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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D495/04—Ortho-condensed systems
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  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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  • 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
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  • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
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  • 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
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  • 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
  • C09B57/00—Other synthetic dyes of known constitution
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  • 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
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  • 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
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  • 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
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  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
  • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • 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
  • C08K2003/2237—Oxides; Hydroxides of metals of titanium
  • C08K2003/2241—Titanium dioxide
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1011—Condensed systems
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
  • C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur

Definitions

• the present invention relates to a condensed thiophene compound and a composition for forming a wavelength conversion film containing the same.
• 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.
• RGB-LED method As a method of arranging this LED chip, there is an RGB-LED method in which three-color LEDs are mounted.
• the complexity of LED emission control and the low performance of red LEDs are considered to be problems, and wavelength conversion methods that can solve these problems are attracting attention.
• 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.
• wavelength conversion materials For example, a pyridine-phthalimide condensate (Patent Document 1, etc.), a coumarin derivative (Patent Document 2, etc.), a perylene derivative (Patent Document 3, etc.), a rhodamine derivative (Patent Document 4), and a pyrromethene derivative (Patent Documents 5, 6, etc.) have been disclosed.
• Patent Document 7 discloses that a composition containing a binder resin made of a specific methacrylic polymer, a specific fluorescent dye, and a photopolymerizable acrylic acid ester serves as a red conversion material with high performance and good light resistance.
• 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.).
• wavelength conversion film-forming compositions are required to further improve the wavelength conversion efficiency and durability of wavelength conversion materials from the viewpoint of improving the performance of displays.
• Patent Document 11 discloses a fused ring thiophene compound having a specific structure, which is a fluorescent dye for staining intracellular lipid droplets.
• the fused-ring thiophene compound has excellent light resistance and has a maximum absorption wavelength and a maximum fluorescence wavelength in the visible light region, so it is expected to be used as a wavelength conversion material, but there is room for further improvement in conversion efficiency.
• 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 JP 2018-145422 A
• the present invention has been made in view of the above circumstances, and aims to provide a novel fused ring thiophene compound suitable as a phosphor for a wavelength conversion film, and a composition for forming a wavelength conversion film that contains the fused ring thiophene compound and provides a wavelength conversion film with excellent wavelength conversion efficiency and durability.
• the present inventors found that the above problems could be solved by including a novel condensed thiophene compound as the phosphor in a composition for forming a wavelength conversion film containing a phosphor and a binder, and completed the present invention.
• a condensed thiophene compound represented by the following formula (1) (wherein Ar 1 and Ar 2 are each independently an optionally substituted aromatic ring or an optionally substituted heteroaromatic ring, R 1 to R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group, and all of R 1 to R 4 are not hydrogen atoms at the same time, R 1 and R 2 may be bonded to each other to form a ring with the adjacent nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring with the adjacent nitrogen atom, either one or both of R 1 and R 2 may be bonded to Ar 1 to form a ring with the adjacent nitrogen atom, either one or both of R 3 and R 4 may be bonded to
• Y 1 and Y 2 are --SO 2 -- and the other is --S--.
• 3 1 or 2 condensed ring thiophene compounds wherein Ar 1 and Ar 2 are an optionally substituted aromatic ring or an optionally substituted heteroaromatic ring. 4. The fused ring thiophene compound according to any one of 1 to 3, wherein R 1 to R 4 are optionally substituted aryl groups. 5.
• composition for forming a wavelength-converting film of 5 containing (C) light-scattering particles 7. 6. The composition for forming a wavelength conversion film according to 6, wherein the light scattering particles (C) are titanium oxide particles. 8. 7. The composition for forming a wavelength conversion film according to any one of 5 to 7, wherein the binder (B) contains a resin. 9. 7. The composition for forming a wavelength conversion film according to any one of 5 to 7, wherein the binder (B) contains a polymerizable monomer and a photopolymerization initiator. 10. 7.
• the binder (B) contains an alkali-soluble resin, a polymerizable monomer and a photopolymerization initiator.
• 11. 10 The composition for forming a wavelength conversion film according to any one of 5 to 10, wherein the content of the phosphor (A) is 0.1% by mass or more based on the solid content. 12.
• 13. 12 The composition for forming a wavelength conversion film according to any one of 5 to 12, wherein the film formed from the composition has a haze value of 18% or more.
• the present invention it is possible to provide a novel fused-ring thiophene compound suitable as a phosphor for a wavelength conversion film, and to provide a composition for forming a wavelength-converting film that provides a wavelength-converting film with excellent wavelength conversion efficiency and durability by using the fused-ring thiophene compound.
• the fused-ring thiophene compound of the present invention is a fused-ring thiophene compound represented by the following formula (1).
• Ar 1 and Ar 2 are each independently an optionally substituted aromatic ring or an optionally substituted heteroaromatic ring
• R 1 ⁇ R Four are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group
• R 1 ⁇ R Four are not all hydrogen atoms at the same time
• R 1 and R 2 may combine with each other to form a ring with the adjacent nitrogen atom
• R 3 and R Four may combine with each other to form a ring with the adjacent nitrogen atom
• R 1 and R 2 one or both of Ar 1 to form a ring with the adjacent nitrogen atom
• R 3 and R Four one or both of Ar 2 to form a ring with the adjacent nitrogen atom
• Y 1 and Y 2 is -SO 2 - and the other is -S- or -SO 2 -.
• the aromatic rings represented by Ar 1 and Ar 2 include a benzene ring as a monocyclic aromatic hydrocarbon ring, and a naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyrene ring, triphenylene ring and the like as a polycyclic aromatic hydrocarbon ring.
• the aromatic rings represented by Ar 1 and Ar 2 may have a substituent.
• substituents include a halogen atom described later, an alkyl group described later, a cycloalkyl group described later, a halogenated alkyl group described later, an aryl group described later, a heteroaryl group described later, a cyano group, a nitro group and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the heteroaromatic rings represented by Ar 1 and Ar 2 include pyrrole, thiophene, furan, imidazole, pyrazole, thiazole, oxazole, pyridine, and pyrazine rings as monocyclic heteroaromatic rings, and indole, isoindole, benzimidazole, quinoline, isoquinoline, and quinoxaline rings as polycyclic heteroaromatic rings.
• the heteroaromatic rings represented by Ar 1 and Ar 2 may have a substituent.
• substituents include a halogen atom described later, an alkyl group described later, a cycloalkyl group described later, a halogenated alkyl group described later, an aryl group described later, a heteroaryl group described later, a cyano group, a nitro group and the like.
• the number of substituents is, for example, preferably 1 to 6, more preferably 1 to 3.
• Ar 1 and Ar 2 are preferably substituted or unsubstituted aromatic rings, more preferably substituted or unsubstituted monocyclic aromatic hydrocarbon rings, from the viewpoint of increasing the maximum absorption wavelength and the maximum fluorescence wavelength and further improving light resistance.
• Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
• the alkyl group may be linear or branched, and specific examples include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups, with alkyl groups having 1 to 6 carbon atoms being preferred.
• the above alkyl group may have a substituent.
• substituents include the halogen atom described above, the cycloalkyl group described later, the aryl group described later, the heteroaryl group described later, the cyano group, and the nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the cycloalkyl group includes a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group, and a cycloalkyl group having 4 to 8 carbon atoms is preferable.
• the cycloalkyl group may have a substituent.
• substituents include the halogen atom described above, the alkyl group described above, an aryl group described later, a heteroaryl group described later, a cyano group, a nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the halogenated alkyl group includes a trifluoromethyl group, a pentafluoroethyl group, and the like.
• the aryl group may be a monocyclic aryl group, a condensed aryl group, or a polycyclic aryl group.
• Specific examples include a phenyl group as a monocyclic aryl group, a naphthyl group, anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, a triphenylenyl group, etc. as a condensed aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group as a polycyclic aryl group, and an aryl group having 6 to 14 carbon atoms. is preferred.
• the aryl group may have a substituent.
• substituents include the above halogen atoms, the above alkyl groups, the above aryl groups, heteroaryl groups described later, cyano groups, and nitro groups.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the heteroaryl group may be either a monocyclic heteroaryl group or a condensed heteroaryl group.
• monocyclic heteroaryl groups include pyrrolyl, thienyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridyl, and pyrazyl groups
• condensed heteroaryl groups include indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl, and quinoxalyl groups. mentioned.
• the heteroaryl group may have a substituent.
• substituents include the above halogen atoms, the above alkyl groups, the above aryl groups, the above heteroaryl groups, cyano groups, and nitro groups.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• R 1 and R 2 are preferably substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups, more preferably substituted or unsubstituted aryl groups, and still more preferably unsubstituted aryl groups.
• R 1 and R 2 may combine with each other to form a ring together with the adjacent nitrogen atoms.
• Examples of the ring formed by bonding R 1 and R 2 together with the adjacent nitrogen atoms include the following groups.
• R 1 and R 2 may combine with Ar 1 to form a ring with the adjacent nitrogen atom.
• the ring formed by combining one or both of R 1 and R 2 with Ar 1 to form the adjacent nitrogen atom include the following groups.
• R 3 and R 4 are preferably substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups, more preferably substituted or unsubstituted aryl groups, and still more preferably unsubstituted aryl groups.
• R 3 and R 4 above may combine with each other to form a ring together with the adjacent nitrogen atoms.
• Examples of the ring in which R 3 and R 4 are bonded to each other to form the adjacent nitrogen atom include, for example, the groups shown above as specific examples of the ring in which R 1 and R 2 are bonded to each other to form the adjacent nitrogen atom.
• R 3 and R 4 may combine with Ar 2 to form a ring with the adjacent nitrogen atom.
• the ring in which one or both of R 3 and R 4 are bonded to Ar 2 to form the ring together with the adjacent nitrogen atom include, for example, the groups shown above as specific examples of the ring in which either one or both of R 1 and R 2 are bonded to Ar 1 together with the adjacent nitrogen atom.
• the bonding position of the group represented by -NR 1 R 2 to Ar 1 and the bonding position of the group represented by -NR 3 R 4 to Ar 2 are not particularly limited.
• Ar 1 and Ar 2 are benzene rings, a compound represented by the following formula (1') is likely to be formed.
• one of Y 1 and Y 2 is --SO 2 -- and the other is --S- or --SO 2 --.
• one of Y 1 and Y 2 is -SO 2 - and the other is -S-.
• the compound represented by the above formula (1) is used as a green light emitter, one of Y 1 and Y 2 is preferably -S- and the other is -SO 2 -.
• both Y 1 and Y 2 are preferably -SO 2 -.
• a compound represented by the following formula (1-1) is preferable as the fused ring thiophene compound that satisfies the above conditions.
• R 1a to R 4a are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group.
• Preferred specific examples of the compound represented by the above formula (1) include compounds represented by the following formulas (1-1B) and (1-2B).
• the fused-ring thiophene compound represented by formula (1) may exist as a solvate, and both are included in the scope of the present invention.
• the solvate is not particularly limited as long as it is a solvate of the condensed thiophene compound represented by the above formula (1) and a solvent.
• Solvents for forming solvates include dichloromethane, chloroform, acetonitrile, diethyl ether, ethyl acetate, methanol, ethanol, cyclohexane, toluene, acetone, N,N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and the like.
• the compound represented by the above formula (1) not only has excellent light resistance but also excellent conversion efficiency, and is suitable as a wavelength conversion material for display applications as a phosphor.
• the compound represented by the above formula (1) can be synthesized with reference to a known method, for example, it can be synthesized by a procedure similar to that described in paragraph [0084] onwards of JP-A-2018-145422.
• composition for forming a wavelength conversion film of the present invention is characterized by containing (A) a phosphor composed of a condensed thiophene compound represented by the above formula (1), and (B) a binder.
• solid content means components other than the solvent which comprise the composition for wavelength conversion film formation.
• the content of the phosphor of component (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more in the solid content.
• the upper limit of the content of the phosphor of component (A) is not particularly limited, but considering that the fluorescence quantum yield decreases when the concentration of the phosphor is increased, it is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, and even more preferably 5% by mass or less.
• composition for forming a wavelength conversion film of the present invention may contain a phosphor other than the condensed thiophene compound represented by the above formula (1) as a phosphor within a range that does not impair the effects of the present invention.
• Examples of other phosphors include cyanine dyes such as 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; pyridine dyes such as 1-ethyl-2-[4-(p-dimethylaminophenyl)-1,3-butadienyl]-pyridium-perchlorate; rhodamine dyes such as rhodamine B and rhodamine 6G; 1H,4H-tetrahydro-8-trifluoromethylquinolidino(9,9a,1-gh)coumarin, 3-(2'-benzothiazolyl)-7-diethylaminocoumarin, 3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin; coumarin dyes; Solvent Yellow 11, Solvent Yellow 116, and other naphthalimide dyes. Red-converting phosphors or green-converting phosphors such as fused
• the content is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably not included (0% by mass) in the solid content.
• the binder (B) may be selected from known resins and the like used as binders in the composition for forming a wavelength conversion film.
• the resin can be appropriately selected from resins used as the base resin of the composition for forming the wavelength conversion film.
• resins used as the base resin of the composition for forming the wavelength conversion film examples include polyolefin resins such as polystyrene (PS), polyethylene (PE), polypropylene (PP), polyester, polyimide, polyamide, and polymethylpentene; acrylic resins such as polymethyl methacrylate (PMMA), methyl methacrylate-methacrylic acid copolymer, and benzyl methacrylate-methacrylic acid copolymer; ethylene-vinyl acetate copolymer (EVA); cellulose ester resins such as lat (PVB); triacetyl cellulose (TAC) and nitrocellulose;
• the resin may be an alkali-soluble resin, which will be described later, or may contain both an alkali-soluble resin and other resins.
• acrylic resins are preferred, and methyl methacrylate-methacrylic acid copolymers are more preferred.
• Commercially available products may be used for each of the above resins, and those obtained by reaction of unsaturated double bond groups may be synthesized according to conventional methods such as radical polymerization using a polymerization initiator.
• 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
• an average molecular weight is a polystyrene conversion value by a 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.
• monofunctional monomers include mono(meth)acrylates represented by the following formula (M1), mono(meth)acrylamide compounds represented by the following formula (M2), and amide compounds represented by the following formula (M3).
• 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 above hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in R m2 is preferably 10 or less from the viewpoint of excellent ejection stability in the inkjet method and excellent effect of improving the external quantum efficiency.
• the hydrocarbon group may be substituted and may have, for example, an ether bond.
• R m1 is the same as above.
• R m3 and R m4 each independently represent a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the hydrocarbon group may be linear, branched or cyclic.
• R m3 and R m4 may combine with each other to form a ring.
• the total number of carbon atoms in R m3 and R m4 is preferably 10 or less in terms of excellent ejection stability in the inkjet method and excellent effect of improving the external quantum efficiency.
• the hydrocarbon group may be substituted and may have, for example, an ether bond.
• R m5 represents a hydrogen atom or a methyl group
• R m6 represents a monovalent hydrocarbon group having an ethylenically unsaturated group.
• the above hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in R m6 is preferably 10 or less from the viewpoint of excellent ejection stability in the inkjet method and excellent effect of improving the external quantum efficiency.
• the hydrocarbon groups may be substituted and may have, for example, ether linkages.
• mono(meth)acrylates represented by formula (M1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, but Xyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate,
• mono(meth)acrylamide compound represented by the formula (M2) include 4-(meth)acryloylmorpholine, (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, and the like.
• amide compound represented by the above formula (M3) examples include N-vinylformamide, N-vinylacetamide, N-allylformamide, N-allylacetamide and the like.
• ethoxyethoxyethyl (meth)acrylate N-vinylformamide, 4-(meth)acryloylmorpholine, N,N-dimethylacrylamide, and N,N-diethyl(meth)acrylamide are preferably used.
• the monofunctional monomer preferably has a viscosity of 10,000 mPa ⁇ s or less, more preferably 8,000 mPa ⁇ s or less, still more preferably 5,000 mPa ⁇ s or less, and still more preferably 1,000 mPa ⁇ s or less, from the viewpoint of easily improving ejection stability in the inkjet method.
• 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.
• a monomer having a high viscosity can also be suitably used by combining with a monomer having a low viscosity.
• a highly viscous monomer can also be suitably used.
• bifunctional monomers include di(meth)acrylates represented by the following formula (M4) and di(meth)acrylamide compounds represented by the following formula (M5).
• a plurality of R m7 each independently represents a hydrogen atom or a methyl group
• R m8 represents a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the divalent hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less from the viewpoint of excellent ejection stability and an excellent effect of improving the external quantum efficiency.
• the divalent hydrocarbon group may be substituted, and may have an ether bond, for example.
• a plurality of R m9 each independently represent a hydrogen atom or a methyl group
• a plurality of R m10 each independently represent a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the above monovalent hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in R m10 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 above monovalent hydrocarbon group may be substituted, and may have an ether bond, for example.
• R m11 represents a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the divalent hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less from the viewpoint of excellent ejection stability and an excellent effect of improving the external quantum efficiency.
• the divalent hydrocarbon group may be substituted, and may have an ether bond, for example.
• di(meth)acrylate represented by formula (M4) 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, 1,10-decanediol 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, triprop
• di(meth)acrylamide compound represented by the above formula (M5) examples include N,N-[oxybis(2,1-ethanediyloxy-3,1-propanediyl)]bisacrylamide and the like.
• a commercial product may be used as the di(meth)acrylamide compound, and specific examples include FOM-03008 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.).
• dipropylene glycol 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, and 1,10-decanediol di(meth)acrylate are preferably used.
• the bifunctional monomer preferably has a viscosity of 10,000 mPa ⁇ s or less, more preferably 8,000 mPa ⁇ s or less, even more preferably 5,000 mPa ⁇ s or less, and still more preferably 1,000 mPa ⁇ s or less, from the viewpoint of easily improving ejection stability in the inkjet method.
• the above viscosity is the viscosity at 25°C.
• a monomer having a high viscosity can also be suitably used by combining with a monomer having a low viscosity.
• a highly viscous monomer can also be suitably used.
• tri- or higher functional monomers examples include tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates represented by the following formula (M6), tri(meth)acrylamide compounds represented by the following formula (M7), and tetra(meth)acrylamide compounds.
• a plurality of R m12 each independently represents a hydrogen atom or a methyl group
• R m13 represents a trivalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the above trivalent hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in the hydrocarbon group is preferably 10 or less, more preferably 5 or less, from the viewpoint of excellent ejection stability and an excellent effect of improving the external quantum efficiency.
• the trivalent hydrocarbon group may be substituted, and may have an ether bond, for example.
• a plurality of R m14 each independently represent a hydrogen atom or a methyl group
• a plurality of R m15 each independently represent a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the above monovalent hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in R m15 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 above monovalent hydrocarbon group may be substituted, and may have an ether bond, for example.
• a plurality of R m16 each independently represent a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group).
• the divalent hydrocarbon group may be linear, branched or cyclic.
• the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less from the viewpoint of excellent ejection stability and an excellent effect of improving the external quantum efficiency.
• the divalent hydrocarbon group may be substituted, and may have an ether bond, for example.
• tri(meth)acrylate represented by formula (M6) include glycerin tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate.
• tetra(meth)acrylate examples include pentaerythritol tetraacrylate and ditrimethylolpropane tetraacrylate.
• penta(meth)acrylate examples include dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
• tri(meth)acrylamide compound represented by the above formula (M7) include N,N-bis(2-acrylamidoethyl)acrylamide.
• a commercial product may be used as the tri(meth)acrylamide compound, and a specific example thereof includes FOM-03007 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).
• tetra(meth)acrylamide compounds include N-[tris(3-acrylamidopropoxymethyl)methyl]acrylamide, N,N-1,2-ethanediylbis ⁇ N-[2-(acryloylamino)ethyl]acrylamide ⁇ , and the like.
• Commercially available tetra(meth)acrylamide compounds may be used, and specific examples thereof include FOM-03006 and FOM-03009 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.).
• glycerin tri(meth)acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferably used among the above-described trifunctional or higher-functional monomers.
• the trifunctional monomer preferably has a viscosity of 10,000 mPa ⁇ s or less, more preferably 8,000 mPa ⁇ s or less, even more preferably 5,000 mPa ⁇ s or less, and still more preferably 1,000 mPa ⁇ s or less, in terms of easily improving ejection stability in the inkjet method.
• the above viscosity is the viscosity at 25°C.
• a monomer having a high viscosity can also be suitably used by combining with a monomer having a low viscosity.
• a highly viscous monomer can also be suitably used.
• a photoradical polymerization initiator As 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. On the other hand, from the viewpoint that a cured film (a cured product of the composition for forming a wavelength conversion film) can be formed without being inhibited by oxygen in the curing process, 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 examples include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-tri methylpentylphosphine 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 acylphosphine oxide compounds such as Omnirad (registered trademark; hereinafter the same) TPO-H, Omnirad TPO-L, Omnirad 819 manufactured by IGM Resin; Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 1 27, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG and other alkylphenone compounds; Omnirad MBF, "Omnirad 754" and other intramolecular hydrogen abstraction type compounds; Oxime ester compounds such as cure OXE02, Irgacure OXE03, Irgacure OXE04, TR-PBG-304 and TR-PBG-305 manufactured by Changzhou Power Electronics New Materials Co., Ltd., and NCI-831 and NCI-930 manufactured by ADEKA Corporation.
• Omnirad registered trademark; hereinafter the same
• TPO-H Omnirad TPO-
• the oxime ester compounds include, for example, the compound described in JP-A-2004-534797, the compound described in JP-A-2000-80068, the compound described in International Publication No. 2012/45736, the compound described in International Publication No. 2015/36910, the compound described in JP-A-2006-36750, and JP-A-2008-179611.
• a chain transfer agent may be used in combination. By using a chain transfer agent, the reaction rate of the photoradical reaction can be increased.
• a chain transfer agent is defined in the Dictionary of Polymers, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
• the chain transfer agent for example, a group of compounds having SH, PH, SiH and GeH in the molecule is used. They can either hydrogen-donate to less active radical species to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
• thiol compounds eg, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
• polyfunctional thiol compounds are particularly preferred.
• polyfunctional thiol any compound having two or more thiol (SH) groups may be used.
• polyfunctional thiol compounds include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate (PETP), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglyco rate), Karenz (registered trademark, hereinafter the same) MT BD1, Karenz MT PE1, Karenz MT NR1 (manufactured by Showa Denko K.K.), and the like.
• EGTP ethylene glycol bisthiopropionate
• BDTP butanediol bisthio
• photocationic polymerization initiators include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; polyaryliodonium salts such as diphenyliodonium hexafluoroantimonate and p-nonylphenyliodonium hexafluoroantimonate.
• the photocationic polymerization initiator can also be obtained as a commercial product.
• commercially available products include sulfonium salt-based photocationic polymerization initiators such as CPI-100P manufactured by San-Apro Co., Ltd., Omnicat (registered trademark; hereinafter the same) 270 manufactured by IGM Resin, Irgacure 290 manufactured by BASF Japan; and iodonium salt-based photocationic polymerization initiators such as Omnicat 250 manufactured by IGM Resin.
• the content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to 100% by mass of the polymerizable monomer.
• 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 film forming properties and the transparency, heat resistance, and light resistance of the cured film.
• an alkali-soluble resin When blending a polymerizable monomer and a photopolymerization initiator, an alkali-soluble resin may be further blended.
• the composition By adding an alkali-soluble resin to the composition for forming a wavelength conversion film of the present invention, the composition can be used as a composition for forming a resist film.
• an alkali-soluble resin is a resin having an alkali-soluble group.
• alkali-soluble groups include phenolic hydroxy groups, carboxyl groups, acid anhydride groups, imide groups, sulfonyl groups, phosphoric acid groups, boronic acid groups, active methylene groups, and the like.
• the active methylene group means a methylene group ( --CH.sub.2-- ) having a carbonyl group at an adjacent position and having reactivity with a nucleophilic reagent.
• a group represented by the following formula (b1) is more preferable as the active methylene group.
• R b represents an alkyl group, an alkoxy group or a phenyl group, and the dashed line represents a bond.
• the alkyl group represented by R b includes, for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.
• Specific examples of such alkyl groups include methyl, ethyl, n-propyl and i-propyl groups. Among these, a methyl group, an ethyl group and an n-propyl group are preferred.
• the alkoxy group represented by R b includes, for example, an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 5 carbon atoms.
• Specific examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups. Among these, methoxy group, ethoxy group, n-propoxy group and the like are preferable.
• an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxy group and having a number average molecular weight of 2,000 to 50,000 is preferable.
• the alkali-soluble resin preferably has a number average molecular weight in the range of 2,000 to 50,000, but if the number average molecular weight is 50,000 or less, development residue is less likely to occur, and the required sensitivity can be obtained. On the other hand, when the number-average molecular weight is 2,000 or more, film loss in the exposed areas is less likely to occur during development, and sufficient curability can be obtained.
• the alkali-soluble resin is not particularly limited as long as it has the structure described above, and there are no particular restrictions on the skeleton of the main chain of the polymer that constitutes the resin, the types of side chains, and the like.
• alkali-soluble resin examples include acrylic resins, polyhydroxystyrene resins, polyimide precursors, polyimides, polyesters, and the like.
• an alkali-soluble resin made of a copolymer obtained by polymerizing multiple types of monomers can also be used.
• the alkali-soluble resin may be a blend of multiple types of alkali-soluble resins.
• an acrylic polymer which is an acrylic resin
• the acrylic polymer refers to a resin obtained by a polymerization reaction of a monomer having an unsaturated double bond group and a reaction of the unsaturated double bond group portion.
• the alkali-soluble acrylic polymer include a copolymer formed of a monomer exhibiting alkali solubility, that is, a monomer having at least one selected from the above-described alkali-soluble groups, and at least one monomer selected from the group of monomers copolymerizable with these monomers as essential structural units.
• the number average molecular weight of the alkali-soluble resin is preferably 2,000 to 50,000. When the number average molecular weight is 50,000 or less, residue is less likely to occur.
• the above "monomers having at least one selected from alkali-soluble groups” include monomers having a carboxyl group, and monomers having a phenolic hydroxy group and an imide group. These monomers are not limited to having one carboxyl group or phenolic hydroxy group, and may have a plurality of them.
• monomers having a carboxy group examples include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide and the like.
• Monomers having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, 4-hydroxyphenylmethacrylate and the like.
• Examples of monomers having an imide group include maleimide and the like.
• the ratio of the monomer having an alkali-soluble group and an unsaturated double bond group is preferably 5 to 90 mol%, more preferably 10 to 60 mol%, and most preferably 10 to 40 mol% of all the monomers used for producing the alkali-soluble acrylic polymer. Sufficient alkali solubility is obtained when the ratio of the monomer having an alkali-soluble group and an unsaturated double bond group is 10% by mass or more.
• the alkali-soluble acrylic polymer may be further copolymerized with a monomer having a hydroxyalkyl group and an unsaturated double bond group in order to further stabilize the pattern shape after curing.
• monomers having a hydroxyalkyl group and an unsaturated double bond group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and the like.
• the ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group in the production of the alkali-soluble acrylic polymer is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass.
• the ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group is 10% by mass or more, an effect of stabilizing the pattern shape of the copolymer can be obtained.
• the ratio is 60% by mass or less, the content of the alkali-soluble group is in an appropriate range, and sufficient properties such as developability can be obtained.
• the alkali-soluble acrylic polymer may further be copolymerized with an N-substituted maleimide compound in order to increase the Tg of the copolymer.
• N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. From the viewpoint of transparency, those having no aromatic ring are preferred, from the viewpoints of developability, transparency and heat resistance, those having an alicyclic skeleton are more preferred, and cyclohexylmaleimide is even more preferred.
• the ratio of the N-substituted maleimide in the production of the alkali-soluble acrylic polymer is preferably 10-60% by mass, more preferably 15-50% by mass, and even more preferably 20-40% by mass.
• the ratio of the N-substituted maleimide is 10% by mass or more, the Tg of the copolymer becomes high, so that the finally obtained wavelength conversion film also has a high Tg, and sufficient heat resistance and light resistance can be obtained. Sufficient transparency is obtained as the ratio is 60 mass % or less.
• the alkali-soluble acrylic polymer may be a copolymer containing monomers other than the above-described monomers (hereinafter referred to as other monomers) as constitutional units.
• Other monomers are not particularly limited as long as they are copolymerizable with at least one selected from the group consisting of monomers having a carboxyl group and monomers having a phenolic hydroxy group, as long as they do not impair the characteristics of the alkali-soluble acrylic polymer.
• Specific examples of such monomers include acrylate compounds, methacrylate compounds, acrylamide compounds, acrylonitrile, styrene compounds and vinyl compounds.
• Specific examples of the other monomers are listed below, but are not limited thereto.
• acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2 -methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecy
• methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytri Ethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, ⁇ -butyrol
• acrylamide compounds include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.
• vinyl compounds include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.
• styrene compound examples include styrene having no hydroxy group. Specific examples thereof include styrene, ⁇ -methylstyrene, chlorostyrene, bromostyrene and the like.
• the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less.
• the ratio of other monomers is 80% by mass or less, the effects of the present invention can be sufficiently obtained.
• the method for obtaining the alkali-soluble acrylic polymer is not particularly limited, for example, a monomer having at least one selected from the group consisting of a carboxy group, a phenolic hydroxy group, a group that generates a carboxylic acid by the action of heat or acid, and a group that generates a phenolic hydroxy group by the action of heat or acid; a monomer having a hydroxyalkyl group; A monomer having at least one group selected from a self-crosslinkable group such as an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group and a blocked isocyanate group; optionally, another copolymerizable monomer;
• the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble acrylic polymer and the alkali-soluble acrylic polymer. Specific examples include the following solvents.
• solvents used in the above reaction include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone.
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate and the like are preferable from the viewpoint of good coating properties and high safety.
• These may be used individually by 1 type, and may be used in combination of 2 or more type.
• the alkali-soluble acrylic polymer thus obtained is usually in the form of a solution dissolved in a solvent.
• the solution of the specific copolymer obtained as described above is put into diethyl ether, water, or the like under stirring to reprecipitate, and after filtering and washing the generated precipitate, the powder of the specific copolymer can be obtained by drying at room temperature or by heating under normal pressure or reduced pressure.
• the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If the purification cannot be sufficiently performed in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the powder of the specific copolymer may be used as it is, or the powder may be redissolved in an appropriate solvent, for example, the solvent used in the polymerization reaction described above and used in the form of a solution.
• polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, and polyimide such as carboxylic acid group-containing polyimide can be used, and if they are alkali-soluble, the type can be used without particular limitation.
• the polyamic acid which is a polyimide precursor, can generally be obtained by polycondensing (a) a tetracarboxylic dianhydride and (b) a diamine compound.
• tetracarboxylic dianhydride is not particularly limited, and specific examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride and other aromatic tetracarboxylic acids, 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,3,
• the diamine compound (b) is also not particularly limited, and specific examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, and bis(4-amino-3).
• -carboxyphenyl)sulfone bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxy phenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoro
• the compounding ratio of both compounds that is, the total number of moles of (b) the diamine compound/(a) the total number of moles of the tetracarboxylic dianhydride is preferably 0.7 to 1.2. Similar to a conventional polycondensation reaction, the closer this molar ratio is to 1, the higher the polymerization degree of polyamic acid produced and the higher the molecular weight.
• the terminal amino groups of the residual polyamic acid can be reacted with a carboxylic acid anhydride to protect the terminal amino groups.
• carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.
• the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride is usually -20 to 150°C, preferably -5 to 100°C.
• the reaction temperature is appropriately selected in the range of 5 to 40° C. and the reaction time is in the range of 1 to 48 hours.
• the reaction temperature can be selected from -20 to 150°C, preferably from -5 to 100°C.
• the reaction between the diamine compound and the tetracarboxylic dianhydride can be carried out in a solvent.
• Solvents that can be used at that time include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, ⁇ -butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, and 2-methoxypropionate.
• the solution containing polyamic acid thus obtained can be used as it is for preparing a negative photosensitive resin composition.
• the polyamic acid can also be used after being precipitated and isolated in a poor solvent such as water, methanol, or ethanol.
• any polyimide can also be used as the alkali-soluble resin.
• the polyimide used in the present invention is obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as the polyamic acid.
• the polyimide preferably has a group selected from a carboxyl group and a phenolic hydroxy group to impart alkali solubility.
• Examples of the method for introducing a carboxyl group or a phenolic hydroxy group into a polyimide include a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of blocking an amine end with an acid anhydride having a carboxyl group or a phenolic hydroxy group, and a method of making the imidization ratio 99% or less when imidating a polyimide precursor such as polyamic acid.
• Such a polyimide can be obtained by synthesizing a polyimide precursor such as the polyamic acid described above and then subjecting it to chemical imidization or thermal imidization.
• a chemical imidization method a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100° C. is generally used.
• a thermal imidization method a method of heating a polyimide precursor solution at a temperature of 180 to 250° C. while dehydrating it is generally used.
• a phenol novolac resin can also be used as the alkali-soluble resin.
• Polyester polycarboxylic acid can also be used as the alkali-soluble resin.
• a polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in WO 2009/051186.
• acid dianhydrides include the above-mentioned (a) tetracarboxylic dianhydrides.
• Diols include aromatic diols such as bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, benzene-1,3-dimethanol and benzene-1,4-dimethanol; alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol; aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol. is mentioned.
• the alkali-soluble resin of the present invention is preferably a copolymer that further has a self-crosslinking group or a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group (hereinafter also referred to as a crosslinkable group).
• self-crosslinkable groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, oxetane groups, vinyl groups, and blocked isocyanate groups.
• crosslinkable groups include N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, blocked isocyanate groups, and the like.
• the content is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin, and more preferably 0.1 to 0.8 from the viewpoint of developability and solvent resistance.
• the alkali-soluble resin further has a repeating unit having at least one selected from the crosslinkable group and the self-crosslinkable group
• a repeating unit having at least one selected from the crosslinkable group and the self-crosslinkable group for example, in the case of an alkali-soluble acrylic polymer, an unsaturated compound having radical polymerizability and at least one selected from the crosslinkable group and the self-crosslinkable group may be copolymerized.
• unsaturated compounds having radical polymerizability and further having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide.
• monomers having radical polymerizability and further having a hydroxymethylamide group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.
• radically polymerizable monomers having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.
• radically polymerizable unsaturated compounds having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, and 6 ⁇ -ethyl acrylate.
• Examples of unsaturated compounds having radical polymerizability and having an oxetane group include (meth)acrylic acid esters having an oxetane group.
• Specific examples of such monomers include 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane.
• 3-(methacryloyloxymethyl)-3-ethyl-oxetane and 3-(acryloyloxymethyl)-3-ethyl-oxetane are preferred.
• monomers having radical polymerizability and further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.
• monomers having radical polymerizability and a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.
• the content of structural units derived from unsaturated compounds having radical polymerizability and having at least one group selected from the crosslinkable group and the self-crosslinkable group is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, of all repeating units possessed by the alkali-soluble resin.
• the content of this structural unit is 10% by mass or more, the heat resistance and surface hardness of the cured film are improved.
• the content of this structural unit is 70% by mass or less, the storage stability of the radiation-sensitive resin composition is improved.
• the alkali-soluble resin of the present invention When used in combination with the aforementioned polymerizable monomer, it is preferred that the alkali-soluble resin has a substituent capable of reacting with the polymerizable monomer.
• a method for obtaining an alkali-soluble resin having a substituent capable of reacting with a polymerizable monomer is not particularly limited as long as a resin having stable properties can be obtained.
• the alkali-soluble resin is an alkali-soluble acrylic polymer, if the former method is performed, the polymerizable monomer and the reactive substituent group may react with each other during the polymerization process and gelation may proceed, so synthesis by the latter method is preferred.
• Specific examples thereof include a method of adding glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc. to an alkali-soluble acrylic polymer synthesized using a monomer having radical polymerizability and a carboxyl group or a phenolic hydroxyl group.
• a monomer having radical polymerizability and a carboxyl group or a phenolic hydroxyl group At this time, by reducing the molar ratio of the monomer to be added to the carboxyl group or phenolic hydroxyl group in the resin, it is possible to introduce a substituent capable of reacting with the polymerizable monomer while maintaining the alkali solubility of the resin derived from the carboxyl group or phenolic hydroxyl group.
• Another example is a method of adding a polymerizable monomer capable of thermal reaction with a thermally reactive group in a resin to an alkali-soluble acrylic polymer obtained by copolymerizing a monomer having a thermally reactive group and a monomer having a reactive substituent.
• Specific examples include a method of adding (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, etc. to an alkali-soluble acrylic polymer obtained by copolymerizing glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, etc.
• the proportion of repeating units having a substituent capable of reacting with a polymerizable monomer is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, more preferably 10 to 40% by mass, in all repeating units of the alkali-soluble resin.
• the content of this structural unit is 5% by mass or more, the heat resistance and chemical resistance of the cured film are improved.
• the content of this structural unit is 60% by mass or less, the pattern formability of the radiation-sensitive resin composition is improved.
• the alkali-soluble resin may be a mixture of multiple types of alkali-soluble resins.
• the content thereof is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total 100% by mass of the polymerizable monomer and the alkali-soluble resin, from the viewpoint of film-forming properties.
• the upper limit of the content thereof is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of pattern formability.
• the content of the binder (B) is preferably 70 to 99.9% by mass, more preferably 85 to 99.9% by mass, and even more preferably 90 to 99% by mass in the solid content.
• composition for forming a wavelength conversion film of the present invention may further contain (C) light scattering particles.
• the light scattering particles scatter the light entering the wavelength conversion film in the film, thereby substantially increasing the optical path length in the wavelength conversion film and improving the light absorption rate.
• the light scattering particles can be appropriately selected according to the purpose, and may be organic fine particles or inorganic fine particles. Among these, inorganic fine particles having a large refractive index are preferable from the viewpoint of enhancing the scattering performance of the particles.
• organic fine particles examples include polymethylmethacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, styrene beads, crosslinked polystyrene beads, polyvinyl chloride beads, and benzoguanamine-melamine formaldehyde beads.
• the inorganic fine particles include inorganic oxide particles made of at least one oxide selected from silicon, zirconium, titanium, indium, zinc, antimony, cerium, niobium, tungsten, and the like.
• Specific examples of the inorganic oxide particles include SiO 2 , ZrO 2 , TiO 2 (hereinafter also referred to as titanium oxide particles), BaTiO 3 , In 2 O 3 , ZnO, Sb 2 O 3 , ITO, CeO 2 , Nb 2 O 5 and WO 3 .
• TiO2 , BaTiO3 , ZrO2 , CeO2 and Nb2O5 are preferred, and TiO2 is more preferred .
• rutile type TiO 2 is preferable to anatase type because it has lower catalytic activity and therefore has higher film durability and also has a higher refractive index.
• These particles may be surface-treated.
• specific materials for surface treatment include different inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, organosiloxanes, and organic acids such as stearic acid.
• one of these surface treatment materials may be used alone, or a plurality of them may be used in combination.
• the average particle size of the light scattering 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, from the viewpoint of the storage stability of the composition, since sedimentation tends to occur if the particle size is too large.
• the average particle size of the light scattering particles is the average particle size determined by transmission electron microscope observation.
• titanium oxide particles include, but are not limited to, 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 180 nm). It should be noted that the average particle size of the exemplified light scattering particles may vary by ⁇ 10 nm.
• the content of the light scattering particles (C) is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and even more preferably 0.3 to 10% by mass in the solid content.
• composition for forming a wavelength conversion film of the present invention may optionally contain various known additives such as component (C), light stabilizers, antioxidants, surfactants, polymer dispersants, flame retardants, clarifying agents, ultraviolet absorbers, cross-linking agents, and fillers.
• component (C) light stabilizers, antioxidants, surfactants, polymer dispersants, flame retardants, clarifying agents, ultraviolet absorbers, cross-linking agents, and fillers.
• 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.
• a polymer dispersant is a polymer compound that has a weight average molecular weight of 750 or more and a functional group that has an affinity for light scattering particles.
• the polymer dispersant has the function of dispersing the light scattering particles.
• the polymer dispersant adsorbs to the light scattering particles via a functional group having an affinity for the light scattering particles, and disperses the light scattering particles in the composition due to electrostatic repulsion and/or steric repulsion between the polymer dispersants.
• the polymer dispersant is preferably bonded to the surface of the light scattering particles and adsorbed to the light scattering particles, but may be free in the wavelength-converting film-forming composition.
• Functional groups that have affinity for light scattering particles include acidic functional groups, basic functional groups and nonionic functional groups.
• the acidic functional group has a dissociative proton and may be neutralized with a base such as an amine or hydroxide ion, and the basic functional group may be neutralized with an acid such as an organic acid or an inorganic acid.
• acidic functional groups include a carboxy group (--COOH), a sulfo group (--SO 3 H), a sulfate group (--OSO 3 H), a phosphonic acid group (--PO(OH) 2 ), a phosphoric acid group (--OPO(OH) 2 ), a phosphinic acid group (--PO(OH)--), and a mercapto group (--SH).
• Basic functional groups include primary amino groups, secondary amino groups, tertiary amino groups, ammonium groups, imino groups, and nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole and triazole.
• nonionic functional groups include hydroxy group, ether group, thioether group, sulfinyl group (-SO-), sulfonyl group ( -SO2- ), carbonyl group, formyl group, ester group, carbonate group, amide group, carbamoyl group, ureido group, thioamide group, thioureido group, sulfamoyl group, cyano group, alkenyl group, alkynyl group, phosphine oxide group, phosphine sulfide group and the like.
• the polymeric dispersant may be a polymer (homopolymer) of a single monomer, or a copolymer (copolymer) of a plurality of types of monomers. Further, the polymeric dispersant may be any of random copolymers, block copolymers and graft copolymers. When the polymeric dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer.
• polymeric dispersants include acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyethers, phenol resins, silicone resins, polyurea resins, amino resins, epoxy resins, polyethyleneimine, polyallylamine, polyimides, and the like.
• the polymer dispersant can be used as the polymer dispersant.
• the DISPERBYK series and BYK series manufactured by BYK the Efka series manufactured by BASF, the Solsperse series manufactured by Lubrizol, the Ajinomoto Fine-Techno Co., Ltd.
• Ajisper PB series, the TEGO series manufactured by Evonik, and the Disparon series manufactured by Kusumoto Kasei Co., Ltd. can be used.
• DISPERBYK-130 DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, and DISPERBYK-1 manufactured by BYK.
• the amount of the dispersant is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, relative to the light scattering particles.
• composition for forming a wavelength conversion film 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; ether solvents such as diethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone; Halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, 1,2-dichloroethane and chloroform; Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-
• Glycol ether solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol diglycidyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; ethylene glycol, propylene glycol, hexylene glycol , 3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol
• the solid content concentration of the wavelength-converting film-forming composition varies depending on the thickness of the intended wavelength-converting film, the coating method, etc., and cannot be generally defined.
• the upper limit of the viscosity at 25° C. of the wavelength conversion film-forming composition 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.
• the wavelength-converting film-forming composition of the present invention can be prepared by mixing the components (A) and (B) described above, the component (C) used as necessary, other additives such as surfactants, and a solvent in any order.
• a wavelength conversion film can be obtained by applying the above-described composition for forming a wavelength conversion film of the present invention, for example, onto a substrate, evaporating the solvent by heating or the like as necessary, and further irradiating with active energy rays (for example, ultraviolet light) as necessary.
• active energy rays for example, ultraviolet light
• the coating method 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, variable roll blade coater, two stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater, inkjet method, 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 a film can be formed, but light sources such as mercury lamps, metal halide lamps, xenon lamps, and LEDs can be used, and light other than the intended exposure wavelength can be removed by combining a band-pass filter as necessary.
• 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 dose is preferably 10 to 4,000 mJ/cm 2 .
• ultraviolet light irradiation may be performed after heating, ultraviolet light irradiation may be performed before heating, or ultraviolet light irradiation may be performed after heating, followed by further heating.
• 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 of the wavelength conversion film is not particularly limited, but is preferably 18% or more, more preferably 30% or more, and more preferably 40% or more from the viewpoint of increasing the amount of light that can be absorbed by the phosphor by scattering incident light within the film.
• 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.
• the conditions for measuring the haze value include, for example, conditions for measuring a film having a thickness of 10 ⁇ m formed from a composition containing 6.7% by mass of titanium oxide particles.
• the substrate may be appropriately selected from those used as base substrates for forming this type of film, but a glass substrate or polymer plate having a transmittance of 50% or more for light in the visible region of 400 to 800 nm is preferable.
• glass include soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
• polymers include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone, and the like.
• a coating film is formed using a composition (negative photosensitive resin composition) containing an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator
• a mask having a predetermined pattern is mounted on the resulting coating film, irradiated with light such as ultraviolet rays, and developed with an alkaline developer to wash out the unexposed areas.
• a leaf pattern is obtained.
• alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; alkaline aqueous solutions such as aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine. Further, known surfactants and the like for developing solutions can be added to these developers.
• alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide
• quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline
• alkaline aqueous solutions such as aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine.
• aqueous solution of tetraethylammonium hydroxide is generally used as a photoresist developer, and the composition of the present invention can also be satisfactorily developed using this alkaline developer without causing problems such as swelling.
• any method such as a liquid heaping method, a dipping method, or a rocking immersion method can be used.
• the development time at that time is usually 15 to 180 seconds.
• the photosensitive resin film is washed with running water and then air-dried using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate and obtain a patterned film.
• the washing time is usually about 20 to 120 seconds.
• the resulting patterned film is post-baked for thermosetting, thereby obtaining a film having excellent heat resistance, transparency, flatness, low water absorption, chemical resistance, etc., and a good relief pattern.
• a hot plate, an oven, or the like can be used for heating the pattern forming film.
• the post-baking method generally includes a method of treating at a heating temperature selected from the range of 140 to 270°C for 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. By post-baking under such conditions, a cured film having a good pattern shape can be obtained.
• the wavelength conversion film obtained from the composition of the present invention is excellent in wavelength conversion efficiency and durability, so it can be suitably used as a wavelength conversion film (color conversion film) for displays such as micro LED displays, organic EL displays, liquid crystal displays, and illumination.
• the molecular weight of the polymer was measured using a GPC system manufactured by JASCO Corporation as an apparatus and Shodex (registered trademark) KF-804L and 803L as columns under the following conditions. Column oven: 40°C Flow rate: 1 mL/min Eluent: Tetrahydrofuran
• ⁇ MMA methyl methacrylate
• MAA methacrylic acid
• AIBN ⁇ , ⁇ '-azobisisobutyronitrile
• CPN cyclopentanone
• A11 3-(2-benzothiazolyl)-7-(diethylamino) coumarin (coumarin 6, manufactured by Tokyo Chemical Industry Co., Ltd.)
• ⁇ A12 a compound represented by the following formula (X1)
• ⁇ B2 HDDA (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• B3 NDDA (1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• B4 Irgacure OXE02 (manufactured by BASF)
• B5 KAYARAD DPHA (dipentaerythritol polyacrylate, manufactured by Nippon Kay
• Tri-tert-butylphosphonium tetrafluoroborate (tert-Bu 3 PHBF 4 ) purchased from Fuji Film Wako Pure Chemical Industries, Ltd. was used. Thin layer chromatography (TLC) was performed using glass plates coated with 0.25 mm of silica gel 60F-254 (Merck). Silica gel column chromatography was performed using silica gel 60N spherical neutral (Kanto Kagaku Co., Ltd.) as a packing material.
• a diphenylamino group was introduced into compound 2 using the Buchwald-Hartwig coupling reaction, and compound 3 was obtained with a yield of 26%. Specifically, synthesis was performed as follows.
• N 2 ,N 2 ,N 7 ,N 7 -tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 3; 1.75 g, 3.04 mmol) was dissolved in chloroform (175 mL).
• Meta-chloroperbenzoic acid m-CPBA (containing 30% by mass of water); 1.65 g, 6.70 mmol
• Saturated sodium bicarbonate was added and extracted with chloroform three times.
• Anhydrous sodium sulfate was added to the combined organic layer for dehydration, and the filtrate was concentrated under reduced pressure.
• a diphenylaminophenyl group was introduced into compound 2 using a coupling reaction, and compound 5 was obtained with a yield of 43%. Specifically, synthesis was performed as follows.
• N 2 ,N 2 ,N 7 ,N 7 -tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 3; 100 mg, 0.174 mmol) was dissolved in 1,2-dichloroethane (10 mL). Meta-chloroperbenzoic acid (m-CPBA (containing 30% by mass of water); 450 mg, 1.83 mmol) was added thereto. The temperature was raised to 70° C. and stirred for 29 hours. A saturated sodium bicarbonate aqueous solution was added, and the mixture was extracted with chloroform three times.
• Fluorescent dye compound A10 ACS Materials Lett. Fluorescent dye compound A10 represented by the following formula was obtained according to the synthesis method described in 2021, 3, 42-49.
• the solvent of the dispersion was used as the diluent, and the 50% cumulative diameter (D50) of the particles in the dispersion was calculated on a volume basis using the analysis software MicrotracDMS manufactured by Nikkiso Co., Ltd. from the scattering that occurred when the diluted sample was irradiated with a laser beam.
• a light scattering particle dispersion liquid 2 was obtained by performing 5-pass treatment under the conditions of a liquid feeding speed of 40 ml/min and a disk peripheral speed of 8 m/s in a state of being filled with 60% by volume of zirconia beads having a diameter of 0.2 mm using a bead mill device Labominister DMS65 manufactured by Ashizawa Finetech Co., Ltd.
• the particle size distribution of the resulting dispersion was measured using Nanotrac UPA (manufactured by Microtrac).
• Preparation Example 3 Preparation of Light Scattering Particle Dispersion Liquid 3 To a 500 ml styrene bottle, Particle Dispersant D4 was added in an amount of 20% by mass in terms of solid content relative to Light Scattering Particles C1, CPN was further added to adjust the solid content concentration to 30% by mass, and disper stirring was performed for 30 minutes at 1,000 rpm to obtain a slurry.
• a light scattering particle dispersion liquid 3 was obtained by performing 10 passes under the conditions of a liquid feeding speed of 60 ml/min and a disk peripheral speed of 8 m/s in a state of being filled with zirconia beads having a diameter of 0.2 mm at 60% by volume using a bead mill device Labominister DMS65 manufactured by Ashizawa Finetech Co., Ltd.
• the particle size distribution of the resulting dispersion was measured using Nanotrac UPA (manufactured by Microtrac).
• CPN was used as the diluted solution
• the analysis software MicrotracDMS manufactured by Nikkiso Co., Ltd. was used to calculate the 50% cumulative diameter (D50) of the particles in the dispersion on a volume basis from the scattering that occurred when the diluted sample was irradiated with a laser beam.
• the substrate C was stored in the atmosphere and shielded from light. After that, using a fluorescence spectrometer (F-7000 manufactured by Hitachi, Ltd.), all the substrates were excited at a predetermined excitation wavelength and measured for fluorescence spectra. The value obtained by dividing the peak intensity of the fluorescence spectrum of substrate A by the peak intensity of the fluorescence spectrum of substrate C was the fluorescence intensity maintenance rate under a nitrogen atmosphere, and the value obtained by dividing the peak intensity of the fluorescence spectrum of substrate B by the peak intensity of the fluorescence spectrum of substrate C was taken as the fluorescence intensity maintenance rate in air. Table 2 shows the evaluation results.
• Examples 1 to 9 which satisfy the requirements of the present invention, had a high fluorescence intensity retention rate after light irradiation in a nitrogen atmosphere and exhibited excellent light resistance compared to Comparative Example 1, which used a dye that did not satisfy the requirements of the present invention.
• Examples 1 to 3 and 5 to 9 exhibited a high fluorescence intensity retention rate after light irradiation even in the air, and exhibited excellent light resistance as compared with Comparative Example 1.
• the resin compositions of Examples 14 and 15 and Comparative Examples 8 to 10 were applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds.
• This coating film was irradiated with ultraviolet light having a light intensity of 3 mW/cm 2 at 365 nm and an exposure amount of 500 mJ/cm 2 using a PLA-600FA ultraviolet irradiation apparatus manufactured by Canon Inc. Then, post-baking was performed at 160° C. for 30 minutes to obtain a coating film sample having a film thickness of 10 ⁇ m.
• the haze value of the resulting coating film sample was measured using a turbidity meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd., according to a measurement method conforming to ASTM D 1003-61.
• the coating film sample was superimposed on a blue LED light (luminescence peak wavelength 450 nm) manufactured by CCS Co., Ltd., the LED light was turned on, and the light emitted through the coating film sample was measured using a spectral irradiance meter USR-45 manufactured by Ushio Denki Co., Ltd., and the result (I) was obtained.
• the light emitted only from the LED light except for the coating film sample was measured in the same manner as the result (II).
• the photon number of light with a wavelength of 480 nm or less in result (II) was defined as the "excitation light photon number”.
• the number of photons of light with a wavelength of 480 nm or less in result (I) was defined as the "number of transmitted light photons.”
• the number of photons of light with a wavelength of 480 nm or longer in result (I) was defined as the "number of emitted photons.”
• “Blue light absorption rate” and “conversion efficiency” were calculated by the following formulas.
• Tables 5 and 6 show the evaluation results of (2) and (3) above.

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