Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/006—Preparation of organic pigments
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0084—Dispersions of dyes
  • C09B67/0085—Non common dispersing agents
  • C09B67/009—Non common dispersing agents polymeric dispersing agent
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/41—Organic pigments; Organic dyes
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/02—Diffusing elements; Afocal elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/851—Wavelength conversion means
  • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
  • H10H20/8512—Wavelength conversion materials

Definitions

• the present invention relates to a composition for forming a wavelength conversion film for displays, and more specifically, to a composition for forming a wavelength conversion film for displays that is suitably used for various displays such as liquid crystal displays, organic EL displays and micro LED displays.
• Micro LED displays are expected to be next-generation displays following liquid crystal displays and organic EL displays because they are capable of high contrast and high brightness, and have a wide range of applications such as large screens and transparent displays.
• a micro LED display usually has a micro LED chip in each pixel.
• As a method of arranging this LED chip there is an RGB-LED method in which LEDs of three colors are mounted.
• a wavelength conversion method that can solve this problem is attracting attention. In the wavelength conversion method, only a blue LED chip is used and red and green lights are extracted by a wavelength conversion material, and there is an advantage that the three primary colors can be produced using only the blue LED chip.
• Patent Document 3 Those using derivatives (Patent Document 3, etc.), those using rhodamine derivatives (Patent Document 4), and those using pyrromethene derivatives (Patent Documents 5 and 6, etc.) are disclosed.
• wavelength conversion materials are generally required to have properties such as good wavelength conversion efficiency, color purity and light resistance.
• a composition containing a binder resin made of a specific methacrylic polymer, a specific fluorescent dye, and a photopolymerizable acrylic acid ester has high performance and good light resistance. It is disclosed to be a material.
• a technique of adding a light stabilizer has been disclosed in order to prevent deterioration of the organic light-emitting material and improve its durability (Patent Document 8, etc.).
• Patent Document 8 by adding fine particles to the wavelength conversion material, light scattering in the color conversion layer increases the optical path length and improves the blue light absorption rate, and at the same time, the light reflected at the interface is scattered again. is known to improve luminous efficiency (Patent Documents 9, 10, etc.).
• the composition for forming a wavelength conversion film for a display is required to further improve the wavelength conversion efficiency of the wavelength conversion material from the viewpoint of improving the performance of the display, and from the viewpoint of productivity. , further improvement of the storage stability of the composition is required.
• JP-A-2002-348568 JP 2007-273440 A Japanese Patent Application Laid-Open No. 2002-317175 Japanese Patent Application Laid-Open No. 2001-164245 JP 2011-241160 A JP 2014-136771 A JP 2006-89724 A JP 2011-149028 A WO2020/189678 WO2019/181698
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a wavelength conversion film having excellent wavelength conversion efficiency and a composition for forming a wavelength conversion film for a display having excellent storage stability. .
• the inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found a composition for forming a wavelength conversion film for a display containing titanium oxide particles having an average particle size within a specific range and having a viscosity adjusted to a specific range. found that can solve the above problems, and completed the present invention.
• the present invention provides the following composition for forming a wavelength conversion film for displays.
• A a phosphor, (B) titanium oxide particles, and (C) a binder,
• the (B) titanium oxide particles may have a surface coated with an inorganic compound and have an average particle size of more than 50 nm to less than 200 nm,
• a composition for forming a wavelength conversion film for a display which has a viscosity of 10,000 mPa ⁇ s or less at 25°C.
• 2. 1.
• composition for forming a wavelength-converting film for a display according to 1 or 2 wherein the (B) titanium oxide particles are particles whose surfaces are not coated. 4. 3. The composition for forming a wavelength conversion film for a display according to any one of 1 to 3, wherein the content of the titanium oxide particles (B) is 3 to 10% by mass based on the solid content. 5. 4. The composition for forming a wavelength conversion film for a display according to any one of 1 to 4, wherein (A) the phosphor is an organic dye. 6. 5. The composition for forming a wavelength conversion film for a display according to any one of 1 to 5, wherein the film formed from the above composition has a haze value of 18% or more.
• the present invention it is possible to provide a wavelength conversion film-forming composition for a display that provides a wavelength conversion film with excellent wavelength conversion efficiency and also has excellent storage stability.
• the composition for forming a wavelength conversion film for a display of the present invention contains (A) a phosphor, (B) titanium oxide particles, and (C) a binder, and the surface of the (B) titanium oxide particles is an inorganic compound. and has an average particle size of more than 50 nm and less than 200 nm, and a viscosity at 25° C. of 10,000 mPa ⁇ s or less. (B) When the surface of the titanium oxide particles is coated with an inorganic compound, the average particle size is the average particle size of the titanium oxide particles coated with the inorganic compound.
• solid content means components other than the solvent which comprise the composition for wavelength conversion film formation for displays.
• the (A) phosphor can be appropriately selected from conventionally known inorganic phosphors, organic dyes, semiconductor nanoparticles (quantum dots, quantum rods, etc.), etc., but it is possible to improve the definition of the display and the storage stability of the composition. from the point of view, organic dyes are preferred. In addition, in the present invention, it is preferable not to include semiconductor nanoparticles.
• organic dyes include compounds having condensed aryl rings such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene, and derivatives thereof; furan, pyrrole, thiophene, silole, 9- Compounds having a heteroaryl ring such as silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, naphthyridine, quinoxaline, and pyrrolopyridine, and their Derivatives; 1,4-distyrylbenzene, 4,4'-bis(2-(4-diphenylaminophenyl)ethen
• organic dyes among the above organic dyes, coumarin derivatives, naphthophosphoroxide derivatives, pyrromethene derivatives and perylene derivatives are preferred.
• a coumarin derivative represented by the following formula (1) is preferable.
• R 1 and R 2 each independently represent an alkyl group having 2 to 10 carbon atoms
• R 3 and R 4 each independently represent an alkyl group having 2 to 8 carbon atoms.
• R 3 and R 4 may combine with each other to form a ring with the nitrogen atom.
• the alkyl group having 2 to 10 carbon atoms may be linear, branched or cyclic, and specific examples thereof include ethyl, n-propyl, i-propyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, cyclohexylmethyl, and neopentyl groups.
• the alkyl group having 2 to 8 carbon atoms may be linear, branched or cyclic, and specific examples thereof include those having 2 to 8 carbon atoms among the alkyl groups having 2 to 10 carbon atoms.
• R 1 and R 2 is preferably a linear alkyl group and the other is preferably a branched or cyclic alkyl group, more preferably a combination of an n-hexyl group and a cyclohexylmethyl group.
• R 3 and R 4 are preferably ethyl, n-propyl, n-butyl, n-hexyl, n-octyl and 2-ethylhexyl groups, more preferably n-butyl and n-hexyl groups.
• Preferred examples of the coumarin derivative represented by formula (1) include, but are not limited to, compounds represented by the following formula (1A).
• the coumarin derivative represented by formula (1A) above can be synthesized, for example, using a known reaction as shown in the scheme below.
• a compound A-1 is synthesized by reacting it with halogenated hexane in the presence of a base in a solvent.
• the amount of halogenated cyclohexylmethane and 1-halogenated hexane to be used is preferably about 0.5 mol each per 1 mol of m-aminophenol.
• sodium carbonate, potassium carbonate, or the like can be used, and the amount thereof to be used is preferably 1 to 2 mol, more preferably about 1 to 1.5 mol, per 1 mol of m-aminophenol.
• the reaction temperature may be any temperature from room temperature to the boiling point of the solvent, preferably 50 to 100°C, more preferably 60 to 90°C.
• the reaction time is usually about 1 to 48 hours, preferably about 12 to 36 hours, more preferably about 18 to 24 hours, within the above temperature range.
• the reaction atmosphere is not particularly limited, an inert gas atmosphere such as nitrogen gas is preferable. After completion of the reaction, post-treatment is performed according to a conventional method, and purification is performed as necessary to obtain compound A-1.
• the benzene ring of compound A-1 is formylated to synthesize compound A-2.
• Formylation can be performed by any method, but the so-called Vilsmeier-Hack reaction using a dehydrating chlorinating agent such as phosphorus oxychloride or thionyl chloride and N,N-dimethylformamide (DMF) is preferred.
• a DMF solution of compound A-1 is added to a solution prepared by adding a dehydrating chlorinating agent to DMF, and after heating and stirring, water is added for hydrolysis to lead to compound A-2.
• the reaction temperature is preferably about 50-100°C, more preferably 60-80°C.
• the reaction time is usually about 1 to 24 hours, preferably 1 to 12 hours, more preferably 1 to 6 hours.
• the reaction atmosphere is not particularly limited, it may be an air atmosphere or an inert gas atmosphere such as nitrogen gas.
• the reaction temperature is preferably the temperature at which the solvent used is refluxed.
• the reaction time is generally about 1 to 12 hours, preferably about 1 to 6 hours.
• the reaction atmosphere is not particularly limited, it may be an air atmosphere or an inert gas atmosphere such as nitrogen gas.
• the fourth step for example, compound A-3 and sulfonic acid chloride are heated and reacted according to the reaction described in Dyes and Pigments, Vol. After the resulting product is washed with water, water and dibutylamine are added for further reaction to obtain the coumarin derivative represented by formula (1A).
• the amount of sulfonic acid chloride used is preferably 1.5 to 3 mol, more preferably 2 to 2.5 mol, per 1 mol of compound A-3.
• the amount of dibutylamine used is preferably 1 to 3 mol, more preferably 1.5 to 2 mol, per 1 mol of compound A-3.
• the reaction temperature in the reaction with sulfonic acid chloride is preferably 50 to 180°C, more preferably 80 to 150°C, even more preferably 100 to 140°C, and the reaction time is usually about 1 to 12 hours. About 2 to 6 hours is preferable.
• the reaction temperature in the reaction with dibutylamine is preferably 10 to 50°C, more preferably 15 to 40°C, even more preferably 20 to 30°C, and the reaction time is usually about 0.5 to 12 hours. , preferably about 1 to 4 hours.
• the reaction atmosphere is not particularly limited, it may be an air atmosphere or an inert gas atmosphere such as nitrogen gas.
• naphthophosphole oxide derivatives represented by the following formula (1B).
• a specific example of the pyrromethene derivative is a pyrromethene derivative represented by the following formula (1C).
• perylene derivative is a perylene derivative represented by the following formula (1D).
• the content of the phosphor (A) is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, more preferably 0.2% to 7% by mass, based on the solid content. 3 to 5% by mass is even more preferred.
• the (B) titanium oxide particles are blended as light scattering particles.
• the titanium oxide particles are not particularly limited, but may be appropriately selected, for example, from those conventionally used for wavelength conversion materials.
• the optical path length in the film of light entering the wavelength conversion film is extended, and the wavelength is converted inside the wavelength conversion film.
• the wavelength conversion efficiency is improved, and that light returning to the inside of the film is scattered again by reflection at the interface of the wavelength conversion film, thereby improving the light extraction efficiency.
• Both anatase-type and rutile-type titanium oxide particles can be used, but considering the ultraviolet light transmittance at 365 nm, rutile-type titanium oxide is more preferable because it has a higher transmittance.
• the titanium oxide particles may be surface-treated, but in the present invention, those not surface-treated are preferred in consideration of the storage stability of the composition.
• specific materials for surface treatment include heterogeneous inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, organosiloxanes, and organic acids such as stearic acid. be done. These surface treatment materials may be used singly or in combination.
• the average particle size of the titanium oxide particles is more than 50 nm and less than 200 nm.
• the lower limit of the average particle size is preferably 60 nm or more, more preferably 70 nm or more.
• the average particle diameter exceeding 100 nm is more preferable from the viewpoint of low total light reflectance at the i-line (365 nm).
• the upper limit of the average particle size is preferably 190 nm or less, more preferably 180 nm or less.
• the average particle size is the particle size measured by observation with a transmission electron microscope
• the dynamic light scattering particle size is the cumulative frequency distribution in the volume-based particle size distribution measurement by the dynamic light scattering method. is the particle diameter (median diameter D 50 ) at which D is 50%.
• titanium oxide particles may be used, and specific examples include PT-401M (rutile type, average particle size 70 nm), PT-401L (rutile type, average particle size 130 nm), PT-501R (rutile type, average particle size of 180 nm) and the like, but are not limited to these. It should be noted that the average particle size of the exemplified titanium oxide particles may vary by ⁇ 10 nm.
• the content of the titanium oxide particles (B) is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, more preferably 0.3% in the solid content. ⁇ 10% by mass is more preferred, and 3 to 10% by mass is even more preferred.
• the binder (C) may be selected from known resins and the like used as binders in the composition for forming a wavelength conversion film for displays.
• polyolefin resins such as methylpentene
• acrylic resins such as polymethyl methacrylate (PMMA), methyl methacrylate-methacrylic acid copolymer, benzyl methacrylate-methacrylic acid copolymer, ethylene-vinyl acetate copolymer (EVA);
• PMMA polymethyl methacrylate
• EVA ethylene-vinyl acetate copolymer
• Examples include polyvinyl butyrate (PVB); cellulose ester resins such as triacetyl cellulose (TAC) and nitrocellulose.
• acrylic resins are preferred, and methyl methacrylate-methacrylic acid copolymers are more preferred.
• a commercially available product may be used, or a product synthesized according to a conventional method such as radical polymerization using a polymerization initiator may be used.
• the average molecular weight of the resin is not particularly limited, but its weight average molecular weight (Mw) is usually 5,000 to 100,000, preferably 10,000 to 50,000.
• Mw weight average molecular weight
• the average molecular weight is a value converted to polystyrene by gel permeation chromatography.
• a polymerizable monomer and a photopolymerization initiator may be blended and polymerized after film formation. These can also be used in combination with the resins described above.
• the polymerizable monomer is not particularly limited as long as it is used together with a photopolymerization initiator and is polymerized by light irradiation, but an ethylenically unsaturated monomer is preferred.
• any of monofunctional monomers, bifunctional monomers and tri- or higher-functional monomers can be used as the ethylenically unsaturated monomers.
• Examples of monofunctional monomers include mono(meth)acrylates represented by the following formula (M1).
• R m1 represents a hydrogen atom or a methyl group
• R m2 represents a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in the hydrocarbon group is preferably 7 or less from the viewpoint of excellent ejection stability in the inkjet method and excellent effect of improving the external quantum efficiency.
• the monofunctional monomer is preferably not a monomer in which R m2 in formula (M1) above is a hydrocarbon group having 8 or more carbon atoms.
• the hydrocarbon groups may be substituted and may have, for example, ether linkages.
• monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, ) acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl ( meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, die
• the monofunctional monomer has a viscosity of 10,000 mPa ⁇ s or less, 8,000 mPa ⁇ s or less, 5,000 mPa ⁇ s or less, or 1,000 mPa ⁇ s or less from the viewpoint of easily improving ejection stability in the inkjet method.
• Monomers are preferred.
• the viscosity of a monomer having an ethylenically unsaturated group such as a monofunctional monomer is the viscosity at 25°C measured by an EMS viscometer, for example.
• bifunctional monomers examples include di(meth)acrylates represented by the following formula (M2).
• a plurality of R m3 each independently represents a hydrogen atom or a methyl group
• R m4 represents a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in the hydrocarbon group is preferably 7 or less from the viewpoint of excellent ejection stability and an excellent effect of improving the external quantum efficiency.
• the hydrocarbon groups may be substituted and may have, for example, ether linkages.
• bifunctional monomers include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1 ,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, Two hydroxyl groups of tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)
• the bifunctional monomer a monomer having a viscosity of 10,000 mPa ⁇ s or less, 5,000 mPa ⁇ s or less, or 1,000 mPa ⁇ s or less is preferable from the viewpoint of easily improving ejection stability in the inkjet method.
• the above viscosity is the viscosity at 25°C.
• trifunctional monomers examples include tri(meth)acrylates represented by the following formula (M3).
• a plurality of R m5 each independently represents a hydrogen atom or a methyl group
• R m6 represents a trivalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in the hydrocarbon group is preferably 4 or less from the viewpoint of excellent ejection stability and an excellent effect of improving the external quantum efficiency.
• the hydrocarbon groups may be substituted and may have, for example, ether linkages.
• trifunctional monomers include glycerin tri(meth)acrylate and trimethylolethane tri(meth)acrylate. Among these, glycerin tri(meth)acrylate is preferably used.
• a monomer having a viscosity of 10,000 mPa ⁇ s or less, 5,000 mPa ⁇ s or less, or 1,000 mPa ⁇ s or less is preferable from the viewpoint of easily improving ejection stability in the inkjet method.
• the above viscosity is the viscosity at 25°C.
• the photopolymerization initiator a photoradical polymerization initiator, a photocationic polymerization initiator, etc. can be used. Considering compatibility with general manufacturing methods of the wavelength conversion member, it is preferable to use a photoradical polymerizable compound, and the pixel portion (cured product of the ink composition) can be formed without being inhibited by oxygen in the curing process. From the point of view, it is preferable to use a photo-cationically polymerizable compound.
• photoradical polymerization initiator a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is preferably used.
• Molecular cleavage type photoradical polymerization initiators include, for example, benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenyl (2,4,6- trimethylbenzoyl)ethylphosphinate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl Phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide.
• molecular cleavage type photoradical polymerization initiators include, for example, 1-hydroxycyclohexylphenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2, 2-dimethoxy-1,2-diphenylethan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2- Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one may be used in combination.
• hydrogen abstraction type photoradical polymerization initiators examples include benzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenylsulfide.
• a molecular cleavage type radical photopolymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.
• the photoradical polymerization initiator can also be obtained as a commercial product.
• Commercially available products include Omnirad (registered trademark; hereinafter the same) manufactured by IGM Resin, acylphosphine oxide compounds such as TPO-H, Omnirad TPO-L, Omnirad 819; Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG, and other alkylphenone-based compounds; Omnirad MBF, "Omnirad 754,” and other intramolecular hydrogen abstraction compounds; Irgacure (registered trademark) manufactured by BASF Japan.
• Omnirad registered trademark
• Irgacure registered trademark
• OXE01 Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, oximes such as TR-PBG-304 and TR-PBG-305 manufactured by Changzhou Power Electronics New Materials Co., Ltd., NCI-831 and NCI-930 manufactured by ADEKA Co., Ltd. Examples include ester compounds.
• the oxime ester compounds include, for example, compounds described in JP-A-2004-534797, compounds described in JP-A-2000-80068, compounds described in International Publication No. 2012/45736, international Compounds described in Publication No. 2015/36910, compounds described in JP-A-2006-36750, compounds described in JP-A-2008-179611, compounds described in International Publication No. 2009/131189, Special Table 2012 -526185, the compound described in JP-A-2012-519191, the compound described in WO 2006/18973, the compound described in WO 2008/78678, JP 2011-132215
• Examples include oxime ester compounds such as those described in JP-A-2003-120003.
• Photocationic polymerization initiators include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate, p-nonylphenyliodonium hexafluoroantimonate and the like. and polyaryliodonium salts of.
• the photocationic polymerization initiator can also be obtained as a commercial product.
• Examples of such commercially available products include CPI-100P manufactured by San-Apro Co., Ltd., Omnicat (registered trademark; the same applies hereinafter) 270 manufactured by IGM Resin, Irgacure 290 manufactured by BASF Japan, etc.
• the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass with respect to 100% by mass of the polymerizable monomer. is even more preferred.
• the upper limit of the content is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of storage stability of the composition.
• the content of the binder (C) is preferably 70 to 99.8% by mass, more preferably 85 to 99.8% by mass, and even more preferably 90 to 99% by mass in the solid content.
• the composition for forming a wavelength conversion film for a display of the present invention contains, in addition to the above components (A) to (C), a light stabilizer, an antioxidant, a surfactant, a flame retardant, a transparentizing agent, if necessary.
• Various known additives such as agents, ultraviolet absorbers, cross-linking agents and fillers may be included.
• the surfactant a fluorosurfactant is preferred, and a nonionic fluorosurfactant is more preferred. Specific examples thereof include Futergent series, 212M, 215M, 250, 222F, FTX-218 and DFX-18 manufactured by Neos Co., Ltd., but are not limited to these.
• a surfactant When a surfactant is used, its blending amount is not particularly limited, but it is preferably 0.01 to 1% by mass, and 0.01 to 0.5% by mass in the solid content of the composition for forming a wavelength conversion film for a display. more preferred.
• composition for forming a wavelength conversion film for displays of the present invention may contain a solvent as necessary.
• aromatic or halogenated aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and chlorobenzene; aliphatic hydrocarbons such as n-heptane, n-hexane and cyclohexane; diethyl ether, tetrahydrofuran, ether solvents such as dioxane and 1,2-dimethoxyethane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone; ethyl acetate, n-hexyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene carbonate, Ester solvents such as diisopropyl malonate; Halogenated aromatic hydrocarbon solvent
• the composition for forming a wavelength conversion film for a display contains a solvent
• the solid content concentration of the composition for forming a wavelength conversion film for a display varies depending on the desired thickness of the wavelength conversion film, the coating method, and the like. Therefore, it cannot be defined unconditionally, but it is usually 10 to 70% by mass, preferably 20 to 60% by mass.
• the upper limit of the viscosity at 25° C. of the composition for forming a wavelength conversion film for a display is 10,000 mPa ⁇ s or less, preferably 1,000 mPa ⁇ s or less. Considering storage stability, the lower limit is preferably 5 mPa ⁇ s or more, more preferably 10 mPa ⁇ s or more.
• a viscosity means the measured value by an EMS viscometer.
• composition for forming a wavelength conversion film for a display of the present invention is obtained by mixing the above-described components (A) to (C), other additives such as surfactants used as necessary, and a solvent in any order.
• other additives such as surfactants used as necessary, and a solvent in any order.
• composition for forming a wavelength conversion film for a display of the present invention described above is applied, for example, onto a substrate, and if necessary, the solvent is evaporated by heating or the like, and if necessary, an active energy ray (for example, ultraviolet light) is applied.
• a wavelength conversion film can be obtained by irradiation.
• coating methods include reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, variver roll blade coater, two stream coater, Examples include methods using a rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater, inkjet, and the like.
• Heating can be performed, for example, using a general heating device such as an oven or a hot plate.
• the heating conditions are not particularly limited as long as the film can be formed, but the temperature is preferably 60 to 200° C. for 5 minutes to 2 hours, and more preferably 80 to 200° C. for 15 minutes to 1 hour. In addition, you may heat-harden in steps.
• Irradiation of ultraviolet light is not particularly limited as long as it can form a film, but light sources such as mercury lamps, metal halide lamps, xenon lamps, LEDs, etc. are used, and if necessary, bandpass filters are combined to expose wavelengths other than the intended exposure wavelength. can be irradiated with light from which the light is removed.
• the wavelength of the light to be irradiated is preferably 200 to 440 nm, and particularly preferably includes light with a wavelength of 300 to 400 nm.
• the exposure amount is preferably 10 to 4,000 mJ/cm 2 .
• ultraviolet light irradiation may be performed after heating, ultraviolet light irradiation may be performed and then heating may be performed, ultraviolet light irradiation may be performed after heating, and then further heating may be performed. good too.
• the thickness of the wavelength conversion film is not particularly limited, but is usually 1 to 1,000 ⁇ m, preferably 3 to 500 ⁇ m, more preferably 5 to 100 ⁇ m.
• the haze value of the wavelength conversion film is not particularly limited, but from the viewpoint of increasing the amount of light that can be absorbed by the phosphor by scattering incident light within the film, it is preferably 18% or more, More preferably 30% or more, more preferably 40% or more. Although the upper limit of the haze value is not particularly limited, it is usually about 95%.
• the haze value in the present invention is a value measured according to ASTM D1003-61. In the present invention, the haze value is measured under conditions for measuring a film having a thickness of 6 ⁇ m formed from a composition containing 3.16 to 4.74% by mass of titanium oxide particles, for example. is mentioned.
• the base material may be appropriately selected from those used as a base material for forming this type of film.
• Glass substrates and polymer plates are preferred.
• Specific examples of glass include soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
• Specific examples of polymers include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone, and the like.
• the wavelength conversion film obtained from the composition of the present invention is excellent in wavelength conversion efficiency, it is suitable as a wavelength conversion film (color conversion film) for displays such as micro LED displays, organic EL displays, liquid crystal displays, and illumination. can be used.
• Dye B a compound represented by the following formula (1B), C-Naphox-TEG, manufactured by Tokyo Chemical Industry Co., Ltd.
• Dye C a compound represented by the following formula (1C), BDP FL, manufactured by Tokyo Chemical Industry Co., Ltd.
• Dye D a compound represented by the following formula (1D), FL 305, manufactured by BASF
• the titanium mixed solution after preparation had a pH of 11.2 and a TiO 2 concentration of 3.0% by mass.
• 1,500 g of the titanium mixed solution was put into a 3-liter SUS autoclave container, and hydrothermally treated at 150° C. for 5 hours. After cooling to room temperature, the hydrothermally treated solution taken out was an aqueous dispersion of milky white titanium oxide colloidal particles.
• the resulting dispersion had a pH of 12.2, a TiO concentration of 3.0% by mass, a dynamic light scattering particle size of 141 nm, and an average first-order Bale-shaped particles with a particle size of 94 nm were observed.
• aqueous dispersion of titanium oxide colloidal particles was washed with water by an ultrafiltration device to remove excess electrolyte, thereby obtaining a dispersion having a TiO 2 concentration of 3.0% by mass.
• the resulting titanium oxide colloidal particles were used as titanium oxide particles to serve as nuclei.
• the resulting dispersion was an aqueous dispersion of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles, and contained colloidal particles having a pH of 8.2 and a primary particle diameter of 5 nm or less.
• the obtained colloidal particles of silicon dioxide-stannic oxide composite oxide were used as coated particles.
• the mixture was held at a temperature of 95° C. for 2 hours to denature. An aqueous dispersion of titanium oxide colloidal particles was obtained. Thereafter, the resulting aqueous dispersion of modified titanium oxide colloidal particles is passed through a column filled with a hydrogen-type cation exchange resin (Amberlite (registered trademark) IR-120B) to form an aqueous dispersion of acidic modified titanium oxide colloidal particles. I got the liquid.
• a hydrogen-type cation exchange resin Amberlite (registered trademark) IR-120B
• methanol dispersion was put into an evaporator equipped with an eggplant-shaped flask and concentrated. Water was distilled off at 590 Torr while methanol was added to obtain 129.8 g of a methanol dispersion of modified titanium oxide colloidal particles. rice field.
• the obtained methanol dispersion has a viscosity of 1.2 mPa s, a pH of 6.4 (diluted with the same mass of water as the dispersion), a solid content concentration of 30.5% by mass, a water content of 0.8% by mass, and dynamic light scattering. A particle diameter of 140 nm was observed under a transmission electron microscope, and bale-shaped particles having an average primary particle diameter of 101 nm were observed.
• composition for forming wavelength conversion film Preparation of composition for forming wavelength conversion film and its evaluation (1) Preparation of composition for forming wavelength conversion film The resulting mixture was filtered using a polytetrafluoroethylene (PTFE) filter with a pore size of 5.0 ⁇ m to prepare a composition for forming a wavelength conversion film.
• PTFE polytetrafluoroethylene
• Evaluation 2 Evaluation of film properties
• the wavelength conversion film forming compositions of Examples 1 to 7, 9 and 10 and Comparative Examples 1, 2 and 4 to 8 were applied onto a quartz substrate using a spin coater. After that, pre-baking was performed on a hot plate at 110° C. for 120 seconds to obtain a coating film sample having a film thickness of 6 ⁇ m. After that, the coating film samples of Examples 1 to 6 and 9 and Comparative Examples 1, 2, 4 to 6 and 9 were post-baked at 160° C. for 60 minutes. The coating film samples of Example 7 and Comparative Example 7 were post-baked at 120° C. for 60 minutes.
• a batch type UV irradiation device high pressure mercury lamp 2 kW ⁇ 1 lamp
• eye graphic A cured film was formed on the non-alkali glass substrate by irradiating the entire surface of the resin film with ultraviolet light having an exposure amount of 1000 mJ/cm 2 at 365 nm.
• the haze value of the resulting coating film sample was measured using a turbidity meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. by a measurement method conforming to ASTM D1003-61.
• the coating film sample is placed on a blue LED light (emission peak wavelength of 450 nm) manufactured by CCS Corporation, the LED light is turned on, and the light emitted through the coating film sample is It was measured using a spectral irradiance meter USR-45, and was designated as result (1). Similarly, the light emitted only from the LED light except for the coating film sample was measured in the same manner as the result (2).
• a blue LED light emission peak wavelength of 450 nm
• the number of photons of light with a wavelength of 480 nm or less in result (2) was defined as the "number of excitation light photons.”
• the number of photons of light with a wavelength of 480 nm or less in result (1) was defined as the "number of transmitted light photons.”
• the number of photons of light with a wavelength exceeding 480 nm in result (1) was defined as the "number of emitted photons.”
• “Blue light absorption rate” and "conversion efficiency” were calculated by the following formulas.
• Evaluation 3 Evaluation of film formability
• the state of the coating film was visually observed. was confirmed, and the film formability was evaluated.
• Judgment criteria are as follows. The results obtained are shown in Tables 3 and 4. ⁇ criterion> A: A uniform coating film was obtained, and the film-forming property was good. B: Coating unevenness occurred, and the film-forming property was poor. It was remarkably expressed to the extent that it could be confirmed, and the film formability was extremely poor. Therefore, in Comparative Example 3, the "conversion efficiency" measurement of Evaluation 2 was impossible.

Landscapes

• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Optics & Photonics (AREA)
• General Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Dispersion Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Electroluminescent Light Sources (AREA)
• Paints Or Removers (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=86335403

Family Applications (1)

Country Status (5)

Citations (6)

Family Cites Families (8)

• 2022
  • 2022-09-14 CN CN202280071104.4A patent/CN118235068A/zh not_active Withdrawn
  • 2022-09-14 KR KR1020247015311A patent/KR20240101801A/ko active Pending
  • 2022-09-14 WO PCT/JP2022/034294 patent/WO2023084906A1/ja not_active Ceased
  • 2022-09-14 JP JP2023559449A patent/JP7708205B2/ja active Active
  • 2022-09-27 TW TW111136559A patent/TW202336212A/zh unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events