Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0041—Optical brightening agents, organic pigments
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/07—Aldehydes; Ketones
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
  • C08K5/357—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/02—Diffusing elements; Afocal elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • 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
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
• • 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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • 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

Definitions

• the present invention relates to a composition for forming a wavelength conversion film.
• Micro LED displays are expected to be the next generation of displays after 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 tiny LED chip is typically placed in each pixel.
• RGB-LED method As a method for arranging this LED chip, there is an RGB-LED method in which three-color LEDs are mounted, but problems with this method include the complexity of LED light emission control and the low performance of red LEDs. Wavelength conversion methods that can solve this problem are attracting attention.
• the wavelength conversion method uses only a blue LED chip and extracts red and green light using a wavelength conversion material, and has the advantage of being able to create the three primary colors using only the blue LED chip.
• wavelength conversion materials such as those using pyridine-phthalimide condensates (Patent Document 1, etc.), coumarin derivatives (Patent Document 2, etc.), and perylene.
• Patent Document 3 Those using derivatives (Patent Document 3, etc.), those using rhodamine derivatives (Patent Document 4), and those using pyrromethene derivatives (Patent Documents 5, 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 ester has high performance and good light resistance. It is disclosed that it can be used as a material. Further, in order to prevent deterioration of organic light-emitting materials and improve durability, a technique of adding a light stabilizer has also been disclosed (Patent Document 8, etc.). Furthermore, by adding fine particles to the wavelength conversion material, light scattering within the color conversion layer increases the optical path length and improves the blue light absorption rate, and the light reflected at the interface is scattered again. It is known that the luminous efficiency is improved by (Patent Documents 9, 10, etc.).
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a wavelength conversion film that provides a wavelength conversion film with excellent wavelength conversion efficiency and durability.
• a composition for forming a wavelength conversion film containing an organic phosphor, a cation-curable compound, and a photoacid generator has improved wavelength conversion efficiency and durability.
• the inventors have discovered that a wavelength conversion film with excellent properties can be provided, and have completed the present invention.
• the present invention provides the following composition for forming a wavelength conversion film.
• a composition for forming a wavelength conversion film containing (A) an organic phosphor, (B) a cationic curable compound, and (C) a photoacid generator.
• the organic phosphor (A) is one or more selected from the group consisting of fused ring thiophene compounds and perylene derivatives.
• the composition for forming a wavelength conversion film according to 2 wherein the perylene derivative is a perylene derivative represented by the following formula (A3).
• R A and R B are each independently a group represented by the following formula (a4-1) or (a4-2).
• G 1 is O or NR 43
• a 1 is an ethylene group or a propylene group
• n is an integer from 1 to 10
• R 41 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
• R43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
• an aryl group that may have a substituent or a heteroaryl group that may have a substituent The dashed lines are bonds.
• G 2 is O or NR 43 , L 2 is a single bond or an alkylene group which may have a substituent, R42 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
• R43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
• R44 is a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or a substituent.
• an optionally substituted heteroaryl group an optionally substituted alkylcarbonyl group, an optionally substituted alkenylcarbonyl group, an optionally substituted arylcarbonyl group, or an optionally substituted arylcarbonyl group; is an optionally heteroarylcarbonyl group
• R 42 and R 43 may combine with each other to form a ring with the nitrogen atom
• R 42 will not become OR 44
• L 2 is an alkylene group which may have a substituent
• R 42 cannot be a hydrogen atom
• R 42 is an alkyl group which may have a substituent
• L 2 is a single bond
• the dashed lines are bonds.
• R A and R B are groups represented by formula (a4-2), L 2 is a single bond, and R 42 is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Except in case. ] 5.
• the above (B) cationic curable compound is a compound having an epoxy group (excluding alkali-soluble resins), a compound having an oxetane group (excluding alkali-soluble resins), an N-alkoxymethylol compound, and a side chain.
• the cationic curable compound (B) is selected from the group consisting of compounds having an epoxy group (excluding alkali-soluble resins), compounds having an oxetane group (excluding alkali-soluble resins), and N-alkoxymethylol compounds.
• One or more selected types Furthermore, (D) a wavelength conversion film according to any one of 1 to 4 containing an alkali-soluble resin having a reactive functional group in a side chain for reacting with the cation-curable compound and having no cation-curable functional group. Forming composition. 7. 6. The composition for forming a wavelength conversion film according to 6, wherein the reactive functional group is a hydroxyl group. 8.
• the photoacid generator (C) is selected from the group consisting of onium salt compounds, metallocene complex compounds, iron arene complex compounds, disulfone compounds, sulfonic acid derivative compounds, triazine compounds, acetophenone derivative compounds, and diazomethane compounds.
• (E) the composition for forming a wavelength conversion film according to any one of 1 to 9 containing light scattering particles.
• 11. 10 Composition for forming a wavelength conversion film, wherein the light scattering particles (E) are titanium oxide particles. 12.
• composition for forming a wavelength conversion film according to 10 or 11 wherein the content of the light scattering particles (E) is 1% by mass or more based on the solid content.
• the composition for forming a wavelength conversion film according to any one of 1 to 12 wherein the content of the organic phosphor (A) is 0.1% by mass or more based on the solid content.
• the present invention it is possible to provide a composition for forming a wavelength conversion film that provides a wavelength conversion film with excellent wavelength conversion efficiency and durability.
• the composition for forming a wavelength conversion film of the present invention is characterized by containing (A) an organic phosphor, (B) a cationic curable compound, and (C) a photoacid generator.
• a solid content means the component other than the solvent which comprises the composition for wavelength conversion film formation.
• organic phosphor (A) examples include compounds having a fused aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene, and derivatives thereof; furan, pyrrole, and thiophene.
• a fused aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene, and derivatives thereof; furan, pyrrole, and thiophene.
• silole 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, etc.
• condensed thiophene compounds consisting of condensed thiophenes in which multiple thiophene rings are connected and derivatives thereof; 1,4-distyrylbenzene, 4,4'-bis(2-(4-diphenylamino Stilbene derivatives such as phenyl)ethenyl)biphenyl, 4,4'-bis(N-(stilben-4-yl)-N-phenylamino)stilbene; aromatic acetylene derivatives; tetraphenylbutadiene derivatives; aldazine derivatives; pyrromethene derivatives; Diketopyrrolo[3,4-c]pyrrole derivatives; Coumarin 7, Coumarin 153, coumarin compounds without benzothiazolyl group and derivatives thereof; Naphthophosphor oxide derivatives; imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole,
• azole derivatives and their metal complexes cyanine compounds such as indocyanine green; xanthene compounds and thioxanthene compounds such as fluorescein, eosin, and rhodamine; polyphenylene compounds, naphthalimide derivatives, phthalocyanine derivatives and their metal complexes, porphyrin derivatives and its metal complexes; oxazine compounds such as Nile Red and Nile Blue; helicene compounds; N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1 - Aromatic amine derivatives such as diamine; organometallic complex compounds such as iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os), rhenium (Re), etc. Examples include, but are not limited to, the following.
• fused ring thiophene compound a fused ring thiophene compound represented by the following formula (A1) and a fused ring thiophene compound represented by the following formula (A2) are preferable.
• Ar 11 and Ar 12 are each independently an aromatic ring which may have a substituent, and R 11 and R 12 are each independently a hydrogen atom and a substituent. R 11 and R 12 may bond with each other to form a ring with the adjacent nitrogen atom, and either or both of R 11 and R 12 may bond with Ar 12 to form a ring with the adjacent nitrogen atom.
• one of Y 11 and Y 12 is -SO 2 -, and the other is -S- or -SO 2 -.
• the aromatic rings represented by Ar 11 and Ar 12 include a monocyclic aromatic hydrocarbon ring such as a benzene ring, and polycyclic aromatic hydrocarbon rings such as a naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, and pyrene ring. , triphenylene ring, etc.
• the aromatic rings represented by Ar 11 and Ar 12 may have a substituent.
• substituents include a halogen atom, an alkyl group described below, a cycloalkyl group described below, a halogenated alkyl group, an aryl group described below, a heteroaryl group described below, a cyano group, a nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• Ar 11 and Ar 12 are preferably substituted or unsubstituted aromatic rings from the viewpoint of increasing absorption maximum wavelength and fluorescence maximum wavelength and further improving light resistance, and substituted or unsubstituted monocyclic aromatic carbonized rings are preferred.
• a hydrogen ring is more preferred.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Examples include alkyl groups having 1 to 10 carbon atoms such as tert-butyl group, and alkyl groups having 1 to 6 carbon atoms are preferred.
• the above alkyl group may have a substituent.
• substituents include a halogen atom, a cycloalkyl group described below, an aryl group described below, a heteroaryl group described below, a cyano group, a nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• cycloalkyl group examples include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group, with cycloalkyl groups having 4 to 8 carbon atoms being preferred.
• the above cycloalkyl group may have a substituent.
• substituents include a halogen atom, the alkyl group described above, an aryl group described below, a heteroaryl group described below, a cyano group, a nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the aryl group may be a monocyclic aryl group, a condensed aryl group, or a polycyclic aryl group, and specific examples thereof include a phenyl group as a monocyclic aryl group, and a naphthyl group and anthracenyl group as a condensed aryl group.
• polycyclic aryl groups include aryl groups having 6 to 18 carbon atoms such as biphenyl group and terphenyl group; aryl groups having 6 to 14 carbon atoms; Groups are preferred.
• the above aryl group may have a substituent.
• substituents include a halogen atom, the above-mentioned alkyl group, the above-mentioned aryl group, the below-mentioned heteroaryl group, cyano group, and nitro group.
• 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 ring heteroaryl group, and examples of the monocyclic heteroaryl group include pyrrolyl group, thienyl group, furanyl group, imidazolyl group, pyrazolyl group, thiazolyl group, oxazolyl group, and pyridyl group.
• Examples of the condensed heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.
• the above heteroaryl group may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above aryl group, the above heteroaryl group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• R 11 and R 12 are preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group, and even more preferably an unsubstituted aryl group.
• R 11 and R 12 may be bonded to each other to form a ring with adjacent nitrogen atoms.
• Examples of the ring formed by bonding R 11 and R 12 together with adjacent nitrogen atoms include the following groups.
• R 11 and R 12 may be bonded to Ar 12 to form a ring with the adjacent nitrogen atom.
• Examples of the ring in which either one or both of R 11 and R 12 is bonded to Ar 12 and formed together with the adjacent nitrogen atom include the following groups.
• the bonding position of the group represented by --NR 11 R 12 to Ar 12 is not particularly limited.
• Ar 12 is a benzene ring
• a compound represented by the following formula (A1') is likely to be formed.
• Ar 11 , Y 11 and Y 12 are the same as above.
• R 11 and R 12 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, and an optionally substituted aryl group. group, or a heteroaryl group which may have a substituent, R 11 and R 12 may be bonded to each other to form a ring with the adjacent nitrogen atom, and either R 11 or R 12 One or both may be bonded to an adjacent benzene ring to form a ring with the adjacent nitrogen atom.
• one of Y 11 and Y 12 is -SO 2 -, and the other is -S- or -SO 2 -.
• one of Y 11 and Y 12 is preferably -SO 2 - and the other is -S-, and Y 11 is -S- and it is more preferable that Y 12 is -SO 2 -.
• Y 11 and Y 12 are -S- or -SO 2 -, and Y 12 is -SO 2 - It is preferable that Y 11 and Y 12 are both -SO 2 -.
• R 11a and R 12a each independently have a hydrogen atom, an alkyl group that may have a substituent, and a substituent.
• Preferred specific examples of the compound represented by the above formula (A1) include compounds represented by the following formulas (A1-6) to (A1-8).
• the fused ring thiophene compound represented by the above formula (A1) 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 fused ring thiophene compound represented by the above formula (A1) and a solvent.
• the solvent for forming a solvate include dichloromethane, chloroform, acetonitrile, diethyl ether, ethyl acetate, methanol, ethanol, cyclohexane, toluene, acetone, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.
• the compound represented by the above formula (A1) not only has excellent light resistance but also excellent conversion efficiency, and is suitable as a wavelength conversion material for display use as a phosphor.
• the compound represented by the above formula (A1) can be synthesized by a known method, for example, by the method described in JP 2018-145422A.
• Ar 21 and Ar 22 are each independently an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent
• R 21 to R 24 are each Independently, a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
• R 21 to R 24 may not all be hydrogen atoms at the same time, and R 21 and R 22 may be bonded to each other to form a ring with the adjacent nitrogen atom, R 23 and R 24 may bond with each other to form a ring with the adjacent nitrogen atom, and either one or both of R 21 and R 22 may bond with Ar 21 to form a ring with the adjacent nitrogen atom. Either one or both of R 23 and R 24 may be bonded to Ar 22 to form a ring together with the adjacent nitrogen atom, and Y 21 and Y 22 may have one of -SO 2 - and the other is -S- or -SO 2 -.
• the aromatic rings represented by Ar 21 and Ar 22 include a benzene ring as a monocyclic aromatic hydrocarbon ring, and a naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, and pyrene ring as polycyclic aromatic hydrocarbon rings. , triphenylene ring, etc.
• the aromatic rings represented by Ar 21 and Ar 22 may have a substituent.
• substituents include the below-mentioned halogen atom, the below-mentioned alkyl group, the below-mentioned cycloalkyl group, the below-mentioned halogenated alkyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• heteroaromatic ring represented by Ar 21 and Ar 22 examples include a pyrrole ring, a thiophene ring, a furan ring, an imidazole ring, a pyrazole ring, a thiazole ring, an oxazole ring, a pyridine ring, and a pyrazine ring as monocyclic heteroaromatic rings.
• polycyclic heteroaromatic ring include an indole ring, isoindole ring, benzimidazole ring, quinoline ring, isoquinoline ring, and quinoxaline ring.
• the heteroaromatic ring represented by Ar 21 and Ar 22 may have a substituent.
• substituents include the below-mentioned halogen atom, the below-mentioned alkyl group, the below-mentioned cycloalkyl group, the below-mentioned halogenated alkyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, cyano group, and nitro group.
• the number of substituents, if present, is, for example, preferably 1 to 6, more preferably 1 to 3.
• Ar 21 and Ar 22 are preferably substituted or unsubstituted aromatic rings, from the viewpoint of increasing absorption maximum wavelength and fluorescence maximum wavelength and further improving light resistance, and substituted or unsubstituted monocyclic aromatic carbonized rings are preferred.
• a hydrogen ring is more preferred.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• the alkyl group may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, Examples include alkyl groups having 1 to 10 carbon atoms such as tert-butyl group, and alkyl groups having 1 to 6 carbon atoms are preferred.
• the above alkyl group may have a substituent.
• substituents include the above-mentioned halogen atom, the below-mentioned cycloalkyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• cycloalkyl group examples include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group, with cycloalkyl groups having 4 to 8 carbon atoms being preferred.
• the above cycloalkyl group may have a substituent.
• substituents include the above-mentioned halogen atom, the above-mentioned alkyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• halogenated alkyl group examples include a trifluoromethyl group and a pentafluoroethyl group.
• the aryl group may be a monocyclic aryl group, a condensed aryl group, or a polycyclic aryl group, and specific examples thereof include a phenyl group as a monocyclic aryl group, and a naphthyl group and anthracenyl group as a condensed aryl group.
• polycyclic aryl groups include aryl groups having 6 to 18 carbon atoms such as biphenyl group and terphenyl group; aryl groups having 6 to 14 carbon atoms; Groups are preferred.
• the above aryl group may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above aryl group, the below-mentioned heteroaryl group, cyano group, and nitro group.
• 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 ring heteroaryl group, and examples of the monocyclic heteroaryl group include pyrrolyl group, thienyl group, furanyl group, imidazolyl group, pyrazolyl group, thiazolyl group, oxazolyl group, and pyridyl group.
• Examples of the condensed heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.
• the above heteroaryl group may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above aryl group, the above heteroaryl group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• R 21 and R 22 are preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group, and even more preferably an unsubstituted aryl group.
• R 21 and R 22 may be bonded to each other to form a ring with adjacent nitrogen atoms.
• Examples of the ring formed by bonding R 21 and R 22 together with adjacent nitrogen atoms include the following groups.
• either one or both of R 21 and R 22 may be bonded to Ar 21 to form a ring with the adjacent nitrogen atom.
• Examples of the ring in which either one or both of R 21 and R 22 is bonded to Ar 21 and formed together with the adjacent nitrogen atom include the following groups.
• R 23 and R 24 are preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group, and even more preferably an unsubstituted aryl group.
• R 23 and R 24 may be bonded to each other to form a ring with adjacent nitrogen atoms.
• Examples of the ring in which R 23 and R 24 are bonded to each other and formed together with an adjacent nitrogen atom include, for example, the ring in which R 21 and R 22 are bonded to each other and formed together with an adjacent nitrogen atom, as described above. Examples include the groups shown.
• either one or both of R 23 and R 24 may be bonded to Ar 22 to form a ring with the adjacent nitrogen atom.
• the ring in which either one or both of R 23 and R 24 are bonded to Ar 22 and formed together with the adjacent nitrogen atom include, for example, in the above, one or both of R 21 and R 22 is Ar
• the groups shown as specific examples of the ring together with the adjacent nitrogen atom bonded to 21 can be mentioned.
• the bonding position of the group represented by -NR 21 R 22 to Ar 21 and the bonding position of the group represented by -NR 23 R 24 to Ar 22 are as follows: There are no particular restrictions. For example, when Ar 21 and Ar 22 are benzene rings, a compound represented by the following formula (A2') is likely to be formed.
• R 21 to R 24 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, and group or a heteroaryl group which may have a substituent, R 21 to R 24 do not all become hydrogen atoms at the same time, and R 21 and R 22 are bonded to each other to form an adjacent nitrogen atom.
• R 23 and R 24 may be bonded to each other to form a ring together with adjacent nitrogen atoms, and either one or both of R 21 and R 22 may be bonded to an adjacent benzene ring. may be combined with the adjacent nitrogen atom to form a ring, and either one or both of R 23 and R 24 may be combined with the adjacent benzene ring to form a ring with the adjacent nitrogen atom.
• one of Y 21 and Y 22 is -SO 2 -, and the other is -S- or -SO 2 -.
• one of Y 21 and Y 22 is -SO 2 - and the other is -S-.
• the compound represented by the above formula (A2) is used as a green light emitter, it is preferable that one of Y 21 and Y 22 is -S- and the other is -SO 2 -, and the above
• both Y 21 and Y 22 are preferably -SO 2 -.
• R 21a to R 24a are each independently a hydrogen atom, an alkyl group that may have a substituent, and a substituent.
• Preferred specific examples of the compound represented by the above formula (A2) include compounds represented by the following formulas (A2-4) and (A2-5).
• the fused ring thiophene compound represented by the above formula (A2) 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 fused ring thiophene compound represented by the above formula (A2) and a solvent.
• the solvent for forming a solvate include dichloromethane, chloroform, acetonitrile, diethyl ether, ethyl acetate, methanol, ethanol, cyclohexane, toluene, acetone, N,N-dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.
• the compound represented by the above formula (A2) not only has excellent light resistance but also excellent conversion efficiency, and is suitable as a wavelength conversion material for display use as a phosphor.
• the compound represented by the above formula (A2) can be synthesized with reference to known methods, for example, synthesized by the same procedure as the method described in JP-A-2018-145422 starting from paragraph [0084]. can do.
• perylene derivative a perylene derivative represented by the following formula (A3) and a perylene derivative represented by the following formula (A4) are preferable.
• R A and R B are each independently a group represented by the following formula (a4-1) or (a4-2).
• G 1 is O or NR 43 , with O being preferred.
• a 1 is an ethylene group or a propylene group, and an ethylene group is preferable.
• n is an integer of 1 to 10, preferably 1 to 8, and more preferably 1 to 6.
• R 41 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
• the alkyl group represented by R 41 may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. , sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, decyl group, eicosanyl group, and other alkyl groups having 1 to 40 carbon atoms; 20 alkyl groups are preferred.
• the alkyl group represented by R 41 above may have a substituent.
• substituents include the below-mentioned halogen atom, the below-mentioned cycloalkyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the cycloalkyl group represented by R 41 include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; Alkyl groups are preferred.
• the cycloalkyl group represented by R 41 above may have a substituent.
• substituents include the above-mentioned halogen atom, the above-mentioned alkyl group, the below-mentioned alkenyl group, the below-mentioned alkynyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, isobutynyl group, s-butynyl group, t-butynyl group, and the like.
• alkenyl group represented by R 41 examples include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, butenyl group, isobutenyl group, s-butenyl group, t-butenyl group, and the like.
• the alkenyl group represented by R 41 above may have a substituent.
• substituents include the above-mentioned halogen atom, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the aryl group represented by R 41 may be any of a monocyclic aryl group, a condensed aryl group, and a polycyclic aryl group, and specific examples thereof include a phenyl group as a monocyclic aryl group, and a condensed aryl group. Examples of the group include naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, pyrenyl group, triphenylenyl group, etc.
• Polycyclic aryl groups include aryl groups having 6 to 18 carbon atoms such as biphenyl group and terphenyl group, and carbon Preferably, the number of aryl groups is 6 to 14.
• the aryl group represented by R 41 above may have a substituent.
• substituents include the above-mentioned halogen atom, the above-mentioned alkyl group, the below-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, nitro group, etc.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• halogenated alkyl group examples include a trifluoromethyl group and a pentafluoroethyl group.
• the heteroaryl group represented by R 41 may be either a monocyclic heteroaryl group or a condensed ring heteroaryl group, and examples of the monocyclic heteroaryl group include pyrrolyl group, thienyl group, furanyl group, imidazolyl group, pyrazolyl group, and thiazolyl group.
• Examples of the condensed heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.
• the heteroaryl group represented by R 41 above may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above halogenated alkyl group, the above alkenyl group, the above alkynyl group, the above aryl group, the above heteroaryl group, the cyano group, and the nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• alkylcarbonyl group represented by R 41 examples include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, c-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, t-butylcarbonyl group, c-butylcarbonyl group, 1-methyl-c-propylcarbonyl group, 2-methyl-c-propylcarbonyl group, n-pentylcarbonyl group, 1-methyl-n- Butylcarbonyl group, 2-methyl-n-butylcarbonyl group, 3-methyl-n-butylcarbonyl group, 1,1-dimethyl-n-propylcarbonyl group, 1,2-dimethyl-n-propylcarbonyl group, 2, 2-dimethyl-n-propylcarbonyl group, 1-ethyl-n-propy
• the alkylcarbonyl group represented by R 41 above may have a substituent.
• substituents include the above halogen atom, the above cycloalkyl group, the above aryl group, the above heteroaryl group, hydroxy group, cyano group, nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• alkenylcarbonyl group represented by R 41 examples include ethenylcarbonyl group, 1-propenylcarbonyl group, 2-propenylcarbonyl group, 1-methyl-1-ethenylcarbonyl group, 1-butenylcarbonyl group, and 2-butenylcarbonyl group.
• the alkenylcarbonyl group represented by R 41 above may have a substituent.
• substituents include the above halogen atom, the above aryl group, the above heteroaryl group, hydroxy group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• Examples of the arylcarbonyl group represented by R 41 include arylcarbonyl groups having 7 to 16 carbon atoms such as benzoyl, naphthoyl and anthracenyl groups, with arylcarbonyl groups having 7 to 11 carbon atoms being preferred.
• the arylcarbonyl group represented by R 41 above may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above halogenated alkyl group, the above alkenyl group, the above alkynyl group, the above aryl group, the above heteroaryl group, the cyano group, and the nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• heteroarylcarbonyl group represented by R 41 examples include pyrrolylcarbonyl group, thienylcarbonyl group, furanylcarbonyl group, imidazolylcarbonyl group, pyrazolylcarbonyl group, thiazolylcarbonyl group, oxazolylcarbonyl group, and pyridylcarbonyl group.
• a heteroarylcarbonyl group having 4 to 12 carbon atoms such as a pyrazylcarbonyl group, an indolylcarbonyl group, an isoindolylcarbonyl group, a benzimidazolylcarbonyl group, a quinolylcarbonyl group, an isoquinolylcarbonyl group, a quinoxalylcarbonyl group, A heteroarylcarbonyl group having 4 to 10 carbon atoms is preferred.
• the above heteroarylcarbonyl group may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above halogenated alkyl group, the above alkenyl group, the above alkynyl group, the above aryl group, the above heteroaryl group, the cyano group, the nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• R43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. It is an aryl group which may have a substituent or a heteroaryl group which may have a substituent.
• the alkyl group represented by R 43 may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. Examples include alkyl groups having 1 to 10 carbon atoms such as , sec-butyl group, and tert-butyl group, with alkyl groups having 1 to 6 carbon atoms being preferred.
• the alkyl group represented by R 43 above may have a substituent.
• substituents include the above-mentioned halogen atom, the below-mentioned cycloalkyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• Examples of the cycloalkyl group represented by R 43 include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; Alkyl groups are preferred.
• the cycloalkyl group represented by R 43 above may have a substituent.
• substituents include the above-mentioned halogen atom, the above-mentioned alkyl group, the below-mentioned alkenyl group, the below-mentioned alkynyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• alkenyl group represented by R 43 examples include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, butenyl group, isobutenyl group, s-butenyl group, t-butenyl group, and the like.
• the alkenyl group represented by R 43 above may have a substituent.
• substituents include the below-mentioned halogen atom, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the aryl group represented by R 43 may be any of a monocyclic aryl group, a condensed aryl group, and a polycyclic aryl group. Specific examples thereof include a phenyl group as a monocyclic aryl group, and a condensed aryl group. Examples of the group include naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, pyrenyl group, triphenylenyl group, etc.
• Polycyclic aryl groups include aryl groups having 6 to 18 carbon atoms such as biphenyl group and terphenyl group, and carbon Preferably, the number of aryl groups is 6 to 14.
• the aryl group represented by R 43 above may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above halogenated alkyl group, the above alkenyl group, the above alkynyl group, the above aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, nitro group, and pentafluorosulfanyl group. etc.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the heteroaryl group represented by R 43 may be either a monocyclic heteroaryl group or a condensed ring heteroaryl group, and examples of the monocyclic heteroaryl group include pyrrolyl group, thienyl group, furanyl group, imidazolyl group, pyrazolyl group, and thiazolyl group.
• Examples of the fused heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.
• the heteroaryl group represented by R 43 above may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above halogenated alkyl group, the above alkenyl group, the above alkynyl group, the above aryl group, the above heteroaryl group, cyano group, nitro group, pentafluorosulfanyl group, etc. .
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• G2 is O or NR43 , preferably O or NH.
• L 2 is a single bond or an alkylene group which may have a substituent.
• the alkylene group represented by L 2 may be linear, branched, or cyclic, and specific examples include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, 1,2-dimethylethylene group, and tetramethyl group. Carbon such as ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group Examples include alkylene groups having 1 to 20 carbon atoms, and alkylene groups having 1 to 14 carbon atoms are preferred.
• the alkylene group represented by L 2 above may have a substituent.
• substituents include the above halogen atom, the above cycloalkyl group, the above aryl group, the above heteroaryl group, the below-mentioned alkylcarbonyloxy group, hydroxy group, cyano group, nitro group, oxo group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• alkylcarbonyloxy group examples include methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, c-propylcarbonyloxy group, n-butylcarbonyloxy group, and i-butylcarbonyloxy group.
• R42 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
• the alkyl group represented by R 42 may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. , sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, decyl group, eicosanyl group, and other alkyl groups having 1 to 40 carbon atoms; 20 alkyl groups are preferred.
• the alkyl group represented by R 42 above may have a substituent.
• substituents include the below-mentioned halogen atom, the below-mentioned cycloalkyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, nitro group, oxo group, and epoxy group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the cycloalkyl group represented by R 42 include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; Alkyl groups are preferred.
• the cycloalkyl group represented by R 42 above may have a substituent.
• substituents include the above-mentioned halogen atom, the above-mentioned alkyl group, the below-mentioned alkenyl group, the below-mentioned alkynyl group, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, isobutynyl group, s-butynyl group, t-butynyl group, and the like.
• alkenyl group represented by R 42 examples include vinyl, 1-propenyl, 2-propenyl, isopropenyl, butenyl, isobutenyl, s-butenyl, t-butenyl, and the like.
• the alkenyl group represented by R 42 above may have a substituent.
• substituents include the above-mentioned halogen atom, the below-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the aryl group represented by R 42 may be any of a monocyclic aryl group, a condensed aryl group, and a polycyclic aryl group, and specific examples thereof include a phenyl group as a monocyclic aryl group, and a condensed aryl group. Examples of the group include naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, pyrenyl group, triphenylenyl group, etc.
• Polycyclic aryl groups include aryl groups having 6 to 18 carbon atoms such as biphenyl group and terphenyl group, and carbon Preferably, the number of aryl groups is 6 to 14.
• the aryl group represented by R 42 above may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the below-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the below-mentioned heteroaryl group, hydroxy group, cyano group, nitro group, pentafluorosulfanyl group.
• substituents include groups. When it has a substituent, the number thereof is preferably 1 to 6, more preferably 1 to 3.
• halogenated alkyl group examples include a trifluoromethyl group and a pentafluoroethyl group.
• the heteroaryl group represented by R 42 may be either a monocyclic heteroaryl group or a condensed ring heteroaryl group, and examples of the monocyclic heteroaryl group include pyrrolyl group, thienyl group, furanyl group, imidazolyl group, pyrazolyl group, and thiazolyl group.
• Examples of the fused heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.
• the heteroaryl group represented by R 42 above may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above halogenated alkyl group, the above alkenyl group, the above alkynyl group, the above aryl group, the above heteroaryl group, the cyano group, and the nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• alkylcarbonyl group represented by R 42 examples include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, c-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, t-butylcarbonyl group, c-butylcarbonyl group, 1-methyl-c-propylcarbonyl group, 2-methyl-c-propylcarbonyl group, n-pentylcarbonyl group, 1-methyl-n- Butylcarbonyl group, 2-methyl-n-butylcarbonyl group, 3-methyl-n-butylcarbonyl group, 1,1-dimethyl-n-propylcarbonyl group, 1,2-dimethyl-n-propylcarbonyl group, 2, 2-dimethyl-n-propylcarbonyl group, 1-ethyl-n-propy
• the alkylcarbonyl group represented by R 42 above may have a substituent.
• substituents include the above halogen atom, the above cycloalkyl group, the above aryl group, the above heteroaryl group, hydroxy group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• alkenylcarbonyl group represented by R 42 examples include ethenylcarbonyl group, 1-propenylcarbonyl group, 2-propenylcarbonyl group, 1-methyl-1-ethenylcarbonyl group, 1-butenylcarbonyl group, and 2-butenylcarbonyl group.
• the alkenylcarbonyl group represented by R 42 above may have a substituent.
• substituents include the above halogen atom, the above aryl group, the above heteroaryl group, hydroxy group, cyano group, and nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• the arylcarbonyl group represented by R 42 includes arylcarbonyl groups having 7 to 16 carbon atoms such as benzoyl group, naphthoyl group, and anthracenyl group, with arylcarbonyl groups having 7 to 11 carbon atoms being preferred.
• the arylcarbonyl group represented by R 42 above may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above halogenated alkyl group, the above alkenyl group, the above alkynyl group, the above aryl group, the above heteroaryl group, the cyano group, and the nitro group.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• heteroarylcarbonyl group represented by R 42 examples include pyrrolylcarbonyl group, thienylcarbonyl group, furanylcarbonyl group, imidazolylcarbonyl group, pyrazolylcarbonyl group, thiazolylcarbonyl group, oxazolylcarbonyl group, and pyridylcarbonyl group.
• a heteroarylcarbonyl group having 4 to 12 carbon atoms such as a pyrazylcarbonyl group, an indolylcarbonyl group, an isoindolylcarbonyl group, a benzimidazolylcarbonyl group, a quinolylcarbonyl group, an isoquinolylcarbonyl group, a quinoxalylcarbonyl group, A heteroarylcarbonyl group having 4 to 10 carbon atoms is preferred.
• the above heteroarylcarbonyl group may have a substituent.
• substituents include the above halogen atom, the above alkyl group, the above halogenated alkyl group, the above alkenyl group, the above alkynyl group, the above aryl group, the above heteroaryl group, the cyano group, the nitro group, and the like.
• the number thereof is preferably 1 to 6, more preferably 1 to 3.
• R43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
• alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and heteroaryl groups, as well as the substituents these groups have. Examples include the same groups as exemplified for R 43 in formula (a4-1) above.
• R44 is a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an aryl group that may have a substituent, or a substituent.
• an optionally substituted heteroaryl group an optionally substituted alkylcarbonyl group, an optionally substituted alkenylcarbonyl group, an optionally substituted arylcarbonyl group, or an optionally substituted arylcarbonyl group;
• R 42 and R 43 may be bonded to each other to form a ring with the nitrogen atom, and L 2 is a single bond.
• R 42 never becomes OR 44
• L 2 is an alkylene group that may have a substituent
• R 42 never becomes a hydrogen atom
• R 42 never becomes OR 44.
• L 2 is a single bond.
• R A and R B may be the same or different, but are preferably the same group.
• R A and R B are groups represented by formula (a4-2), L 2 is a single bond, and R 42 is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Except in case.
• the bonding positions of R A and R B above to the perylene structure are not particularly limited, but these bonding positions are preferably those represented by the following formulas (A4-1) to (A4-3). .
• the group represented by the above formula (a4-1) is preferably a group represented by any of the following formulas (a4-1-1) to (a4-1-4). (In the formula, R 41 and n are the same as above.)
• the group represented by the above formula (a4-2) is preferably a group represented by any of the following formulas (a4-2-1) to (a4-2-2).
• m is an integer from 1 to 20.
• R 42 is the same as above.
• organic phosphor represented by (A4) above include organic phosphors represented by the following formulas (A4-4) to (A4-16).
• the compounds represented by the above formulas (A3) and (A4) not only have excellent heat resistance, solubility, and light resistance, but also have excellent conversion efficiency, and are suitable as wavelength conversion materials for display applications as phosphors.
• the compound represented by the above formula (A4) can be synthesized with reference to known methods, but the synthesis method is not particularly limited as long as the desired compound can be obtained.
• the content of the organic phosphor (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and more preferably 0.5% by mass based on the solid content. It is even more preferable that the amount is % by mass or more.
• the upper limit of the content of the organic phosphor (A) is not particularly limited, but considering that the fluorescence quantum yield decreases when the organic phosphor is highly concentrated, 50% by mass or less in the solid content is It is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, particularly preferably 5% by mass or less. Note that the organic phosphor (A) may be used alone or in combination of two or more.
• composition for forming a wavelength conversion film of the present invention other organic phosphors other than the compounds represented by the above formulas (A1) to (A4) may be used as the organic phosphor to the extent that the effects of the present invention are not impaired. May include.
• organic phosphors mentioned above include cyanine dyes such as 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; 1-ethyl-2-[4-(p-dimethyl Pyridine dyes such as aminophenyl)-1,3-butadienyl]-pyridium-perchlorate; Rhodamine dyes such as Rhodamine B and Rhodamine 6G; Red converting phosphors such as oxazine dyes, 2,3,5,6- 1H,4H-tetrahydro-8-trifluoromethylquinolidino(9,9a,1-gh)coumarin, 3-(2'-benzothiazolyl)-7-diethylaminocoumarin, 3-(2'-benzimidazolyl)-7 Examples include coumarin dyes such as -N,N-diethylaminocoumarin; and green-converting phosphors such as naphthalimide dyes such as Sol
• organic phosphors When other organic phosphors are included, their content is preferably 5% by mass or less in the solid content, more preferably 2% by mass or less, and even more preferably not included (0% by mass).
• the above-mentioned cation-curable compound is a compound that undergoes a polymerization or crosslinking reaction with the acid generated by the acid generator.
• the above-mentioned cationic curable compounds include compounds having an epoxy group (excluding alkali-soluble resins, hereinafter referred to as "epoxy compounds”), compounds having oxetane groups (excluding alkali-soluble resins, hereinafter referred to as "epoxy compounds”), ), N-alkoxymethylol compounds, alkali-soluble resins having at least one cation-curable functional group in the side chain (hereinafter referred to as "cation-curable alkali-soluble resins”), etc. can be mentioned.
• the above cationic curable compounds may be used alone or in combination of two or more.
• Epoxy compound The epoxy compound is not particularly limited as long as it has an epoxy group, but excludes the alkali-soluble resin described below. Further, in the present invention, a compound containing both an epoxy group and an oxetane group corresponds to an epoxy compound.
• the epoxy compounds include aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and the like.
• the epoxy compound preferably contains at least one of an alicyclic epoxy compound and an alicyclic epoxy compound, and more preferably contains at least an alicyclic epoxy compound, and an alicyclic epoxy compound. It is preferable to include both group epoxy compounds and aliphatic epoxy compounds.
• alicyclic epoxy compounds include those containing an aliphatic ring, such as polyglycidyl ethers of polyhydric alcohols having at least one aliphatic ring, and compounds containing cyclohexene and cyclopentene rings as oxidizing agents. Examples include cyclohexene oxide and cyclopentene oxide-containing compounds obtained by epoxidation with. In the present invention, from the viewpoint of curing speed, among the above alicyclic epoxy compounds, epoxy resins having a cyclohexene oxide structure are preferred.
• alicyclic epoxy compound a compound having two or more cyclohexene oxide structures can be preferably used, and examples thereof include a compound represented by the following formula (B1).
• X b1 represents a single bond or a connecting group (a divalent group having one or more atoms).
• the linking group represented by group, and a group in which a plurality of these are connected.
• divalent hydrocarbon group examples include linear or branched alkylene groups having 1 to 30 carbon atoms, and alkylene groups having 1 to 30 carbon atoms having a cycloalkyl ring.
• Examples of the linear or branched alkylene group having 1 to 30 carbon atoms include groups obtained by removing one hydrogen atom from a linear or branched alkyl group having 1 to 30 carbon atoms.
• Examples of the alkylene group having 1 to 30 carbon atoms and having a cycloalkyl ring include a group obtained by removing one hydrogen atom from an alkyl group having 1 to 30 carbon atoms and having a cycloalkyl ring.
• linear or branched alkylene group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, and isopentyl group.
• t-pentyl group hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, t-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group
• Examples include groups obtained by removing one hydrogen atom from a linear or branched alkyl group having 1 to 20 carbon atoms, such as octadecyl group and icosyl group.
• the linear or branched alkylene group having 1 to 20 carbon atoms as the divalent hydrocarbon group include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, etc. can.
• a cycloalkyl group can be used as the alkyl group having a cycloalkyl ring.
• the cycloalkyl group include a monocyclic hydrocarbon group, a bridged hydrocarbon ring group, and the like.
• monocyclic hydrocarbon groups include groups obtained by removing one hydrogen atom from a monocyclic hydrocarbon ring such as a cyclohexyl ring, and hydrogen atoms in the ring of groups obtained by removing one hydrogen atom from a monocyclic hydrocarbon ring.
• Examples include groups in which one or more of the following are substituted with an aliphatic hydrocarbon group.
• Examples of the bridged hydrocarbon ring group include a group obtained by removing one hydrogen atom from a cycloalkyl ring such as a bridged hydrocarbon ring such as a norbornyl ring, and a hydrogen atom in the ring of a group obtained by removing one hydrogen atom from a bridged hydrocarbon ring.
• Examples include groups in which one or more of the following are substituted with an aliphatic hydrocarbon group.
• the monocyclic hydrocarbon group examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, methylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl group.
• bridged hydrocarbon ring group examples include bicyclo[2.1.1]hexyl group, bicyclo[2.2.1]heptyl group, bicyclo[2.2.2]octyl group, and bicyclo[4.3] .1] Decyl group, bicyclo[3.3.1]nonyl group, bornyl group, bornenyl group, norbornyl group, norbornenyl group, 6,6-dimethylbicyclo[3.1.1]heptyl group, tricyclobutyl group, Examples include adamantyl group.
• the alkyl group having a cycloalkyl ring represented by X b1 may be a combination of the above cycloalkyl group and the above linear or branched alkyl group.
• Examples include groups substituted with alkyl groups such as Specifically, 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cycl
• alkenylene group in which part or all of the carbon-carbon double bond is epoxidized includes vinylene group, propenylene group, 1- Examples include linear or branched alkenylene groups having 2 to 8 carbon atoms, such as a butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, and octenylene group.
• X b1 is preferably a linking group, preferably a divalent hydrocarbon group, an ester bond, or a group in which a plurality of these are connected, particularly a divalent hydrocarbon group and an ester bond. It is preferable that it is a group in which these are linked.
• the divalent hydrocarbon group represented by X b1 is an alkylene group obtained by removing one hydrogen atom from a linear or branched alkyl group having 1 to 18 carbon atoms. is preferable, and an alkylene group obtained by removing one hydrogen atom from a linear or branched alkyl group having 1 to 8 carbon atoms is more preferable. An alkylene group with one atom removed is even more preferable, and an alkylene group with one hydrogen atom removed from a linear alkyl group having 1 to 3 carbon atoms is even more preferable.
• preferred compounds having two or more cyclohexene oxide structures include compounds represented by the following formulas (B1-1) to (B1-2).
• alicyclic epoxy compound a compound represented by the following formula (B2) can also be suitably used.
• Z b1 represents an alkylene group having 6 to 30 carbon atoms and having a cycloalkyl ring.
• the alkylene group having 1 to 30 carbon atoms and having a cycloalkyl ring represented by Z b1 includes the same groups as the alkylene group having a cycloalkyl ring represented by X b1 above.
• Z b1 is preferably an alkylene group having 13 to 20 carbon atoms and having two cycloalkyl rings from the viewpoint of obtaining a cured product having a steeper absorption peak in the desired wavelength range.
• a group represented by the following formula (B3) is more preferable.
• R b2 and R b3 represent a hydrogen atom or a methyl group, and * represents a bonding site.
• alicyclic epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3, 4-Epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3, 4-Epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexane-
• alicyclic epoxy compound A cycloalkyl rings derived from epoxycycloalkyl rings such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol may be used.
• alicyclic epoxy compound Commercially available products can be used as the alicyclic epoxy compound, and specific examples include those described in Japanese Patent No. 6103653.
• the above alicyclic epoxy compounds may be used alone or in combination of two or more.
• the content of the alicyclic epoxy compound may be any amount that allows a cured product with excellent film forming properties and curability to be obtained, but preferably 0 parts by mass or more based on 100 parts by mass of the cationic curable compound. More preferably 2 parts by weight or more, even more preferably 5 parts by weight or more, particularly preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, most preferably 20 parts by weight or more. Further, when the content of the epoxy compound is 90 parts by mass or less in 100 parts by mass of the cationically curable compound, the content of the alicyclic epoxy compound is preferably 0 to 80 parts by mass in 100 parts by mass of the cationically curable compound.
• Parts by weight more preferably 10 to 60 parts by weight, even more preferably 15 to 35 parts by weight, even more preferably 20 to 25 parts by weight.
• the above composition can provide a cured product with good curability.
• aromatic epoxy compounds include polyhydric phenols having at least one aromatic ring, polyglycidyl ethers of alkylene oxide adducts thereof, such as bisphenol A, bisphenol F, or alkylene oxide adducts thereof.
• glycidyl ethers of compounds and phenol novolak type epoxy compounds glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; alcoholic compounds such as benzenedimethanol, benzenediethanol, and benzenedibutanol
• Polyglycidyl ethers of aromatic compounds having two or more hydroxyl groups polyglycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid, benzoic acid and toluic acid , polyglycidyl esters of benzoic acids such as naphthoic acid, glycidyl esters of benzoic acid, epoxidized products of styrene oxide or divinylbenzene, and the like.
• polyglycidyl ethers of phenols polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups
• polyglycidyl ethers of polyhydric phenols polyglycidyl esters of benzoic acids
• polyglycidyls of polybasic acids It is preferable to contain at least one member selected from the group of esters, and particularly preferably a polyglycidyl etherified aromatic compound having two or more alcoholic hydroxyl groups. This is because it becomes possible to obtain a cured product with excellent light absorption in a desired wavelength range.
• aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and vinyl polymerization of glycidyl acrylate or glycidyl methacrylate. Examples include synthesized homopolymers, copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, and other vinyl monomers, and the like.
• the polyglycidyl ether of the aliphatic polyhydric alcohol or its alkylene oxide adduct a diglycidyl ether of an aliphatic diol compound is preferable, and a compound represented by the following formula (B4) is particularly preferable.
• the above-mentioned compound has excellent light absorption in a desired wavelength range, and the cured product thereof has good adhesion to the base material. Moreover, the above composition provides a cured product having a steeper absorption peak in a desired wavelength range.
• Z b2 represents a linear or branched alkylene group having 1 to 30 carbon atoms.
• the linear or branched alkylene group having 1 to 30 carbon atoms represented by Z b2 is the same as the linear or branched alkylene group having 1 to 30 carbon atoms represented by Z b1 above.
• the following groups are mentioned.
• one or more methylene groups of the alkylene group having 1 to 30 carbon atoms may be replaced with -O-.
• the methylene group in the above alkylene group is replaced with -O-, it is replaced with -O- under the condition that oxygen atoms in the above alkylene group are not adjacent to each other.
• the above Z b2 is preferably a branched alkylene group from the viewpoint of obtaining a cured product having a steeper absorption peak in a desired wavelength range. This is because, by having the above-mentioned structure, the above-mentioned composition can obtain a cured product having a steeper absorption peak in a desired wavelength range.
• the above Z b2 is preferably a linear or branched alkylene group having 2 to 30 carbon atoms, from the viewpoint of obtaining a cured product having a steeper absorption peak in the desired wavelength range; It is more preferably a linear or branched alkylene group having 28 to 28 carbon atoms, and even more preferably a linear or branched alkylene group having 4 to 26 carbon atoms. Further, when Z b2 is an alkylene group in which the methylene group is not replaced with -O-, the number of carbon atoms is preferably 4 to 10, more preferably 4 to 8.
• Z b2 is an alkylene group in which the methylene group is replaced with -O-
• Z b2 is an alkylene group having 10 to 26 carbon atoms and having a structure obtained by removing the hydroxyl groups at both ends of polyalkylene glycol. It is preferably an alkylene group having 10 to 26 carbon atoms, and more preferably an alkylene group having a structure obtained by removing the hydroxyl groups at both ends from polyethylene glycol or polypropylene glycol, and having 15 to 24 carbon atoms. More preferably, it is an alkylene group having a structure obtained by removing the hydroxyl groups at both ends from glycol or polypropylene glycol. This is because the above composition can provide a cured product having a steeper absorption peak in a desired wavelength range.
• diglycidyl etherified aliphatic diol compound represented by the above formula (B4) examples include diglycidyl of polyalkylene glycol such as diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether.
• Etherified products ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, cyclohexane dimethylol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1 , 9-nonanediol diglycidyl ether and the like.
• Representative aliphatic epoxy compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, Glycidyl ethers of polyhydric alcohols such as tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol; aliphatic polyvalents such as propylene glycol, trimethylolpropane, and glycerin Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to alcohol; diglycidyl esters of aliphatic long-chain dibasic acids, and the like.
• monoglycidyl ethers of aliphatic higher alcohols phenol, cresol, butylphenol, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy Examples include octyl stearate, epoxybutyl stearate, and epoxidized polybutadiene.
• the aliphatic epoxy resin may not contain an aliphatic ring or an aromatic ring.
• aromatic and aliphatic epoxy compounds Commercially available products can be used as the aromatic and aliphatic epoxy compounds, and specific examples include those described in Japanese Patent No. 6103653.
• the content of the epoxy compound may be any amount that allows a cured product with excellent light absorption in the desired wavelength range to be obtained, but for example, it is preferably 10 parts by mass or more in 100 parts by mass of the cationic curable compound. , more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more. By setting the content within the above range, a cured product with excellent film-forming properties and curability can be obtained.
• the oxetane compound may have an oxetane structure and not contain an epoxy structure.
• oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, 3-ethyl-3- ⁇ [(3-ethyl- 3-oxetanyl)methoxy]methyl ⁇ oxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1 -(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3-e
• a preferred oxetane compound is a compound represented by the following formula (B5) (3-ethyl-3- ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ oxetane). I can do it.
• the content of the oxetane compound may be any amount that allows a cured product with excellent light absorption in the desired wavelength range to be obtained, but preferably 1 to 100 parts by mass based on 100 parts by mass of the cationic curable compound, More preferably 25 to 95 parts by weight, even more preferably 50 to 90 parts by weight, even more preferably 60 to 80 parts by weight.
• the content within the above range, it is possible to obtain a cured product with excellent film-forming properties and curability.
• cationic curable compounds such as thiirane compounds and thietane compounds can also be used as the cationic curable compounds.
• cationic curable compounds such as cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro-orthoester compounds, and vinyl compounds such as vinyl ether compounds and ethylenically unsaturated compounds. can be similar to the content described in Japanese Patent No. 6103653 and the like.
• N-alkoxymethylol compounds are crosslinkable compounds that have two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, and when exposed to high temperatures during thermosetting, the crosslinking reaction proceeds through a dehydration condensation reaction. It is something. Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
• alkoxymethylated glycoluril examples include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(butoxymethyl)glycoluril.
• -tetrakis(hydroxymethyl)glycoluril 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea
• examples include 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone.
• N-alkoxymethylol compounds can be used, and specific examples include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd.
• methylated urea resin product name: UFR (registered trademark) 65
• butylated urea resin product name: UFR (registered trademark) 300
• U-VAN10S60 product name: U-VAN10R, U-VAN11HV
• DIC Corporation urea/formaldehyde resins (highly condensed type, trade names: Beckamine (registered trademark) J-300S, Beckamine (registered trademark) P-955, Beckamin (registered trademark) N), etc.
• alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine and the like.
• alkoxymethylated benzoguanamine commercially available products can be used, and specific examples include Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (product name: Nikalac). (registered trademark) BX-4000, BX-37, BL-60, BX-55H), etc.
• alkoxymethylated melamine examples include hexamethoxymethylmelamine and the like.
• alkoxymethylated melamine commercially available products can be used, and specific examples include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: Cymel (registered trademark) 300, Cymel (registered trademark) 301, Cymel (registered trademark) 301, Cymel (registered trademark)).
• butoxymethyl type melamine compound (trade name: Mycoat (registered trademark) 506, same 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical (trade name: Nikalac (registered trademark) MW-30, same) MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compound (product name: Nikalac) (registered trademark) MX-45, MX-410, MX-302), etc.
• It may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
• a melamine compound a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
• examples include high molecular weight compounds made from melamine and benzoguanamine compounds as described in US Pat. No. 6,323,310.
• melamine compound commercially available products can be used, and specific examples thereof include the trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the above-mentioned benzoguanamine compound include: Trade name: Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.) and the like.
• N-alkoxymethylol compound an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc.
• polymers produced using methacrylamide compounds can also be used.
• Such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-ethoxymethyl.
• Examples include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
• the weight average molecular weight (Mw) of such a polymer is preferably 1,000 to 50,000, more preferably 1,500 to 20,000, even more preferably 2,000 to 10,000.
• alkali-soluble resin having at least one cation-curable functional group in the side chain examples include an epoxy group, an oxetane group, an N-alkoxymethyl group, etc. It will be done.
• the above-mentioned cation-curable functional group can be introduced into the cation-curable alkali-soluble resin by using an unsaturated compound having the cation-curable functional group.
• Examples of the unsaturated compound having a cationically curable functional group include (3-ethyloxetan-3-yl)methyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and N-(butoxymethyl)acrylamide.
• Commercially available products can be used as these compounds, and specific examples thereof include OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and M100 (manufactured by Daicel Corporation).
• the content of cationically curable functional groups in the cationically curable alkali-soluble resin is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin, and from the viewpoint of solvent resistance, More preferably, the number is 0.1 to 0.6.
• alkali-soluble resin is a resin having an alkali-soluble group.
• alkali-soluble groups include phenolic hydroxy groups, carboxy groups, acid anhydride groups, imide groups, sulfonyl groups, phosphoric acid, boronic acid groups, and active methylene groups.
• the active methylene group refers to a methylene group (-CH 2 -) having a carbonyl group at an adjacent position and having reactivity with a nucleophile.
• a group represented by the following formula (b1) is more preferable.
• R b4 represents an alkyl group, an alkoxy group, or a phenyl group, and the broken line represents a bond.
• the alkyl group represented by R b4 includes, for example, an alkyl group having 1 to 20 carbon atoms, and 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, methyl, ethyl and n-propyl groups are preferred.
• the alkoxy group represented by R b4 includes, for example, an alkoxy group having 1 to 20 carbon atoms, and preferably an alkoxy group having 1 to 5 carbon atoms.
• Specific examples of such alkoxy groups include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, etc. .
• methoxy, ethoxy and n-propoxy groups are preferred.
• alkali-soluble groups it is preferable to have at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxy group.
• the alkali-soluble resin has only to have the above structure and at least one cation-curable functional group in the side chain, and there are no particular limitations on the main chain skeleton of the polymer constituting the resin. .
• alkali-soluble resin examples include acrylic resins, polyhydroxystyrene resins, polyimide precursors, polyimides, and polyesters.
• 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 reacting an unsaturated double bond group portion through a polymerization reaction of a monomer having an unsaturated double bond group.
• the alkali-soluble acrylic polymer includes a monomer exhibiting alkali solubility, that is, a monomer having at least one type selected from the above-mentioned alkali-soluble groups, and at least one type selected from the group of monomers copolymerizable with these monomers. Examples include copolymers formed with monomers as essential structural units.
• the above-mentioned "monomer having at least one type selected from alkali-soluble groups” includes monomers having a carboxy group, phenolic hydroxy groups, and imide groups. These monomers are not limited to those having one carboxy group or phenolic hydroxy group, but may have a plurality of them.
• Monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, and N-(carboxyphenyl)maleimide. , N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.
• Examples of 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 alkali-soluble group to the monomer having an unsaturated double bond group is preferably 5 to 90 mol% of all the monomers used in the production of the alkali-soluble acrylic polymer. , more preferably 10 to 60 mol%, most preferably 10 to 40 mol%. Sufficient alkali solubility can be 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 above 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, and 2-hydroxyethyl acrylate.
• examples include 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 60% by mass. It is 40% by mass.
• the ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group is 10% by mass or more, the effect of stabilizing the pattern shape of the copolymer can be obtained.
• the ratio is 60% by mass or less, the content of alkali-soluble groups falls within an appropriate range, and sufficient characteristics such as developability can be obtained.
• the above 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 viewpoint of transparency and heat resistance, those having an alicyclic skeleton are more preferred, and cyclohexylmaleimide is even more preferred.
• the ratio of N-substituted maleimide 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 N-substituted maleimide is 10% by mass or more, the Tg of the copolymer becomes high, so that the Tg of the wavelength conversion film finally obtained also becomes high, and sufficient heat resistance and light resistance are obtained. Sufficient transparency can be obtained when the ratio is 60% by mass or less.
• the alkali-soluble acrylic polymer may be a copolymer containing monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as a constituent unit.
• other monomers may be copolymerizable with at least one selected from the group consisting of monomers having a carboxy group and monomers having a phenolic hydroxy group, and the characteristics of the alkali-soluble acrylic polymer.
• monomers having a carboxy group and monomers having a phenolic hydroxy group There is no particular limitation as long as it does not impair the quality.
• Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds. Specific examples of the other monomers will be listed below, but the invention is not limited to these.
• 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
• methacrylic acid ester 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, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3- Methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, ⁇ -butyl meth
• acrylamide compounds include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N- Examples include butoxymethylacrylamide, N-butoxymethylmethacrylamide, and the like.
• 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, Examples include 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide.
• styrene compound examples include styrene that does not have a hydroxyl group. Specific examples 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, 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, but for example, from a carboxy group, a phenolic hydroxy group, a carboxylic acid by the action of heat or an acid, and a group that produces a phenolic hydroxy group by the action of heat or an acid.
• solvent used in the above reaction examples 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, 2-heptanone, ⁇ -butyrolactone, 2-hydroxypropionic acid Ethyl, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxy
• propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. are considered to have good coating properties and high safety. More preferred. These may be used alone or in combination of two or more.
• 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 poured into diethyl ether, water, etc. under stirring to cause reprecipitation, and the resulting precipitate is collected by filtration and washed, followed by normal pressure or reduced pressure.
• the specific copolymer can be made into a powder by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, purified powder of the specific copolymer can be obtained. If sufficient purification is not possible in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the powder of the above-mentioned 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 above-mentioned polymerization reaction, and used as a solution. Good too.
• polyimide precursors such as polyamic acids, polyamic acid esters, partially imidized polyamic acids, etc.
• polyimides such as carboxylic acid group-containing polyimides
• the type can be used without particular limitation.
• the above polyamic acid which is a polyimide precursor, can generally be obtained by polycondensing (x) a tetracarboxylic dianhydride and (y) a diamine compound.
• the above (x) 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'-diphenylsulfone tetracarboxylic dianhydride, etc.
• aromatic tetracarboxylic acid 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, 1,2,3,4-cyclohexanetetracarboxylic dianhydride Acid dianhydrides, cycloaliphatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1,2,3,4 - Mention may be made of aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride. These may be used alone or in combination of two or more.
• the diamine compound (y) is not particularly limited, and specific examples include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diaminobenzoic acid, and 4,6-diaminobenzoic acid.
• the blending ratio of both compounds is: (y) total number of moles of diamine compound/(x) tetracarboxylic dianhydride.
• the total number of moles of the substances is preferably 0.7 to 1.2. As in normal polycondensation reactions, the closer this molar ratio is to 1, the higher the degree of polymerization of the produced polyamic acid and the higher the molecular weight.
• the terminal amino groups of the remaining polyamic acid can be protected by reacting the terminal amino groups with a carboxylic acid anhydride.
• carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, and methyl-5-norbornene-2,3-dicarboxylic acid.
• examples include anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.
• the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride can be selected from any temperature generally from -20 to 150°C, preferably from -5 to 100°C.
• the reaction temperature is appropriately selected within the range of 5 to 40°C and the reaction time is within the range of 1 to 48 hours.
• the reaction temperature can be selected from -20 to 150°C, preferably -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 in this case include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, ⁇ -butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 - Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol
• any polyimide can be used as the alkali-soluble resin.
• the polyimide used in the present invention is one obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as the above polyamic acid.
• the polyimide preferably has a group selected from a carboxy group and a phenolic hydroxy group in order to provide alkaline solubility.
• Methods for introducing a carboxyl group or phenolic hydroxy group into polyimide include a method using a monomer having a carboxyl group or a phenolic hydroxy group, and a method of capping the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxy group. and a method of reducing the imidization rate to 99% or less when imidizing a polyimide precursor such as polyamic acid.
• Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
• a method for chemical imidization a method is generally used in which excess acetic anhydride and pyridine are added to a polyimide precursor solution and the mixture is reacted at room temperature to 100°C.
• a method for thermal imidization a method is generally used in which a polyimide precursor solution is heated at a temperature of 180 to 250° C. while being dehydrated.
• a phenol novolac resin can be further used.
• polyester polycarboxylic acid can also be used as the alkali-soluble resin.
• Polyester polycarboxylic acid can be obtained from acid dianhydride and diol by the method described in WO 2009/051186.
• the acid dianhydride include the above-mentioned (x) tetracarboxylic dianhydride.
• diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F.
• 1,4-cyclohexanediol 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and other alicyclic diols; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc. aliphatic diols and the like.
• the cationically curable alkali-soluble resin may be a mixture of multiple types of cationically curable alkali-soluble resins.
• the above-mentioned cation-curable alkali-soluble resin preferably has a number average molecular weight within the range of 2,000 to 50,000, but if the number average molecular weight is 50,000 or less, development residues are less likely to occur. The required sensitivity can be obtained. On the other hand, when the number average molecular weight is 2,000 or more, film loss in exposed areas is less likely to occur during development, and sufficient curability can be obtained.
• the above cationic curable compounds (B) may be used alone or in combination of two or more.
• a photoacid generator is a catalyst that generates an acid upon irradiation with light and causes cationic polymerization of epoxy groups and oxetane groups by the action of the acid.
• Examples of the photoacid generator include onium salt compounds, metallocene complex compounds, iron arene complex compounds, disulfone compounds, sulfonic acid derivative compounds, triazine compounds, acetophenone derivative compounds, diazomethane compounds, and the like.
• onium salt compounds include sulfonium salts, iodonium salts, phosphonium salts, selenium salts, and the like.
• Specific examples include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluoroantimonate; polyaryliodonium salts such as diphenyliodonium hexafluoroantimonate and P-nonylphenyliodonium hexafluoroantimonate. etc.
• the above onium salt compound can also be obtained as a commercial product.
• Such commercially available products include sulfonium salt-based products such as CPI-100P and CPI-310FG manufactured by Sun-Apro Co., Ltd., Omnicat (registered trademark, hereinafter the same applies) 270 manufactured by IGM Resin, and Irgacure 290 manufactured by BASF Japan.
• Cationic photopolymerization initiators Aromatic sulfonium salt-based cationic photopolymerization initiators such as Adeka Arcles SP-606 manufactured by ADEKA; Iodonium salt-based cationic photopolymerization initiators such as Omnicat 250 manufactured by IGM Resin, etc. .
• the above sulfonium salt (photoacid generator) may be dissolved in advance in a solvent that does not inhibit polymerization or crosslinking reactions in order to facilitate dissolution in the cationically polymerizable compound.
• Such solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol , monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate.
• carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate
• ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and
• Hydrolic alcohols and their derivatives Hydrolic alcohols and their derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, Ethyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3 -Esters such as methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, and the like.
• cyclic ethers such as dioxane
• the proportion of the solvent used is preferably 15 to 1,000 parts by mass, more preferably 30 to 500 parts by mass, based on 100 parts by mass of the sulfonium salt (photoacid generator).
• the above solvents may be used alone or in combination of two or more.
• metallocene complex compound examples include ( ⁇ 5 or ⁇ 6-isopropylbenzene)( ⁇ 5-cyclopentadienyl)iron(II) hexafluorophosphate.
• iron arene complex compound examples include bis( ⁇ 5 -cyclopentadienyl)( ⁇ 6 -isopropylbenzene) iron(II) hexafluorophosphate.
• disulfone compounds include aromatic disulfone compounds such as diphenyldisulfone; N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-( trifluoromethanesulfonyloxy)-1,8-naphthalimide, N-(trifluoromethanesulfonyloxy)-2-alkyl-1,8-naphthalimide, N-(trifluoromethanesulfonyloxy)-3-alkyl-1,8- Examples include sulfonimide compounds such as naphthalimide, N-(trifluoromethanesulfonyloxy)-4-alkyl-1,8-naphthalimide, and derivatives thereof. Among these, sulfonimide compounds and derivatives thereof are preferred
• sulfonic acid derivative compounds include bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane, and 2,2-bis( 4-methylphenylsulfonyl)propane, 2,2-bis(2-naphthylsulfonyl)propane, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-cyclohexylcarbonyl)-2-(p-toluenesulfonyl) ) propane, 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one, and the like.
• triazine compounds examples include 1-methoxy-4-(3,5-di(trichloromethyl)triazinyl)benzene, 1,2-methylenedioxy-4-(3,5-di(trichloromethyl)triazinyl)benzene, Haloalkyltriazinyl arenes such as 1-methoxy-4-(3,5-di(trichloromethyl)triazinyl)naphthalene; 1-methoxy-4-[2-(3,5-ditrichloromethyltriazinyl)ethenyl] Benzene, 1,2-dimethoxy-4-[2-(3,5-ditrichloromethyltriazinyl)ethenyl]benzene, 1-methoxy-2-[2-(3,5-ditrichloromethyltriazinyl) Examples include haloalkyl triazinyl alkenyl arenes such as [ethenyl]benzene.
• acetophenone derivative compounds examples include 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone.
• diazomethane compounds include bis(cyclohexylsulfonyl)diazomethane, bis(t-butylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, and the like.
• the content of the photoacid generator (C) above is preferably 0.1 to 49% by mass, and 0.1 to 20% by mass based on the solid content, from the viewpoint of film formability and the transparency, heat resistance, and light resistance of the cured film. It is more preferably 0.2 to 10% by weight, even more preferably 0.3 to 5% by weight.
• the above photoacid generator (C) may be used alone or in combination of two or more.
• Examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amide group, and the like, with a hydroxyl group being preferred.
• the above-mentioned reactive functional group can be introduced into the alkali-soluble resin containing the reactive functional group by using an unsaturated compound having the reactive functional group.
• unsaturated compounds having reactive functional groups include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.
• the content of reactive functional groups in the alkali-soluble resin containing reactive functional groups is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin, and the content of reactive functional groups is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin. From this point of view, the number is more preferably 0.1 to 0.5.
• alkali-soluble resin in the reactive functional group-containing alkali-soluble resin
• the same ones as the "alkali-soluble resin” in the cation-curable alkali-soluble resin of component (B) can be mentioned, including acrylic resins.
• Acrylic polymers can be used.
• the alkali-soluble acrylic polymer includes a monomer exhibiting alkali solubility, that is, a monomer having at least one type selected from the above-mentioned alkali-soluble groups, and at least one type selected from the group of monomers copolymerizable with these monomers.
• a copolymer formed with a monomer as an essential structural unit can be used.
• the method for obtaining the alkali-soluble acrylic polymer is not particularly limited, but for example, from a carboxy group, a phenolic hydroxy group, a carboxylic acid by the action of heat or an acid, and a group that produces a phenolic hydroxy group by the action of heat or an acid.
• the content of the cationic curable functional group is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin, and from the viewpoint of developability and solvent resistance, the content is 0.1 to 0. .8 pieces is more preferable.
• the solution containing the reactive functional group-containing alkali-soluble resin can be used as it is for preparing a negative photosensitive resin composition. Moreover, the above-mentioned reactive functional group-containing alkali-soluble resin can also be recovered and used by precipitation isolation in a poor solvent such as water, methanol, or ethanol.
• the reactive functional group-containing alkali-soluble resin may be a mixture of multiple types of reactive functional group-containing alkali-soluble resins.
• the above reactive functional group-containing alkali-soluble resin preferably has a number average molecular weight within the range of 2,000 to 50,000, but if the number average molecular weight is 50,000 or less, development residues will occur. The required sensitivity can be obtained. On the other hand, when the number average molecular weight is 2,000 or more, photodeterioration of the organic phosphor can be suppressed.
• the above (D) reactive functional group-containing alkali-soluble resin may be used alone or in combination of two or more.
• the content of the cationic curable compound (B) is set at 1 mass per solid content, from the viewpoint of obtaining a cured product with excellent light absorption in the desired wavelength range. % or more is preferable.
• component (D) When component (D) is not included, its content is more preferably 50 to 99.8% by mass, and more preferably 70 to 99.8% by mass based on the solid content, from the viewpoint of improving the light absorption in the desired wavelength range of the resulting cured product. .5% by mass is even more preferred, and 80 to 99.2% by mass is even more preferred.
• component (D) When component (D) is included, its content is more preferably 1 to 20% by mass, even more preferably 3 to 15% by mass, and even more preferably 5 to 10% by mass based on the solid content from the viewpoint of film forming properties and pattern forming properties. % is more preferred.
• the content of the alkali-soluble resin containing a reactive functional group (D) is usually 0 to 98.8% by mass in the solid content, and from the viewpoint of film forming property and pattern forming property, the content of the alkali-soluble resin containing a reactive functional group is 30 to 98% by mass in the solid content. It is preferably 8% by weight, more preferably 50.0-95.0% by weight, even more preferably 60.0-90.0% by weight, even more preferably 70.0-85.0% by weight.
• the content ratio of both components is preferably 0:100 to 50:50 in terms of mass ratio, and 5:95 from the viewpoint of film forming property and pattern forming property. to 15:85 is more preferable.
• a compound having a particle dispersion effect can also be used as the polymer dispersant (F) described below.
• a compound that includes both definitions of (F) a polymer dispersant corresponds to (D) a reactive functional group-containing alkali-soluble resin.
• the composition for forming a wavelength conversion film of the present invention may further contain (E) light-scattering particles.
• the above-mentioned light scattering particles scatter the light that has entered the wavelength conversion film, thereby substantially increasing the optical path length within the wavelength conversion film and improving the light absorption rate. It has a function of improving luminous efficiency by scattering the light that has been reflected and returned into the wavelength conversion film again.
• the above-mentioned light-scattering particles can be appropriately selected depending on the purpose, and may be organic fine particles or inorganic fine particles.
• organic fine particles or inorganic fine particles are preferred from the viewpoint of improving the scattering performance of the particles.
• the above-mentioned light-scattering particles can be appropriately selected depending on the purpose, and may be organic fine particles or inorganic fine particles.
• organic fine particles or inorganic fine particles are preferred from the viewpoint of improving the scattering performance of the particles.
• organic fine particles examples include polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, styrene beads, cross-linked 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.
• 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 .
• TiO 2 , BaTiO 3 , ZrO 2 , CeO 2 and Nb 2 O 5 are preferred, and TiO 2 is more preferred.
• the rutile type is preferable to the anatase type because it has a lower catalytic activity and thus 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. It will be done. These surface treatment materials may be used alone or in combination.
• the average particle diameter of the light scattering particles is more than 50 nm and less than 200 nm.
• the lower limit of the average particle diameter is preferably 60 nm or more, more preferably 70 nm or more.
• an average particle diameter of more than 100 nm is more preferable from the viewpoint of low total light reflectance at i-line (365 nm).
• the upper limit of the average particle diameter is preferably 190 nm or less, more preferably 180 nm or less, from the viewpoint of storage stability of the composition, since sedimentation tends to occur if it is too large.
• the average particle diameter of the light scattering particles is the average particle diameter determined from observation using a transmission electron microscope.
• titanium oxide particles include PT-401M (rutile type, average particle size 70 nm), PT-401L (rutile type, average particle size 130 nm), Examples include, but are not limited to, PT-501R (rutile type, average particle size 180 nm). Note that the average particle diameter of the illustrated light-scattering particles may vary by ⁇ 10 nm.
• the content of the light scattering particles (E) above is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and more preferably 0.3 to 10% by mass based on the solid content. is even more preferable.
• the composition for forming a wavelength conversion film of the present invention may optionally include a (D) component, (E) component, and (F) a polymer.
• a (D) component may optionally include a (D) component, (E) component, and (F) a polymer.
• Various known additives such as dispersant, (G) surfactant, (H) antioxidant, (I) curing aid, light stabilizer, flame retardant, clarifying agent, ultraviolet absorber, crosslinking agent, filler, etc. It may also contain an agent.
• the polymer dispersant is a polymer compound that has a weight average molecular weight of 750 or more and has a functional group that has an affinity for (E) light scattering particles.
• the polymer dispersant has a function of dispersing light scattering particles.
• the polymeric dispersant is adsorbed to the light-scattering particles via a functional group that has an affinity for the light-scattering particles, and due to electrostatic and/or steric repulsion between the polymeric dispersants, the light-scattering particles are absorbed into the composition. to be dispersed.
• the polymer dispersant is preferably bound to the surface of the light scattering particles and adsorbed to the light scattering particles, but may be free in the composition for forming a wavelength conversion film.
• Examples of the functional group having affinity for light scattering particles include acidic functional groups, basic functional groups, and nonionic functional groups.
• Acidic functional groups have dissociative protons and may be neutralized with bases such as amines and hydroxide ions, and basic functional groups may be neutralized with acids such as organic acids and inorganic acids. You can.
• acidic functional groups include carboxy group (-COOH), sulfo group (-SO 3 H), sulfuric acid group (-OSO 3 H), phosphonic acid group (-PO(OH) 2 ), phosphoric acid group (-OPO( OH) 2 ), phosphinic acid group (-PO(OH)-), mercapto group (-SH), and the like.
• Examples of the basic functional group 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 (-SO 2 -), carbonyl group, formyl group, ester group, carbonate ester group, amide group, Examples include carbamoyl group, ureido group, thioamide group, thioureido group, sulfamoyl group, cyano group, alkenyl group, alkynyl group, phosphine oxide group, and phosphine sulfide group.
• the polymeric dispersant may be a polymer of a single monomer (homopolymer) or a copolymer of multiple types of monomers (copolymer). Further, the polymer dispersant may be a random copolymer, a block copolymer, or a graft copolymer. Further, when the polymer dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer.
• polymer dispersants include acrylic resin, polyester resin, polyurethane resin, polyamide resin, polyether, phenol resin, silicone resin, polyurea resin, amino resin, epoxy resin, polyethyleneimine, polyallylamine, polyimide, etc. It will be done.
• (F) As the polymer dispersant it is also possible to use commercially available products, such as the DISPERBYK series and BYK series manufactured by BYK, the Efka series manufactured by BASF, the Solsperse series manufactured by Lubrizol, and Ajinomoto.
• Ajisper PB series manufactured by Fine Techno Co., Ltd., TEGO series manufactured by Evonik, Disparon series manufactured by Kusumoto Kasei Co., Ltd., etc. can be used.
• DISPERBYK-130 DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, and DISPERBYK-1 manufactured by BYK.
• DISPERBYK-170 DISPERBYK -171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2001, DISP ERBYK-2008, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2022 , DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164; EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4061, EFKA4080, EFKA4300, EFKA4310, EFKA4320,
• a polymeric dispersant When (F) a polymeric dispersant is used, there is no particular restriction on its amount, but it is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on 100% by mass of (E) light-scattering particles.
• the said (F) polymeric dispersant may be used individually by 1 type, or may be used in combination of 2 or more types.
• a fluorine-based surfactant is preferred, and a nonionic fluorine-based surfactant is more preferred. Specific examples thereof include, but are not limited to, the Ftergent series, 212M, 215M, 250, 222F, FTX-218, and DFX-18 manufactured by Neos Co., Ltd.
• G When using a surfactant, there is no particular restriction on its amount, but it is preferably 0.01 to 1% by mass, and 0.01 to 0.5% by mass based on the solid content of the composition for forming a wavelength conversion film. is more preferable.
• Antioxidants include hindered phenol antioxidants, phenolic antioxidants, and the like.
• As the antioxidant commercially available products can be used, and examples include Irganox 1010 manufactured by BASF Japan Co., Ltd. and ADEKA STAB AO-80 manufactured by ADEKA Co., Ltd., but are not limited to these. It's not something you can do.
• an antioxidant there is no particular restriction on its amount, but it is preferably 0.1 to 5.0% by mass, and 0.3 to 1.5% by mass based on the solid content of the composition for forming a wavelength conversion film. More preferred.
• alkali-soluble resins that do not contain reactive functional groups By combining alkali-soluble resins that do not contain reactive functional groups (hereinafter referred to as "alkali-soluble resins that do not contain reactive functional groups"), it becomes possible to form patterns by lithography, and it becomes possible to use them as compositions for forming resist films. .
• Examples of the alkali-soluble resin containing no reactive functional group include a copolymer of methyl methacrylate and methacrylic acid.
• an alkali-soluble resin that does not contain a reactive functional group there is no particular restriction on its amount, but it is preferably 0.01 to 10% by mass, and 0.05% by mass based on the solid content of the composition for forming a wavelength conversion film. More preferably 8% by mass.
• a compound having a particle dispersion effect can also be used as (F) a polymer dispersant.
• a compound that includes both the definitions of (J) reactive functional group-containing alkali-soluble resin and (F) polymer dispersant is considered to fall under (J) reactive functional group-free alkali-soluble resin. do.
• 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; diethyl ether, tetrahydrofuran, Ether solvents such as dioxane and 1,2-dimethoxyethane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone (CPN); ethyl acetate, n-hexyl acetate, ethyl lactate, ⁇ -butyrolactone, Ester solvents such as propylene carbonate and diisopropyl malonate;
• the solid content concentration of the composition for forming a wavelength conversion film varies depending on the thickness of the intended wavelength conversion film, the coating method, etc. Although it cannot be specified, it is usually 10 to 70% by weight, preferably 20 to 60% by weight.
• the upper limit of the viscosity at 25° C. of the composition for forming a wavelength conversion film 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.
• viscosity means a value measured by an EMS viscometer.
• the composition for forming a wavelength conversion film of the present invention includes the above-mentioned components (A), (B), and (C), components (D) to (J) used as necessary, and other additives such as a light stabilizer.
• the agent and the solvent can be mixed in any order.
• the composition for forming a wavelength conversion film of the present invention described above is applied, for example, onto a substrate, the solvent is evaporated by heating etc. as necessary, and further irradiated with active energy rays (for example, ultraviolet light) as necessary. By doing so, a wavelength conversion film can be obtained.
• active energy rays for example, ultraviolet light
• Examples of 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, varibar roll blade coater, two stream coater, Examples include methods using a rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater, inkjet, and the like.
• Heating can be performed using, for example, a general heating device such as an oven or a hot plate.
• the heating conditions are not particularly limited as long as a film can be formed, but 60 to 200°C for 5 minutes to 2 hours is preferable, and 80 to 200°C for 15 minutes to 1 hour is more preferable. Note that heat curing may be performed in stages.
• the irradiated light is preferably 200 to 440 nm, and particularly preferably includes light with a wavelength of 300 to 400 nm.
• the exposure amount is preferably 10 to 4,000 mJ/cm 2 .
• the aforementioned heating step and ultraviolet light exposure step may be performed in any combination in any order.
• irradiation with ultraviolet light may be performed after heating, irradiation with ultraviolet light may be performed before heating, or irradiation with ultraviolet light may be performed after heating, and then further heating. Good too.
• the thickness of the wavelength conversion film is not particularly limited, but is usually 1 to 1,000 ⁇ m, preferably 3 to 500 ⁇ m, and more preferably 5 to 100 ⁇ m.
• the haze of the wavelength conversion film is not particularly limited, but from the viewpoint of increasing the amount of light that can be absorbed by the phosphor by scattering incident light within the film, it is preferably 18% or more, or more. Preferably it is 30% or more, more preferably 40% or more.
• the upper limit of the haze value is not particularly limited, but is usually about 95%.
• the haze value is a value measured according to ASTM D1003-61.
• the conditions for measuring the haze value include, for example, conditions for measuring a film with a thickness of 10 ⁇ m formed from a composition containing 6.7% by mass of titanium oxide particles.
• the above-mentioned base material may be appropriately selected from those used as underlying base materials for forming this type of film, but it may be used if the transmittance of light in the visible range of 400 to 800 nm is 50% or more.
• a glass substrate or a polymer plate is preferred.
• Specific examples of the glass include soda lime glass, barium/strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, and the like.
• Specific examples of the polymer include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone, and the like.
• a cationically curable compound is selected from a compound having an epoxy group (excluding alkali-soluble resins), a compound having an oxetane group (excluding alkali-soluble resins), and an N-alkoxymethylol compound.
• a mask with a predetermined pattern is attached to the resulting coating film, irradiation with light such as ultraviolet rays, and development with an alkaline developer removes the unexposed areas. is washed out, and by heating the remaining patterned film at 80 to 140° C. for 0.5 to 10 minutes as necessary, a sharp relief pattern on the end face can be obtained.
• alkaline developer examples include aqueous solutions of 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 amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like known for use in developing solutions can also be added to these developing solutions.
• an aqueous solution of 0.1 to 2.58% by mass of tetraethylammonium hydroxide is generally used as a developer for photoresists, and this alkaline developer is also used in the composition of the present invention to cause swelling, etc. It can be developed well without causing any problems.
• any method such as a liquid piling method, a dipping method, or a rocking immersion method can be used.
• the developing 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 cleaning time is usually about 20 to 120 seconds.
• the resulting pattern-formed film is post-baked for thermosetting, resulting in a good relief pattern with excellent heat resistance, transparency, flattening properties, low water absorption, chemical resistance, etc.
• a film having the following properties is obtained.
• a hot plate, an oven, or the like can be used to heat the pattern-formed film.
• the post-baking method is generally 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. One method is to do so. By post-baking under such conditions, a cured film having a good pattern shape can be obtained.
• the wavelength conversion film obtained using the composition of the present invention has excellent wavelength conversion efficiency and durability, it can be used as a wavelength conversion film (color conversion film) for displays such as micro LED displays, organic EL displays, liquid crystal displays, lighting, etc. 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, lighting, etc. 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, lighting, etc. It can be suitably used as
• ⁇ MMA Methyl methacrylate
• MAA Methacrylic acid
• OXE-30 (3-ethyloxetan-3-yl)methyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• MI Maleimide (manufactured by Tokyo Chemical Industry Co., Ltd.)
• St Styrene (manufactured by Tokyo Chemical Industry Co., Ltd.)
• M100 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Corporation)
• HEMA 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
• ⁇ CHMI Imilex-C (N-cyclohexylmaleimide, manufactured by Nippon Shokubai Co., Ltd.)
• AIBN ⁇ , ⁇ '-azobisisobutyronitrile
• a diphenylamino group was introduced into Compound 2 using Buchwald-Hartwig coupling reaction, and Compound 3 was obtained in a yield of 26%. Specifically, synthesis was performed as follows.
• organic phosphor A-3 represented by the above formula (A2-4) was obtained in a yield of 33%. 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).
• Metachloroperbenzoic acid (m-CPBA; 1.65 g, 6.70 mmol) was slowly added thereto at 0°C. The mixture was returned to room temperature and stirred for 5 hours. Saturated sodium hydrogen carbonate was added and extracted three times with chloroform. The combined organic layers were dehydrated by adding anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure.
• the organic layer was dehydrated by adding anhydrous sodium sulfate, and the anhydrous sodium sulfate was removed by filtration.
• the filtrate was concentrated under reduced pressure to obtain 1.29 g of a mixture of 1-substituted product and 2-substituted product.
• Diethylene glycol monoisobutyl ether (1.86 g, 11.5 mmol), titanium tetraisopropoxide (0.67 g, 2.37 mmol), and anisole (6 mL) were added to this again, and the temperature was raised to 170°C to remove the distillate. The mixture was stirred for 3 hours while removing the mixture.
• Bromine, iodine, tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba) 3 ), diphenylamine (Ph 2 NH), sodium tert-butoxide (t-BuONa), metachloroperbenzoic acid (m-CPBA) was purchased from Tokyo Kasei Kogyo Co., Ltd.
• Dichloromethane, methanol, tetrahydrofuran, o-xylene, chloroform, hexane, ethyl acetate, sodium thiosulfate, anhydrous sodium sulfate, and sodium hydrogen carbonate were purchased from Junsei Kagaku Co., Ltd.
• Tri-tert-butylphosphonium tetrafluoroborate (tert-Bu 3 PHBF 4 ) was purchased from Fuji Film Wako Pure Chemical Industries, Ltd. Thin layer chromatography (TLC) was performed using a glass plate coated with 0.25 mm of silica gel 60F-254 (Merck). Silica gel chromatography was performed using silica gel 60N spherical neutral (Kanto Kagaku Co., Ltd.) as a packing material.
• the particle size distribution of the obtained dispersion was measured using Nanotrac UPA (manufactured by Microtrac). Using the solvent of the dispersion as the diluent, 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 occurs when the diluted sample is irradiated with laser light. The calculated value was 181 nm.
• Preparation Example 2 Preparation of light scattering particle dispersion 2 (OXT-221 dispersion of E-1) Instead of the acrylic polymer J-1 solution in an amount of 50% by mass in terms of solid content relative to E-1, F-1 in an amount of 10% by mass in terms of solid content was used, and B1-4 was used in place of CPN.
• Light-scattering particle dispersion liquid 2 was prepared in the same manner as in Preparation Example 1 except that the following was used. The particle size distribution of the obtained dispersion was measured using Nanotrac UPA (manufactured by Microtrac).
• CPN was used as the diluent, and the 50% cumulative diameter (D50) of the particles in the dispersion liquid was calculated on a volume basis using analysis software MicrotracDMS manufactured by Nikkiso Co., Ltd. from the scattering that occurred when the diluted sample was irradiated with laser light. However, it was 225 nm.
• Preparation Example 3 Preparation of light scattering particle dispersion 3 (Viscoat #260 dispersion of E-1) After putting 143.3 g of B2-2 and 80.0 g of E-1 into a 500 mL styrene bottle, 26.7 g of F-2 diluted to 30% by mass with B2-2 under disper stirring was added, and 1. A slurry was obtained by stirring with a disper at 000 rpm for 30 minutes. The weight of F-2 added to E-1 was 10% by weight.
• a light scattering particle dispersion liquid 3 was obtained by performing a 5-pass process under the conditions of 40 mL/min and a disk circumferential speed of 8 m/s.
• the particle size distribution of the obtained dispersion was measured using Nanotrac UPA (manufactured by Microtrac). B2-2 was used as the diluent, and the 50% cumulative diameter (D50) of the particles in the dispersion was calculated based on volume using the analysis software MicrotracDMS manufactured by Nikkiso Co., Ltd. from the scattering that occurred when the diluted sample was irradiated with laser light. The calculated value was 134 nm.
• Examples 1 to 34, Comparative Examples 1 to 8 Preparation of a composition for forming a wavelength conversion film and its evaluation (1) Preparation of a composition for forming a wavelength conversion film Each component was mixed in the composition shown in Tables 1 to 5.
• a composition for forming a wavelength conversion film was prepared by filtering the obtained mixture using a polytetrafluoroethylene (PTFE) filter having a pore size of 5.0 ⁇ m. Note that the composition ratios in Tables 1 to 5 represent mass ratios based on solid content.
• PTFE polytetrafluoroethylene
• the paint film sample was placed on a blue LED light (emission peak wavelength: 450 nm) manufactured by CCS Co., Ltd., the LED light was turned on, and the light emitted through the paint film sample was It was measured using a spectral irradiance meter USR-45, and the result was given as (1). Similarly, the light emitted only from the LED light was measured in the same manner, excluding the paint film sample, and the result was obtained as (2).
• a blue LED light emission peak wavelength: 450 nm
• the LED light was turned on, and the light emitted through the paint film sample was It was measured using a spectral irradiance meter USR-45, and the result was given as (1).
• the light emitted only from the LED light was measured in the same manner, excluding the paint film sample, and the result was obtained as (2).
• the number of photons of light with a wavelength of 480 nm or less in result (2) was defined as the "number of excitation light photons.”
• the number of photons of light with a wavelength of 480 nm or less in result (1) was defined as the "number of transmitted light photons.”
• the number of photons of light with a wavelength exceeding 480 nm in result (1) was defined as the "number of emitted photons.”
• “Blue light absorption rate” and "conversion efficiency” were calculated using the following formulas.
• each composition was applied onto a silicon substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100°C for 120 seconds.
• a coating film having a thickness of 11 ⁇ m was formed. Thereafter, this coating film was exposed to ultraviolet rays with a light intensity of 2.9 mW/cm 2 at 365 nm through an i-ray transmission filter using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. at an exposure amount of 2 J/cm 2 at 100 ⁇ m intervals at 100 ⁇ m intervals. Irradiation was performed through a photomask provided with corner light-transmitting sections.
• TMAH tetramethylammonium hydroxide

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