate butylate film, a polyether sulfone film, a polyacrylic resin film, a polyurethane resin film, a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethyl pentene film, a polyether ketone film, and a (meth)acrylonitrile film. The thickness of the transparent resin film is usually about 25 μm to about 1,000 μm.
The refractive index of triacetylcellulose which is preferably used as the transparent base film is 1.48. The barrier layer is not particularly limited as long as it has a function to prevent transmission of oxygen, moisture, nitrogen oxides, sulfur oxides and ozone in air, and may be suitably selected in accordance with the intended use.
The material of the barrier layer may be a material having a function to prevent substances that accelerate degradation of the element, such as moisture and oxygen, from entering the element. Specific examples of the barrier layer include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni; metal oxides such as MgO, SiO, Siθ2, Al2O3, GeO, NiO, CaO, BaO, Fe2O3 , Y2O3, and TiO2, metal nitrides such as SiN; metal oxynitrides such as SiON,' metal fluorides such as MgF2, LiF, AlF3, and CaF2,' copolymers of a dichlorodifluoroethylene with polyethylene, polypropylene, polymethylmethacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, or chlorotrifluoroethylene," copolymers obtained by copolymerization of tetrafluoroethylene with a comonomer mixture containing at least one comonomer; fluorine-containing copolymers having a cyclic structure in the copolymerization main chain, water-absorbing materials having a water absorption coefficient of 1% or higher," and moisture resistant materials having a water absorption coefficient of 0.1% or lower. The thickness of the barrier layer is not particularly limited and may be suitably selected in accordance with the intended use. It is, however, preferably 5 nm to 1, 000 nm, more preferably 7 nm to 750 nm, particularly preferably 10 nm to 500 nm. When the thickness of the barrier layer is less than 5 nm, the barrier function for preventing transmission of oxygen and moisture in air may be insufficient. When the thickness is more than 1,000 nm, the light transmittance may decrease, which may impair the transparency of the transparent substrate. The light transmittance of the barrier layer is usually 80% or higher, preferably 85% or higher, more preferably 90% or higher. The forming method of the barrier layer is not particularly limited and may be suitably selected in accordance with the intended use. Examples of the forming method include a vacuum evaporation method, sputtering method, reactive sputtering method, MBE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high-frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas-source CVD method, and coating method.
■ Light Diffusion Layer -
The light diffusion layer contains at least a binder resin, and a surface-modified fine particle .
When the light diffusion layer is used to function as the after-mentioned color filter, the light diffusion layer contains a colorant. As the binder resin, the binder resins described above in the coating composition of the present invention can be used.
For instance, as illustrated in FIG. 1, in the light diffusion layer 30, a surface-modified fine particle 41 is dispersed in a matrix material 31 (portions of constituents of the light diffusion layer 30 from which the surface-modified fine particle 41 is excluded), which contains a binder resin and a colorant 42. The light diffusion layer 30 may be composed of a plurality of layers. Further, as the surface -modified fine particle 41, two or more types of particles may be used.
The light scattering profile and the haze value of the light diffusion layer 30 are controlled by controlling each refractive index of the matrix material 31 and the surface-modified fine particle 41 and the particle size of the surface -modified fine particle 41. In a light extraction member 1 having the light diffusion layer
30, a bond is formed between the surface-modified fine particle 41, into which a functional group (a surface-modifier) of the binder resin (including an organic polymer) reacting with an inorganic fine particle is introduced, and the binder resin (including the organic polymer) constituting the matrix material 31 of the light diffusion layer, thereby preventing dissociation between the surface-modified fine particle 41 and the matrix material 31 due to heat and improving the durability. In addition, high light extraction efficiency can be obtained at the light diffusion layer 30 owing to light scattering of the surface-modified fine particle 41.
The refractive index of the surface-modified fine particle 41 in the light diffusion layer 30 is not particularly limited and may be suitably selected in accordance with the intended use. The refractive index of the surface-modified fine particle 41 is, however, preferably 2.1 or higher, more preferably 2.15 or higher, particularly preferably 2.2 or higher, in terms that a difference in refractive index from the matrix material 31 is 0.05 or more and a sufficient amount of light scattering can be obtained. By setting the refractive index of the light diffusion layer 30 higher, it is possible to obtain an effect of further improving the light extraction efficiency. The thickness of the light diffusion layer 30 is not particularly limited as long as it is about 0.5 μm to about 50 μm in dry film thickness, and may be suitably selected in accordance with the intended use. It is, however, preferably 1 μm to 20 μm, more preferably 2 μm to 10 μm, particularly preferably 3 μm to 7 μm. In a preferred embodiment of the optical member, the optical member is a film having a transparent substrate 20 provided with a barrier layer, and a light diffusion layer 30 formed on the transparent substrate 20 provided with a barrier layer, wherein in a matrix material 31 of the light diffusion layer 30, a surface-modified fine particle 41 having a refractive index different from that of the matrix material 31 is dispersed; and the refractive index of the matrix material 31 is 1.6 or lower. With this configuration, the total reflection amount in the organic light emitting layer is reduced to one-half or less. In this embodiment, the surface -modified fine particle 41, which is formed by surface treatment of the surface of at least one type inorganic fine particle selected from Zrθ2, Tiθ2, Snθ2, and ZnO, is preferably contained in the matrix material 31 of the light diffusion layer 30. With this, the light diffusion layer 30 will be a high refractive layer having light scattering property. - Color Filter -
5 The application of the light extraction member is not particularly limited, and there may be exemplified all optical members for which high light extraction efficiency and high heat cycle durability are required. Among these optical members, the light extraction member is suitably used as a color filter. i o - ■ Colorant - -
The colorant is not particularly limited and may be suitably selected in accordance with the intended use. Examples of the colorant include high-molecular weight organic materials such as organic pigments, organic dyes, fullerene, polydiacetylene, and
15 polyimide; and organic particles composed of an aromatic hydrocarbon or an aliphatic hydrocarbon (e.g. , aromatic hydrocarbons or aliphatic hydrocarbons having orientation property, or aromatic hydrocarbons or aliphatic hydrocarbons having sublimation property) . Among these, organic pigments, organic dyes, and high-molecular
20 weight organic materials are preferable, with the organic pigments being more preferable. These organic particles may be used alone or in combination.
The organic pigments are not limited in terms of color phase. Examples of the organic pigments include perylene, perinone,
25 quinacridone, quinacridonequinone, anthraquinone, anthanthorone, benzimidazolone, disazo condensates, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone, cyanine or isoviolanthrone compound pigments, and mixtures thereof. Specific examples of the organic pigments include perylene compound pigments such as C.I. Pigment Red 190 (CI. No. 71140), C.I. Pigment Red 224 (CI. No. 71127) and CI. Pigment Violet 29 (CI. No. 71129) ; perinone compound pigments such as CI. Pigment Orange 43 (CI. No. 71105) and CI. Pigment Red 194 (CI. No. 71100); quinacridone compound pigments such as C.I. Pigment Violet 19 (CI. No. 73900), CI. Pigment Violet 42, CI. Pigment Red 122 (CI. No. 73915), CI. Pigment Red 192, CI. Pigment Red 202 (CI. No. 73907), C.I. Pigment Red 207 (CI. No. 73900, 73906) and CI. Pigment Red 209 (CI. No. 73905); quinacridonequinone compound pigments such as CI. Pigment Red 206 (CI. No. 73900/73920), CI. Pigment Orange 48 (CI. No. 73900/73920) and CI. Pigment Orange 49 (CI. No. 73900/73920); anthraquinone compound pigments such as CL Pigment Yellow 147 (CI. No. 60645); anthanthorone compound pigments such as CI. Pigment Red 168 (CI. No. 59300); benzimidazolone compound pigments such as CI. Pigment Brown 25 (CI. No. 12510) , CI. Pigment Violet 32 (CI. No. 12517), CI. Pigment Yellow 180 (CI. No. 21290), CI. Pigment Yellow 181 (CI. No. 11777), CI. Pigment Orange 62 (CI. No. 11775) and CI. Pigment Red 185 (CI. No. 12516); disazo condensate compound pigments such as CI. Pigment Yellow 93 (CI. No. 20710) , CI. Pigment Yellow 94 (CI. No. 20038), CI. Pigment Yellow 95 (CI. No. 20034), CI. Pigment Yellow 128 (CI. No. 20037) , C.I. Pigment Yellow 166 (CI. No. 20035), C.I. Pigment Orange 34 (CI. No. 21115), C.I. Pigment Orange 13 (CI. No. 21110), C.I. Pigment Orange 31 (CI. No. 20050), C.I. Pigment Red 144 (CI. No. 20735), C.I. Pigment Red 166 (CI. No. 20730), C.I. Pigment Red 220 (CI. No. 20055), C.I. Pigment Red 221 (CI. No. 20065), C.I. Pigment Red 242 (CI. No. 20067), C.I. Pigment Red 248, C.I. Pigment Red 262 and C.I. Pigment Brown 23 (CI. No. 20060); disazo compound pigments such as C.I. Pigment Yellow 13 (CI. No. 21100), C.I. Pigment Yellow 83 (CI. No. 21108) and C.I. Pigment Yellow 188 (CI. No. 21094); azo compound pigments such as C.I. Pigment Red 187 (CI. No. 12486), C.I. Pigment Red 170 (CI. No. 12475), C.I. Pigment Yellow 74 (CI. No. 11714), C.I. Pigment Yellow 150 (CI. No. 48545), C.I. Pigment Red 48 (CI. No. 15865), C.I. Pigment Red 53 (CI. No. 15585), C.I. Pigment Orange 64 (CI. No. 12760) and C.I. Pigment Red 247 (CI. No. 15915) ; indanthrone compound pigments such as C.I.
Pigment Blue 60 (CI. No. 69800); phthalocyanine compound pigments such as C.I. Pigment Green 7 (CI. No. 74260) , C.I. Pigment Green 36 (CI. No. 74265), C.I. Pigment Green 37 (CI. No. 74255), C.I. Pigment Blue 16 (CI. No. 74100), C.I. Pigment Blue 75 (CI. No. 74160 :2), C.I. Pigment Blue 15 = 6 (CI. No. 74160) and C.I. Pigment Blue 15:3 (CI. No. 74160); triarylcarbonium compound pigments such as C.I. Pigment Blue 56 (CI. No. 42800) and C.I. Pigment Blue 61 (CI. No. 42765: 1); dioxazine compound pigments such as C.I. Pigment Violet 23 (CI. No. 51319) and C.I. Pigment Violet 37 (CI. No. 51345) ; aminoanthraquinone compound pigments such as C.I. Pigment Red 177 (CI. No. 65300) ; diketopyrrolopyrrole compound pigments such as C.I. Pigment Red 254 (CI. No. 56110), C.I. Pigment Red 255 (CI.
No. 561050), CI. Pigment Red 264, C.I. Pigment Red 272 (CI. No.
561150), C.I. Pigment Orange 71 and CI. Pigment Orange 73; thioindigo compound pigments such as CI. Pigment Red 88 (CI. No. 73312); isoindoline compound pigments such as CI. Pigment Yellow
139 (CI. No. 56298) and CI. Pigment Orange 66 (CI. No. 48210) ; isoindolinone compound pigments such as CI. Pigment Yellow 109
(CI. No. 56284), CI. Pigment Yellow 185 (CI. No. 56290) and CI.
Pigment Orange 61 (CI. No. 11295); pyranthrone compound pigments such as CI. Pigment Orange 40 (CI. No. 59700) and CI. Pigment Red
216 (CI. No. 59710); quinophthalone pigments such as CI. Pigment
Yellow 138; and isoviolanthrone compound pigments such as CI.
Pigment Violet 31 (60010). Among these pigments, preferred are quinacridone compound pigments, diketopyrrolopyrrole compound pigments, dioxazine compound pigments, phthalocyanine compound pigments, and azo compound pigments, with the diketopyrrolopyrrole compound pigments, dioxazine compound pigments, and phthalocyanine compound pigments being more preferable.
The dispersibility and the dispersion stability of the colorant can be improved by using the colorant as a powdery processed pigment in which the colorant is finely dispersed in an acrylic resin, maleic resin, vinyl chloride-vinyl acetate copolymer, ethylcellulose resin or the like.
Next, the following describes the treating method of the pigment. In the present invention, it is preferable that the pigment be preliminarily treated with various types of resins. In other words, after a pigment is synthesized, the resulting pigment is generally died by various drying methods. Typically, a pigment is dispersed in an aqueous medium, dried and supplied in the form of a powder. Drying water requires a large amount of evaporation latent heat, and then a large amount of thermal energy is applied to the aqueous medium so as to be a dry powder. Therefore, it is usual that the pigment is formed of aggregates (secondary particles) in which primary particles aggregate to each other. It is not easy to disperse such a pigment formed of the aggregates in fine particles, and thus it is desired that the pigment be preliminarily treated with resins. Examples of the resins used here include the above-mentioned organic polymers.
As the treatment method, there are flushing treatments and kneading methods using a kneader, extruder, ball mill, double- or triple roll mill or the like . Among these, flushing treatment and a kneading method using double - or triple roll mill are favorably used for forming fine particles.
The flushing treatment is a method in which a water-dispersion liquid containing a common pigment is mixed with a resin solution in which the resin has been dissolved in a water-immiscible solvent so as to extract the pigment into the organic medium from the aqueous medium, thereby treating the pigment with the resin. With this method, the pigment does not undergo drying, and thus aggregation of the pigment can be prevented, and the dispersion is easily carried out. Meanwhile, the kneading method using a double - or triple roll mill is a method in which a pigment and a resin or a resin solution are mixed, and the pigment and the resin are kneaded under application of a high-shearing force to coat a surface of the pigment with the resin, thereby treating the pigment. In the course of this treatment, aggregated pigment particles are dispersed from low-level aggregates to primary particles.
The pigment may also be used as a processed pigment which is preliminarily treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic resin, ethylcellulose resin, nitrocellulose resin or the like. As the form of the processed pigment, preferred are a powder, a paste, and a pellet in each which a resin and a pigment are uniformly dispersed. Unfavorable one is an inhomogeneous agglomerate form in which the resin is gelled.
For the purpose of improving the dispersibility of the pigment, conventionally known pigment dispersants and surfactants may be used in combination. The pigment dispersants and surfactants are not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include cationic surfactants such as phthalocyanine derivatives (EFKA- 745 produced by EFKA) , SOLSPERSE 5000 (produced by Zeneca Inc.); organosiloxane polymer KP341 (produced by Shin-Etsu Chemical Co. , Ltd.), (meth)acrylic (co)polymers of POLYFLOW No. 75, No. 90 and No. 95 (produced by Kyoeisha Chemical Co. , Ltd.), and WOO l (produced by Yusho Co., Ltd.); nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and. sorbitan aliphatic acid ester.' anionic surfactants such as W004, W005, W017 (produced by Yusho Co., Ltd.); polymer dispersants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, and EFKA POLYMER 450 (produced by Morishita Sangyo K. K.), and DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, and DISPERSE AID 9100 (produced by San Nopco Co. Ltd.); various SOLSPERSE dispersants such as SOLSPERSE series of 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 (Zeneca Inc.); ADEKA PULRONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, LlOl, P103, F108, L121, and P- 123(Asahi Denka Kogyo K. K.) , and ISONET S-20 (produced by Sanyo Chemical Industries, Ltd.) . - - Method for Producing Color Filter - - < Color Filter > The color filter can be obtained by curing a coating composition.
For example, the coating composition is applied onto a transparent substrate or a barrier layer, and curing the coating composition with ultraviolet ray, using a mask pattern, thereby forming a pattern in each of RGB colors. Alternatively, patterns can be formed using an inkjet method for individual pixels. The following describes, in detail, a method for producing a color filter, in which a curable composition is applied onto a substrate, an upper electrode in an organic electroluminescence element or a barrier layer in the organic electroluminescence element. The color filter for use in the present invention is prepared using at least three kinds of curable compositions differing in the colorant composition. Out of these three kinds of curable compositions, any one curable composition is applied onto a substrate, exposed through a mask and developed to form pixels in the first color. After the formation of pixels in the first color, other one curable composition selected from those colored curable compositions, which are different in the color and hue from the pixels in the first color, is applied onto the substrate, exposed through a mask and developed to form pixels in the second color. Furthermore, after the formation of pixels in the second color, other one curable composition selected from those colored curable compositions, which are different in the color and hue from the first and second colors, is applied onto the substrate, exposed through a mask and developed to form pixels in the third color, whereby the color filter is obtained. The color filter may also be constructed to have four or more colors by further forming pixels in addition to the first to third colors (for example, green, red and blue). That is, using at least three kinds of the curable compositions in a desired order of colors, a process of applying a curable composition onto a substrate by a coating method such as spin coating, cast coating or roll coating, drying the coating to from a radiation-sensitive layer, exposing the layer through a predetermined mask pattern, and subsequently developing the layer with a developer to form pixels in a desired pattern is repeated at least three times according to the number of colored compositions, whereby the color filter can be obtained. At this time, a step of curing the formed pixels by means of heating and/or exposure may be provided, if desired. This exposure may be effected by irradiating radiation. The radiation used here is preferably an ultraviolet ray such as g-line, h-line or i-line.
The substrate constituting the color filter is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include soda glass used for liquid crystal display devices and the like, Pyrex (registered) glass, quartz glass and those obtained by attaching a transparent electrically conductive film to such a glass. Also, the color filter may be constructed after previously forming a lowrefractive-index layer on such a substrate . Furthermore, the color filter may be constructed directly on the upper electrode or barrier layer constituting an organic electroluminescence device. In some cases, black stripes for isolating individual pixels are formed on the substrate.
The developer is not particularly limited and may be suitably selected in accordance with the intended use. Any developer may be used as long as it dissolves the uncured part of the curable composition for use in the present invention and does not dissolve the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution may be used. The organic solvent is not particularly limited and may be suitably selected in accordance with the intended use. Examples of the organic solvent include the above-described solvents which are used in preparing the curable composition.
The alkaline aqueous solution is not particularly limited and may be suitably selected in accordance with the intended use. The alkaline aqueous solution is suitably an alkaline aqueous solution where an alkaline compound, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole or piperidine, is dissolved to a concentration of
0.001% by mass to 10% by mass, preferably from 0.01% by mass to 1% by mass. In the case of using a developer containing such an alkaline aqueous solution, the coating is generally washed with water after development. (Organic Electroluminescence Display Device)
The organic electroluminescence display device of the present invention is a display device where the light extraction member of the present invention is provided, and a light emitting layer or a plurality of organic compound thin films including a light emitting layer are formed between a pair of electrodes, that is, an anode and a cathode. The organic electroluminescence display device is preferably further provided with an adhesion layer for bonding the light extraction member with the construction part of the organic electroluminescence display device . The organic compound thin film may have a hole injection layer, a hole transporting layer, an electron injection layer, an electron transporting layer, a protective layer and the like, and these layers each may have other functions. For the formation of each layer, various materials can be used. - Anode -
The anode supplies holes to the hole injection layer, hole transporting layer, light emitting layer or the like. The material of the anode is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include a metal, an alloy, a metal oxide, an electrically conductive compound, and a mixture thereof. The material preferably has a work function of 4 eV or more. Specific examples thereof include an electrically conductive metal oxide such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), a metal such as gold, silver, chromium and nickel, a mixture or laminate of such a metal and such an electrically conductive metal oxide, an inorganic electrically conductive substance such as copper iodide and copper sulfide, an organic electrically conductive material such as polyaniline, polythiophene and polypyrrole, and a laminate of such a material with ITO. An electrically conductive metal oxide is preferred, and ITO is more preferred in view of productivity, high electrical conductivity, transparency and the like. The thickness of the anode is not particularly limited and may be suitably selected in accordance with the intended use, and may be suitably selected in accordance with the intended use. The thickness is, however, preferably from 10 nm to 5 μm, more preferably from 50 nm to 1 μm, particularly preferably from 100 nm to 500 nm.
The anode is not particularly limited and may be suitably selected in accordance with the intended use. For example, there may be exemplified a layer formed on soda lime glass, alkali-free glass, a transparent resin substrate or the like. In the case of using glass, the material thereof is preferably alkali-free glass so as to reduce the ion eluted out from the glass. In the case of using soda lime glass, this is preferably used after applying thereto a barrier coat such as silica. The thickness of the substrate is not particularly limited as long as it is sufficiently thick to maintain the mechanical strength. In the case of using glass, the thickness of the glass is not particularly limited as long as it is 0.2 mm or more, and may be suitably selected in accordance with the intended use. A glass having a thickness of 0.7 mm or more is preferred.
A barrier film may also be used as the transparent resin substrate. The barrier film is a film produced by providing a gas-impermeable barrier layer on a plastic support. Examples of the barrier film include those where silicon oxide or aluminum oxide is vapor-deposited (see Japanese Patent Application Publication (JP-B) No. 53- 12953 and Japanese Patent Application Laid-Open (JP-A) No. 58-217344), an organic-inorganic hybrid coating layer is provided (see JP-A Nos. 2000- 323273 and 2004-25732), an inorganic layered compound is provided (see JP-A No. 2001 -205743), an inorganic material is stacked (see, JP-A Nos. 2003-206361 and 2006-263989), an organic layer and an inorganic layer are alternately stacked (see JP-A No. 2007- 30387, U.S. Patent No. 6413645, and Affinito et al. , Thin
Solid Films, pp . 290-291 (1996)), or an organic layer and an inorganic layer are continuously stacked (see U.S. Patent No. 2004-46497). ' In the production of the anode, various methods are employed according to the material. For example, in the case of ITO, examples of the film formation method include an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (e.g., sol-gel method), and a method of coating an indium tin oxide dispersion. When the anode is subjected to cleaning or other treatments, this enables decreasing the driving voltage or improving the light emission efficiency of the display device. For example, in the case of ITO, a UV-ozone treatment or the like is effective. - Cathode -
The cathode supplies electrons to the electron injection layer, electron transporting layer, light emitting layer or the like, and the material therefor is selected by taking into consideration the adhesion to a layer adjacent to the negative electrode, such as electron injection layer, electron transporting layer or light-emitting layer, the ionization potential, the stability and the like. The material of the cathode is not particularly limited and may be suitably selected in accordance with the intended use . For example, a metal, an alloy, a metal oxide, an electrically conductive compound or a mixture thereof can be used. Specific examples of the material include an alkali metal (e.g., Li, Na, K) or a fluoride thereof, an alkaline earth metal (e. g. , Mg, Ca) or a fluoride thereof, gold, silver, lead, aluminum, an alloy or mixed metal of sodium and potassium, an alloy or mixed metal of lithium and aluminum, an alloy or mixed metal of magnesium and silver, and a rare earth metal such as indium and ytterbium. Among these, preferred is a material having a work function of 4 eV or less, and more preferred are aluminum, an alloy or mixed metal of lithium and aluminum, and an alloy or mixed metal of magnesium and silver. The thickness of the cathode is not particularly limited and may be suitably selected in accordance with the intended use. The thickness is, however, preferably from 10 nm to 5 μm, more preferably from 50 nm to 1 μm, still more preferably from 100 nm to 1 μm. Examples of the production method of the cathode include an electron beam method, a sputtering method, a resistance heating vapor deposition method and a coating method, and a single metal component may be vapor-deposited or two or more components may be simultaneously vapor-deposited. Furthermore, an alloy electrode may also be formed by simultaneously vapor-depositing a plurality of metals, or an alloy previously prepared may be vapor-deposited.
The sheet resistance of the anode and cathode is preferably lower, and is preferably several hundreds of Ω/square or less.
The invasion of a gas can be prevented not only by laminating the above-mentioned barrier film on the cathode but also by forming a protective layer on the display surface . - Light Emitting Layer -
The material for the light emitting layer is not particularly limited and may be any material as long as it can form a layer having functions to receive, at the time of electric field application, holes from the anode, hole injecting layer or hole transporting layer, and to receive electrons from the cathode, electron injection layer or electron transporting layer, and offer the field of recombination of holes and electrons to emit light. Examples thereof include various metal complexes as typified by a metal complex or rare earth complex of benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perynone derivatives, oxadiazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidine compound or 8-quinolinol derivatives! and a polymer compound such as polythiophene, polyphenylene and polyphenylenevinylene.
The thickness of the light emitting layer is not particularly limited and may be suitably selected in accordance with the intended use. The thickness is, however, preferably from 1 nm to 5 μm, more preferably from 5 nm to 1 μm, still more preferably from 10 nm to 500 nm.
The method of forming the light emitting layer is not particularly limited, and may be suitably selected in accordance with the intended use. Examples of the method include a resistance heating vapor deposition method, an electron beam method, a sputtering method, a molecular lamination method, a coating method (e. g. , spin coating, casting, dip coating) and a LB method. Among these, resistance heating vapor deposition method and coating method are preferred. The details on the hole transporting layer, electron transporting layer, hole injection layer, electron injection layer, a charge blocking layer etc. and a driving method of the organic electroluminescence display element composed of these layers are not particularly limited and may be suitably selected in accordance with the intended use. Those described, for example, in Japanese Patent Application Laid-Open (JP-A) Nos. 2009-016184, 2009-016579, and 2009-031750 can be used. - Attaching Method of Light Extraction Member ■
As a method of providing a light extraction member of the present invention in an organic electroluminescence display device, there may be exemplified an embodiment where an optical member (light diffusion film) is attached, via an adhesion layer, on an upper electrode or a barrier layer which has been provided over an upper electrode. - - Adhesion Layer ■ ■ The refractive index of the adhesion layer formed of an adhesive is not particularly limited and may be suitably selected in accordance with the intended use . It is, however, preferably equal to or greater than that of the organic layer including the light emitting layer. If the refractive index is excessively large, the efficiency decreases due to reflection at the interface. Therefore, the difference in the refractive index from the organic layer is preferably 0.2 or less. In other words, the refractive index of the adhesion layer is preferably 1.5 to 1.9, more preferably from 1.6 to 1.9, particularly preferably from 1.65 to 1.9, in that an amount of total reflection in an organic EL emitting layer is reduced to one half or less. As another method for suppressing reflection at the interface, there may be used a method of creating a refractive index gradation in the adhesion layer to allow for bonding of the adhesive and the material at both ends of the adhesive without discontinuity in the refractive index.
The adhesive is preferably an adhesive which flows under heating or pressure, more preferably an adhesive which exhibits flowability under heating at 2000C or lower or under pressure of 1 kgf/cm2 or more. By using such an adhesive, the light extraction film (color filter) of the present invention can be attached to an adherend, that is, a display or plastic plate, by fluidizing the adhesive. The adhesive can be fluidized, so that the light extraction member (color filter) can be easily attached to an adherend by lamination or pressing, particularly pressing, or even to an adherend having a curved surface or a complicated shape. To this end, the softening point of the adhesive is preferably 2000C or lower. The softening point of the adhesion layer is preferably 8O0C or more, and in view of the processability, it is more preferably 800C to 1200C. The softening point indicates a temperature at which the viscosity thereof becomes 1012 poises or less (lθ13 Pa s or less), and the adhesive is usually fluidized within a time of from approximately 1 second to approximately 10 seconds at the above-described temperature.
As the adhesive which flows under heating or pressure, for example, thermoplastic resins are exemplified. The thermoplastic resin is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include natural rubber (refractive index n= 1.52), (di)enes such as polyisoprene
(n= 1.52l), poly l, 2-butadiene (n= 1.50), polyisobutene (n=1.505 to 1.51), polybutene (n= 1.513), poly-2-heptyM, 3 -butadiene (n= 1.50), poly-2-tert-butyl- l,3-butadiene (n=1.506) and poly- l, 3"butadiene (n= 1.515), polyethers such as polyoxyethylene (n= 1.456), polyoxypropylene (n= 1.450), polyvinyl ethyl ether (n= 1.454) , polyvinyl hexyl ether (n=1.459) and polyvinyl butyl ether (n=1.456), polyesters such as polyvinyl acetate (n= 1.467) and 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), and poly(meth)acrylic acid esters such as polyethyl acrylate (n= 1.469), polybutyl acrylate (n=1.466), poly-2-ethylhexyl acrylate (n= 1.463), poly-tert-butyl acrylate (n= 1.464), poly-3-ethoxypropyl acrylate (n=1.465), polyoxycarbonyl tetramethylene (n=1.465), polymethyl acrylate (n=1.472 to 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=l. 484), polyethyl methacrylate (n=1.485), poly-2-nitro-2-methylpropyl methacrylate (n= 1.487), poly l. l-diethylpropyl methacrylate (n= 1.489) and polymethyl methacrylate (n= 1.489). Two or more of these acrylic polymers may be copolymerized or blended, if desired. Furthermore, a copolymerized resin of an acrylic resin with a polymer other than acryl, such as epoxy acrylate (n=1.48 to 1.60), urethane acrylate (n= 1.5 to 1.6), polyether acrylate (n=1.48 to 1.49) and polyester acrylate (n=1.48 to 1.54), may also be used. Above all, urethane acrylate, epoxy acrylate and polyether acrylate are excellent in view of adhesive property. Examples of the epoxy acrylate include (meth)acrylic acid adducts of 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol tetraglycidyl ether. A polymer having a hydroxyl group within its molecule, such as epoxy acrylate, is effective in enhancing the adhesion property. These copolymerized resins may be used in combination, if desired. The softening point of the polymer becoming an adhesive is, in view of handleability, preferably 2000C or lower, more preferably 1500C or lower. In light of usage of the display device, the use environment is usually at 800C or lower and therefore, the softening point of the adhesion layer is particularly preferably from 800C to 12O0C in view of the processability. Meanwhile, the mass average molecular weight (a mass average molecular weight measured using a calibration curve of standard polystyrene by gel permeation chromatography; hereinafter the same) of the polymer used is preferably 500 or more. When the molecular weight is 500 or more, the cohesive force of the adhesive composition is sufficiently brought out and the adhesion to an adherend can be unfailingly obtained. In the adhesive for use in the present invention, additives such as diluent, plasticizer, antioxidant, filler, colorant, ultraviolet absorbent and tackifier may be blended, if desired. The thickness of the adhesion layer is not particularly limited and may be suitably selected in accordance with the intended use. It is, however, preferably, in dry film thickness, 10 μm to 100 μm, more preferably 10 μm to 80 μm, particularly preferably 10 μm to 50 μm. When the thickness is less than 10 μm, it may result in insufficient adhesion. When it is more than 100 μm, the adhesive tends to stick out of the outer periphery of the light extraction member, resulting in a troublesome adhesion process.
The material of the adhesive is not particularly limited and may be suitably selected in accordance with the intended use. As for the material of the adhesive, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, tetrahydroxy-phenylmethane-type epoxy resin, novolak'type epoxy resin, resorcin-type epoxy resin, polyalcohol.polyglycol-type epoxy resin, polyolefin-type epoxy resin, and epoxy resin such as alicyclic or halogenated bisphenol, may be used (all have a refractive index of 1.55 to 1.60) . Examples of the material other than epoxy resin include natural rubber (n=1.52), (di)enes such as polyisoprene (n=1.52l), poly l, 2-butadiene (n= 1.50), polyisobutene (n= 1.505 to 1.51), polybutene (n= 1.5125), poly-2-heptyl- l, 3-butadiene (n=1.50), poly2-tert-butyl- l, 3"butadiene (n= 1.506) and poly- l, 3-butadiene (n= 1.515), polyethers such as polyoxyethylene (n=1.4563), polyoxypropylene (n=1.4495), polyvinyl ethyl ether (n=1.454), polyvinyl hexyl ether (n= 1.459 l) and polyvinyl butyl ether (n= 1.4563), polyesters such as polyvinyl acetate (n= 1.4665) and polyvinyl propionate (n= 1.4665), 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), and phenoxy resin (n=1.5 to 1.6). These materials have a suitable visible light transmittance. Besides the above resins, there may be used poly(meth)acrylic acid esters such as polyethyl acrylate (n= 1.4685), polybutyl acrylate (n= 1.466), poly-2-ethylhexyl acrylate (n= 1.463), polytert-butyl acrylate (n=1.4638), poly-3-ethoxypropyl acrylate (n=1.465), polyoxycarbonyl tetramethacrylate (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), polyn-propyl methacrylate (n=1.484), poly3,3, 5-trimethylcyclohexyl methacrylate (n= 1.484), polyethyl methacrylate (n=1.485), poly-2-nitro-2-methylpropyl methacrylate (n= 1.4868), polytetracarbanyl methacrylate (n= 1.4889) , poly l, l-diethylpropyl methacrylate (n= 1.4889) and polymethyl methacrylate (n=1.4893) . Two or more of these acrylic polymers may be copolymerized or blended, if desired.
Furthermore, a copolymerized resin of an acrylic resin with a polymer other than acryl, such as epoxy acrylate, urethane acrylate, polyether acrylate and polyester acrylate, may also be used. Above all, epoxy acrylate and polyether acrylate are excellent in view of adhesion property.
The epoxy acrylate is not particularly limited and may be suitably selected in accordance with the intended use. Examples of the epoxy acrylate include (meth)acrylic acid adducts of 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, allyl alcohol diglycidyl ether, resorcinol diglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol tetraglycidyl ether. The epoxy acrylate has a hydroxyl group within its molecule and therefore, is effective in enhancing the adhesion property. These copolymerized resins may be used in combination, if desired. The mass average molecular weight of the polymer used to become the main component of the adhesive is 1,000 or more. When the molecular weight is 1,000 or more, the cohesive force of the composition is sufficiently brought out and the adhesion to an adherend can be unfailingly obtained.
In addition to these materials, the adhesive may contain, for example, a monomer having a high refractive index and/or a metal oxide ultrafine particle having a high refractive index.
The monomer having a high refractive index is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include bis(4-methacryloylthiophenyl)sulfide, vinylnaphthalene, vinylphenyl sulfide and 4-methacryloxyphenyl-4'-methoxyphenyl thioether.
A curing agent (crosslinking agent) may also be used in the adhesive, and examples of the crosslinking agent which can be used include amines such as triethylenetetramine, xylenediamine and diaminodiphenylmethane, acid anhydrides such as phthalic anhydride, maleic anhydride, dodecylsuccinic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic anhydride, diaminodiphenylsulfone, tris(dimethylaminomethyl)phenol, polyamide resin, dicyandiamide, and ethylmethylimidazole. These crosslinking agents may be used alone or in combination. The amount of the crosslinking agent added is 0.1 parts by mass to 50 parts by mass, preferably 1 part by mass to 30 parts by mass, based on 100 parts by mass of the above-described polymer. If the amount added is less than 0.1 parts by mass, the curing becomes insufficient, whereas if it exceeds 50 parts by mass, excessive crosslinking results adversely affects the adhesion property. In the resin composition of the adhesive for use in the present invention, additives such as diluent, plasticizer, antioxidant, filler, colorant and tackifier may be blended, if desired. The resin composition of the adhesive is applied to partially or entirely cover the substrate of a constituent material where a geometric pattern drawn with an electrically conductive material is provided on the surface of a transparent plastic substrate, and through drying of the solvent and curing under heating, the adhesive film according to the present invention is obtained. This adhesive film having electromagnetic wave shielding property and transparency is directly attached to a display such as CRT, PDP, liquid crystal and EL by the adhesive of the adhesive film, or attached to a plate or sheet such as acrylic plate or glass plate and then used for a display.
The adhesive is preferably transparent. Specifically, the total light transmittance is preferably 70% or higher, more preferably 80% or higher, and particularly preferably from 85% to 92%.
Furthermore, the adhesive preferably has a low haze level. Specifically, the haze level is preferably from 0% to 3%, more preferably from 0% to 1.5%. The adhesive for use in the present invention is preferably colorless so as not to change the display color inherent in the display. However, even if the resin itself is colored, when the thickness of the adhesive is thin, the adhesive can be regarded as being substantially colorless.
The adhesive having the above-described properties is not particularly limited and may be suitably selected in accordance with the intended use. Examples thereof include acrylic resins, crolefin resins, vinyl acetate-based resins, acrylic copolymer-based resins, urethane-based resins, epoxybased resins, vinylidene chloride-based resins, vinyl chloride-based resins, ethylene-vinyl acetate-based resins, polyamide-based resins and polyester-based resins. Among these, acrylic resins are preferred. Even when the same resin is used, the self-adhesion property can be enhanced by such a method as that, at the synthesis of the adhesive by a polymerization method, the amount of the crosslinking agent added is decreased, a tackifier is added, or the terminal group of the molecule is changed. Also, even with the use of the same adhesive, the adhesion can be enhanced by modifying the surface to which the adhesive is to be adhered, that is, by applying surface modification to the transparent plastic film or glass plate. Examples of the surface modification method include a physical method such as corona discharge treatment and plasma glow treatment, and a method of forming an underlying layer for enhancing the adhesion.
The thickness of the adhesive is not particularly limited and may be suitably selected in accordance with the intended use. In view of transparency, colorlessness and handleability, the thickness of the adhesive is, however, preferably about 1 μm to about 50 μm, more preferably about 1 μm to 20 μm. In the case where a change in the display color of the display itself is not caused and the transparency is in the range above, the thickness of the adhesive may exceed the above-described range.
Examples Hereinafter, the present invention will be further described in detail with reference to Examples and Comparative Examples, however, the present invention shall not be construed as being limited thereto. (Example l) - Preparation of Fine Particle Dispersion for Light Extraction Member ■
A titanium oxide fine particle (333 parts by mass) (titania fine particle (Tiθ2), mass average particle diameter (average diameter) : 280 nm, refractive index: 2.54, R-580: produced by Ishihara Sangyo K. K.) as an inorganic oxide fine particle, 30 parts by mass of
3-glycidylpropyltrimethoxysilane as a surface modifier, 1.5 parts by mass of diisopropoxy ethyl acetate aluminum as a reaction catalyst were mixed. After these components were mixed, 9 parts of ion exchanged water were added to the mixture. The mixture was subjected to a reaction at 6O0C for 8 hours, cooled to the room temperature, and 1.8 parts of acetyl acetone were added to the reaction mixture to thereby prepare a fine particle dispersion for light extraction member of Example 1. - Preparation of Coating Composition -
Components described below were added based on the following composition, and mixed uniformly to prepare a coating composition of Example 1.
• benzyl methacrylate/methacrylic acid copolymer ...80 parts by mass (organic polymer: molecular weight 30,000, acid value 120 mgKOH/g)
• dipentaerythritol hexaacrylate (DPHA) binder resin 80 parts by mass
• fine particle dispersion for light extraction member of Example 1 60 parts by mass
• propylene glycol monomethyl ether acetate (solvent) 1,000 parts by mass - Production of Light Extraction Member -
The coating composition of Example 1 was filtrated through a filter with a pore size of 5 μm, the filtered coating composition was applied onto a glass substrate for use in preparation of a color filter by a spin coater so as to have a dry film thickness of 1.0 μm, and dried at 2200C for 60 minutes, thereby producing a light extraction member of Example 1 on the glass substrate .
(Example 2)
■ Preparation of Fine Particle Dispersion for Light Extraction
Member - A fine particle dispersion for light extraction member of
Example 2 was prepared in the same manner as in Example 1, except that 30 parts by mass of acryloyloxypropyltrimethoxysilane were used as a surface modifier instead of 30 parts by mass of 3-glycidylpropyltrimethoxysilane.
- Preparation of Coating Composition and Production of Light Extraction Member -
A coating composition of Example 2 was prepared and a light extraction member of Example 2 was produced in the same manner as in Example 1, except that the fine particle dispersion for light extraction member of Example 2 was used instead of using the fine particle dispersion for light extraction member of Example 1. (Example 3)
■ Preparation of Fine Particle Dispersion for Light Extraction Member -
A fine particle dispersion for light extraction member of Example 3 was prepared in the same manner as in Example 1, except that 30 parts by mass of acryloyloxypropyl trimethoxysilane were used as a surface modifier instead of 30 parts by mass of 3-glycidylpropyltrimethoxysilane; 3 parts by mass of IN nitric acid were used as a catalyst instead of 1.5 parts by mass of diisopropoxy ethyl acetate aluminum; the addition amount of ion exchanged water was changed from 9 parts by mass to 1 part by mass; the reaction condition was changed from 600C for 8 hours to 400C for 8 hours; and 8.3 parts of ion exchanged water were used instead of 1.8 parts by mass of acetylacetone. - Preparation of Coating Composition and Production of Light Extraction Member - A coating composition of Example 3 was prepared and a light extraction member of Example 3 was produced in the same manner as in Example 1, except that the fine particle dispersion for light extraction member of Example 3 was used instead of using the fine particle dispersion for light extraction member of Example 1. (Example 4)
- Preparation of Fine Particle Dispersion for Light Extraction Member -
A fine particle dispersion for light extraction member of Example 4 was prepared in the same manner as in Example 1 , except that 333 parts of a zirconium oxide fine particle (Zrθ2, mass average particle diameter (average diameter) : 440 nm, refractive index: 2.15, UEP zirconia oxide: produced by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) were used as an inorganic oxide fine particle instead of 333 parts by mass of the titanium oxide fine particle.
- Preparation of Coating Composition and Production of Light Extraction Member -
A coating composition of Example 4 was prepared and a light extraction member of Example 4 was produced in the same manner as in Example 1, except that the fine particle dispersion for light extraction member of Example 4 was used instead of using the fine particle dispersion for light extraction member of Example 1. (Example 5)
- Preparation of Fine Particle Dispersion for Light Extraction Member -
A fine particle dispersion for light extraction member of Example 5 was prepared in the same manner as in Example 1, except that 333 parts by mass of a zinc oxide fine particle (ZnO, mass average particle diameter- 600 nm, refractive index- 1.9 to 2.0) produced by Sakai Chemical Industry Co., Ltd.) were used as an inorganic oxide fine particle instead of 333 parts by mass of the titanium oxide fine particle.
- Preparation of Coating Composition and Production of Light Extraction Member -
A coating composition of Example 5 was prepared and a light extraction member of Example 5 was produced in the same manner as in Example 1, except that the fine particle dispersion for light extraction member of Example 5 was used instead of using the fine particle dispersion for light extraction member of Example 1. (Example 6) - Preparation of Coating Composition -
A coating composition of Example 6 was prepared in the same manner as in Example 1, except that a benzyl methacrylate/methacrylic acid copolymer (molecular weight: 35,000, acid value : 150 mgKOH/g) was used as an organic polymer instead of the benzyl methacrylate/methacrylic acid copolymer (molecular weight: 30,000, acid value : 120 mgKOH/g). ■ Production of Light Extraction Member -
A light extraction member of Example 6 was produced in the same manner as in Example 1, except that the coating composition of Example 6 was used instead of the coating composition of Example 1. (Example 7) - Preparation of Coating Composition -
A coating composition of Example 7 was prepared in the same manner as in Example 1, except that the addition amount of the fine particle dispersion for light extraction member of Example 1 was changed from 60 parts by mass to 15 parts by mass.
- Production of Light Extraction Member -
A light extraction member of Example 7 was produced in the same manner as in Example 1, except that the coating composition of Example 7 was used instead of the coating composition of Example 1. (Example 8)
■ Preparation of Coating Composition -
A coating composition of Example 8 was prepared in the same manner as in Example 1, except that the addition amount of the fine particle dispersion for light extraction member of Example 1 was changed from 60 parts by mass to 8 parts by mass.
- Production of Light Extraction Member -
A light extraction member of Example 8 was produced in the same manner as in Example 1, except that the coating composition of Example 8 was used instead of the coating composition of Example 1. (Example 9)
- Preparation of Coating Composition -
A coating composition of Example 9 was prepared in the same manner as in Example 1, except that the acid value of the benzyl methacrylate/methacrylic acid copolymer was changed from 120 mgKOH/g to 50 mgKOH/g.
■ Production of Light Extraction Member - A light extraction member of Example 9 was produced in the same manner as in Example 1, except that the coating composition of Example 9 was used instead of the coating composition of Example 1. (Comparative Example l) - Preparation of Fine Particle Dispersion for Light Extraction Member -
A fine particle dispersion for light extraction member of Comparative Example 1 was prepared in the same manner as in Example 1, except that 333 parts by mass of a titanium oxide fine particle (titania fine particle (Tiθ2), particle diameter (average diameter) : 30 nm, TTO- 51 (A) : produced by Ishihara Sangyo K. K.) were used as an inorganic oxide fine particle, instead of 333 parts by mass of the titanium oxide fine particle (titania fine particle (Tiθ2), mass average particle diameter (average diameter) : 280 nm, refractive index: 2.54, R- 580: produced by Ishihara Sangyo K. K.) . (Comparative Example 2)
- Preparation of Coating Composition and Production of Light Extraction Member ■
Components described below were added based on the following composition, and mixed uniformly to prepare a coating composition of Example 1.
• benzyl methacrylate/methacrylic acid copolymer ...80 parts by mass (organic polymer: molecular weight 30,000, acid value 120 mgKOH/g) • dipentaerythritol hexaacrylate (DPHA) binder resin 80 parts by mass • inorganic oxide fine particle- titanium oxide fine particle (titania fine particle (Tiθ2), mass average particle diameter (average diameter)- 280 nm, refractive index- 2.54, R-580- produced by
Ishihara Sangyo K. K.) 54 parts by mass • propylene glycol monomethyl ether acetate (solvent) 1,000 parts by mass
- Production of Light Extraction Member -
The coating composition was filtrated through a filter with a pore size of 5 μm, the filtered coating composition was applied onto a glass substrate for use in preparation of a color filter by a spin coater so as to have a dry film thickness of 1.0 μm, and dried at 2200C for 60 minutes, thereby producing a light extraction member of Comparative Example 2 on the glass substrate. (Comparative Example 3) - Preparation of Coating Composition -
A coating composition of Comparative Example 3 was prepared in the same manner as in Example 1, except that the fine particle dispersion for light extraction member was not added.
- Production of Light Extraction Member ■ A coating composition of Comparative Example 3 was prepared in the same manner as in Example 1, except that the coating composition of Comparative Example 3 was used instead of the coating composition of Example 1. (Evaluation Method of Light Extraction Efficiency) ■ Production of Organic Electroluminescence Display Device ■
On a fine-particle-containing layer that had been formed on a glass substrate, ITO was deposited by vacuum evaporation so as to form an ITO electrode (anode) having a thickness of 100 nm.
Further, on the ITO electrode (anode), organic compound layers (a hole injection layer, a hole transporting layer, a light emitting layer, and an electron injection layer) were formed in this order. First, the hole injection layer was formed by depositing 2-TNATA [4,4',4"-tris(2-naphthylphenylamino)triphenylamine] so as to have a thickness of 50 nm. Further, on the hole injection layer, the hole transporting layer wad formed by depositing crNPD [N,N'-(dinaphthylphenylamino)pyrene] so as to have a thickness of 50 nm. Furthermore, on the hole transporting layer, the light emitting layer was formed by depositing Alq3 [8-quinolinol-aluminum complex] so as to have a thickness of 50 nm. Finally, on the light emitting layer, the electron injection layer was formed by depositing a pyridine derivative so as to have a thickness of 25 nm (average refractive index of the organic compound layers: 1.80) .
Thereafter, as a reflective cathode, Al was formed by vacuum evaporation so as to have a thickness of 100 nm.
Further, the thus formed laminate was glass sealed in presence of nitrogen, thereby producing a bottom emission type organic electroluminescence display device. ■ Measurement and Evaluation of Light Extraction Efficiency -
With each of the light extraction members of Examples 1 to 9 and Comparative Examples 1 to 3 being disposed on the organic electroluminescence display device, the organic electroluminescence display device was caused to emit light. Using an integrating sphere device that had been attached to the organic electroluminescence display device, the overall amount of light emitted outside the integrating sphere device was measured.
The light extraction members of Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated for the light extraction efficiency, taking, as a standard of comparison (l.O), the light extraction member of Comparative Example 3 containing no surface-modified fine particle . The results are shown in the Table 1 below. - Durability Test -
Deterioration due to heat cycle of each of the light extraction members was measured through the following durability test.
Specifically, the light extraction members of Examples 1 to 9 and Comparative Examples 1 to 3 were left standing at a temperature of 80°C for 20 hours, and thereafter, left standing at room temperature for 4 hours. This procedure was taken as one cycle, and the cycle was repeated 3 times.
The amount of light extraction of each of the light extraction members that had undergone the durability test was measured according to the method described above in the measurement and evaluation of light extraction efficiency, regarding the amount of light extraction measured by the integrating sphere device as the overall amount of light emitted. Using the amount of light extraction measured before the durability test as the standard comparison (1.0), an amount of light extraction after the durability test was determined by conversion calculation. Then, the amount of light extraction after the durability test, i.e, the value changed (decreased) from the amount of light extraction measured before the durability test was used for the evaluation. The results are shown in Table 1 below.
Table 1
to
Figure imgf000070_0001
(Example 10)
< Production of Color Filter >
First, composition solutions in three colors (green, red, and blue) were prepared based on each of the following compositions, followed by dispersion treatment by a sand mill for 24 hours.
(Green color)
• benzyl methacrylate/methacrylic acid copolymer ...80 parts by mass (molecular weight: 30,000, acid value : 120 mgKOH/g)
• propylene glycol monomethyl ether acetate 500 parts by mass - copper phthalocyanine pigment 33 parts by mass
• C.I. Pigment Yellow 185 67 parts by mass
(Red color)
• benzyl methacrylate/methacrylic acid copolymer .... 80 parts by mass (molecular weight: 30,000, acid value : 120 mgKOH/g) - propylene glycol monomethyl ether acetate 500 parts by mass
• C.I. Pigment Red 254 50 parts by mass
• C.I. Pigment Red PR177 50 parts by mass
(Blue color)
• benzyl methacrylate/methacrylic acid copolymer .... 80 parts by mass (molecular weight: 30,000, acid value : 120 mgKOH/g)
• propylene glycol monomethyl ether acetate 500 parts by mass
• C.I. Pigment Blue 15:6 95 parts by mass
• C.I. Pigment Violet 23 5 parts by mass
Next, the following components were added to each of the above composition solutions.
• dipentaerythritol hexaacrylate (DPHA) 80 parts by mass • fine particle dispersion for light extraction member of Example 1 60 parts by mass
• 4- [o-bromo-p -N,N-di(ethoxycarbonyl)aminophenyl]2, 6-di(trichloromethyl) -S-triazine 5 parts by mass • 7- [{4-chloro-6-(diethylamino) -S-triazin-2-yl}amino] -3- phenylcoumarin 2 parts by mass
• hydroquinone monomethyl ether 0.01 parts by mass
• propylene glycol monomethyl ether acetate 500 parts by mass
The above-mentioned composition solutions in three colors were individually, uniformly mixed, and then were individually filtrated through a filter with a pore size of 5 μm to thereby prepare coating compositions (in green, red and blue colors) of Example 10.
Among these coating compositions, the coating composition in green color was applied onto a glass substrate for use in preparation of a color filter by a spin coater so as to have a dry film thickness of 1.0 μm, dried at 12O0C for 2 minutes, and thus a uniform coat film in green color was formed, thereby producing a light extraction member of Example 10 on the glass substrate .
Next, the thus formed coat film of the light extraction member was exposed to light having a wavelength of 365 nm via a mask of 100 μm in thickness by an exposing device at an exposure dose of 300 mJ/cm2. After the exposure, the coat film was developed using a 10% CD- I (Fujifilm Electronics Co. , Ltd.) developer at 26°C for 60 seconds. Subsequently, the light extraction member was rinsed under running water for 20 seconds, dried at 2200C for 60 minutes to thereby form a green-color pattern image (green pixel). The same procedure was applied for the red-color and blue-color coating compositions, on the above-mentioned glass substrate so as to form a red-color pattern image (red pixel) and a blue-color pattern image (blue pixel) in this order on the glass substrate, thereby obtaining a color filter of Example 10. The refractive indices of the green pixel, red pixel and blue pixel (the surface-modified fine particle in the coating compositions) being transmissive to light were measured at wavelengths 550 nm, 630 nm, and 450 nm respectively, and found to be 1.80 (green pixel), 1.78 (red pixel) and 1.82 (blue pixel). << Production of Multi- Color Organic Electroluminescence Display Device »
Next, a production example of an organic electroluminescence display device will be described using FIG. 2. The construction of the display device is a top emission type. First, a TFT substrate 110 was formed as follows. Specifically, a TFT was formed, via a buffer layer, on an insulating substrate. Next, an interlayer-insulating-film layer formed of an SiN film was deposited on the entire surface of the TFT, and then contact holes each reaching a source region and a drain region were formed through a common photo-etching process.
Next, an Al/Ti/Al multilayer-structured conductive layer was deposited on the entire surface of the TFT, followed by patterning through a common photo-etching process, so that a source electrode and a drain electrode reaching to the TFT section were formed. Note that the source electrode was branched from a common source light into four branched lines. Next, a photosensitive resin was applied over the entire surface of the laminate by spin coating to form an inter-layer-insulating film. The inter-layer-insulating film was exposed to light via a mask, and then developed with a predetermined developer to form contact holes corresponding to each of the branched lines of the source electrode, thereby forming a TFT substrate 110 composed of the above-mentioned layers.
Next, an Al film was deposited on the entire surface of the TFT substrate 110 by sputtering, followed by patterning through photo-etching so as to be in a desired shape, thereby forming a divided lower electrodes (lower electrodes 120) each connecting, through each of the contact holes, to the branched lines of the source electrode.
Next, an organic light emitting layer 130 for covering the divided lower electrodes (lower electrodes 120), which were exposed at the bottom of pixel opening portions, was formed by mask vapor deposition. Subsequently, an Al film for covering the organic light emitting layer 130 and having a thickness of 10 nm and an ITO film having a thickness of 30 nm were deposited in this order using mask vapor deposition again to form a common upper electrode (upper electrode 140) . Each region corresponding to each of the divided lower electrodes (lower electrode 120) is a divided pixel part.
Next, an SiN film and an SiON film were deposited over the entire surface of the laminate in this order by a CVD (chemical vapor deposition) method to form a barrier layer 150 of 5 μm in thickness. Further, the adhesive was applied, in a thickness of 10 μm, onto the barrier layer 150 to provide an adhesion layer 180 thereon, and the color filter (light diffusion layer 30) of Example 10 was attached on the adhesion layer 180, thereby producing a multi-color organic electroluminescence display device.
Industrial Applicability
The fine particle dispersion for light extraction member of the present invention is capable of improving the light extraction efficiency and suppressing deterioration of a light extraction member due to the heat cycle, and thus it is suitably used for light extraction members such as color filters.
Reference Signs List
1 light extraction member 20 transparent substrate provided with a barrier layer
30 light diffusion layer
31 matrix material
41 surface -modified fine particle
42 colorant 100 organic electroluminescence display device
110 TFT substrate
120 lower electrode
130 organic electroluminescence layer
140 upper electrode 150 barrier layer
180 adhesion layer

Claims

1. A fine particle dispersion for light extraction member, the fine particle dispersion comprising: a surface-modified fine particle, and a dispersion medium, the surface-modified fine particle being dispersed in the dispersion medium, wherein the surface-modified fine particle comprises an inorganic oxide fine particle having a mass average particle diameter greater than 100 nm and a surface modifier containing one of a hydrolysate obtained by hydrolysis of an organosilane compound represented by General Formula (l) below and a partial condensate obtained by partial condensation of the organosilane compound, and the surface of the inorganic oxide fine particle is covered with the surface modifier,
(R1)m - Si -(X)4_m
General Formula (l) where, R1 represents any one of an oxygen-containing 3- or 4-membered condensed ring compound, an alkyl group substituted with a substituent containing an unsaturated bond, and an aryl group substituted with a substituent containing an unsaturated bond," X represents one of a hydroxyl group and a hydrolyzable group ; and m represents an integer of 1 to 3.
2. The fine particle dispersion according to claim 1, wherein the inorganic oxide fine particle has a mass average particle diameter of 1,000 nm or smaller.
3. The fine particle dispersion according to one of claims 1 and 2, wherein the inorganic oxide fine particle contains at least one selected from Zrθ2, Tiθ2 and ZnO .
4. The fine particle dispersion according to any one of claims 1 to 3, wherein the inorganic oxide fine particle has a refractive index of
2.1 to 4.0.
5. The fine particle dispersion according to any one of claims 1 to 4, wherein R1 is the oxygen-containing 3- or 4-membered condensed ring compound. 6. A coating composition comprising: the fine particle dispersion for light extraction member according to any one of claims 1 to 5, an organic polymer, and a binder resin. 7. The coating composition according to claim 6, wherein the organic polymer has an acid value of 120 mgKOH/g to 200 mgKOH/g.
8. The coating composition according to one of claims 6 and 7, wherein the inorganic oxide fine particle is contained in an amount of 5% by mass to 25% by mass relative to the total solid content of the coating composition.
9. A light extraction member comprising: the coating composition according to any one of claims 6 to 8.
10. The light extraction member according to claim 9, wherein the light extraction member is used as a color filter. 11. An organic electroluminescence display device comprising: the light extraction member according to one of claims 9 and
10.
12. The organic electroluminescence display device according to claim 11, further comprising an adhesion layer, wherein the adhesion layer has a refractive index of 1.5 to 1.9. 13. The organic electroluminescence display device according to claim 12, wherein the adhesion layer has a thickness of 10 μm to 100 μm.
PCT/JP2010/056488 2009-04-22 2010-04-05 Fine particle dispersion for light extraction member, coating composition, light extraction member, and organic electroluminescence display device WO2010122913A1 (en)

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