Wavelength conversion film-forming composition and method for improving light fastness thereof

Abstract

To provide a wavelength conversion material having improved light resistance to excitation light as compared with a conventional wavelength conversion material.SOLUTION: A wavelength conversion film-forming composition comprising: (A) an organic phosphor; (B) a radically curable compound; and (C) a cationically curable compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition for forming a wavelength conversion film and a method for improving the light resistance thereof. [Background technology]

[0002] Micro LED displays are expected to be the next generation display following LCD displays and OLED displays, as they are capable of high contrast and high brightness and have a wide range of applications, including large screens and transparent displays. In a microLED display, each pixel typically contains a tiny LED chip. One method of arranging these LED chips is the RGB-LED method, which implements three-color LEDs, but this method has issues such as the complexity of LED light emission control and the low performance of red LEDs, and wavelength conversion methods that can solve these issues are attracting attention. The wavelength conversion method uses only a blue LED chip and extracts red and green light using a wavelength conversion material, which has the advantage of being able to produce the three primary colors using only a blue LED chip.

[0003] Conventionally, techniques using organic light-emitting materials have been proposed as wavelength conversion materials, and for example, those using pyridine-phthalimide condensates (Patent Document 1, etc.), those using coumarin derivatives (Patent Document 2, etc.), those using perylene derivatives (Patent Document 3, etc.), those using rhodamine derivatives (Patent Document 4), and those using pyrromethene derivatives (Patent Documents 5 and 6, etc.) have been disclosed.

[0004] These wavelength converting materials are generally required to have properties such as good wavelength conversion efficiency, color purity, and light resistance. In this regard, for example, Patent Document 7 discloses that a composition containing a binder resin made of a specific methacrylic polymer, a specific organic phosphor, and a photopolymerizable acrylic acid ester serves as a high-performance, light-resistant red-color conversion material. Furthermore, a technique of adding a light stabilizer to prevent deterioration of organic light-emitting materials and improve durability has also been disclosed (Patent Document 8, etc.). Furthermore, it is known that adding fine particles to the wavelength conversion material increases the optical path length due to light scattering within the color conversion layer, improving the blue light absorption rate, and also improves the luminous efficiency by re-scattering light reflected at the interface (Patent Documents 9, 10, etc.). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-348568 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-273440 [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-317175 [Patent Document 4] Japanese Patent Application Laid-Open No. 2001-164245 [Patent Document 5] Japanese Patent Application Laid-Open No. 2011-241160 [Patent Document 6] Japanese Patent Application Laid-Open No. 2014-136771 [Patent Document 7] Japanese Patent Application Laid-Open No. 2006-89724 [Patent Document 8] Japanese Patent Application Laid-Open No. 2011-149028 [Patent Document 9] International Publication No. 2020 / 189678 [Patent Document 10] International Publication No. 2019 / 181698 Summary of the Invention [Problem to be solved by the invention]

[0006] However, conventional wavelength converting materials have not always been sufficiently light-resistant to excitation light (hereinafter sometimes simply referred to as "light resistance"). Therefore, an object of the present invention is to provide a wavelength converting material having improved light resistance to excitation light compared to conventional wavelength converting materials. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems and have found that the light resistance of wavelength converting materials can be improved by using a certain type of compound as a component. As a result of further research, they have completed the present invention.

[0008] That is, the present invention provides the following composition for forming a wavelength conversion film, etc. [1] A composition for forming a wavelength conversion film, comprising: (A) Organic fluorophores; (B) a radically curable compound; and (C) Cationic curable compounds. [2] The composition for forming a wavelength conversion film according to [1], wherein the polymerizable functional group in the radically curable compound (B) is a (meth)acryloyl group. [3] The composition for forming a wavelength conversion film according to [1] or [2], wherein the (C) cationically curable compound is one or more compounds selected from the group consisting of compounds having an epoxy group, compounds having an oxetane group, and N-alkoxymethylol compounds. [4] The composition for forming a wavelength-converting film according to any one of [1] to [3], further comprising (D) a photoradical initiator. [5] The composition for forming a wavelength-converting film according to any one of [1] to [4], further comprising (E) a photoacid generator. [6] The composition for forming a wavelength-converting film according to any one of [1] to [5], wherein the composition for forming a wavelength-converting film has a viscosity of less than 100 mPa·s. [7] The composition for forming a wavelength conversion film according to any one of [1] to [6], wherein the (A) organic phosphor is one or more compounds selected from the group consisting of fused thiophene compounds and perylene compounds. [8] The composition for forming a wavelength-converting film according to any one of [1] to [7], wherein the content of the (A) organic phosphor is 0.05 mass % or more relative to the mass of the composition for forming a wavelength-converting film. [9] The composition for forming a wavelength-converting film according to any one of [1] to [8], further comprising (F) light-scattering particles.

[10] The composition for forming a wavelength-converting film according to [9], wherein the (F) light-scattering particles are titanium oxide particles.

[11] The composition for forming a wavelength-converting film according to [9] or

[10] , wherein the content of the (F) light-scattering particles is 1 mass % or more relative to the mass of the composition for forming a wavelength-converting film.

[12] The composition for forming a wavelength conversion film according to any one of [9] to

[11] , wherein a film formed from the composition has a haze value of 18% or more.

[13] The composition for forming a wavelength conversion film according to any one of [1] to

[12] , wherein the content of the cationically curable compound (C) is 1 to 50% based on the total content of the radically curable compound (B) and the cationically curable compound (C).

[14] does not contain a solvent capable of dissolving the above components (A) to (C), or further contains a solvent capable of dissolving the above components (A) to (C), The composition for forming a wavelength-converting film according to any one of [1] to

[13] , wherein when the composition further contains a solvent, the amount of the solvent relative to the composition for forming a wavelength-converting film is 30 mass % or less.

[15]

[14] The composition for forming a wavelength conversion film according to

[14] , wherein when the composition further contains a solvent, the amount of the solvent is 1 mass % or less.

[16] [1] The wavelength conversion film-forming composition 1 is irradiated with a blue LED for a certain period of time, and the blue light absorptance maintenance rate (blue light absorptance maintenance rate 1) of the composition 1 before and after the blue LED irradiation is measured. When composition 2, which is a composition different from composition 1 in that it does not contain component (C), is irradiated with blue LED for the above-mentioned certain period of time, the maintenance rate of blue light absorptance in composition 2 before and after blue LED irradiation (blue light absorptance maintenance rate 2) is Blue light absorption rate maintenance rate 1 > Blue light absorption rate maintenance rate 2 That is, The composition for forming a wavelength conversion film according to any one of [1] to

[15] .

[17] The composition for forming a wavelength-conversion film according to any one of [1] to

[16] , wherein the (A) organic phosphor is not present as solid particles in the composition for forming a wavelength-conversion film, and contains an organic phosphor that is not present as solid particles in the film when the composition for forming a wavelength-conversion film is irradiated with excitation light to form a film.

[18] The composition for forming a wavelength conversion film according to any one of [1] to

[17] , which is a composition for forming a wavelength conversion film for a display.

[19] A wavelength conversion film obtained from the composition for forming a wavelength conversion film according to any one of [1] to

[18] .

[20] The wavelength conversion film according to

[19] , which is a wavelength conversion film for a display. [twenty one] (A) an organic phosphor and (B) Radical curing compound A method for improving the light resistance of a composition for forming a wavelength conversion film, comprising: A method comprising the step of causing (C) a cationically curable compound to be present in a composition comprising (A) an organic fluorescent material and (B) a radically curable compound. [Effects of the Invention]

[0009] According to the present invention, the composition for forming a wavelength-converting film is provided as a wavelength converting material having improved light resistance to excitation light compared to conventional wavelength converting materials. The composition for forming a wavelength conversion film of the present invention has curability superior to that of the (C) cationically curable compound and equivalent to that of the (B) radically curable compound. That is, the composition for forming a wavelength conversion film of the present invention can achieve the effect that the (B) radically curable compound and the (C) cationically curable compound can improve the other properties while maintaining their respective advantageous properties in terms of light resistance and curability. In the composition for forming a wavelength conversion film of the present invention, the amount of both the (B) radically curable compound and the (C) cationic curable compound are relatively small in the total amount of curable compounds. Considering this, the above-mentioned effects achieved by the composition for forming a wavelength conversion film of the present invention are synergistic effects that could not be predicted from the prior art. Among the compositions for forming a wavelength-converting film of the present invention, a composition for forming a wavelength-converting film in which the components (A), (B), and (C) are optimized or a composition for forming a wavelength-converting film further containing a photoradical initiator (D) provides a wavelength-converting material with further improved light resistance. In the composition for forming a wavelength-converting film of the present invention, which further contains the above-mentioned (E) photoacid generator, the curability of the wavelength-converting material is improved. Among the compositions for forming a wavelength-converting film of the present invention, those compositions for forming a wavelength-converting film further containing a solvent, in which the amount of the solvent relative to the composition for forming a wavelength-converting film is 30% by mass or less, are more suitably used as compositions for inkjet printing. Among the compositions for forming a wavelength conversion film of the present invention, a composition in which the blue light absorptance retention rate 1>the blue light absorptance retention rate 2 as described above provides a wavelength converting material with more reliably improved light resistance. The present invention also provides compositions for forming wavelength-converting films for various applications, such as compositions for forming wavelength-converting films for displays (particularly, micro LED displays). Without being bound by theory, the improved light resistance of the wavelength conversion film-forming composition of the present invention may be due to the fact that, when the applied composition is exposed to light to form a film, the amount of acrylic residues remaining in the unpolymerized state of the radical curable compound (B) present in the composition, which may cause film degradation, can be reduced. More specifically, the following possibilities are considered: 1) When a radically curable compound is exposed to light, it cures rapidly and the viscosity drops sharply, making it difficult for the localized unreacted monomer to cure, resulting in a small amount of unreacted monomer remaining. 2) On the other hand, in the case of a cationically curable compound, even when exposed to light, the curing proceeds slowly and a low viscosity state is maintained. 3) In the composition for forming a wavelength conversion film of the present invention, the composition remains uncured even after exposure due to the presence of unpolymerized polymerizable groups (e.g., epoxy groups), and the viscosity of the entire curable compound is kept relatively low due to the low viscosity of the cationic curable compound, so that the time during which the small amount of remaining monomers of the radical curable compound are in contact with each other becomes longer, and polymerization easily proceeds due to a continuous reaction (drive-in reaction). According to this presumed principle, in the composition for forming a wavelength conversion film of the present invention, the amount of acrylic residues remaining in the uncured parts of the radical curable compound (B) that may cause deterioration of the film can be reduced by the cationic curable compound (C). As a result, the composition for forming a wavelength conversion film of the present invention can maintain the light resistance of the film formed from the composition for forming the wavelength conversion film for a longer period of time, and the light resistance may be improved. In the present invention, the cationically curable compound (C) may act as a component that delays the curing of the composition for forming a wavelength conversion film during film formation and maintains the viscosity of the composition for forming a wavelength conversion film at a low level. In other words, in the present invention, a component that delays curing and / or a component that maintains a low viscosity state is used, and an example of such a component may be the cationically curable compound (C).

[0010] In the prior art, no attempt has been made even to improve the light resistance of a wavelength-converting film formed from a composition for forming a wavelength-converting film. In other words, the problem that the present invention aims to solve is a novel problem that has not been solved in the past. Furthermore, the use of a (C) cationic curable compound together with a (B) radical curable compound as the curable compound has not been considered or even thought of in the past. Moreover, as described above, the composition for forming a wavelength conversion film of the present invention has excellent light resistance to excitation light and also excellent curability, and therefore exhibits the particularly remarkable effect of achieving both light resistance and film curability. In consideration of these points, it is clear that the present invention is one that even a person skilled in the art could not have arrived at from the prior art. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 10 is a graph showing the light absorptance of the wavelength-converting film-forming compositions obtained in Example 3 and Comparative Example 2 at the initial stage (0-hour light resistance test) and after a 90-hour light resistance test, and the light absorptance of a blue LED. DETAILED DESCRIPTION OF THE INVENTION

[0012] The composition for forming a wavelength conversion film of the present invention is a composition for forming a wavelength conversion film, which contains the following: (A) Organic fluorophores; (B) a radically curable compound; and (C) Cationic curable compounds. That is, the composition for forming a wavelength conversion film of the present invention is a so-called hybrid curable composition that uses two types of curable compounds with different curing properties, namely (B) a radically curable compound and (C) a cationically curable compound. The components of the composition for forming a wavelength conversion film of the present invention, the production method, etc. will be further explained below.

[0013] [(A) Organic fluorescent material] The organic phosphor (A) used in the present invention is not particularly limited as long as it can achieve the object of the present invention, and is only required to be suitable as a phosphor while maintaining a desired film remaining ratio even when a wavelength-converting film is formed, the wavelength-converting film is exposed to light in the atmosphere, and then heat-treated. The organic phosphor is preferably one that can exhibit its properties as a phosphor better. For example, when forming a wavelength conversion film for a micro LED display, it is preferable that the wavelength conversion film maintains the desired film remaining rate even when exposed to air and then heat-treated, and exhibits better wavelength conversion efficiency, color purity, light resistance, and other properties as a micro LED display.

[0014] The (A) organic phosphor is sometimes generally referred to as an organic fluorescent dye or simply as a fluorescent pigment, but in this specification it will be referred to as an organic phosphor. The definition of an organic phosphor generally refers to fluorescent dye molecules, and does not include non-fluorescent pigments (dyes) or pigments. Among the (A) organic phosphors of the present invention, preferred are those that do not exist as solid particles in the composition for forming a wavelength conversion film of the present invention, and that do not exist as solid particles in the film formed by irradiating the composition for forming a wavelength conversion film with excitation light. Examples of organic fluorescent substances include compounds having a condensed aryl ring such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene, and derivatives thereof; furan, pyrrole, thiophene, silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, and naphthacene. Compounds containing heteroaryl rings such as phthyridine, quinoxaline, and pyrrolopyridine, and their derivatives; stilbene compounds such as 1,4-distyrylbenzene, 4,4'-bis(2-(4-diphenylaminophenyl)ethenyl)biphenyl, and 4,4'-bis(N-(stilben-4-yl)-N-phenylamino)stilbene; aromatic acetylene compounds; tetraphenylbutadiene compounds; aldazine compounds; pyrromethene compounds; diketopyrrolo[3,4-c]pyrrole compounds; and kumari. Coumarin compounds such as Coumarin 6, Coumarin 7, Coumarin 153, and compounds disclosed in Patent Document 7; azole compounds such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, and triazole, and their metal complexes; cyanine compounds such as indocyanine green; xanthene compounds and thioxanthene compounds such as fluorescein, eosin, and rhodamine; polyphenylene compounds, naphthalimide compounds, phthalocyanine compounds, and their metal complexes. oxazine-based compounds such as Nile Red and Nile Blue; helicene-based compounds; aromatic amine-based compounds such as N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine; and organometallic complex compounds such as iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re), but are not limited to these.

[0015] Of the above organic fluorescent materials, compounds having a fused aryl ring or derivatives thereof, and thiophene compounds are preferred. Among the compounds having a fused aryl ring and derivatives thereof, perylene compounds are more preferred. Among the thiophene compounds, fused thiophene compounds are particularly preferred. Of the fused thiophene compounds, specifically, those represented by the following formula can be mentioned as a preferred embodiment. [ka] [In the formula, Ar 1 represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, Ar 2 is a divalent π-conjugated unit, R 1 represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group, or a group represented by the following formula (L): R 2 and R 3 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, R 2 and R 3 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 2 and R 3 Either or both of Ar 2 may be bonded to form a ring together with the adjacent nitrogen atom, n represents 1 or 2. When n is 2, two Ar 2 may be the same or different. [ka] (In the formula, L k represents a single bond, a k-valent hydrocarbon group, or a k-valent heteroaromatic group, where k is the valence of L and represents 2, 3, or 4, and * represents a bond. 1 , Ar 2 , R 2 , R 3 and n are the same as above.)

[0016] Ar 1 Examples of the aromatic ring represented by the formula (I) include a benzene ring as a monocyclic aromatic hydrocarbon ring, and a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a pyrene ring, and a triphenylene ring as a polycyclic aromatic hydrocarbon ring.

[0017] Ar 1 The aromatic ring represented by may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a heteroaryl group, a cyano group, and a nitro group, which will be described later. When the aromatic ring has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0018] Ar 1 Examples of the heteroaromatic ring represented by the formula (I) 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, and examples of the polycyclic heteroaromatic rings include an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, an isoquinoline ring, and a quinoxaline ring.

[0019] Ar 1 The heteroaromatic ring represented by may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a heteroaryl group, a cyano group, and a nitro group, which will be described later. When the heteroaromatic ring has a substituent, the number of the substituents is, for example, preferably 1 to 6, and more preferably 1 to 3.

[0020] Among them, Ar1 As the aromatic ring, from the viewpoint of increasing the absorption maximum wavelength and the fluorescence maximum wavelength and further improving light resistance, a substituted or unsubstituted aromatic ring and a substituted heteroaromatic ring are preferable, and a substituted or unsubstituted monocyclic aromatic hydrocarbon ring and a substituted heteroaromatic ring are more preferable.

[0021] Ar 2 Examples of the divalent π-conjugated unit represented by the formula (I) include an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, an arylene group which may have a substituent, and a heteroarylene group which may have a substituent.

[0022] Ar 2 The alkenylene group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkenylene groups having 2 to 8 carbon atoms such as vinylene group, propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, and octenylene group, and alkenylene groups having 2 to 4 carbon atoms are preferred.

[0023] Ar 2 The alkenylene group represented by the following formula may have a substituent. Examples of the substituent include a halogen atom, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a carbonyl group, a cyano group, and a nitro group, which are described below. When the alkenylene group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0024] Ar 2 The alkynylene group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkynylene groups having 2 to 8 carbon atoms, such as an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, and an octynylene group, with an alkenylene group having 2 to 4 carbon atoms being preferred.

[0025] Ar 2The alkynylene group represented by the following formula may have a substituent. Examples of the substituent include a halogen atom, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a carbonyl group, a cyano group, and a nitro group, which are described below. When the alkynylene group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0026] Ar 2 Examples of the arylene group represented by the formula (I) include a phenylene group, a naphthylene group, an anthracenylene group, a phenanthrenylene group, a fluorenylene group, a pyrenylene group, and a triphenylenylene group.

[0027] Ar 2 The arylene group represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a carbonyl group, a cyano group, and a nitro group, which are all described below. When the arylene group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0028] Ar 2 Examples of the heteroarylene group represented by the formula (I) include a pyrrolylene group, a thienylene group, a furanylene group, an imidazolene group, a pyrazolene group, a thiazolene group, an oxazolene group, a pyridylene group, a pyrazylene group, an indolylene group, an isoindolylene group, a benzimidazolylene group, a quinolylene group, an isoquinolylene group, and a quinoxalylene group.

[0029] Ar 2 The heteroarylene group represented by the following formula may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a carbonyl group, a cyano group, and a nitro group, which are all described below. When the heteroarylene group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0030] Among them, Ar 2 From the viewpoint of electron donating property, a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group is preferable, a substituted or unsubstituted arylene group is more preferable, an unsubstituted arylene group is further preferable, an unsubstituted phenylene group is particularly preferable, and a p-phenylene group is most preferable. 2 may be the same or different.

[0031] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0032] The alkyl group may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and an alkyl group having 1 to 6 carbon atoms is preferred.

[0033] The alkyl group may have a substituent. Examples of the substituent include the halogen atoms, the cycloalkyl group described below, the aryl group described below, the heteroaryl group described below, a cyano group, and a nitro group. When the alkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0034] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, and cycloalkyl groups having 4 to 8 carbon atoms are preferred.

[0035] The cycloalkyl group may have a substituent. Examples of the substituent include the halogen atoms, the alkyl groups, the alkenyl groups described below, the alkynyl groups described below, the aryl groups described below, the heteroaryl groups described below, a cyano group, and a nitro group. When the cycloalkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0036] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0037] Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, an s-butenyl group, and a t-butenyl group.

[0038] Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, an isobutynyl group, an s-butynyl group, and a t-butynyl group.

[0039] The aryl group may be any of a monocyclic aryl group, a fused ring aryl group, and a polycyclic aryl group. Specific examples of the monocyclic aryl group include a phenyl group, and specific examples of the fused ring aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, and a triphenylenyl group. Specific examples of the polycyclic aryl group include aryl groups having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group, with an aryl group having 6 to 14 carbon atoms being preferred.

[0040] The aryl group may have a substituent. Examples of the substituent include the halogen atom, the alkyl group, the alkenyl group, the alkynyl group, the aryl group, the heteroaryl group described below, a cyano group, and a nitro group. When the aryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0041] The heteroaryl group may be either a monocyclic heteroaryl group or a fused-ring heteroaryl group. Examples of the monocyclic heteroaryl group include a pyrrolidyl group, a pyrrolyl group, a thienyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an oxazolyl group, a piperidyl group, a pyridyl group, and a pyrazyl group. Examples of the fused-ring heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.

[0042] The heteroaryl group may have a substituent. Examples of the substituent include the halogen atom, the alkyl group, the alkenyl group, the alkynyl group, the aryl group, the heteroaryl group, a cyano group, and a nitro group. When the heteroaryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0043] R 1 The alkyl group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and an alkyl group having 1 to 6 carbon atoms is preferred.

[0044] Above R 1 The alkyl group represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heteroaryl group, a cyano group, and a nitro group, which will be described later. When the alkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0045] R 1 Examples of the alkenyl group represented by the formula (I) include a vinyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, an s-butenyl group, and a t-butenyl group.

[0046] Above R 1 The alkenyl group represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heteroaryl group, a cyano group, and a nitro group, which will be described later. When the alkenyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0047] R 1 Examples of the alkynyl group represented by the formula (I) include an ethynyl group, a 1-propynyl group, a propargyl group, a butynyl group, an isobutynyl group, an s-butynyl group, and a t-butynyl group.

[0048] Above R 1The alkynyl group represented by the following formula (I) may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heteroaryl group, a cyano group, and a nitro group, which will be described later. When the alkynyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0049] R 1 Examples of the cycloalkyl group represented by the formula (I) include cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and a cycloalkyl group having 4 to 8 carbon atoms is preferred.

[0050] Above R 1 The cycloalkyl group represented by the following formula may have a substituent. Examples of the substituent include a halogen atom described below, the alkyl group described above, a halogenated alkyl group described below, the alkenyl group described above, the alkynyl group described above, an aryl group described below, a heteroaryl group described below, a cyano group, and a nitro group. When the cycloalkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0051] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0052] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0053] R 1 The aryl group represented by the formula (I) may be any of a monocyclic aryl group, a fused ring aryl group, and a polycyclic aryl group, and specific examples thereof include a phenyl group as a monocyclic aryl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, a triphenylenyl group, and the like as a fused ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group or a terphenyl group as a polycyclic aryl group, and an aryl group having 6 to 14 carbon atoms is preferred.

[0054] Above R 1The aryl group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups described below, cyano groups, nitro groups, and pentafluorosulfanyl groups. When the aryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0055] R 1 The heteroaryl group represented by the formula (I) may be either a monocyclic heteroaryl group or a fused-ring heteroaryl group. Examples of the monocyclic heteroaryl group include a pyrrolyl group, a thienyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, and a pyrazyl group. Examples of the fused-ring heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.

[0056] Above R 1 The heteroaryl group represented by the formula (I) may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, halogenated alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, cyano groups, nitro groups, and pentafluorosulfanyl groups. When the heteroaryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0057] R 1 The alkylsulfonyl group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkylsulfonyl groups having 1 to 18 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, an isobutylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, a pentylsulfonyl group, an isopentylsulfonyl group, a neopentylsulfonyl group, a tert-pentylsulfonyl group, an octylsulfonyl group, and an octadecylsulfonyl group, and preferably an alkylsulfonyl group having 1 to 6 carbon atoms.

[0058] R 1 The arylsulfonyl group represented by the formula (I) may be any of a monocyclic arylsulfonyl group, a fused arylsulfonyl group, and a polycyclic arylsulfonyl group, and specific examples thereof include a phenylsulfonyl group and a tolylsulfonyl group (tosyl group) as a monocyclic aryl group, a naphthylsulfonyl group, an anthracenylsulfonyl group, a phenanthrenylsulfonyl group, a fluorenylsulfonyl group, a pyrenylsulfonyl group, and a triphenylenylsulfonyl group, and examples of a polycyclic arylsulfonyl group include an arylsulfonyl group having 6 to 18 carbon atoms such as a biphenylsulfonyl group and a terphenylsulfonyl group, and an arylsulfonyl group having 6 to 14 carbon atoms is preferred.

[0059] R 1 The alkylthio group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 18 carbon atoms, such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio, and alkyl groups having 1 to 6 carbon atoms are preferred.

[0060] R 1 The arylthio group represented by the formula (I) may be any of a monocyclic arylthio group, a fused arylthio group, and a polycyclic arylthio group, and specific examples thereof include a phenylthio group as a monocyclic aryl group, a naphthylthio group, an anthracenylthio group, a phenanthrenylthio group, a fluorenylthio group, a pyrenylthio group, and a triphenylenylthio group, and a polycyclic aryl group such as a biphenylthio group and a terphenylthio group, and an arylthio group having 6 to 20 carbon atoms is preferred.

[0061] R 2 and R 3The alkyl group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and an alkyl group having 1 to 6 carbon atoms is preferred.

[0062] Above R 2 and R 3 The alkyl group represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heteroaryl group, a cyano group, and a nitro group, which will be described later. When the alkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0063] R 2 and R 3 Examples of the cycloalkyl group represented by the formula (I) include cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and a cycloalkyl group having 4 to 8 carbon atoms is preferred.

[0064] Above R 2 and R 3 The cycloalkyl group represented by the following formula may have a substituent. Examples of the substituent include a halogen atom described below, the alkyl group described above, a halogenated alkyl group described below, an aryl group described below, a heteroaryl group described below, a cyano group, and a nitro group. When the cycloalkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0065] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0066] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0067] R 2 and R 3The aryl group represented by the formula (I) may be any of a monocyclic aryl group, a fused ring aryl group, and a polycyclic aryl group, and specific examples thereof include a phenyl group as a monocyclic aryl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, a triphenylenyl group, and the like as a fused ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group or a terphenyl group as a polycyclic aryl group, and an aryl group having 6 to 14 carbon atoms is preferred.

[0068] The aryl group may have a substituent. Examples of the substituent include the halogen atom, the alkyl group, the aryl group, the halogenated alkyl group, the heteroaryl group described below, a cyano group, a nitro group, and a pentafluorosulfanyl group. When the aryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0069] R 2 and R 3 The heteroaryl group represented by the formula (I) may be either a monocyclic heteroaryl group or a fused-ring heteroaryl group. Examples of the monocyclic heteroaryl group include a pyrrolyl group, a thienyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, and a pyrazyl group. Examples of the fused-ring heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.

[0070] The heteroaryl group may have a substituent. Examples of the substituent include the halogen atom, the alkyl group, the halogenated alkyl group, the aryl group, the heteroaryl group, a cyano group, a nitro group, and a pentafluorosulfanyl group. When the heteroaryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0071] Also, R 2 and R 3is preferably a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, more preferably an alkyl group or a substituted or unsubstituted aryl group, and even more preferably an unsubstituted aryl group.

[0072] Above R 2 and R 3 may be bonded to each other to form a ring together with the adjacent nitrogen atom. 2 and R 3 However, examples of the ring formed by bonding together with the adjacent nitrogen atoms include groups represented by the following formulae (1-a) and (1-b).

[0073] [ka]

[0074] Also, the above R 2 and R 3 is R 2 and R 3 Either one or both of the adjacent Ar 2 may bond to the adjacent nitrogen atom to form a ring. 2 and R 3 Either or both of Ar 2 Examples of the ring formed by bonding with the adjacent nitrogen atom include a group represented by the following formula (1-c):

[0075] [ka]

[0076] In the group represented by the above formula (L), Ar 1 , Ar 2 , R 2 , R 3 and n is the same as above.

[0077] The above L kExamples of the divalent hydrocarbon group represented by the formula include alkylene groups having 1 to 20 carbon atoms, alkenylene groups having 2 to 20 carbon atoms, alkynylene groups having 2 to 20 carbon atoms, and arylene groups having 6 to 20 carbon atoms.

[0078] The alkylene group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a 1,2-dimethylethylene group, a tetramethylethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group.

[0079] The alkenylene group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, and a nonenylene group.

[0080] The alkynylene group having 2 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, and a 1,3-butadiynylene group.

[0081] Examples of the arylene group having 6 to 20 carbon atoms include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,2-naphthalene-diyl group, a 2,3-naphthalenediyl group, a 1,4-naphthalenediyl group, a 1,5-naphthalenediyl group, a 2,6-naphthalenediyl group, a 2,7-naphthalenediyl group, a 1,8-naphthalenediyl group, a 1,2-anthracene-diyl group, a 1,3-anthracene-diyl group, a 1,4- Examples include anthracenediyl groups, 1,5-anthracenediyl groups, 1,6-anthracenediyl groups, 1,7-anthracenediyl groups, 1,8-anthracenediyl groups, 2,3-anthracenediyl groups, 2,6-anthracenediyl groups, 2,7-anthracenediyl groups, 2,9-anthracenediyl groups, 2,10-anthracenediyl groups, 9,10-anthracenediyl groups, and the following formulae (L1-1) to (L1-4).

[0082] [ka] (In the formula, * represents a bond.)

[0083] The above L k Examples of the divalent heteroaromatic group represented by the following formula include heteroarylene groups having 3 to 20 carbon atoms.

[0084] Examples of the heteroarylene group having 3 to 20 carbon atoms include a pyrrolylene group, a thienylene group, a furanylene group, an imidazolene group, a pyrazolene group, a thiazolene group, an oxazolene group, a pyridylene group, a pyrazylene group, an indolylene group, an isoindolylene group, a benzimidazolylene group, a quinolylene group, an isoquinolylene group, a quinoxalylene group, a 9-phenylcarbazole-3,6-diyl group, a 9-phenylcarbazole-2,7-diyl group, a 9-phenylcarbazole-3,6-dimethyl-2,7-diyl group, and a group represented by the following formula (L2-1):

[0085] [ka] (In the formula, * represents a bond.)

[0086] n is 1 or 2, with 1 being preferred.

[0087] In addition, Ar in the above formula (1) 1 , Ar 2 , R 2 , R 3 and n are Ar in the above formula (L), respectively. 1 , Ar 2 , R 2 , R 3 and n may be the same or different.

[0088] In the present invention, as the phosphor represented by the above formula (1), a fused ring thiophene compound represented by the following formula (1') is easily produced.

[0089] [ka] [(wherein, Ar 1 , Ar 2 , R 1 , R 2 , R 3 and n are the same as above.) [ka] (In the formula, Ar 1 , Ar 2 , R 2 , R 3 , n, L k , k and * are the same as above.)

[0090] In the present invention, preferred embodiments of the phosphor represented by the above formula (1) include a fused thiophene compound represented by the following formula (A1) and a fused thiophene compound represented by the following formula (A2), which will be described later. These fused thiophene compounds will be described in detail below.

[0091] [Fused thiophene compound represented by formula (A1)] [ka] [(wherein, Ar 1 represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, Ar 2 is a divalent π-conjugated unit, R 1a represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group or an arylthio group, R 2 and R 3 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, R 2 and R 3 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 2 and R 3 Either or both of Ar 2 may be bonded to form a ring together with the adjacent nitrogen atom, n represents 1 or 2. When n is 2, two Ar 2 may be the same or different.)

[0092] In formula (A1), Ar 1 , Ar 2 , R 2 , R 3 Specific examples of are the same as those given in the explanation of formula (1) above.

[0093] R 1aSpecific examples of the halogen atom, optionally substituted alkyl group, optionally substituted cycloalkyl group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted aryl group, optionally substituted heteroaryl group, alkylsulfonyl group, arylsulfonyl group, alkylthio group and arylthio group in the above R 1 The same examples as those given in the explanation of the first embodiment are included.

[0094] A preferred embodiment of the fused thiophene compound represented by the above formula (A1) includes, for example, a fused thiophene compound represented by the following formula (A1').

[0095] [ka] (In the formula, Ar 1 , Ar 2 , R 1a , R 2 , R 3 and n are the same as above.)

[0096] A more preferred embodiment of the fused thiophene compound represented by the above formula (A1) is, for example, a fused thiophene compound represented by the following formula (A1″).

[0097] [ka] (In the formula, R 1a , R 2 and R 3 is the same as above.)

[0098] Specific examples of the fused thiophene compound represented by the above (A1) include, but are not limited to, the fused thiophene compounds represented by the following formulas (A1-1) to (A1-12).

[0099] [ka]

[0100] [Fused thiophene compound represented by formula (A2)] [ka] [In the formula, Ar 1 represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, Ar 2 is a divalent π-conjugated unit, R 1b is a group represented by the following formula (L): R 2 and R 3 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, R 2 and R 3 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 2 and R 3 Either or both of Ar 2 may be bonded to form a ring together with the adjacent nitrogen atom, n represents 1 or 2. When n is 2, two Ar 2 may be the same or different. [ka] (In the formula, L k represents a single bond, a k-valent hydrocarbon group, or a k-valent heteroaromatic group, where k is the valence of L and represents 2, 3, or 4, and * represents a bond. 1 , Ar 2 , R 2 , R 3 and n are the same as above.)

[0101] In formula (A2), Ar 1 , Ar 2 , R 2 and R 3 Specific examples of are the same as those exemplified in the explanation of formula (1) above. 1 , Ar 2 , R 2 , R 3 and L k Specific examples of are the same as those given in the explanation of formula (1) above.

[0102] A preferred embodiment of the fused thiophene compound represented by the above formula (A2) includes, for example, a fused thiophene compound represented by the following formula (A2').

[0103] [ka] [(wherein, R 1b is a group represented by the following formula (L'): 1 , Ar 2 , R 2 , R 3 and n are the same as above.) [ka] (In the formula, Ar 1 , Ar 2 , R 2 , R 3 , n, L k , k and * are the same as above.)

[0104] A more preferred embodiment of the fused thiophene compound represented by the above formula (A2) is, for example, a fused thiophene compound represented by the following formula (A2″).

[0105] [ka] [(wherein, R 1bis a group represented by the following formula (L"). 2 and R 3 is the same as above.) [ka] (In the formula, R 2 , R 3 , L k , k and * are the same as above.)

[0106] Specific examples of the fused thiophene compound represented by (A2) above include, but are not limited to, the fused thiophene compounds represented by the following formulae (A2-1) to (A2-7): In the present application, the compound represented by the following formula (A2-5) may also be simply abbreviated as "A-1."

[0107] [ka]

[0108] The compound represented by the above formula (1) not only has excellent light resistance but also has excellent conversion efficiency, and is suitable as a phosphor for use as a wavelength conversion material in displays.

[0109] The compound represented by formula (1) above can be synthesized with reference to known methods, but the synthesis method is not particularly limited as long as the desired compound is obtained. For example, the method described in paragraphs

[0085] and after of JP 2018-39963 A can be used as a method for synthesizing a fused thiophene compound represented by formula (A1). Furthermore, when the compound represented by formula (1) above is a fused thiophene compound represented by formula (A2) above, it can be synthesized, for example, by subjecting compounds represented by the following (A2''') to coupling reaction conditions using a transition metal catalyst, or by subjecting a compound represented by the following (A2''') to coupling reaction conditions using a transition metal catalyst with bis(pinacolato)diboron, an aromatic dihalide, a heteroaromatic dihalide, an aromatic diboronic acid, a heteroaromatic diboronic acid, an aromatic diboronic acid ester, a heteroaromatic diboronic acid ester, an organozinc reagent, or a Grignard reagent.

[0110] [ka] [(wherein, X 1b is a chlorine atom, a bromine atom, an iodine atom, an ethynyl group, MX, or a group represented by the following formula (A2'''-a): M is a zinc atom or a magnesium atom, X is a chlorine atom, a bromine atom, or an iodine atom, and Ar 1 , Ar 2 , R 2 , R 3 and n are the same as above.) [ka] (In the formula, R 4 and R 5 R each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. 4 and R 5 may be linked to each other to form a ring together with the adjacent -OBO-. * represents a bond.)]

[0111] R4 and R 5 The alkyl group represented by the formula (I) may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and an alkyl group having 1 to 6 carbon atoms is preferred.

[0112] Above R 4 and R 5 The alkyl group represented by the formula (I) may have a substituent. Examples of the substituent include a cycloalkyl group described below, a halogen atom described below, an aryl group described below, a heteroaryl group described below, a cyano group, and a nitro group. When the alkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0113] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, and cycloalkyl groups having 4 to 8 carbon atoms are preferred.

[0114] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0115] R 4 and R 5 The aryl group represented by the formula (I) may be any of a monocyclic aryl group, a fused ring aryl group, and a polycyclic aryl group, and specific examples thereof include a phenyl group as a monocyclic aryl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, a triphenylenyl group, and the like as a fused ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group or a terphenyl group as a polycyclic aryl group, and an aryl group having 6 to 14 carbon atoms is preferred.

[0116] The aryl group may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, aryl groups, halogenated alkyl groups described below, heteroaryl groups described below, cyano groups, nitro groups, and pentafluorosulfanyl groups. When the aryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0117] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0118] The heteroaryl group may be either a monocyclic heteroaryl group or a fused-ring heteroaryl group. Examples of the monocyclic heteroaryl group include a pyrrolyl group, a thienyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, and a pyrazyl group. Examples of the fused-ring heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.

[0119] R 4 and R 5 Examples of the ring formed by linking together with adjacent -OBO- include a group represented by the following formula (A2'''-a-1).

[0120] [ka]

[0121] Coupling reaction conditions using a transition metal catalyst include known methods, such as those described in Experimental Chemistry Lectures, 5th Edition, Vol. 18 (edited by the Chemical Society of Japan); Organic Synthesis Strategies Learned from Named Reactions (Laszlo Kurti, Barbara Czako, Kagaku Dojin), etc.

[0122] Furthermore, perylene-based compounds can also be suitably used as the organic phosphor (A) in the wavelength conversion film-forming composition of the present invention. Perylene-based compounds are compounds having perylene as a skeleton. Preferred perylene-based compounds include, but are not limited to, the compound represented by the following formula (A3) (Oracet® FL Red 305, manufactured by BASF), Lumogen® F Yellow 083 (manufactured by BASF), and Solvent Green 5. The compound represented by the following formula (A3) (Oracet® FL Red 305, manufactured by BASF) is more preferred. In the present application, the compound represented by the following formula (A3) may also be abbreviated simply as "A-2."

[0123] [ka]

[0124] The proportion of the content of the (A) organic phosphor relative to the total mass of the composition for forming a wavelength-converting film is not limited as long as the desired effect of the present invention is achieved. Examples of such a proportion include 0.01 mass % or more, and preferably 0.05 mass % or more. The upper limit of such a proportion may be changed depending on the types and amounts of other components, and may be, for example, 5 mass %. The organic fluorescent materials may be used singly or in combination of two or more.

[0125] [(B) Radical curable compound] The radically curable compound (B) in the present invention is not limited as long as it is a radically polymerizable compound that can achieve the desired effects of the present invention. The radically curable compound (B) means, for example, a compound having one or more radically polymerizable functional groups in the molecule. The radically polymerizable functional group is particularly preferably a radically polymerizable functional group that undergoes a polymerization reaction due to radicals from a photopolymerization initiator. Specific examples include radically polymerizable functional groups such as a (meth)acryloyl group and a vinyl group. Of these, a (meth)acryloyl group is preferred. The (B) radically curable compound includes, for example, a (meth)acrylic acid ester having one or more (meth)acryloyloxy groups in the molecule. The (meth)acrylic acid ester may be a hydroxyl group-containing (meth)acrylic acid ester. The composition of the present invention may contain only one type of the (B) radically curable compound, or two or more types.

[0126] Specific examples of (meth)acrylic acid esters having one (meth)acryloyloxy group in the molecule include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. , diethylaminoethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethoxylated-o-phenylphenol acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, mono(2-acryloyloxyethyl)succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, and the like.

[0127] Among these, ethoxylated-o-phenylphenol acrylate is more preferred as the (meth)acrylic acid ester having one (meth)acryloyloxy group in the molecule, from the viewpoint of more effectively achieving the effects of the present invention.

[0128] As the (meth)acrylic acid ester having two or more (meth)acryloyloxy groups in the molecule, (meth)acrylic acid esters of polyhydric alcohols such as diols and triols can be used, and more specifically, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Examples of suitable acrylates include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, glycerin di(meth)acrylate, hydrogenated bisphenol A or hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and trimethylolpropane tri(meth)acrylate.

[0129] Examples of hydroxyl group-containing (meth)acrylic acid esters having two or more (meth)acryloyloxy groups in the molecule include glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol monohydroxypenta(meth)acrylate.

[0130] Among these, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are more preferred as the (meth)acrylic acid ester having two or more (meth)acryloyloxy groups in the molecule, from the viewpoint of more effectively achieving the effects of the present invention.

[0131] From the viewpoint of curability, the number of radically polymerizable functional groups in the (B) radically curable compound in the composition of the present invention is preferably 1 or more, and more preferably 2 or more. From the viewpoint of reducing the viscosity of the composition, the upper limit of the number of functional groups is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. However, when two or more (B) radically curable compounds are used in combination in the composition, the balance between curability and viscosity can be freely adjusted by adjusting the ratio of the (B) radically curable compounds contained, so the number of functional groups is not particularly limited.

[0132] The content of the (B) radically curable compound in the composition of the present invention is not particularly limited, but from the viewpoint of more effectively exhibiting the effects of the present invention, the content may be, for example, 10 to 85 mass % relative to the mass of the composition for forming a wavelength conversion film, and the proportion is preferably 20 mass % or more, and more preferably 30 mass % or more.

[0133] When a polyfunctional (meth)acrylic acid ester is included as component (B), there is no particular restriction on the content of the compound, but from the viewpoint of more effectively achieving the effects of the present invention, the content of the compound is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to 100% by mass of the total of other radically curable compounds. There is no particular restriction on the upper limit of the content, but when a (meth)acrylic acid ester with three or more functional groups is included, it is preferably less than 30% by mass from the viewpoint of low viscosity. The radically curable compound used in the present invention may be a commercially available product, and specific examples thereof include Viscoat #260 (trade name, manufactured by Osaka Organic Chemical Industry Ltd.) and Viscoat #230 (trade name, manufactured by Osaka Organic Chemical Industry Ltd.), and NOD-N (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) In the present application, Viscoat #260 may be abbreviated as "B-1", Viscoat #230 as "B-2", and NOD-N as "B-3". In the present invention, a compound having both radical curability and cation curability, i.e., a dual-curable compound, may be used. In the present invention, a dual-curable compound is considered to be a radical curable compound. An example of a dual-curable compound is 4-hydroxybutyl acrylate glycidyl ether (product name: 4HBAGE, manufactured by Mitsubishi Chemical Corporation). In the present application, 4HBAGE may also be abbreviated as "H-1."

[0134] [(C) Cationic curable compound] The cationically curable compound used in the present invention is not limited as long as it is a compound that undergoes a polymerizing or crosslinking reaction in response to an acid generated by an acid generator. Examples of the cationically curable compound include a compound having an epoxy group (hereinafter referred to as an "epoxy compound"), a compound having an oxetane group (hereinafter referred to as an "oxetane compound"), and an N-alkoxymethylol compound. The above cationically curable compounds may be used alone or in combination of two or more.

[0135] [Epoxy compounds] The epoxy compound is not particularly limited as long as it has an epoxy group. In the present invention, a compound containing both an epoxy group and an oxetane group is considered to be an epoxy compound.

[0136] Examples of the epoxy compound include aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds. In the present invention, among these, the epoxy compound preferably contains at least one of an alicyclic epoxy compound and an aliphatic epoxy compound, and more preferably contains at least an alicyclic epoxy compound. The epoxy compound may contain both an alicyclic epoxy compound and an aliphatic epoxy compound. By using the epoxy compound, the composition can obtain a cured product that has excellent light absorption in a desired wavelength range and good adhesion to a substrate.

[0137] Specific examples of the alicyclic epoxy compound include those containing an aliphatic ring, such as polyglycidyl ethers of polyhydric alcohols having at least one aliphatic ring, and cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by epoxidizing cyclohexene- or cyclopentene ring-containing compounds with an oxidizing agent. In the present invention, among the above alicyclic epoxy compounds, epoxy resins having a cyclohexene oxide structure are preferred in terms of curing speed.

[0138] As the alicyclic epoxy compound, a compound having two or more cyclohexene oxide structures can be preferably used, and examples thereof include compounds represented by the following formula (C1).

[0139] [ka] (In the formula, X c1 represents a single bond or a linking group (a divalent group having one or more atoms).

[0140] X c1 Examples of the linking group represented by the formula (I) include a divalent hydrocarbon group, an alkenylene group in which some or all of the carbon-carbon double bonds have been epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and groups in which multiple of these groups are linked together.

[0141] Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 30 carbon atoms and an alkylene group having 3 to 30 carbon atoms and having a cycloalkyl ring.

[0142] Examples of the linear or branched alkylene group having 1 to 30 carbon atoms include groups in which one hydrogen atom has been removed from a linear or branched alkyl group having 1 to 30 carbon atoms. Examples of the alkylene group having 3 to 30 carbon atoms and a cycloalkyl ring include groups in which one hydrogen atom has been removed from an alkyl group having 3 to 30 carbon atoms and a cycloalkyl ring.

[0143] Specific examples of the linear or branched alkylene group having 1 to 30 carbon atoms include groups in which one hydrogen atom has been removed from a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, 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, octadecyl group, and icosyl group. Examples of the linear or branched alkylene group having 1 to 20 carbon atoms as the divalent hydrocarbon group include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.

[0144] The alkyl group having a cycloalkyl ring and having 3 to 30 carbon atoms may be a cycloalkyl group. Examples of the cycloalkyl group include a monocyclic hydrocarbon group and a crosslinked hydrocarbon ring group. Examples of the monocyclic hydrocarbon group include a group in which one hydrogen atom has been removed from a monocyclic hydrocarbon ring such as a cyclohexyl ring, and a group in which one or more hydrogen atoms in the ring of the group in which one hydrogen atom has been removed from a monocyclic hydrocarbon ring have been substituted with an aliphatic hydrocarbon group. Examples of the bridged hydrocarbon ring group include a group in which one hydrogen atom has been removed from a cycloalkyl ring such as a bridged hydrocarbon ring such as a norbornyl ring, and a group in which one or more hydrogen atoms in the ring of a group in which one hydrogen atom has been removed from a bridged hydrocarbon ring have been substituted with an aliphatic hydrocarbon group.

[0145] Specific examples of the monocyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a methylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a tetramethylcyclohexyl group, a pentamethylcyclohexyl group, an ethylcyclohexyl group, and a methylcycloheptyl group, and among these, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group are preferred.

[0146] Specific examples of the bridged hydrocarbon ring group include a bicyclo[2.1.1]hexyl group, a bicyclo[2.2.1]heptyl group, a bicyclo[2.2.2]octyl group, a bicyclo[4.3.1]decyl group, a bicyclo[3.3.1]nonyl group, a bornyl group, a bornenyl group, a norbornyl group, a norbornenyl group, a 6,6-dimethylbicyclo[3.1.1]heptyl group, a tricyclobutyl group, and an adamantyl group.

[0147] The alkyl group having 3 to 30 carbon atoms and a cycloalkyl ring may be a group formed by combining the above-mentioned cycloalkyl group with the above-mentioned linear or branched alkyl group. Examples include a group in which one or more hydrogen atoms in the linear or branched alkyl group are substituted with the above-mentioned cycloalkyl group, a group in which one or more methylene groups in the linear or branched alkyl group are substituted with a group in which one hydrogen atom has been removed from the above-mentioned cycloalkyl group, and a group in which one or more hydrogen atoms of the above-mentioned cycloalkyl group are substituted with the above-mentioned linear or branched alkyl group.

[0148] Examples of the alkylene group having 3 to 30 carbon atoms and having a cycloalkyl ring as the divalent hydrocarbon group include groups in which one hydrogen atom has been removed from the alkyl group having 3 to 30 carbon atoms and having a cycloalkyl ring. Specific examples include cycloalkylene groups (including cycloalkylidene groups) such as a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

[0149] Examples of the alkenylene group in the alkenylene group in which some or all of the carbon-carbon double bonds have been epoxidized (hereinafter, also referred to as "epoxidized alkenylene group") include linear or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, and octenylene group.

[0150] In the present invention, X c1 is preferably a linking group, and is preferably a divalent hydrocarbon group, an ester bond, or a group in which a plurality of these are linked together, and is particularly preferably a group in which a divalent hydrocarbon group and an ester bond are linked together. In the present invention, X c1 is preferably an alkylene group obtained by removing one hydrogen atom from a linear or branched alkyl group having 1 to 18 carbon atoms, more preferably an alkylene group obtained by removing one hydrogen atom from a linear or branched alkyl group having 1 to 8 carbon atoms, even more preferably an alkylene group obtained by removing one hydrogen atom from a linear or branched alkyl group having 1 to 5 carbon atoms, and even more preferably an alkylene group obtained by removing one hydrogen atom from a linear alkyl group having 1 to 3 carbon atoms.

[0151] In the present invention, suitable compounds having two or more cyclohexene oxide structures include compounds represented by the following formulae (C1-1) to (C1-4).

[0152] [ka]

[0153] As the alicyclic epoxy compound, a compound represented by the following formula (C2) can also be suitably used.

[0154] [ka] (In the formula, Z c1 represents an alkylene group having 3 to 30 carbon atoms and a cycloalkyl ring.

[0155] Z c1 The alkylene group having 3 to 30 carbon atoms and a cycloalkyl ring represented by the formula: c1 Examples include the same alkylene group having 3 to 30 carbon atoms and a cycloalkyl ring represented by the following formula: In the present invention, Z c1 From the viewpoint of obtaining a cured product having a steeper absorption peak in a desired wavelength range, is preferably an alkylene group having 13 to 20 carbon atoms and two cycloalkyl rings, and more preferably a group represented by the following formula (C3):

[0156] [ka] (In the formula, R c2 and R c3 represents a hydrogen atom or a methyl group, and * represents the point of attachment.)

[0157] Specific examples of the alicyclic epoxy compound 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- Examples of epoxy groups include 5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. In the present invention, from the viewpoint of being able to obtain a cured product having excellent light absorption in the desired wavelength region, among these, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate are preferred. In addition, those containing both an aliphatic ring and an aromatic ring are considered to be alicyclic epoxy compounds.

[0158] Furthermore, as the alicyclic epoxy compound, a compound having a structure in which an oxiranyl group is directly bonded via a single bond to a cycloalkyl ring derived from an epoxycycloalkyl ring, such as a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, as a constituent unit, and having a structure in which epoxy groups of the epoxycycloalkyl ring are polymerized together as a main chain structure (hereinafter, this may be referred to as "alicyclic epoxy compound A") can also be used.

[0159] As the alicyclic epoxy compound, commercially available products can be used, and specific examples include those described in Japanese Patent No. 6103653 and the like.

[0160] The alicyclic epoxy compounds may be used alone or in combination of two or more. For example, it is also preferable to use a compound having two or more cyclohexene oxide structures and the alicyclic epoxy compound A in combination. This is because a cured product having excellent light absorption in the desired wavelength region can be obtained.

[0161] The content of the alicyclic epoxy compound may be any amount that allows a cured product having excellent film-forming properties and curability to be obtained, but is preferably 0 parts by mass or more, more preferably 2 parts by mass or more, even more preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and most preferably 20 parts by mass or more, per 100 parts by mass of the cationic curable compound. When the content of the epoxy compound is 90 parts by mass or less in 100 parts by mass of the cationic curable compound, the content of the alicyclic epoxy compound is preferably 0 to 80 parts by mass, more preferably 10 to 60 parts by mass, even more preferably 15 to 35 parts by mass, and still more preferably 20 to 25 parts by mass in 100 parts by mass of the cationic curable compound. By setting the content within the above range, it is possible to obtain a cured product with excellent film-forming properties. Furthermore, the composition can give a cured product with good curability.

[0162] Specific examples of the aromatic epoxy compound include polyglycidyl ethers of polyhydric phenols having at least one aromatic ring or their alkylene oxide adducts, such as glycidyl ethers of bisphenol A, bisphenol F, or compounds obtained by further adding alkylene oxide to these, and phenol novolac epoxy compounds; glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol; polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, such as benzenedimethanol, benzenediethanol, and benzenedibutanol; polyglycidyl esters of polybasic aromatic compounds having two or more carboxylic acids, such as phthalic acid, terephthalic acid, and trimellitic acid; polyglycidyl esters of benzoic acids, such as benzoic acid, toluic acid, and naphthoic acid; glycidyl esters of benzoic acid; and epoxidized products of styrene oxide or divinylbenzene. Among these, it is preferable to contain at least one selected from the group consisting of 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, and polyglycidyl esters of polybasic acids, and it is particularly preferable to contain polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, as this makes it possible to obtain a cured product with excellent light absorption in the desired wavelength region.

[0163] Specific examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyl esters of aliphatic long-chain polybasic acids.

[0164] As the polyglycidyl ether of the aliphatic polyhydric alcohol or its alkylene oxide adduct, a diglycidyl ether of an aliphatic diol compound is preferred, and a compound represented by the following formula (C4) is particularly preferred. By using this compound, the composition has excellent light absorption in the desired wavelength range, and the cured product thereof has good adhesion to the substrate. Furthermore, the composition gives a cured product having a steeper absorption peak in the desired wavelength range.

[0165] [ka] (In the formula, Z c2 represents a linear or branched alkylene group having 1 to 30 carbon atoms.

[0166] Z c2 As the linear or branched alkylene group having 1 to 30 carbon atoms represented by the formula (I), the above X c1 and the like. One or more methylene groups of the alkylene group having 1 to 30 carbon atoms may be replaced with -O-. When a methylene group in the alkylene group is replaced with -O-, the replacement with -O- is provided so that oxygen atoms are not adjacent to each other in the alkylene group.

[0167] Above Z c2 is preferably a branched alkylene group from the viewpoint of obtaining a cured product having a steeper absorption peak in a desired wavelength range, because the composition having the above structure can obtain a cured product having a steeper absorption peak in a desired wavelength range. Above Z c2From the viewpoint of obtaining a cured product having a steeper absorption peak in a desired wavelength range, Z is preferably a linear or branched alkylene group having 2 to 30 carbon atoms, more preferably a linear or branched alkylene group having 3 to 28 carbon atoms, and even more preferably a linear or branched alkylene group having 4 to 26 carbon atoms. c2 However, when the methylene group is an alkylene group in which no -O- is substituted, the number of carbon atoms is preferably 4 to 10, and more preferably 4 to 8. c2 is an alkylene group in which a methylene group is replaced by -O-, Z c2 is preferably an alkylene group having 10 to 26 carbon atoms and having a structure obtained by removing hydroxyl groups at both ends from polyalkylene glycol, more preferably an alkylene group having 10 to 26 carbon atoms and having a structure obtained by removing hydroxyl groups at both ends from polyethylene glycol or polypropylene glycol, and even more preferably an alkylene group having 15 to 24 carbon atoms and having a structure obtained by removing hydroxyl groups at both ends from polyethylene glycol or polypropylene glycol. This is because the composition can give a cured product having a steeper absorption peak in the desired wavelength range.

[0168] Specific examples of the diglycidyl etherified products of the aliphatic diol compound represented by the above formula (C4) include diglycidyl etherified products of polyalkylene glycols such as diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, cyclohexanedimethylol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,9-nonanediol diglycidyl ether.

[0169] Representative examples of the aliphatic epoxy compound include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, or glycerin; and diglycidyl esters of aliphatic long-chain dibasic acids. Further examples include monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, and monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, and epoxidized polybutadiene. The aliphatic epoxy resin may be one that does not contain an aliphatic ring or an aromatic ring.

[0170] As the aromatic and aliphatic epoxy compounds, commercially available products can be used, and specific examples include those described in Japanese Patent No. 6103653.

[0171] The content of the epoxy compound may be any amount that can give a cured product having excellent light absorption in the desired wavelength region, and is, for example, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, per 100 parts by mass of the cationic curable compound. By setting the content within the above range, a cured product having excellent film-forming properties and curability can be obtained.

[0172] [Oxetane compounds] The oxetane compound may be one that has an oxetane structure but does not contain an epoxy structure. Specific examples of such 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-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3'-(1,3-(2-methyleneyl)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanyl tris(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene(3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis(3 -ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, Examples include ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether.

[0173] In the present invention, a suitable example of the oxetane compound is the compound represented by the following formula (C5) (3-ethyl-3-{[(3-ethyl-3-oxetanyl)methoxy]methyl}oxetane).

[0174] [ka]

[0175] The content of the oxetane compound may be any amount that can give a cured product with excellent light absorption in the desired wavelength region, and is preferably 1 to 100 parts by mass, more preferably 25 to 95 parts by mass, even more preferably 50 to 90 parts by mass, and even more preferably 60 to 80 parts by mass, per 100 parts by mass of the cationic curable compound. By setting the content within the above range, it is possible to give a cured product with excellent film-forming properties and curability.

[0176] As the cationically curable compound, other compounds such as thiirane compounds and thietane compounds can also be used. Other compounds that can be used as such cationically 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 those described in Japanese Patent No. 6103653, etc.

[0177] [N-Alkoxymethylol Compounds] N-alkoxymethylol compounds are crosslinkable compounds having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, and when exposed to high temperatures during thermal curing, they undergo a crosslinking reaction via a dehydration condensation reaction. Examples of such compounds include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

[0178] Specific examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone.

[0179] Commercially available N-alkoxymethylol compounds can be used, and specific examples thereof include glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174), and the like.

[0180] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine.

[0181] Commercially available alkoxymethylated benzoguanamines can be used, and specific examples thereof include those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123) and Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

[0182] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine.

[0183] Commercially available alkoxymethylated melamines can be used. Specific examples of commercially available alkoxymethylated melamines include methoxymethyl-type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, and 350) and butoxymethyl-type melamine compounds (trade names: Mycoat (registered trademark) 506 and 508) manufactured by Mitsui Cytec Co., Ltd.; methoxymethyl-type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, and MX-035) manufactured by Sanwa Chemical; and butoxymethyl-type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, and MX-302) manufactured by Sanwa Chemical.

[0184] The compound may also be a compound obtained by condensing a melamine compound, urea compound, glycoluril compound, or benzoguanamine compound in which the hydrogen atom of the amino group has been substituted with a methylol group or an alkoxymethyl group. Examples include high-molecular-weight compounds produced from melamine compounds and benzoguanamine compounds, as described in U.S. Patent No. 6,323,310. The melamine compound may be a commercially available product, such as Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and a commercially available benzoguanamine compound may be Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0185] As the cationically curable compound, commercially available products can be used, and specific examples thereof include Epogosey (registered trademark) HD(D) (trade name, manufactured by Yokkaichi Synthetic Co., Ltd.), X-40-2669 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), TTA26 (trade name, manufactured by Sun Chemical Co., Ltd.), and CELLOXIDE 2021P (trade name, manufactured by Daicel Corporation). In the present application, Epogosey (registered trademark) HD(D) may be abbreviated as "C-1," X-40-2669 as "C-2," CELLOXIDE 2021P as "C-3," and TTA26 as "C-4."

[0186] The content of the (C) cationically curable compound is not limited as long as the desired effects of the present invention are achieved. The content of the (C) cationically curable compound is, for example, 1 to 50% of the total content (by mass) of the (B) radically curable compound and the (C) cationically curable compound, preferably 3 to 50%, and more preferably 5 to 50%.

[0187] [(D) Photoradical initiator] The photoradical initiator (D) is not particularly limited as long as the object of the present invention can be achieved. It is also suitable for a general method of producing a wavelength conversion member.

[0188] As the photoradical initiator, a molecular cleavage type or hydrogen abstraction type photoradical initiator is preferably used.

[0189] Examples of molecular cleavage type photoradical initiators include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide. Other molecular cleavage type photoradical initiators that may be used in combination include, for example, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0190] Examples of hydrogen abstraction type photoradical initiators include benzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenyl sulfide. A molecular cleavage type photoradical initiator and a hydrogen abstraction type photoradical initiator may be used in combination.

[0191] Photoradical initiators are also available as commercially available products. Examples of such commercially available products include acylphosphine oxide compounds such as Omnirad (registered trademark, hereinafter the same) TPO-H, Omnirad TPO-L, and Omnirad 819 manufactured by IGM Resins; alkylphenone compounds such as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG; intramolecular hydrogen abstraction compounds such as Omnirad MBF and Omnirad 754; and Irgacure (registered trademark, hereinafter the same) OXE01, Irgacure OXE02, Irgacure OXE03, and Irgacure OXE04 manufactured by BASF Japan Ltd. OXE04, TR-PBG-304 and TR-PBG-305 manufactured by Changzhou Strong Electronic New Materials Co., Ltd., and oxime ester compounds such as NCI-730, NCI-831, and NCI-930 manufactured by ADEKA Corporation. In the present application, Omnirad 819 may be abbreviated as "D-1," and Omnirad 184 may be abbreviated as "D-2."

[0192] In addition to these, the oxime ester compounds include, for example, compounds described in JP-T-2004-534797, compounds described in JP-A-2000-80068, compounds described in WO 2012 / 45736, compounds described in WO 2015 / 36910, compounds described in JP-A-2006-36750, compounds described in JP-A-2008-179611, compounds described in WO 2009 / 131189, compounds described in JP-T-2012-526185, compounds described in JP-T-2012-519191, compounds described in WO 2006 / 18973, compounds described in WO 2008 / 78678, and oxime ester compounds such as compounds described in JP-A-2011-132215.

[0193] When the above-mentioned (D) photoradical initiator is used, a chain transfer agent may be used in combination. By using a chain transfer agent, the reaction rate of the photoradical reaction can be increased.

[0194] Chain transfer agents are defined in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include compounds having SH, PH, SiH, and GeH in the molecule. These donate hydrogen to low-activity radical species to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds (e.g., 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) are particularly preferred, and polyfunctional thiol compounds are particularly preferred. Polyfunctional thiols may be compounds having two or more thiol (SH) groups. Examples of polyfunctional thiol compounds include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate (PETP), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), Karenz (registered trademark, the same applies hereinafter) MT BD1, Karenz MT PE1, Karenz MT NR1 (all manufactured by Resonac Corporation), and the like.

[0195] The content of the (D) photoradical initiator is not particularly limited, but from the viewpoint of more effectively achieving the effects of the present invention, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, relative to the mass of the composition for forming a wavelength conversion film. Furthermore, from the viewpoint of more effectively achieving the effects of the present invention, the upper limit of the content is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, relative to the mass of the composition for forming a wavelength conversion film.

[0196] The content of the (D) photoradical initiator may be, for example, 0.1 to 5 mass % relative to the total amount of the composition for forming a wavelength conversion film of the present invention.

[0197] (E) Photoacid generator The photoacid generator is a catalyst that generates an acid when irradiated with light, and cationic polymerizes 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, and diazomethane compounds.

[0198] Examples of onium salt compounds include sulfonium salts, iodonium salts, phosphonium salts, and selenium salts. Specific examples thereof include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; and polyaryliodonium salts such as diphenyliodonium hexafluoroantimonate and p-nonylphenyliodonium hexafluoroantimonate.

[0199] Specific examples of preferred sulfonium salts in the present invention include those represented by the following formula (E-1).

[0200] [ka]

[0201] The onium salt compounds are also commercially available. Examples of such commercially available products include sulfonium salt-based cationic photopolymerization initiators such as CPI-100P and CPI-310FG manufactured by San-Apro Co., Ltd., Omnicat (registered trademark; the same applies hereinafter) 270 manufactured by IGM Resin, and Irgacure 290 manufactured by BASF Japan Ltd.; aromatic sulfonium salt-based cationic photopolymerization initiators such as ADEKA Arcles SP-606 manufactured by ADEKA; and iodonium salt-based cationic photopolymerization initiators such as Omnicat 250 manufactured by IGM Resin. In the present application, CPI-310FG may be abbreviated as "E-1."

[0202] The sulfonium salt (photoacid generator) may be dissolved in advance in a solvent that does not inhibit the polymerization or crosslinking reaction, in order to facilitate dissolution in the cationically polymerizable compound.

[0203] Examples of 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; monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate. polyhydric alcohols and derivatives thereof, such as diol ethers; cyclic ethers, such as dioxane; esters, such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons, such as toluene and xylene.

[0204] When a solvent is used, the proportion of the solvent used is preferably 15 to 1,000 parts by mass, more preferably 30 to 500 parts by mass, per 100 parts by mass of the sulfonium salt (photoacid generator). The solvents may be used alone or in combination of two or more.

[0205] Examples of the metallocene complex compounds include (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) hexafluorophosphate.

[0206] Iron arene complex compounds include bis(η 5 -cyclopentadienyl)(η 6 -isopropylbenzene)iron(II) hexafluorophosphate, etc.

[0207] Examples of disulfone compounds include aromatic disulfone compounds such as diphenyl disulfone; sulfonimide compounds such as 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-naphthalimide, and N-(trifluoromethanesulfonyloxy)-4-alkyl-1,8-naphthalimide, and derivatives thereof. Among these, sulfonimide compounds and derivatives thereof are preferred, and N-(trifluoromethanesulfonyloxy)-1,8-naphthalimide and derivatives thereof are more preferred.

[0208] Examples of sulfonic acid derivative compounds include bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane, 2,2-bis(2-naphthylsulfonyl)propane, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.

[0209] Examples of the triazine compounds include haloalkyltriazinylarenes such as 1-methoxy-4-(3,5-di(trichloromethyl)triazinyl)benzene, 1,2-methylenedioxy-4-(3,5-di(trichloromethyl)triazinyl)benzene, and 1-methoxy-4-(3,5-di(trichloromethyl)triazinyl)naphthalene; and haloalkyltriazinylalkenylarenes such as 1-methoxy-4-[2-(3,5-ditrichloromethyltriazinyl)ethenyl]benzene, 1,2-dimethoxy-4-[2-(3,5-ditrichloromethyltriazinyl)ethenyl]benzene, and 1-methoxy-2-[2-(3,5-ditrichloromethyltriazinyl)ethenyl]benzene.

[0210] Examples of acetophenone derivative compounds include 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone.

[0211] Examples of the diazomethane compounds include bis(cyclohexylsulfonyl)diazomethane, bis(t-butylsulfonyl)diazomethane, and bis(p-toluenesulfonyl)diazomethane.

[0212] The content of the (E) photoacid generator is preferably 0.1 to 49 mass %, more preferably 0.1 to 20 mass %, still more preferably 0.2 to 10 mass %, and still more preferably 0.3 to 5 mass %, based on the mass of the composition for forming a wavelength-converting film, from the viewpoints of film-forming ability and the transparency, heat resistance, and light resistance of the cured film. The (E) photoacid generator may be used alone or in combination of two or more.

[0213] [(F) Light scattering particles] The composition for forming a wavelength conversion film of the present invention may further contain (F) light-scattering particles. The light-scattering particles have the function of scattering light that has entered the wavelength conversion film within the film, thereby essentially extending the optical path length within the wavelength conversion film and improving the light absorptance, and of re-scattering light that has been reflected at the interface of the wavelength conversion film and returned to the wavelength conversion film, thereby improving the luminous efficiency.

[0214] The light-scattering particles can be appropriately selected depending on the purpose, and may be organic or inorganic fine particles. Among these, inorganic fine particles with a high refractive index are preferred in terms of enhancing the scattering performance of the particles.

[0215] Examples of the organic fine particles 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.

[0216] Examples of 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, etc. Specific examples of the inorganic oxide particles include SiO2, ZrO2, TiO2 (sometimes referred to as titanium oxide particles in this application), BaTiO3, In2O3, ZnO, Sb2O3, ITO, CeO2, Nb2O5, and WO3. Of these, TiO2, BaTiO3, ZrO2, CeO2, and Nb2O5 are preferred, with TiO2 being more preferred. Furthermore, among TiO2, rutile-type TiO2 is preferred over anatase-type TiO2 because it has lower catalytic activity, resulting in higher film durability, and also has a higher refractive index.

[0217] These particles may be surface-treated. When performing the surface treatment, specific examples of the surface treatment material include different inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, organosiloxanes, organic acids such as stearic acid, etc. These surface treatment agents may be used alone or in combination of two or more.

[0218] The average particle diameter of the light-scattering particles is more than 50 nm and less than 300 nm. From the viewpoint of wavelength conversion efficiency, the lower limit of the average particle diameter is preferably 60 nm or more, more preferably 70 nm or more. In consideration of patterning characteristics in addition to the viewpoint of wavelength conversion efficiency, 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 290 nm or less, more preferably 200 nm or less, from the viewpoint of storage stability of the composition, since if the average particle diameter is too large, sedimentation will be likely. The average particle diameter of the light-scattering particles is the average particle diameter determined by observation with a transmission electron microscope.

[0219] Commercially available light-scattering particles may be used. Specific examples of titanium oxide particles include, but are not limited to, PT-401M (rutile type, average particle diameter 70 nm), PT-401L (rutile type, average particle diameter 130 nm), and PT-501R (rutile type, average particle diameter 180 nm), all manufactured by Ishihara Sangyo Kaisha, Ltd. The average particle diameter of the light-scattering particles exemplified above may vary by ±10 nm. In the present application, PT-401L may also be abbreviated as "F-1."

[0220] The content of the (F) light-scattering particles may also be 1% by mass or more relative to the mass of the composition for forming a wavelength-converting film, the upper limit of which may vary depending on the types and amounts of other components, and may be, for example, 10% by mass.

[0221] Furthermore, the composition for forming a wavelength conversion film of the present invention may contain, in addition to the (A) organic phosphor, (B) radically curable compound, and (C) cationic curable compound, various known additives such as (F) light-scattering particles, (D) photoradical initiator, and (E) photoacid generator, as needed, a light stabilizer, an antioxidant, a surfactant, a polymer dispersant, a flame retardant, a clarifying agent, an ultraviolet absorber, and a filler.

[0222] Examples of antioxidants include hindered phenol-based antioxidants, phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. These may be used alone or in combination of two or more. As the antioxidant, commercially available products can be used, and examples thereof include Irganox 245 and Irganox 1010 manufactured by BASF Japan Ltd., and Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-60, Adeka Stab AO-80, and Adeka Stab AO330 manufactured by ADEKA Corporation, but are not limited to these. When an antioxidant is used, the amount thereof to be added is not particularly limited, but is preferably 0.1 to 5.0 mass % relative to the mass of the composition for forming a wavelength conversion film, and more preferably 0.3 to 1.5 mass %.

[0223] As the surfactant, a fluorine-based surfactant is preferred, and a nonionic fluorine-based surfactant is more preferred. Specific examples include the Ftergent series manufactured by Neos Corporation, such as 212M, 215M, 250, 222F, FTX-218, and DFX-18, but are not limited to these. When a surfactant is used, the amount thereof to be added is not particularly limited, but is preferably 0.01 to 1 mass % relative to the mass of the composition for forming a wavelength conversion film, and more preferably 0.01 to 0.5 mass %.

[0224] The polymer dispersant is a polymer compound having a weight-average molecular weight of 750 or more and having functional groups that have affinity for light-scattering particles. The polymer dispersant has the function of dispersing the light-scattering particles. The polymer dispersant adsorbs to the light-scattering particles via the functional groups that have affinity for the light-scattering particles, and disperses the light-scattering particles in the composition due to electrostatic and / or steric repulsion between the polymer dispersants. The polymer dispersant is preferably bonded to the surface of the light-scattering particles and adsorbed to the light-scattering particles, but may be free in the composition for forming a wavelength conversion film.

[0225] The functional group having affinity for the (F) light-scattering particles includes an acidic functional group, a basic functional group, and a nonionic functional group. The acidic functional group has a dissociable proton and may be neutralized with a base such as an amine or hydroxide ion, while the basic functional group may be neutralized with an acid such as an organic acid or an inorganic acid.

[0226] Examples of acidic functional groups include carboxyl group (-COOH), sulfo group (-SO3H), sulfate group (-OSO3H), phosphonic acid group (-PO(OH)2), phosphoric acid group (-OPO(OH)2), phosphinic acid group (-PO(OH)-), and mercapto group (-SH).

[0227] Examples of basic functional groups include primary amino groups, secondary amino groups, tertiary amino groups, ammonium groups, and imino groups, as well as nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole, and triazole.

[0228] Examples of nonionic functional groups include a hydroxy group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group (-SO2-), a carbonyl group, a formyl group, an ester group, a carbonate ester group, an amide group, a carbamoyl group, a ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group, and a phosphine sulfide group.

[0229] The polymeric dispersant may be a polymer (homopolymer) of a single monomer or a copolymer (copolymer) of multiple types of monomers. The polymeric dispersant may be a random copolymer, a block copolymer, or a graft copolymer. When the polymeric dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer. Specific examples of polymeric dispersants include acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyethers, phenolic resins, silicone resins, polyurea resins, amino resins, epoxy resins, polyethyleneimines, polyallylamine, polyimides, etc.

[0230] As the polymer dispersant, commercially available products can be used, such as the DISPERBYK series and BYK series manufactured by BYK, the Efka series manufactured by BASF, the Solsperse series manufactured by Lubrizol Corporation, the Ajisper PB series manufactured by Ajinomoto Fine-Techno Co., Ltd., the TEGO series manufactured by Evonik, and the Disparlon series manufactured by Kusumoto Chemicals Co., Ltd.

[0231] Specific examples of the commercially available products include DISPERBYK-130, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, and DISPERBYK-184. 84, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2022, DISPER BYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164; EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4061, EFKA4080, EFKA4300, EFKA4310, EFKA4320, EFKA4330, EFKA4340, EFKA4560, EFKA4585, EFKA5207, EFKA1501, EFKA1502, EFKA1503 and EFKA PX-4701 manufactured by BASF; Lubrizol's Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 11200, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, and Solsperse 280 00, Solsperse 32000, Solsperse 32500, Solsperse 32550, Solsperse 32600, Solsperse 33000, Solsperse 34750, Solsperse 35100, Solsperse 35200, Solsperse 36000, Solsperse 37500, Solsperse 38500, Solsperse 39000, Solsperse 41000, Solsperse 54000, Solsperse 71000 and Solsperse 76500; Ajisper PB821, Ajisper PB822, Ajisper PB881, PN411 and PA111 manufactured by Ajinomoto Fine-Techno Co., Inc.; Examples include TEGO Dispers 650, TEGO Dispers 660C, TEGO Dispers 662C, TEGO Dispers 670, TEGO Dispers 685, TEGO Dispers 700, TEGO Dispers 710, and TEGO Dispers 760W manufactured by Evonik Corporation, and Disparlon AQ-320, Disparlon AQ-330, Disparlon AQ-340, Disparlon AQ-360, and Disparlon AQ-380 manufactured by Kusumoto Chemicals Co., Ltd. In the present application, Disparlon AQ-320 may be abbreviated as "G-1," and Disparlon AQ-330 may be abbreviated as "G-2."

[0232] When a polymer dispersant is used, the amount thereof to be added is not particularly limited, but is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on the light scattering particles.

[0233] Furthermore, the composition for forming a wavelength conversion film of the present invention may contain a solvent, if necessary.Specific examples thereof include aromatic or halogenated aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene; aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ethyl acetate, normal hexyl acetate, ethyl lactate, γ-butyrolactone, and propylene carbonate. ester solvents such as ethyl 3-ethoxypropionate, diisopropyl malonate, and ethyl 3-ethoxypropionate; halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, 1,2-dichloroethane, and chloroform; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, cyclohexanol, diacetone alcohol, and 2-benzooxyethanol; ethylene glycol mononitrate, diisopropyl malonate, and ethyl 3-ethoxypropionate; Examples of suitable organic solvents include glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol diglycidyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; glycol solvents such as ethylene glycol, propylene glycol, hexylene glycol, 3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol; nitrile solvents such as acetonitrile; and sulfur-containing solvents such as dimethyl sulfoxide.These may be used alone or in combination of two or more.

[0234] The organic fluorescent substance (A) may exist as a solvate. The solvate is not particularly limited as long as it is a solvate of the compound represented by formula (1) and a solvent. Examples of solvents that can form a solvate include dichloromethane, chloroform, acetonitrile, diethyl ether, ethyl acetate, methanol, ethanol, cyclohexane, toluene, acetone, N,N-dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran.

[0235] When the composition for forming a wavelength-converting film contains a solvent, the solids concentration of the composition for forming a wavelength-converting film cannot be generally defined because it varies depending on the intended thickness of the wavelength-converting film, the coating method, etc., but is usually 70 to 100 mass %, preferably 95 to 100 mass %. The term "solid content" as used herein refers to all components in the wavelength conversion film-forming composition that remain in the film after the wavelength conversion film is formed, and is defined as film-forming components other than the solvent. In the composition for forming a wavelength conversion film of the present invention, a solvent for dissolving the above components (A) to (C) may or may not be used. When the composition for forming a wavelength-converting film of the present invention further contains a solvent that dissolves the above components (A) to (C), the amount of the solvent relative to the composition for forming a wavelength-converting film is, for example, 30% by mass or less. A composition for forming a wavelength-converting film of the present invention in which the amount is 1% by mass or less is preferred. Of the compositions for forming a wavelength conversion film of the present invention, those that do not contain a solvent that dissolves the above components (A) to (C) or that contain such a solvent in an amount of approximately 0% by mass are more preferred. "Almost 0% by mass" means, for example, an amount that achieves light resistance equivalent to that of "0% by mass" (approximately ±10%).

[0236] The upper limit of the viscosity of the composition for forming a wavelength conversion film at 25° C. is 10,000 mPa s or less, preferably 1,000 mPa s or less, and more preferably 100 mPa s or less. In consideration of storage stability, the lower limit is preferably 5 mPa s or more, and more preferably 10 mPa s or more. In the present invention, viscosity refers to a value measured using an EMS viscometer.

[0237] [Wavelength-converting film-forming composition of the present invention] The composition for forming a wavelength conversion film of the present invention contains the above-mentioned (A) organic phosphor, (B) radically curable compound, and (C) cationically curable compound. Among the compositions for forming a wavelength conversion film of the present invention, a composition further containing (D) a photoradical initiator, (E) a photoacid generator, and (F) light-scattering particles is preferred, and a composition containing, for example, a dispersant as other components (additives) is more preferred. The production method of the composition for forming a wavelength conversion film of the present invention is not limited, and the composition may be produced using conventional techniques. The composition for forming a wavelength conversion film of the present invention can be prepared by mixing, in any order, the above-mentioned (A) organic phosphor, (B) radical curable compound, and (C) cationically curable compound, as well as the above-mentioned (D) photoradical initiator, (E) photoacid generator, (F) light-scattering particles, other additives, and, as needed, a predetermined solvent.

[0238] [Wavelength-converting film using the wavelength-converting film-forming composition of the present invention, and preparation of the wavelength-converting film] The wavelength-converting film can be obtained by applying the wavelength-converting film-forming composition of the present invention described above, for example, to a substrate, evaporating the solvent by heating (this heating is also referred to as "pre-baking") as necessary, and then irradiating the composition with active energy rays (for example, ultraviolet light). Examples of the application method include methods using a 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, barrier roll blade coater, two-stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater, inkjet, etc.

[0239] Heating can be carried out using 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 heating at 60 to 200° C. for 2 minutes to 2 hours is preferred, and heating at 80 to 200° C. for 15 minutes to 1 hour is more preferred. Heat curing may also be carried out in stages.

[0240] The ultraviolet light irradiation is not particularly limited as long as it can form a film, but light sources such as mercury lamps, metal halide lamps, xenon lamps, and LEDs can be used, and if necessary, a bandpass filter can be used to remove light other than the desired exposure wavelength. The wavelength of the irradiated light is preferably 200 to 440 nm, and particularly preferably includes light with a wavelength of 300 to 400 nm. The exposure dose is 10 to 12,000 mJ / cm. 2 is preferred.

[0241] The heating step and the ultraviolet light exposure step may be combined in any order, for example, heating may be performed before ultraviolet light irradiation, ultraviolet light irradiation may be performed before heating, or heating may be performed after ultraviolet light irradiation, and then heating may be performed again.

[0242] The thickness of the wavelength converting film (that is, the wavelength converting film immediately before exposure to ultraviolet light) is not particularly limited, but is usually 1 to 1,000 μm, preferably 3 to 500 μm, more preferably 5 to 100 μm. The haze of the wavelength conversion film is not particularly limited, but is preferably 18% or more, more preferably 30% or more, and even more preferably 40% or more, from the viewpoint of scattering incident light within the film and thereby increasing the amount of light that can be absorbed by the phosphor. The upper limit of the haze value is not particularly limited, but is usually about 95%. In the present invention, the haze value is a value measured in accordance with JIS K7105-1981. In the present invention, the haze value is measured, for example, on a 7 μm-thick film formed from a composition containing 6% by mass of titanium oxide particles.

[0243] The substrate may be appropriately selected from those used as base substrates for forming this type of film, but a glass substrate or polymer plate having a transmittance of 50% or more for light in the visible region of 400 to 800 nm is preferred. Specific examples of glass include soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Specific examples of polymers include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

[0244] A typical post-baking method involves treating the film at a heating temperature selected from the range of 100 to 270° C. for 5 to 30 minutes on a hot plate or for 30 to 90 minutes in an oven. Post-baking under these conditions allows a cured film having a good pattern shape to be obtained.

[0245] The wavelength conversion film formed by the wavelength conversion film-forming composition of the present invention has excellent light resistance and curability, and can therefore be suitably used as a wavelength conversion film (color conversion film) for displays such as micro LED displays, organic EL displays, and liquid crystal displays, as well as for lighting.

[0246] [Blue light absorptance maintenance rate in the composition for forming a wavelength conversion film of the present invention] In this application, the "blue light absorptance maintenance rate" before and after blue LED irradiation when irradiated with a blue LED for a certain period of time is the ratio of the blue light absorptance after irradiation with the blue LED to the blue light absorptance before said irradiation. When determining the blue light absorptance maintenance rate, the illuminance and irradiation time of the blue LED are not limited and may be set appropriately. The brightness of the LED may be, for example, 1500 nits. The longer the irradiation time, the easier it is to compare the lightfastness. However, since a difference that allows a comparison of the lightfastness can be confirmed after an irradiation time of around 100 hours, the irradiation time may be, for example, 80 to 160 hours. The parameters and calculation method used to determine the blue light absorptance are not limited. The blue light absorptance may be determined, for example, from the peak height of irradiance occurring in the blue wavelength region (approximately 430 to 490 nm). In the composition for forming a wavelength conversion film of the present invention, the blue light absorptance maintenance rate is not limited.

[0247] In the composition for forming a wavelength conversion film of the present invention, when a certain composition ("composition 1") is irradiated with a blue LED for a certain period of time, the maintenance rate of blue light absorptance in composition 1 before and after blue LED irradiation ("blue light absorptance maintenance rate 1") is obtained; and when a composition ("composition 2") which is different from composition 1 in that it does not contain component (C) is irradiated with a blue LED for the certain period of time, the maintenance rate of blue light absorptance in composition 2 before and after blue LED irradiation ("blue light absorptance maintenance rate 2") is obtained; Blue light absorption rate maintenance rate 1 > Blue light absorption rate maintenance rate 2 It is preferable that the following relationship holds: In other words, the composition for forming a wavelength conversion film of the present invention, for which the above relationship holds, is preferable because it has even better light resistance.

[0248] Further, according to the present invention, (A) an organic phosphor and (B) Radical curing compound Also provided is a method for improving the light resistance of a composition for forming a wavelength conversion film, comprising the compound. The method comprises: The method includes a step of allowing a composition containing (A) an organic fluorescent material and (B) a radically curable compound to be in the presence of (C) a cationically curable compound. Here, the step of causing the (C) cationic curable compound to be present in the composition containing the (A) organic phosphor and the (B) radical curable compound is not limited, and may be any step that causes the wavelength-conversion film-forming composition to contain the (C) cationic curable compound together with the (A) organic phosphor and the (B) radical curable compound. That is, the step may be a step of blending the (C) cationic curable compound into the precursor composition at any time during the production of the wavelength-conversion film-forming composition. In the present application, there are no limitations on the degree of improvement in "improving lightfastness" or "improving lightfastness." In other words, in the present application, when the lightfastness of a composition obtained by applying a certain treatment to a composition exceeds the lightfastness of the composition before the treatment, it means that "improving lightfastness" or "improving lightfastness" has been achieved.

[0249] The components (A) to (C) in the method for improving the light resistance of the composition for forming a wavelength-converting film according to the present invention are the same as those described above for the composition for forming a wavelength-converting film according to the present invention. Furthermore, the same explanations as those for the composition for forming a wavelength-converting film according to the present invention, other than the explanations for the components (A) to (C), also apply to the composition for forming a wavelength-converting film having improved light resistance by the method of the present invention. [Example]

[0250] EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0251] The abbreviations used in this example have the following meanings: [Component (A): Organic fluorescent material] A-1: Organic phosphor represented by the above formula (A2-5), synthetic product (see Synthesis Example 1) A-2: A compound represented by the following formula (A3), FL 305 (manufactured by BASF) [ka] [Component (B): Radical-curable compound] B-1: Viscoat #260 (1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) B-2: Viscoat #230 (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) B-3: NOD-N (1,9-nonanediol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) [Component (C): Cationic curable compound] C-1: Epogose® HD(D) (1,6-hexanediol diglycidyl ether, manufactured by Yokkaichi Synthetic Co., Ltd.) C-2: X-40-2669 (Shin-Etsu Chemical Co., Ltd.) C-3: CELLOXIDE 2021P (manufactured by Daicel Corporation) C-4: TTA26 (Sun Chemical Co., Ltd.) [Component (D): Photoradical initiator] ·D-1: Omnirad 819 (Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, manufactured by IGM Resins BV) D-2: Omnirad 184 (1-hydroxycyclohexyl-phenyl ketone, manufactured by BASF Japan Ltd.) [Component (E): Photoacid generator] E-1: CPI-310FG (aromatic sulfonium salt, manufactured by San-Apro Co., Ltd.) [(F) Component: Light scattering particles] F-1: PT-401L (titanium oxide particles, rutile type, average particle size 130 nm, manufactured by Ishihara Sangyo Kaisha, Ltd.) [Component (G): Polymer dispersant] G-1: Disparlon AQ-320 (polyether phosphate ester, manufactured by Kusumoto Chemicals Co., Ltd.) G-2: Disparlon AQ-330 (polyether phosphate ester, manufactured by Kusumoto Chemicals Co., Ltd.) [Component (H): Bi-curable compound] H-1: 4HBAGE (4-hydroxybutyl acrylate glycidyl ether, manufactured by Mitsubishi Chemical Corporation)

[0252] 1 H-NMR spectra were measured using a nuclear magnetic resonance spectrometer AVANCE III HD (Bruker). Chemical shift values ​​are expressed in ppm, and deuterated chloroform was used as the solvent. 1 In the H-NMR spectrum, the signal derived from the residual protons of the solvent was used, and chloroform was set as the internal standard at δ 7.26 ppm. Thin-layer chromatography (TLC) was performed on glass plates coated with 0.25 mm of silica gel 60F-254 (Merck). Silica gel chromatography was performed using silica gel 60N spherical neutral (Kanto Chemical Co., Ltd.) as the packing material.

[0253] [Reference Synthesis Example 1] 4-(3-bromobenzo[b]thiophen-2-yl)-N,N-diphenylaniline (Compound K2) [ka]

[0254] Under a N2 gas atmosphere, 2,3-dibromobenzo[b]thiophene (Compound K1; 5.00 g, 17.1 mmol), 4-(diphenylamino)phenylboronic acid (5.94 g, 20.5 mmol), sodium carbonate (5.44 g, 51.3 mmol), and tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4; 988 mg, 0.855 mmol) were dissolved in a mixed solvent of 1,4-dioxane (100 mL) and water (50 mL). The mixture was heated to 90 °C and stirred for 18 hours. After adding cold water, the mixture was extracted three times with ethyl acetate. The combined organic layer was dehydrated over anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure. The concentrate (developing solvent: hexane / ethyl acetate=10 / 1; Rf=0.6) was purified by silica gel column chromatography (hexane → hexane / chloroform=3 / 1) to obtain compound K2 as a yellow solid in a yield of 88% (6.86 g, 15.0 mmol). 1 H-NMR(500MHz, CDCl3):δ 7.84(d,J=8.0Hz,1H),7.79(d,J=8.0Hz,1H),7.65-7.63(m,2H),7.47-7.44(m,1 H),7.39-7.36(m,1H),7.32-7.28(m,4H),7.18-7.16(m,4H),7.13-7.07(m,4H).

[0255] [Reference Synthesis Example 2]: 3-Bromo-2-[4-(diphenylamino)phenyl]benzo[b]thiophene 1,1-dioxide (Compound K3) [ka]

[0256] 4-(3-Bromobenzo[b]thiophen-2-yl)-N,N-diphenylaniline (Compound K2; 500 mg, 1.10 mmol) was dissolved in dichloromethane (20 mL). Metachloroperbenzoic acid (m-CPBA (30% by weight water content); 1.08 g, 4.38 mmol) was slowly added to the solution at 0 °C. The mixture was returned to room temperature and stirred for 18 hours. Saturated aqueous sodium bicarbonate was added, and the mixture was extracted three times with chloroform. The combined organic layer was dehydrated with anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure. The concentrate (developing solvent: hexane / ethyl acetate = 3 / 1; Rf = 0.5) was purified by silica gel column chromatography (hexane → hexane / chloroform = 3 / 1 → hexane / chloroform = 1 / 1) to obtain Compound K3 as a yellow solid in a 53% yield (286 mg, 0.586 mmol). 1H-NMR(500MHz, CDCl3):δ 7.83-7.80(m,2H),7.75(d,J=8.0Hz,1H),7.68-7.63(m,2H),7.57-7.54(m,1H),7.33-7.30(m,4H),7.18(d,J=8.0Hz,4H),7.14-7.08(m,4H).

[0257] [Reference Synthesis Example 3]: 2,2'-(9H-fluoren-9-ylidene-4,1-phenylene)bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane] (Compound K5) [ka]

[0258] Under a N2 gas atmosphere, 9,9-bis(4-bromophenyl)fluorene (compound K4; 2.33 g, 4.89 mmol), bis(pinacolato)diboron (4.97 g, 19.57 mmol), potassium acetate (AcOK; 2.54 g, 25.88 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (Pd(dppf)Cl2; 278 mg, 0.38 mmol) were added to 1,4-dioxane (200 mL). The mixture was heated to 100 °C and stirred for 20 h. Chloroform and water were added for extraction, and the resulting organic layer was concentrated. The concentrate was purified by silica gel column chromatography (chloroform / hexane = 1 / 3) to obtain compound K5 as a white solid in a 65% yield (1.83 g, 3.21 mmol). 1H-NMR(500MHz, CDCl3):δ 7.74(d,J=7.5Hz,2H),7.67(d,J=8.0Hz,4H),7.36(d,J=7.5Hz,2H),7.33(dd,J =7.5Hz,7.5Hz,2H),7.23(d,J=7.5Hz,2H),7.10(d,J=8.0Hz,4H),1.29(s,24H).

[0259] [Synthesis Example 1]: 3,3'-[(9H-fluorene-9,9-diyl)bis(4,1-phenylene)]bis{2-[4-(diphenylamino)phenyl]benzo[b]thiophene 1,1-dioxide} (Compound A2-5) [ka]

[0260] Under a N2 gas atmosphere, 3-bromo-2-[4-(diphenylamino)phenyl]benzo[b]thiophene 1,1-dioxide (Compound K3; 2.46 g, 5.04 mmol) obtained in Reference Synthesis Example 2, 2,2'-(9H-fluoren-9-ylidene-4,1-phenylene)bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane] (Compound K5; 1.61 g, 2.82 mmol) obtained in Reference Synthesis Example 3, sodium carbonate (1.25 g, 11.79 mmol), and tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4; 415 mg, 0.36 mmol) were dissolved in a mixed solvent of 1,4-dioxane (100 mL) and water (50 mL). The mixture was heated to 90 °C and stirred for 20 hours. The organic layer was extracted with chloroform and water, and the concentrate was purified by silica gel column chromatography (chloroform / hexane = 1 / 2) to give compound A2-5 as an orange solid in a yield of 79% (2.28 g, 2.01 mmol). 1 H-NMR(500MHz, CDCl3):δ 7.77-7.84(m,4H),7.46-7.51(m,4H),7.34-7.41(m,4H),7.32-7.29(d,J= 8.0Hz,4H),7.17-7.28(m,20H),7.04-7.12(m,12H),6.84(d,J=8.0Hz,4H).

[0261] (E) Preparation of a dispersion of light-scattering particles [Preparation Example 1] Preparation of light scattering particle dispersion 1 (PT-401L Viscoat #260 dispersion) A 50 mL plastic bottle was charged with 30% by weight of G-1 (Disparlon AQ-320) based on the solid content of light-scattering particles F-1 (PT-401L), and then B-1 (Viscoat #260) was added to adjust the light-scattering particle concentration to 30% by weight. Zirconia balls with a diameter of 1 mm were then added to the container, and the mixture was ball-milled by stirring for 48 hours using a VMR-5R mix rotor (manufactured by AS ONE Corporation). Light-scattering particle dispersion 1 was obtained. The particle size distribution of the resulting dispersion was measured using a Nanotrac UPA (manufactured by Microtrac). The dispersion solvent was used as a dilution solution. The 50% cumulative diameter (D50) of the particles in the dispersion was calculated on a volume basis using MicrotracDMS (manufactured by Nikkiso Co., Ltd.) analysis software based on the scattering generated when the diluted sample was irradiated with laser light. The result was 174 nm.

[0262] [Preparation Example 2] Preparation of Light Scattering Particle Dispersion 2 (PT-401L Viscoat #260 Dispersion) Light-scattering particles 2 were obtained in the same manner as in Preparation Example 1, except that G-2 (Disparlon AQ-330) was used instead of G-1 (Disparlon AQ-320) as the dispersant. The 50% cumulative diameter (D50) was calculated to be 185 nm.

[0263] [Preparation Example 3] Preparation of Light Scattering Particle Dispersion 3 (PT-401L in Viscoat #230 Dispersion) Light scattering particles 3 were obtained in the same manner as in Preparation Example 1, except that B-2 (Viscoat #230) was used instead of B-1 (Viscoat #260) as the monomer component. The 50% cumulative diameter (D50) was calculated to be 188 nm.

[0264] [Preparation Example 4] Preparation of Light Scattering Particle Dispersion 4 (NOD-N Dispersion of PT-401L) Light-scattering particles 4 were obtained in the same manner as in Preparation Example 1, except that B-3 (NOD-N) was used instead of B-1 (Viscoat #260) as the monomer component. The 50% cumulative diameter (D50) was calculated to be 189 nm.

[0265] [Preparation Example 5] Preparation of Light-Scattering Particle Dispersion 5 (Epogose® HD(D) Dispersion of PT-401L) Light-scattering particles 5 were obtained in the same manner as in Preparation Example 1, except that C-1 (Epogose® HD(D)) was used instead of B-1 (Viscoat #260) as the monomer component, and G-1 (Disparlon AQ-320) was added in an amount of 10% by mass instead of 30% by mass in terms of solid content to light-scattering particles F-1 (PT-401L). The 50% cumulative diameter (D50) was calculated to be 240 nm.

[0266] [Examples 1 to 31, Comparative Examples 1 to 4] Preparation of compositions for forming wavelength conversion films and evaluation of the thin films (1) Preparation of wavelength conversion film-forming composition Compositions for forming wavelength conversion films were prepared by mixing the components according to the compositions shown in Tables 1-1 to 1-7 and filtering the resulting mixtures using a polytetrafluoroethylene (PTFE) filter with a pore size of 5.0 μm. The composition ratios in Tables 1-1 to 1-7 represent mass ratios in the compositions. The "proportion of cationically curable compound" in the lower part of the tables means the proportion (%) of the content of the cationically curable compound relative to the total content of the radically curable compound and the cationically curable compound. The components in Tables 1-1 to 1-7 are represented by the abbreviations mentioned above.

[0267] <Composition> [Table 1-1]

[0268] <Composition> [Table 1-2]

[0269] <Composition> [Table 1-3]

[0270] <Composition> [Table 1-4]

[0271] <Composition> [Table 1-5]

[0272] <Composition> [Table 1-6]

[0273] <Composition> [Table 1-7]

[0274] (2) Evaluation 1: Evaluation of light resistance of wavelength conversion film The wavelength conversion film-forming compositions of Examples 1 to 31 and Comparative Examples 1 to 4 were applied to a quartz substrate using a spin coater, and then processed according to the patterns shown in Tables 2-1 to 2-3 to obtain coating film samples (film thickness: 7 μm). The results are shown in Tables 3-1 to 3-4.

[0275] [Table 2-1]

[0276] All of the coating samples were then placed on top of a blue LED light (emission peak wavelength 450 nm) manufactured by CCS Inc., the LED light was turned on, and the light emitted through the coating samples was measured using a USR-45 spectroradiometer manufactured by Ushio Inc., and the result was recorded as (I). Similarly, the light emitted from only the LED light was measured in the same way, excluding the coating sample, and the result was reported as Result (II). From the obtained spectral irradiance spectrum, the number of photons of light with wavelengths of 480 nm or less in Result (II) was taken as the "number of excitation light photons." Similarly, the number of photons of light with wavelengths of 480 nm or less in Result (I) was taken as the "number of transmitted light photons." Similarly, the number of photons of light with wavelengths of more than 480 nm in Result (I) was taken as the "number of emission photons." The "blue light absorptance" and "conversion efficiency" were calculated using the following formulas. Blue light absorption rate = (number of excitation light photons - number of transmitted light photons) ÷ number of excitation light photons Conversion efficiency = number of emitted photons ÷ number of excited light photons After the above measurements, the coating film samples were irradiated with light at a wavelength of 450 nm for approximately 100 hours using a blue LED exposure device manufactured by CCS Inc. in a nitrogen atmosphere in a glove box manufactured by VAC. The same measurements as above were performed on the coating film samples after light irradiation, and the "blue light absorptance" was calculated. The "blue light absorptance" after light irradiation divided by the "blue light absorptance" before light irradiation was used as the "blue light absorptance retention rate after light resistance test" for Examples 1 to 31 and Comparative Examples 1 to 4. Relative evaluation was performed, and a judgment was made as to whether the blue light absorptance retention rate was higher or lower than that of the comparative example referenced in the manner shown in Table 2-2 below.

[0277] [Table 2-2]

[0278] The reason for the judgment as shown in Table 2-2 above is that the blue light absorptance value before the light resistance test differs depending on the organic phosphor used, so it is necessary to refer to different comparative examples depending on the organic phosphor. The judgment criteria are as follows. The obtained results are shown in Tables 3-1 to 3-4. <Lightfastness criteria> A: The blue light absorptance maintenance rate is higher than that of the comparative example. B: The blue light absorptance maintenance rate is equal to or lower than that of the comparative example.

[0279] (3) Evaluation 2: Evaluation of curability of Examples 1 to 31 and Comparative Examples 1 to 4 The wavelength conversion film-forming compositions of Examples 1 to 31 and Comparative Examples 1 to 4 were applied onto a quartz substrate using a spin coater, and then processed according to the patterns shown in Table 2-3 to obtain coating film samples (film thickness: 7 μm).

[0280] [Table 2-3]

[0281] Thereafter, a Bemcot (registered trademark) was pressed against the edge of the obtained coating film sample to check whether the film had cured after exposure. The criteria for judging curability are as follows. The results obtained are shown in Table ○. <Curability criteria> A: There is no tack on the film surface. B: There is tack on the film surface.

[0282] (4) Evaluation 3: Evaluation of haze values ​​of Examples 1 to 31 and Comparative Examples 1 to 4 The haze value of the coating film sample obtained in (6) above was measured according to JIS K7105-1981 using a turbidity meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. The results obtained are shown in Tables 3-1 to 3-4.

[0283] <Test Results> [Table 3-1]

[0284] <Test Results> [Table 3-2]

[0285] <Test Results> [Table 3-3]

[0286] <Test Results> [Table 3-4]

[0287] The results of Examples 1 to 31, which are embodiments of the present invention, show that all of the compositions for forming wavelength conversion films containing an organic fluorescent substance, a radically curable compound, and a cationically curable compound are excellent in not only light resistance but also curability. On the other hand, in Comparative Examples 2 to 4, which did not contain a cationic curable compound but contained an organic phosphor and a radical curable compound, the light resistance (blue light absorptance retention rate) was poor. In Comparative Examples 2 to 4, the film formability of the wavelength conversion film was also poorer than in Examples 1 to 31. In addition, Comparative Example 1, which did not contain a radically curable compound but contained an organic fluorescent material and a cationically curable compound, resulted in poor curability. [Industrial Applicability]

[0288] According to the present invention, a composition for forming a wavelength-converting film having excellent light resistance and curability is provided. Therefore, the present invention can be used as a composition for forming a wavelength-converting film for various applications, and is expected to be applicable to a wide variety of industrial fields requiring wavelength-converting films (particularly, the manufacture of displays such as micro LED displays).

Claims

1. A composition for forming a wavelength-converting film, comprising: (A) an organic phosphor; (B) a radically curable compound; and (C) a cationically curable compound.

2. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the polymerizable functional group in the radically curable compound (B) is a (meth)acryloyl group.

3. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the (C) cationically curable compound is one or more compounds selected from the group consisting of compounds having an epoxy group, compounds having an oxetane group, and N-alkoxymethylol compounds.

4. The composition for forming a wavelength conversion film according to claim 1 , further comprising (D) a photoradical initiator.

5. The composition for forming a wavelength-converting film according to claim 1 , further comprising (E) a photoacid generator.

6. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the composition for forming a wavelength conversion film has a viscosity of less than 100 mPa·s.

7. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the organic fluorescent substance (A) is one or more compounds selected from the group consisting of fused ring thiophene compounds and perylene compounds.

8. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the content of the organic phosphor (A) is 0.05% by mass or more relative to the mass of the composition for forming a wavelength conversion film.

9. The composition for forming a wavelength conversion film according to claim 1 , further comprising (F) light-scattering particles.

10. 10. The composition for forming a wavelength conversion film according to claim 9, wherein the (F) light-scattering particles are titanium oxide particles.

11. 10. The composition for forming a wavelength conversion film according to claim 9, wherein the content of the (F) light-scattering particles is 1 mass % or more relative to the mass of the composition for forming a wavelength conversion film.

12. The composition for forming a wavelength conversion film according to claim 9 , wherein a film formed from the composition has a haze value of 18% or more.

13. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the content of the cationically curable compound (C) is 1 to 50% based on the total content of the radically curable compound (B) and the cationically curable compound (C).

14. does not contain a solvent capable of dissolving the above components (A) to (C), or further contains a solvent capable of dissolving the above components (A) to (C), 2. The composition for forming a wavelength conversion film according to claim 1, wherein when the composition further contains a solvent, the amount of the solvent relative to the composition for forming a wavelength conversion film is 30% by mass or less.

15. The composition for forming a wavelength conversion film according to claim 14 , wherein when the composition further contains a solvent, the amount of the solvent is 1 mass % or less.

16. a maintenance rate of blue light absorptance in composition 1 (blue light absorptance maintenance rate 1) before and after blue LED irradiation when composition 1, which is the composition for forming a wavelength conversion film according to claim 1, is irradiated with blue LED for a certain period of time; The composition 2, which is different from the composition 1 in that it does not contain the component (C), is irradiated with blue LED for the above-mentioned certain period of time, and the blue light absorptance maintenance rate (blue light absorptance maintenance rate 2) of the composition 2 before and after the blue LED irradiation is measured. Blue light absorption rate maintenance rate 1 > Blue light absorption rate maintenance rate 2 That is, The composition for forming a wavelength converting film according to claim 1 .

17. 2. The composition for forming a wavelength-conversion film according to claim 1, wherein the organic phosphor (A) is not present as solid particles in the composition for forming a wavelength-conversion film, and contains an organic phosphor that is not present as solid particles in a film formed by irradiating the composition for forming a wavelength-conversion film with excitation light.

18. The composition for forming a wavelength-converting film according to any one of claims 1 to 17, which is a composition for forming a wavelength-converting film for a display.

19. A wavelength conversion film obtained from the composition for forming a wavelength conversion film according to any one of claims 1 to 17.

20. 20. The wavelength conversion film according to claim 19, which is a wavelength conversion film for a display.

21. (A) an organic phosphor; and (B) Radical curable compound A method for improving the light resistance of a composition for forming a wavelength conversion film, comprising: A method comprising the step of causing (C) a cationically curable compound to be present in a composition comprising (A) an organic fluorescent material and (B) a radically curable compound.

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