Composition for forming wavelength conversion film

Abstract

Provided is a composition for forming a wavelength conversion film, which has excellent curability in air and forms a wavelength conversion film having good light resistance. The composition for forming a wavelength conversion film contains (A) an organic phosphor, (B) a cationic curable compound, and (C) a photoacid generator.

Description

Technical Field

[0001] The present invention relates to a composition for forming a wavelength conversion film. Background Art

[0002] Micro LED displays are expected to be the next generation of displays after LCD and OLED displays because they can achieve high contrast and high brightness, and have a wide range of applications such as large screens and transparent displays.

[0003] In micro-LED displays, a tiny LED chip is typically configured for each pixel.

[0004] As a method of configuring the LED chip, there is an RGB-LED method of installing three-color LEDs, but in this method, the complexity of LED light emission control and the low performance of the red LED are problems, and a wavelength conversion method that can solve this problem has attracted attention.

[0005] In the wavelength conversion method, only blue LED chips are used, and red and green light are extracted using wavelength conversion materials. Therefore, it has the advantage of being able to produce the three primary colors using only blue LED chips.

[0006] In the past, technologies using organic light-emitting materials as wavelength conversion materials have been proposed, for example, schemes using pyridine-phthalimide condensates (Patent Document 1, etc.), schemes using coumarin derivatives (Patent Document 2, etc.), schemes using perylene derivatives (Patent Document 3, etc.), schemes using rhodamine derivatives (Patent Document 4), and schemes using pyrromethene derivatives (Patent Documents 5, 6, etc.).

[0007] These wavelength conversion materials are generally required to have properties such as good wavelength conversion efficiency, color purity and light resistance.

[0008] In this regard, for example, Patent Document 7 discloses that a composition containing a specific binder resin containing a methacrylic polymer, a specific fluorescent dye, and a photopolymerizable acrylate is a high-performance red conversion material having good light resistance.

[0009] In addition, in order to prevent the degradation of organic light-emitting materials and improve durability, a technology of adding a light stabilizer is also disclosed (Patent Document 8, etc.).

[0010] Furthermore, it is known that by adding microparticles to the wavelength conversion material, the optical path length is increased due to light scattering in the color conversion layer, the blue light absorption rate is improved, and the luminous efficiency is improved by re-scattering the light reflected at the interface (Patent Documents 9, 10, etc.).

[0011] However, with the development of display technology in recent years, the wavelength conversion efficiency and durability of the wavelength conversion material have been required to be further improved in the composition for forming a wavelength conversion film from the viewpoint of improving the performance of the display.

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: Japanese Patent Application Publication No. 2002-348568

[0015] Patent Document 2: Japanese Patent Application Publication No. 2007-273440

[0016] Patent Document 3: Japanese Patent Application Publication No. 2002-317175

[0017] Patent Document 4: Japanese Patent Application Publication No. 2001-164245

[0018] Patent Document 5: Japanese Patent Application Publication No. 2011-241160

[0019] Patent Document 6: Japanese Patent Application Publication No. 2014-136771

[0020] Patent Document 7: Japanese Patent Application Publication No. 2006-89724

[0021] Patent Document 8: Japanese Patent Application Publication No. 2011-149028

[0022] Patent Document 9: International Publication No. 2020 / 189678

[0023] Patent Document 10: International Publication No. 2019 / 181698 Summary of the invention

[0024] Problems to be solved by the invention

[0025] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a composition for forming a wavelength conversion film which forms a wavelength conversion film having excellent wavelength conversion efficiency and durability.

[0026] Means for solving problems

[0027] The present inventors have conducted intensive studies to solve the above problems and have found that a wavelength conversion film-forming composition containing an organic phosphor, a cationically curable compound and a photoacid generator can form a wavelength conversion film having excellent wavelength conversion efficiency and durability, thereby completing the present invention.

[0028] That is, the present invention provides the following wavelength conversion film-forming composition.

[0029] 1. A wavelength conversion film-forming composition comprising (A) an organic phosphor, (B) a cationically curable compound, and (C) a photoacid generator.

[0030] 2. The composition for forming a wavelength conversion film according to 1, wherein the (A) organic phosphor is at least one selected from a condensed ring thiophene compound and a perylene derivative.

[0031] 3. The wavelength conversion film-forming composition according to 2, wherein the perylene derivative is a perylene derivative represented by the following formula (A3):

[0032] [Chemistry 1]

[0033]

[0034] 4. The wavelength conversion film-forming composition according to 2, wherein the perylene derivative is a perylene derivative represented by the following formula (A4):

[0035] [Chemistry 2]

[0036]

[0037] In the formula, R A and R B are each independently a group represented by the following formula (a4-1) or (a4-2),

[0038] [Chemistry 3]

[0039]

[0040] G 1 O or NR 43 ,

[0041] A 1 is ethylene or propylene,

[0042] n is an integer from 1 to 10,

[0043] R 41 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, or a heteroarylcarbonyl group which may have a substituent,

[0044] R 43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent,

[0045] The dotted line is the bonding end.

[0046] [Chemistry 4]

[0047]

[0048] G 2 O or NR 43 ,

[0049] L 2 is a single bond or an alkylene group which may have a substituent,

[0050] R 42 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, a heteroarylcarbonyl group which may have a substituent, or OR 44 ,

[0051] R 43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent,

[0052] R 44 is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, or a heteroarylcarbonyl group which may have a substituent,

[0053] G 2 NR 43 And L 2 When it is a single bond, R 42 and R 43 may bond to each other to form a ring together with the nitrogen atom,

[0054] L 2 When it is a single bond, R 42 Not an OR 44 ,

[0055] L 2 When it is an alkylene group which may have a substituent, R 42 Not a hydrogen atom,

[0056] R 42 When L is an alkyl group which may have a substituent, 2 is a single bond,

[0057] The dotted line is the bonding end.

[0058] Among them, R is not included A and R Bis a group represented by the formula (a4-2), L 2 is a single bond, and R 42 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0059] 5. A composition for forming a wavelength conversion film according to any one of 1 to 4, wherein the (B) cationic curable compound is one or more selected from a compound having an epoxy group (excluding alkali-soluble resins), a compound having an oxetane group (excluding alkali-soluble resins), an N-alkoxymethylol compound, and an alkali-soluble resin having at least one cationic curable functional group in a side chain.

[0060] 6. The composition for forming a wavelength conversion film according to any one of 1 to 4, wherein the (B) cationic curable compound is one or more selected from a compound having an epoxy group (excluding alkali-soluble resins), a compound having an oxetane group (excluding alkali-soluble resins), and an N-alkoxymethylol compound,

[0061] The composition further contains (D) an alkali-soluble resin having a reactive functional group for reacting with the cationically curable compound in a side chain and having no cationically curable functional group.

[0062] 7. The wavelength conversion film-forming composition according to 6, wherein the reactive functional group is a hydroxyl group.

[0063] 8. The composition for forming a wavelength conversion film according to any one of 1 to 7, wherein the (C) photoacid generator is one or more selected from onium salt compounds, metallocene complex compounds, iron arene complex compounds, disulfone compounds, sulfonic acid derivative compounds, triazine compounds, acetophenone derivative compounds, and diazomethane compounds.

[0064] 9. The wavelength conversion film-forming composition according to 8, wherein the (C) photoacid generator is an onium salt compound.

[0065] 10. The composition for forming a wavelength conversion film according to any one of 1 to 9, further comprising (E) light scattering particles.

[0066] 11. The composition for forming a wavelength conversion film according to 10, wherein the (E) light scattering particles are titanium oxide particles.

[0067] 12. The wavelength conversion film-forming composition according to 10 or 11, wherein the content of the (E) light-scattering particles is 1% by mass or more in the solid content.

[0068] 13. The wavelength conversion film-forming composition according to any one of 1 to 12, wherein the content of the (A) organic phosphor is 0.1% by mass or more in the solid content.

[0069] 14. The composition for forming a wavelength conversion film according to any one of 1 to 13, which is a composition for forming a wavelength conversion film for a display.

[0070] 15. A wavelength conversion film obtained from the composition for forming a wavelength conversion film according to any one of 1 to 14.

[0071] Effects of the Invention

[0072] According to the present invention, it is possible to provide a composition for forming a wavelength conversion film which forms a wavelength conversion film having excellent wavelength conversion efficiency and durability. DETAILED DESCRIPTION

[0073] The present invention is described in more detail below.

[0074] The wavelength conversion film-forming composition of the present invention is characterized by containing (A) an organic phosphor, (B) a cationically curable compound, and (C) a photoacid generator. In the following description, the solid content refers to components other than the solvent constituting the wavelength conversion film-forming composition.

[0075] Examples of the organic phosphor (A) include compounds having a fused aromatic ring, such as naphthalene, anthracene, phenanthrene, pyrene, Z, tetracene, benzo[9,10]phenanthrene, perylene, fluoranthene, fluorene, indene, and derivatives thereof; compounds having a heteroaromatic ring, such as furan, pyrrole, thiophene, silole, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyridine, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, and the like; Compounds and derivatives thereof; condensed ring thiophene compounds containing condensed ring thiophene and derivatives thereof formed by linking a plurality of thiophene rings; stilbene derivatives such as 1,4-distyrylbenzene, 4,4'-bis(2-(4-diphenylaminophenyl)vinyl)biphenyl, 4,4'-bis(N-(stilbene-4-yl)-N-phenylamino)stilbene; aromatic acetylene derivatives; tetraphenylbutadiene derivatives; aldazine derivatives; pyrromethene derivatives e) derivatives; diketopyrrolo[3,4-c]pyrrole derivatives; coumarin 7, coumarin 153, coumarin compounds without benzothiazolyl groups, and their derivatives; naphthophosphazoline oxide derivatives; azole derivatives such as imidazole, thiazole, thiadiazole, carbazole, oxazole, oxadiazole, triazole, and their metal complexes; cyanine compounds such as indocyanine green; xanthene compounds such as fluorescein / eosin / rhodamine, thioxanthene compounds; polyphenylene compounds, naphthalimide derivatives , phthalocyanine derivatives and their metal complexes, porphyrin derivatives and their metal complexes; oxazine compounds such as Nile Red and Nile Blue; helicene compounds; aromatic amine derivatives such as N,N'-diphenyl-N,N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine; organic metal complex compounds such as iridium (Ir), ruthenium (Ru), rhodium (Rh), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re), etc., but are not limited to these.

[0076] In the present invention, among the above-mentioned (A) organic phosphors, condensed ring thiophene compounds and perylene derivatives are preferred.

[0077] As the condensed ring thiophene compound, a condensed ring thiophene compound represented by the following formula (A1) and a condensed ring thiophene compound represented by the following formula (A2) are preferred.

[0078] [Chemistry 5]

[0079]

[0080] In the formula, Ar 11 and Ar 12 Each independently represents an aromatic ring which may have a substituent, R 11 and R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R11 and R 12 can be bonded to each other to form a ring together with the adjacent nitrogen atom, R 11 and R 12 Either or both of Ar 12 bonded to form a ring with the adjacent nitrogen atom, Y 11 and Y 12 One of them is -SO 2 -, the other is -S- or -SO 2 -.

[0081] As Ar 11 and Ar 12 The aromatic ring represented by includes 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 benzo[9,10]phenanthrene ring as a polycyclic aromatic hydrocarbon ring.

[0082] By Ar 11 and Ar 12 The aromatic ring represented by may have a substituent. Examples of the substituent include a halogen atom, an alkyl group described below, a cycloalkyl group described below, a haloalkyl group, an aryl group described below, a heteroaryl group described below, a cyano group, a nitro group, and the like. When there is a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0083] Among them, as Ar 11 and Ar 12 From the viewpoint of making the absorption maximum wavelength and the fluorescence maximum wavelength larger and further improving the light resistance, a substituted or unsubstituted aromatic ring is preferred, and a substituted or unsubstituted monocyclic aromatic hydrocarbon ring is more preferred.

[0084] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0085] The alkyl group may be straight chain or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. An alkyl group having 1 to 6 carbon atoms is preferred.

[0086] The above alkyl group may have a substituent. Examples of the substituent include a halogen atom, a cycloalkyl group described below, an aryl group described below, a heteroaryl group described below, a cyano group, a nitro group, etc. When the alkyl group has a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0087] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. A cycloalkyl group having 4 to 8 carbon atoms is preferred.

[0088] The cycloalkyl group may have a substituent. Examples of the substituent include a halogen atom, the alkyl group, the aryl group described below, the heteroaryl group described below, a cyano group, a nitro group, and the like. When the cycloalkyl group has a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0089] The aryl group may be any of a monocyclic aryl group, a condensed ring aryl group and a polycyclic aryl group. 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 benzo[9,10]phenanthrenyl group and the like as a condensed ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group, preferably an aryl group having 6 to 14 carbon atoms.

[0090] The above aryl group may have a substituent. Examples of the substituent include a halogen atom, the above alkyl group, the above aryl group, the heteroaryl group described below, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0091] The heteroaryl group may be any of a monocyclic heteroaryl group and a condensed-ring heteroaryl group. Examples of the monocyclic heteroaryl group include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridyl, pyrazinyl, and the like. Examples of the condensed-ring heteroaryl group include indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl, quinoxalinyl, and the like.

[0092] The above heteroaryl group may have a substituent. Examples of the substituent include the above halogen atom, the above alkyl group, the above aryl group, the above heteroaryl group, a cyano group, a nitro group, and the like. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0093] Among them, as R 11 and R 12 , preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group, further preferably an unsubstituted aryl group.

[0094] The above R 11 and R 12 They may be bonded to each other to form a ring together with the adjacent nitrogen atom. 11 and R 12 Examples of the ring formed by bonding to each other together with the adjacent nitrogen atom include the following groups.

[0095] [Chemistry 6]

[0096]

[0097] In addition, regarding the above R 11 and R 12 For R 11 and R 12Either or both of Ar 12 is bonded to form a ring together with the adjacent nitrogen atom. 11 and R 12 Either or both of Ar 12 Examples of the ring formed by bonding together with the adjacent nitrogen atom include the following groups.

[0098] [Chemistry 7]

[0099]

[0100] In the compound represented by the above formula (A1), -NR 11 R 12 The group represented by Ar 12 There is no particular restriction on the bonding position of Ar. 12 In the case of a benzene ring, a compound represented by the following formula (A1′) is easily formed.

[0101] [Chemistry 8]

[0102]

[0103] In the formula, Ar 11 , Y 11 and Y 12 Same as above. 11 and R 12 are each independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R 11 and R 12 can be bonded to each other to form a ring together with the adjacent nitrogen atom, R 11 and R 12 Either or both of may be bonded to a proximal benzene ring to form a ring together with the adjacent nitrogen atom.

[0104] In the above formula (A1), Y 11 and Y 12 One of them is -SO 2 -, the other is -S- or -SO 2 -. As Y 11 and Y 12 If the wavelength conversion efficiency and durability of the obtained wavelength conversion film are taken into consideration, one of them is preferably -SO 2 -, the other is -S-, more preferably Y 11 -S-,Y 12 For-SO 2 -. In addition, when the compound represented by the above formula (A1) is used as a red light emitting body, as Y 11 and Y12 , preferably Y 11 -S- or -SO 2 -, Y 12 For-SO 2 -, more preferably Y 11 and Y 12 All-SO 2 -.

[0105] As the fused ring thiophene compound satisfying the above-mentioned conditions, a compound represented by the following formula (A1-1) or formula (A1-2) is preferred.

[0106] [Chemistry 9]

[0107]

[0108] (Where Ar 11 ,Ar 12 , R 11 , R 12 , Y 11 and Y 12 Same as above.)

[0109] Furthermore, compounds represented by the following formulae (A1-3) to (A1-5) are more preferred.

[0110] [Chemistry 10]

[0111]

[0112] (Where Ar 11 and Ar 12 Same as above. 11a and R 12a Each is independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.)

[0113] Preferred specific examples of the compound represented by the above formula (A1) include compounds represented by the following formulae (A1-6) to (A1-8).

[0114] [Chemistry 11]

[0115]

[0116] In addition, with respect to the above-mentioned condensed ring thiophene compound, the condensed ring thiophene compound represented by the above-mentioned formula (A1) sometimes exists as a solvate, which is included in the scope of the present invention. It should be noted that as the solvate, there is no particular limitation as long as it is a solvate of the condensed ring thiophene compound represented by the above-mentioned formula (A1) and a solvent. As the solvent for forming the solvate, dichloromethane, chloroform, acetonitrile, diethyl ether, ethyl acetate, methanol, ethanol, cyclohexane, toluene, acetone, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, etc. can be listed.

[0117] The compound represented by the above formula (A1) is excellent not only in light resistance but also in conversion efficiency, and is suitable as a wavelength conversion material for display applications as a phosphor.

[0118] The compound represented by the above formula (A1) can be synthesized by a known method, for example, by the method described in JP-A-2018-145422.

[0119] [Chemistry 12]

[0120]

[0121] In the formula, Ar 21 and Ar 22 are each independently an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, R 21 ~R 24 are each independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R 21 ~R 24 All of them do not become hydrogen atoms at the same time, R 21 and R 22 can be bonded to each other to form a ring together with the adjacent nitrogen atom, R 23 and R 24 can be bonded to each other to form a ring together with the adjacent nitrogen atom, R 21 and R 22 Either or both of Ar 21 bonded to form a ring with the adjacent nitrogen atom, R 23 and R 24 Either or both of Ar 22 bonded to form a ring with the adjacent nitrogen atom, Y 21 and Y 22 One of them is -SO 2 -, the other is -S- or -SO 2 -.

[0122] As Ar 21 and Ar 22The aromatic ring represented by includes 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 benzo[9,10]phenanthrene ring as a polycyclic aromatic hydrocarbon ring.

[0123] By Ar 21 and Ar 22 The aromatic ring represented by may have a substituent. Examples of the substituent include a halogen atom described below, an alkyl group described below, a cycloalkyl group described below, a haloalkyl group described below, an aryl group described below, a heteroaryl group described below, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0124] As Ar 21 and Ar 22 The heteroaromatic ring represented by , as a monocyclic heteroaromatic ring, there can be listed a pyrrole ring, a thiophene ring, a furan ring, an imidazole ring, a pyrazole ring, a thiazole ring, an oxazole ring, a pyridine ring, a pyrazine ring and the like, and as a polycyclic heteroaromatic ring, there can be listed an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring and the like.

[0125] By Ar 21 and Ar 22 The heteroaromatic ring represented by may have a substituent. Examples of the substituent include a halogen atom described below, an alkyl group described below, a cycloalkyl group described below, a haloalkyl group described below, an aryl group described below, a heteroaryl group described below, a cyano group, a nitro group, and the like. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0126] Among them, as Ar 21 and Ar 22 From the viewpoint of making the absorption maximum wavelength and the fluorescence maximum wavelength larger and further improving the light resistance, a substituted or unsubstituted aromatic ring is preferred, and a substituted or unsubstituted monocyclic aromatic hydrocarbon ring is more preferred.

[0127] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0128] The alkyl group may be straight chain or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. An alkyl group having 1 to 6 carbon atoms is preferred.

[0129] The above alkyl group may have a substituent. Examples of the substituent include the above halogen atoms, the cycloalkyl group described below, the aryl group described below, the heteroaryl group described below, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0130] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl. A cycloalkyl group having 4 to 8 carbon atoms is preferred.

[0131] The cycloalkyl group may have a substituent. Examples of the substituent include the halogen atom, the alkyl group, the aryl group described below, the heteroaryl group described below, a cyano group, a nitro group, and the like. When the cycloalkyl group has a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0132] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0133] The aryl group may be any of a monocyclic aryl group, a condensed ring aryl group and a polycyclic aryl group. 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 benzo[9,10]phenanthrenyl group and the like as a condensed ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group, preferably an aryl group having 6 to 14 carbon atoms.

[0134] The above aryl group may have a substituent. Examples of the substituent include the above halogen atom, the above alkyl group, the above aryl group, the heteroaryl group described below, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0135] The heteroaryl group may be any of a monocyclic heteroaryl group and a condensed-ring heteroaryl group. Examples of the monocyclic heteroaryl group include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridyl, pyrazinyl, and the like. Examples of the condensed-ring heteroaryl group include indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl, quinoxalinyl, and the like.

[0136] The above heteroaryl group may have a substituent. Examples of the substituent include the above halogen atom, the above alkyl group, the above aryl group, the above heteroaryl group, a cyano group, a nitro group, and the like. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0137] Among them, as R 21 and R 22 , preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group, further preferably an unsubstituted aryl group.

[0138] The above R 21 and R 22 They may be bonded to each other to form a ring together with the adjacent nitrogen atom. 21 and R 22 Examples of the ring formed by bonding to each other together with the adjacent nitrogen atom include the following groups.

[0139] [Chemistry 13]

[0140]

[0141] In addition, regarding the above R 21 and R 22 For R 21 and R 22 Either or both of Ar 21 is bonded to form a ring together with the adjacent nitrogen atom. 21 and R 22 Either or both of Ar 21 Examples of the ring formed by bonding together with the adjacent nitrogen atom include the following groups.

[0142] [Chemistry 14]

[0143]

[0144] In addition, as R 23 and R 24 , preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, more preferably a substituted or unsubstituted aryl group, further preferably an unsubstituted aryl group.

[0145] The above R 23 and R 24 They may be bonded to each other to form a ring together with the adjacent nitrogen atom. 23 and R 24 The ring formed by bonding to each other together with the adjacent nitrogen atom includes, for example, the above-mentioned R 21 and R 22 The groups shown in the specific examples of the ring formed together with the adjacent nitrogen atom are bonded to each other.

[0146] In addition, regarding the above R 23 and R 24 For R 23 and R 24 Either or both of Ar 22 is bonded to form a ring together with the adjacent nitrogen atom. 23 and R 24 Either or both of Ar 22 The ring formed by bonding with the adjacent nitrogen atom includes, for example, the above-mentioned R 21 and R 22 Either or both of Ar 21 The group shown as the specific example of the ring formed together with the adjacent nitrogen atom is bonded.

[0147] In the compound represented by the above formula (A2), -NR 21 R 22The group represented by Ar 21 The bonding position of -NR 23 R 24 The group represented by Ar 22 There is no particular restriction on the bonding position of Ar. 21 and Ar 22 In the case of a benzene ring, a compound represented by the following formula (A2') is easily formed.

[0148] [Chemistry 15]

[0149]

[0150] Where Y 21 and Y 22 Same as above. 21 ~R 24 are each independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and R 21 ~R 24 All of them do not become hydrogen atoms at the same time, R 21 and R 22 can be bonded to each other to form a ring together with the adjacent nitrogen atom, R 23 and R 24 can be bonded to each other to form a ring together with the adjacent nitrogen atom, R 21 and R 22 Either or both of may be bonded to the adjacent benzene ring to form a ring together with the adjacent nitrogen atom, R 23 and R 24 Either or both of may be bonded to a proximal benzene ring to form a ring together with the adjacent nitrogen atom.

[0151] In the above formula (A2), Y 21 and Y 22 One of them is -SO 2 -, the other is -S- or -SO 2 -. As Y 21 and Y 22 If the wavelength conversion efficiency of the obtained wavelength conversion film is considered, one of them is preferably -SO 2 -, and the other is -S-. In addition, when the compound represented by the above formula (A2) is used as a green light emitter, as Y 21 and Y 22 , preferably one is -S- and the other is -SO 2 -, when the compound represented by the above formula (A2) is used as a red light emitting body, preferably Y 21 and Y 22 All-SO 2 -.

[0152] As the fused ring thiophene compound satisfying the above-mentioned conditions, a compound represented by the following formula (A2-1) is preferred.

[0153] [Chemistry 16]

[0154]

[0155] (Where Ar 21 ,Ar 22 , R 21 ~R 24 , Y 21 and Y 22 Same as above.)

[0156] Furthermore, compounds represented by the following formulae (A2-2) and (A2-2) are more preferred.

[0157] [Chemistry 17]

[0158]

[0159] (Where Ar 21 and Ar 22 Same as above. 21a ~R 24a Each is independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.)

[0160] Preferred specific examples of the compound represented by the above formula (A2) include compounds represented by the following formulae (A2-4) and (A2-5).

[0161] [Chemistry 18]

[0162]

[0163] In addition, with respect to the above-mentioned condensed ring thiophene compound, the condensed ring thiophene compound represented by the above-mentioned formula (A2) sometimes exists as a solvate, which is included in the scope of the present invention. It should be noted that as the solvate, as long as it is a solvate of the condensed ring thiophene compound represented by the above-mentioned formula (A2) and a solvent, it is not particularly limited. As the solvent for forming the solvate, dichloromethane, chloroform, acetonitrile, diethyl ether, ethyl acetate, methanol, ethanol, cyclohexane, toluene, acetone, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, etc. can be listed.

[0164] The compound represented by the above formula (A2) is excellent not only in light resistance but also in conversion efficiency, and is suitable as a wavelength conversion material for display applications as a phosphor.

[0165] The compound represented by the above formula (A2) can be synthesized by referring to a known method, for example, by the same steps as the method described in paragraph

[0084] and thereafter of JP-A-2018-145422.

[0166] As the perylene derivative, a perylene derivative represented by the following formula (A3) and a perylene derivative represented by the following formula (A4) are preferred.

[0167] [Chemistry 19]

[0168]

[0169] [Chemistry 20]

[0170]

[0171] In the formula, R A and R B Each independently is a group represented by the following formula (a4-1) or (a4-2).

[0172] [Chemistry 21]

[0173]

[0174] (In the formula, the dotted line is the bonding end.)

[0175] G 1 O or NR 43 , preferably O.

[0176] A 1 It is ethylene or propylene, preferably ethylene.

[0177] n is an integer of 1-10, preferably 1-8, more preferably 1-6.

[0178] R 41 It is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, or a heteroarylcarbonyl group which may have a substituent.

[0179] As R 41 The alkyl group represented may be any of linear and branched ones, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, decyl, eicosyl and the like, and alkyl groups having 1 to 40 carbon atoms are preferred. alkyl groups having 1 to 20 carbon atoms are preferred.

[0180] From the above R 41The alkyl group represented by may have a substituent. Examples of the substituent include a halogen atom described below, a cycloalkyl group described below, an aryl group described below, a heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0181] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0182] As R 41 Examples of the cycloalkyl group represented by include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, and cycloalkyl groups having 3 to 8 carbon atoms are preferred.

[0183] From the above R 41 The cycloalkyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the alkenyl group described below, the alkynyl group described below, the aryl group described below, the heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0184] Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, isobutynyl, sec-butynyl, and tert-butynyl.

[0185] As R 41 Examples of the alkenyl group represented by include vinyl, 1-propenyl, 2-propenyl, isopropenyl, butenyl, isobutenyl, sec-butenyl and tert-butenyl.

[0186] From the above R 41 The alkenyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the aryl group described below, the heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, and the like. When having a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0187] As R 41 The aryl group represented by may be any of a monocyclic aryl group, a condensed ring aryl group and a polycyclic aryl group. Specific examples thereof include a phenyl group as a monocyclic aryl group, a naphthyl group, anthracenyl group, phenanthrenyl group, a fluorenyl group, a pyrenyl group, a benzo[9,10]phenanthrenyl group and the like as a condensed ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group, preferably an aryl group having 6 to 14 carbon atoms.

[0188] From the above R 41 The aryl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the halogenated alkyl group described below, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, etc. When there is a substituent, the number thereof is preferably 1 to 6, and more preferably 1 to 3.

[0189] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0190] As R 41 The heteroaryl represented by may be any of a monocyclic heteroaryl and a condensed-ring heteroaryl. Examples of the monocyclic heteroaryl include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridyl, pyrazinyl and the like. Examples of the condensed-ring heteroaryl include indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl, quinoxalinyl and the like.

[0191] From the above R 41 The heteroaryl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, cyano group, nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0192] As R 41The alkylcarbonyl represented by the present invention includes methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, cyclopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, cyclobutylcarbonyl, 1-methylcyclopropylcarbonyl, 2-methylcyclopropylcarbonyl, n-pentylcarbonyl, 1-methyl-n-butylcarbonyl, 2-methyl-n-butylcarbonyl, 3-methyl-n-butylcarbonyl, 1,1-dimethyl-n-propylcarbonyl, 1,2-dimethyl-n-propylcarbonyl, 2,2-dimethyl-n-propylcarbonyl, 1-ethyl-n-propylcarbonyl, cyclopentylcarbonyl, 1-methylcyclobutylcarbonyl, 2-methyl Cyclobutylcarbonyl, 3-methylcyclobutylcarbonyl, 1,2-dimethylcyclopropylcarbonyl, 2,3-dimethylcyclopropylcarbonyl, 1-ethylcyclopropylcarbonyl, 2-ethylcyclopropylcarbonyl, n-hexylcarbonyl, 1-methyl-n-pentylcarbonyl, 2-methyl-n-pentylcarbonyl, 3-methyl-n-pentylcarbonyl, 4-methyl-n-pentylcarbonyl, 1,1-dimethyl-n-butylcarbonyl, 1,2-dimethyl-n-butylcarbonyl, 1,3-dimethyl-n-butylcarbonyl, 2,2-dimethyl-n-butylcarbonyl, 2,3-dimethyl-n-butylcarbonyl, 3,3-dimethyl-n-butylcarbonyl, 1-ethyl-n-butylcarbonyl, 2-ethyl-n-butylcarbonyl, 1,1,2-trimethyl-n-propylcarbonyl, 1,2,2-trimethyl-n-propylcarbonyl, 1-ethyl-1-methyl-n-propylcarbonyl, 1-ethyl-2-methyl-n-propylcarbonyl, cyclohexylcarbonyl, 1-methylcyclopentylcarbonyl, 2-methylcyclopentylcarbonyl, 3-methylcyclopentylcarbonyl, 1-ethylcyclobutylcarbonyl, 2-ethylcyclobutylcarbonyl, 3-ethylcyclobutylcarbonyl, 1,2-dimethylcyclobutylcarbonyl, 1,3-dimethylcyclobutylcarbonyl, 2,2-dimethylcyclobutylcarbonyl, 2,3-dimethylcyclobutylcarbonyl, 2,4-dimethylcyclobutylcarbonyl Alkylcarbonyl groups having 2 to 11 carbon atoms such as butylcarbonyl, 3,3-dimethylcyclobutylcarbonyl, 1-n-propylcyclopropylcarbonyl, 2-n-propylcyclopropylcarbonyl, 1-isopropylcyclopropylcarbonyl, 2-isopropylcyclopropylcarbonyl, 1,2,2-trimethylcyclopropylcarbonyl, 1,2,3-trimethylcyclopropylcarbonyl, 2,2,3-trimethylcyclopropylcarbonyl, 1-ethyl-2-methylcyclopropylcarbonyl, 2-ethyl-1-methylcyclopropylcarbonyl, 2-ethyl-2-methylcyclopropylcarbonyl and 2-ethyl-3-methylcyclopropylcarbonyl are preferred. Alkylcarbonyl groups having 2 to 6 carbon atoms are preferred.

[0193] From the above R 41 The alkylcarbonyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, hydroxyl group, cyano group, nitro group, etc. When having a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0194] As R 41The alkenylcarbonyl represented by the present invention includes vinylcarbonyl, 1-propenylcarbonyl, 2-propenylcarbonyl, 1-methyl-1-vinylcarbonyl, 1-butenylcarbonyl, 2-butenylcarbonyl, 3-butenylcarbonyl, 2-methyl-1-propenylcarbonyl, 2-methyl-2-propenylcarbonyl, 1-ethylvinylcarbonyl, 1-methyl-1-propenylcarbonyl, 1-methyl-2-propenylcarbonyl, 1-pentenylcarbonyl, 2-pentenylcarbonyl, 3-pentenylcarbonyl, 4-pentenylcarbonyl, 1-n-propylvinylcarbonyl, 1-methyl-1-butenylcarbonyl, 1-methyl-2-butenylcarbonyl, 1-methyl-3-butenylcarbonyl, 2-ethyl-2-propenylcarbonyl, 2-methyl 1-methyl-1-butenylcarbonyl, 2-methyl-2-butenylcarbonyl, 2-methyl-3-butenylcarbonyl, 3-methyl-1-butenylcarbonyl, 3-methyl-2-butenylcarbonyl, 3-methyl-3-butenylcarbonyl, 1,1-dimethyl-2-propenylcarbonyl, 1-isopropylvinylcarbonyl, 1,2-dimethyl-1-propenylcarbonyl, 1,2-dimethyl-2-propenylcarbonyl, 1-cyclopentenylcarbonyl, 2-cyclopentenylcarbonyl, 3-cyclopentenylcarbonyl, 1-hexenylcarbonyl, 2-hexenylcarbonyl, 3-hexenylcarbonyl, 4-hexenylcarbonyl, 5-hexenylcarbonyl, 1-methyl-1-pentenylcarbonyl, 1-methyl-2-pentenylcarbonyl, 1-methyl- 3-pentenylcarbonyl, 1-methyl-4-pentenylcarbonyl, 1-n-butylvinylcarbonyl, 2-methyl-1-pentenylcarbonyl, 2-methyl-2-pentenylcarbonyl, 2-methyl-3-pentenylcarbonyl, 2-methyl-4-pentenylcarbonyl, 2-n-propyl-2-propenylcarbonyl, 3-methyl-1-pentenylcarbonyl, 3-methyl-2-pentenylcarbonyl, 3-methyl-3-pentenylcarbonyl, 3-methyl-4-pentenylcarbonyl, 3-ethyl-3-butenylcarbonyl, 4-methyl-1-pentenylcarbonyl, 4-methyl-2-pentenylcarbonyl, 4-methyl-3-pentenylcarbonyl, 4-methyl-4-pentenylcarbonyl, 1,1-dimethyl-2-butenylcarbonyl, 1,1-dimethyl-3-butenylcarbonyl, 1,2-dimethyl-1-butenylcarbonyl, 1,2-dimethyl-2-butenylcarbonyl, 1,2-dimethyl-3-butenylcarbonyl, 1-methyl-2-ethyl-2-propenylcarbonyl, 1-sec-butylvinylcarbonyl, 1,3-dimethyl-1-butenylcarbonyl, 1,3-dimethyl-2-butenylcarbonyl, 1,3-dimethyl-3-butenylcarbonyl, 1-isobutylvinylcarbonyl, 2,2-dimethyl-3-butenylcarbonyl, 2,3-dimethyl-1-butenylcarbonyl, 2,3-dimethyl-2-butenylcarbonyl, 2,3-dimethyl-3-butenylcarbonyl, 2-isopropyl-2-propenylcarbonyl, 3,3-dimethyl-1-butenylcarbonyl, 1-ethyl-1-butenylcarbonyl, 1-ethyl-2-butenylcarbonyl, 1-ethyl-3-butenylcarbonyl, 1-n-propyl-1-propenylcarbonyl, 1-n-propyl-2-propenylcarbonyl, 2-ethyl-1-butenylcarbonyl, 2-ethyl-2-butenylcarbonyl, 2-ethyl-3-butenylcarbonyl, 1,1,2-trimethyl-2-propenylcarbonyl, 1-tert-butylvinylcarbonyl, 1-methyl-1-ethyl-2-propenylcarbonyl, 1-ethyl-2-methyl-1-propenylcarbonyl, 1-ethyl-2-methyl-2-propenylcarbonyl, 1-isopropyl-1-propenylcarbonyl, 1-isopropyl-2-propenylcarbonyl, 1-methyl-2- Alkenylcarbonyl having 3 to 11 carbon atoms, such as cyclopentenylcarbonyl, 1-methyl-3-cyclopentenylcarbonyl, 2-methyl-1-cyclopentenylcarbonyl, 2-methyl-2-cyclopentenylcarbonyl, 2-methyl-3-cyclopentenylcarbonyl, 2-methyl-4-cyclopentenylcarbonyl, 2-methyl-5-cyclopentenylcarbonyl, 2-methylenecyclopentylcarbonyl, 3-methyl-1-cyclopentenylcarbonyl, 3-methyl-2-cyclopentenylcarbonyl, 3-methyl-3-cyclopentenylcarbonyl, 3-methyl-4-cyclopentenylcarbonyl, 3-methyl-5-cyclopentenylcarbonyl, 3-methylenecyclopentylcarbonyl, 1-cyclohexenylcarbonyl, 2-cyclohexenylcarbonyl, and 3-cyclohexenylcarbonyl, is preferably an alkenylcarbonyl having 3 to 6 carbon atoms.

[0195] From the above R 41 The alkenylcarbonyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the above-mentioned aryl groups, the above-mentioned heteroaryl groups, hydroxyl groups, cyano groups, nitro groups, and the like. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0196] As R 41 Examples of the arylcarbonyl group represented by include arylcarbonyl groups having 7 to 16 carbon atoms, such as benzoyl, naphthoyl and anthracenyl, and arylcarbonyl groups having 7 to 11 carbon atoms are preferred.

[0197] From the above R 41 The arylcarbonyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, cyano group, nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0198] As R 41The heteroarylcarbonyl represented by ] includes heteroarylcarbonyl groups having 4 to 12 carbon atoms, such as pyrrolylcarbonyl, thienylcarbonyl, furylcarbonyl, imidazolylcarbonyl, pyrazolylcarbonyl, thiazolylcarbonyl, oxazolylcarbonyl, pyridylcarbonyl, pyrazinylcarbonyl, indolylcarbonyl, isoindolylcarbonyl, benzimidazolylcarbonyl, quinolylcarbonyl, isoquinolylcarbonyl and quinoxalinylcarbonyl, and is preferably a heteroarylcarbonyl group having 4 to 12 carbon atoms.

[0199] The above-mentioned heteroarylcarbonyl group may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, cyano group, nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0200] R 43 It is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

[0201] As R 43 The alkyl group represented may be any of linear and branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, and alkyl groups having 1 to 6 carbon atoms are preferred.

[0202] From the above R 43 The alkyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the cycloalkyl group described below, the aryl group described below, the heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0203] As R 43 Examples of the cycloalkyl group represented by include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, and cycloalkyl groups having 3 to 8 carbon atoms are preferred.

[0204] From the above R 43 The cycloalkyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the alkenyl group described below, the alkynyl group described below, the aryl group described below, the heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0205] As R 43 Examples of the alkenyl group represented by include vinyl, 1-propenyl, 2-propenyl, isopropenyl, butenyl, isobutenyl, sec-butenyl and tert-butenyl.

[0206] From the above R 43The alkenyl group represented by may have a substituent. Examples of the substituent include a halogen atom described below, an aryl group described below, a heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, and the like. When having a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0207] As R 43 The aryl group represented by may be any of a monocyclic aryl group, a condensed ring aryl group and a polycyclic aryl group. Specific examples thereof include a phenyl group as a monocyclic aryl group, a naphthyl group, anthracenyl group, phenanthrenyl group, a fluorenyl group, a pyrenyl group, a benzo[9,10]phenanthrenyl group and the like as a condensed ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group, preferably an aryl group having 6 to 14 carbon atoms.

[0208] From the above R 43 The aryl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the heteroaryl group described later, hydroxyl group, cyano group, nitro group, pentafluorosulfanyl group, etc. In the case of having a substituent, the number thereof is preferably 1 to 6, and more preferably 1 to 3.

[0209] As R 43 The heteroaryl represented by may be any of a monocyclic heteroaryl and a condensed-ring heteroaryl. Examples of the monocyclic heteroaryl include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridyl, pyrazinyl and the like. Examples of the condensed-ring heteroaryl include indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl, quinoxalinyl and the like.

[0210] From the above R 43 The heteroaryl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, cyano group, nitro group, pentafluorosulfanyl group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0211] [Chemistry 22]

[0212]

[0213] (In the formula, the dotted line is the bonding end.)

[0214] G 2 O or NR 43 , preferably O or NH.

[0215] L 2 It is a single bond or an alkylene group which may have a substituent.

[0216] As L 2 The alkylene group represented by may be any of linear, branched or cyclic, and specific examples include methylene, methylmethylene, dimethylmethylene, ethylene, 1,2-dimethylethylene, tetramethylethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene and other alkylene groups having 1 to 20 carbon atoms, preferably alkylene groups having 1 to 14 carbon atoms.

[0217] From the above L 2 The alkylene group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, the alkylcarbonyloxy group described later, a hydroxyl group, a cyano group, a nitro group, an oxo group, etc. When there is a substituent, the number thereof is preferably 1 to 6, and more preferably 1 to 3.

[0218] Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, a cyclopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a cyclobutylcarbonyloxy group, a 1-methylcyclopropylcarbonyloxy group, a 2-methylcyclopropylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, a cyclopentylcarbonyloxy group, a 1-methylcyclobutylcarbonyloxy group, 2-methylcyclobutylcarbonyloxy, 3-methylcyclobutylcarbonyloxy, 1,2-dimethylcyclopropylcarbonyloxy, 2,3-dimethylcyclopropylcarbonyloxy, 1-ethylcyclopropylcarbonyloxy, 2-ethylcyclopropylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butyl carbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, cyclohexylcarbonyloxy, 1-methylcyclopentylcarbonyloxy, 2-methylcyclopentylcarbonyloxy, 3-methylcyclopentylcarbonyloxy, 1-ethylcyclobutylcarbonyloxy, 2-ethylcyclobutylcarbonyloxy, 3-ethylcyclobutylcarbonyloxy, 1,2-dimethylcyclobutylcarbonyloxy, 1,3-dimethylcyclobutylcarbonyloxy, 2,2-dimethylcyclobutylcarbonyloxy, 2,3-dimethylcyclobutylcarbonyloxy, 2,4-dimethylcyclobutylcarbonyloxy, Alkylcarbonyloxy groups having 2 to 11 carbon atoms such as methylcyclobutylcarbonyloxy, 3,3-dimethylcyclobutylcarbonyloxy, 1-n-propylcyclopropylcarbonyloxy, 2-n-propylcyclopropylcarbonyloxy, 1-isopropylcyclopropylcarbonyloxy, 2-isopropylcyclopropylcarbonyloxy, 1,2,2-trimethylcyclopropylcarbonyloxy, 1,2,3-trimethylcyclopropylcarbonyloxy, 2,2,3-trimethylcyclopropylcarbonyloxy, 1-ethyl-2-methylcyclopropylcarbonyloxy, 2-ethyl-1-methylcyclopropylcarbonyloxy, 2-ethyl-2-methylcyclopropylcarbonyloxy and 2-ethyl-3-methylcyclopropylcarbonyloxy are preferred. Alkylcarbonyloxy groups having 2 to 6 carbon atoms are preferred.

[0219] R 42is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, a heteroarylcarbonyl group which may have a substituent, or OR 44 .

[0220] As R 42 The alkyl group represented may be any of linear and branched ones, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, decyl, eicosyl and the like, and alkyl groups having 1 to 40 carbon atoms are preferred. alkyl groups having 1 to 20 carbon atoms are preferred.

[0221] From the above R 42 The alkyl group represented by may have a substituent. Examples of the substituent include a halogen atom described below, a cycloalkyl group described below, an aryl group described below, a heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, an oxo group, an epoxy group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0222] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0223] As R 42 Examples of the cycloalkyl group represented by include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, and cycloalkyl groups having 3 to 8 carbon atoms are preferred.

[0224] From the above R 42 The cycloalkyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the alkenyl group described below, the alkynyl group described below, the aryl group described below, the heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0225] Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, isobutynyl, sec-butynyl, and tert-butynyl.

[0226] As R 42 Examples of the alkenyl group represented by include vinyl, 1-propenyl, 2-propenyl, isopropenyl, butenyl, isobutenyl, sec-butenyl and tert-butenyl.

[0227] From the above R 42 The alkenyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the aryl group described below, the heteroaryl group described below, a hydroxyl group, a cyano group, a nitro group, and the like. When having a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0228] As R 42 The aryl group represented by may be any of a monocyclic aryl group, a condensed ring aryl group and a polycyclic aryl group. Specific examples thereof include a phenyl group as a monocyclic aryl group, a naphthyl group, anthracenyl group, phenanthrenyl group, a fluorenyl group, a pyrenyl group, a benzo[9,10]phenanthrenyl group and the like as a condensed ring aryl group, and an aryl group having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group, preferably an aryl group having 6 to 14 carbon atoms.

[0229] From the above R 42 The aryl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the halogenated alkyl group described below, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the heteroaryl group described below, hydroxyl group, cyano group, nitro group, pentafluorosulfanyl group, etc. In the case of having a substituent, the number thereof is preferably 1 to 6, and more preferably 1 to 3.

[0230] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0231] As R 42 The heteroaryl represented by may be any of a monocyclic heteroaryl and a condensed-ring heteroaryl. Examples of the monocyclic heteroaryl include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, pyridyl, pyrazinyl and the like. Examples of the condensed-ring heteroaryl include indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl, quinoxalinyl and the like.

[0232] From the above R 42 The heteroaryl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, cyano group, nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0233] As R 42The alkylcarbonyl represented by the present invention includes methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, cyclopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, tert-butylcarbonyl, cyclobutylcarbonyl, 1-methylcyclopropylcarbonyl, 2-methylcyclopropylcarbonyl, n-pentylcarbonyl, 1-methyl-n-butylcarbonyl, 2-methyl-n-butylcarbonyl, 3-methyl-n-butylcarbonyl, 1,1-dimethyl-n-propylcarbonyl, 1,2-dimethyl-n-propylcarbonyl, 2,2-dimethyl-n-propylcarbonyl, 1-ethyl-n-propylcarbonyl, cyclopentylcarbonyl, 1-methylcyclobutylcarbonyl, 2-methyl Cyclobutylcarbonyl, 3-methylcyclobutylcarbonyl, 1,2-dimethylcyclopropylcarbonyl, 2,3-dimethylcyclopropylcarbonyl, 1-ethylcyclopropylcarbonyl, 2-ethylcyclopropylcarbonyl, n-hexylcarbonyl, 1-methyl-n-pentylcarbonyl, 2-methyl-n-pentylcarbonyl, 3-methyl-n-pentylcarbonyl, 4-methyl-n-pentylcarbonyl, 1,1-dimethyl-n-butylcarbonyl, 1,2-dimethyl-n-butylcarbonyl, 1,3-dimethyl-n-butylcarbonyl, 2,2-dimethyl-n-butylcarbonyl, 2,3-dimethyl-n-butylcarbonyl, 3,3-dimethyl-n-butylcarbonyl, 1-ethyl-n-butylcarbonyl, 2-ethyl-n-butylcarbonyl, 1,1,2-trimethyl-n-propylcarbonyl, 1,2,2-trimethyl-n-propylcarbonyl, 1-ethyl-1-methyl-n-propylcarbonyl, 1-ethyl-2-methyl-n-propylcarbonyl, cyclohexylcarbonyl, 1-methylcyclopentylcarbonyl, 2-methylcyclopentylcarbonyl, 3-methylcyclopentylcarbonyl, 1-ethylcyclobutylcarbonyl, 2-ethylcyclobutylcarbonyl, 3-ethylcyclobutylcarbonyl, 1,2-dimethylcyclobutylcarbonyl, 1,3-dimethylcyclobutylcarbonyl, 2,2-dimethylcyclobutylcarbonyl, 2,3-dimethylcyclobutylcarbonyl, 2,4-dimethylcyclobutylcarbonyl Alkylcarbonyl groups having 2 to 11 carbon atoms such as butylcarbonyl, 3,3-dimethylcyclobutylcarbonyl, 1-n-propylcyclopropylcarbonyl, 2-n-propylcyclopropylcarbonyl, 1-isopropylcyclopropylcarbonyl, 2-isopropylcyclopropylcarbonyl, 1,2,2-trimethylcyclopropylcarbonyl, 1,2,3-trimethylcyclopropylcarbonyl, 2,2,3-trimethylcyclopropylcarbonyl, 1-ethyl-2-methylcyclopropylcarbonyl, 2-ethyl-1-methylcyclopropylcarbonyl, 2-ethyl-2-methylcyclopropylcarbonyl and 2-ethyl-3-methylcyclopropylcarbonyl are preferred. Alkylcarbonyl groups having 2 to 6 carbon atoms are preferred.

[0234] From the above R 42 The alkylcarbonyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, hydroxyl group, cyano group, nitro group, etc. When having a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0235] As R 42The alkenylcarbonyl represented by the present invention includes vinylcarbonyl, 1-propenylcarbonyl, 2-propenylcarbonyl, 1-methyl-1-vinylcarbonyl, 1-butenylcarbonyl, 2-butenylcarbonyl, 3-butenylcarbonyl, 2-methyl-1-propenylcarbonyl, 2-methyl-2-propenylcarbonyl, 1-ethylvinylcarbonyl, 1-methyl-1-propenylcarbonyl, 1-methyl-2-propenylcarbonyl, 1-pentenylcarbonyl, 2-pentenylcarbonyl, 3-pentenylcarbonyl, 4-pentenylcarbonyl, 1-n-propylvinylcarbonyl, 1-methyl-1-butenylcarbonyl, 1-methyl-2-butenylcarbonyl, 1-methyl-3-butenylcarbonyl, 2-ethyl-2-propenylcarbonyl, 2-methyl 1-methyl-1-butenylcarbonyl, 2-methyl-2-butenylcarbonyl, 2-methyl-3-butenylcarbonyl, 3-methyl-1-butenylcarbonyl, 3-methyl-2-butenylcarbonyl, 3-methyl-3-butenylcarbonyl, 1,1-dimethyl-2-propenylcarbonyl, 1-isopropylvinylcarbonyl, 1,2-dimethyl-1-propenylcarbonyl, 1,2-dimethyl-2-propenylcarbonyl, 1-cyclopentenylcarbonyl, 2-cyclopentenylcarbonyl, 3-cyclopentenylcarbonyl, 1-hexenylcarbonyl, 2-hexenylcarbonyl, 3-hexenylcarbonyl, 4-hexenylcarbonyl, 5-hexenylcarbonyl, 1-methyl-1-pentenylcarbonyl, 1-methyl-2-pentenylcarbonyl, 1-methyl- 3-pentenylcarbonyl, 1-methyl-4-pentenylcarbonyl, 1-n-butylvinylcarbonyl, 2-methyl-1-pentenylcarbonyl, 2-methyl-2-pentenylcarbonyl, 2-methyl-3-pentenylcarbonyl, 2-methyl-4-pentenylcarbonyl, 2-n-propyl-2-propenylcarbonyl, 3-methyl-1-pentenylcarbonyl, 3-methyl-2-pentenylcarbonyl, 3-methyl-3-pentenylcarbonyl, 3-methyl-4-pentenylcarbonyl, 3-ethyl-3-butenylcarbonyl, 4-methyl-1-pentenylcarbonyl, 4-methyl-2-pentenylcarbonyl, 4-methyl-3-pentenylcarbonyl, 4-methyl-4-pentenylcarbonyl, 1,1-dimethyl-2-butenylcarbonyl, 1,1-dimethyl-3-butenylcarbonyl, 1,2-dimethyl-1-butenylcarbonyl, 1,2-dimethyl-2-butenylcarbonyl, 1,2-dimethyl-3-butenylcarbonyl, 1-methyl-2-ethyl-2-propenylcarbonyl, 1-sec-butylvinylcarbonyl, 1,3-dimethyl-1-butenylcarbonyl, 1,3-dimethyl-2-butenylcarbonyl, 1,3-dimethyl-3-butenylcarbonyl, 1-isobutylvinylcarbonyl, 2,2-dimethyl-3-butenylcarbonyl, 2,3-dimethyl-1-butenylcarbonyl, 2,3-dimethyl-2-butenylcarbonyl, 2,3-dimethyl-3-butenylcarbonyl, 2-isopropyl-2-propenylcarbonyl, 3,3-dimethyl-1-butenylcarbonyl, 1-ethyl-1-butenylcarbonyl, 1-ethyl-2-butenylcarbonyl, 1-ethyl-3-butenylcarbonyl, 1-n-propyl-1-propenylcarbonyl, 1-n-propyl-2-propenylcarbonyl, 2-ethyl-1-butenylcarbonyl, 2-ethyl-2-butenylcarbonyl, 2-ethyl-3-butenylcarbonyl, 1,1,2-trimethyl-2-propenylcarbonyl, 1-tert-butylvinylcarbonyl, 1-methyl-1-ethyl-2-propenylcarbonyl, 1-ethyl-2-methyl-1-propenylcarbonyl, 1-ethyl-2-methyl-2-propenylcarbonyl, 1-isopropyl-1-propenylcarbonyl, 1-isopropyl-2-propenylcarbonyl, 1-methyl-2- Alkenylcarbonyl having 3 to 11 carbon atoms, such as cyclopentenylcarbonyl, 1-methyl-3-cyclopentenylcarbonyl, 2-methyl-1-cyclopentenylcarbonyl, 2-methyl-2-cyclopentenylcarbonyl, 2-methyl-3-cyclopentenylcarbonyl, 2-methyl-4-cyclopentenylcarbonyl, 2-methyl-5-cyclopentenylcarbonyl, 2-methylenecyclopentylcarbonyl, 3-methyl-1-cyclopentenylcarbonyl, 3-methyl-2-cyclopentenylcarbonyl, 3-methyl-3-cyclopentenylcarbonyl, 3-methyl-4-cyclopentenylcarbonyl, 3-methyl-5-cyclopentenylcarbonyl, 3-methylenecyclopentylcarbonyl, 1-cyclohexenylcarbonyl, 2-cyclohexenylcarbonyl, and 3-cyclohexenylcarbonyl, is preferably an alkenylcarbonyl having 3 to 6 carbon atoms.

[0236] From the above R 42 The alkenylcarbonyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atoms, the above-mentioned aryl groups, the above-mentioned heteroaryl groups, hydroxyl groups, cyano groups, nitro groups, and the like. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0237] As R 42 Examples of the arylcarbonyl group represented by include arylcarbonyl groups having 7 to 16 carbon atoms, such as benzoyl, naphthoyl and anthracenyl, and arylcarbonyl groups having 7 to 11 carbon atoms are preferred.

[0238] From the above R 42 The arylcarbonyl group represented by may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, cyano group, nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0239] As R 42The heteroarylcarbonyl represented by ] includes heteroarylcarbonyl groups having 4 to 12 carbon atoms, such as pyrrolylcarbonyl, thienylcarbonyl, furylcarbonyl, imidazolylcarbonyl, pyrazolylcarbonyl, thiazolylcarbonyl, oxazolylcarbonyl, pyridylcarbonyl, pyrazinylcarbonyl, indolylcarbonyl, isoindolylcarbonyl, benzimidazolylcarbonyl, quinolylcarbonyl, isoquinolylcarbonyl and quinoxalinylcarbonyl, and is preferably a heteroarylcarbonyl group having 4 to 12 carbon atoms.

[0240] The above-mentioned heteroarylcarbonyl group may have a substituent. Examples of the substituent include the above-mentioned halogen atom, the above-mentioned alkyl group, the above-mentioned halogenated alkyl group, the above-mentioned alkenyl group, the above-mentioned alkynyl group, the above-mentioned aryl group, the above-mentioned heteroaryl group, cyano group, nitro group, etc. When there is a substituent, the number of the substituent is preferably 1 to 6, and more preferably 1 to 3.

[0241] R 43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. Examples of these alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, and heteroaryl groups, and substituents which these groups may have, include those which are the same as R in the above formula (a4-1). 43 The same groups as exemplified in .

[0242] R 44 is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, or a heteroarylcarbonyl group which may have a substituent. Examples of the alkyl group, cycloalkyl group, alkenyl group, aryl group, heteroaryl group, alkylcarbonyl group, alkenylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, and the substituents which these groups have include the same as those mentioned above for R 42 The same groups as exemplified in .

[0243] It should be noted that in formula (a4-1), G 2 NR 43 And L 2 When it is a single bond, R 42 and R 43 can be bonded to each other to form a ring together with the nitrogen atom, L 2 When it is a single bond, R 42 Not an OR 44 , L 2 When it is an alkylene group which may have a substituent, R 42 does not become a hydrogen atom, R 42 When L is an alkyl group which may have a substituent, 2 For a single key.

[0244] The above R A and R BThey may be the same as or different from each other, and are more preferably the same group.

[0245] Among them, R is not included A and R B is a group represented by the formula (a4-2), L 2 is a single bond, and R 42 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0246] The above R A and R B The bonding position of the perylene structure is not particularly limited, but the bonding positions are preferably those represented by the following formulae (A4-1) to (A4-3).

[0247] [Chemistry 23]

[0248]

[0249] (Where R A and R B Same as above.)

[0250] As the group represented by the above formula (a4-1), a group represented by any one of the following formulae (a4-1-1) to (a4-1-4) is preferred.

[0251] [Chemistry 24]

[0252]

[0253] (Where R 41 and n are the same as above. )

[0254] As the group represented by the above formula (a4-2), a group represented by any one of the following formulae (a4-2-1) to (a4-2-2) is preferred.

[0255] [Chemistry 25]

[0256]

[0257] (wherein m is an integer from 1 to 20. 42 Same as above.)

[0258] Specific examples of the organic phosphor represented by (A4) include organic phosphors represented by the following formulae (A4-4) to (A4-16).

[0259] [Chemistry 26]

[0260]

[0261] [Chemistry 27]

[0262]

[0263] The compounds represented by the above formulae (A3) and (A4) are excellent not only in heat resistance, solubility and light resistance but also in conversion efficiency, and are suitable as phosphors for wavelength conversion materials for display applications.

[0264] The compound represented by the above formula (A3) can use a commercial product. In addition, it can be synthesized with reference to a known method, for example, it can be synthesized using the same steps as the method described in paragraph

[0061] and thereafter in Japanese Patent Publication No. 2017-504078.

[0265] The compound represented by the above formula (A4) can be synthesized by referring to a known method, and the synthesis method is not particularly limited as long as the target compound can be obtained.

[0266] The content of the organic phosphor (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more in the solid content, if the wavelength conversion efficiency of the obtained wavelength conversion film is taken into consideration. On the other hand, the upper limit of the content of the organic phosphor (A) is not particularly limited, but if the fluorescence quantum yield decreases when the organic phosphor is highly concentrated, it is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less in the solid content.

[0267] In addition, the above-mentioned (A) organic phosphor may be used alone or in combination of two or more.

[0268] Furthermore, the wavelength conversion film-forming composition of the present invention may contain, as an organic phosphor, another organic phosphor other than the compounds represented by the above formulae (A1) to (A4) within a range not impairing the effects of the present invention. Examples of the other organic phosphors include cyanine pigments such as 4-dicyanomethylidene-2-methyl-6-(p-dimethylaminophenyl)-4H-pyran; pyridine pigments such as 1-ethyl-2-[4-(p-dimethylaminophenyl)-1,3-butadienyl]-pyridinium-perchlorate; rhodamine pigments such as rhodamine B and rhodamine 6G; red conversion phosphors such as oxazine pigments; coumarin pigments such as 2,3,5,6-1H,4H-tetrahydro-8-trifluoromethylquinolizino(9,9a,1-gh)coumarin, 3-(2'-benzothiazolyl)-7-diethylaminocoumarin, and 3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin; and green conversion phosphors such as naphthalimide pigments such as solvent yellow 11 and solvent yellow 116.

[0269] When other organic phosphors are contained, the content thereof is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably no content (0% by mass) in the solid content.

[0270] (B) Cationic curable compound

[0271] The above-mentioned cationic curable compounds include compounds that undergo polymerization or cross-linking reactions using the acid generated by the acid generator. Examples of the above-mentioned cationic curable compounds include compounds having an epoxy group (however, alkali-soluble resins are not included. Hereinafter, they are referred to as "epoxy compounds"), compounds having an oxetane group (however, alkali-soluble resins are not included. Hereinafter, they are referred to as "oxetane compounds"), N-alkoxymethylol compounds, and alkali-soluble resins having at least one cationic curable functional group in the side chain (hereinafter referred to as "cationic curing alkali-soluble resins"), etc.

[0272] The above-mentioned cationic curable compounds may be used alone or in combination of two or more.

[0273] [Epoxides]

[0274] The epoxy compound is not particularly limited as long as it is a compound having an epoxy group, and does not include the alkali-soluble resin described later. In addition, in the present invention, a compound containing both an epoxy group and an oxetanyl group belongs to the epoxy compound.

[0275] Examples of the epoxy compound include aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, and the like. In the present invention, among these, the epoxy compound preferably includes at least one of an alicyclic epoxy compound and an aliphatic epoxy compound, and more preferably includes at least an alicyclic epoxy compound, and preferably includes both an alicyclic epoxy compound and an aliphatic epoxy compound. By using the epoxy compound, the composition can obtain a cured product having excellent light absorption in a desired wavelength region and good adhesion to a substrate.

[0276] Specific examples of the alicyclic epoxy compounds include any compound containing an aliphatic ring, and include polyglycidyl ethers of polyhydric alcohols having at least one aliphatic ring, and compounds containing cyclohexene oxide and cyclopentene oxide obtained by epoxidizing a compound containing a cyclohexene or cyclopentene ring with an oxidizing agent, etc. In the present invention, from the perspective of the curing speed, epoxy resins having a cyclohexene oxide structure are preferred among the alicyclic epoxy compounds.

[0277] As the alicyclic epoxy compound, a compound having two or more cyclohexene oxide structures can be preferably used, and examples thereof include a compound represented by the following formula (B1).

[0278] [Chemistry 28]

[0279]

[0280] (Where X b1 represents a single bond or a connecting group (a divalent group having one or more atoms).

[0281] As X b1 Examples of the linking group represented by include a divalent hydrocarbon group, an alkenylene group obtained by epoxidizing a part or all of a carbon-carbon double bond, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked.

[0282] Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 30 carbon atoms and an alkylene group having 1 to 30 carbon atoms and having a cycloalkyl ring.

[0283] Examples of the linear or branched alkylene group having 1 to 30 carbon atoms include groups formed by removing one hydrogen atom from a linear or branched alkyl group having 1 to 30 carbon atoms. Examples of the alkylene group having 1 to 30 carbon atoms and having a cycloalkyl ring include groups formed by removing one hydrogen atom from an alkyl group having 1 to 30 carbon atoms and having a cycloalkyl ring.

[0284] Specific examples of the above-mentioned straight-chain or branched alkylene groups include groups formed by removing one hydrogen atom from a straight-chain or branched alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl.

[0285] Examples of the linear or branched alkylene group having 1 to 20 carbon atoms in the divalent hydrocarbon group include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene.

[0286] As the alkyl group having a cycloalkyl ring, a cycloalkyl group can be used. Examples of the cycloalkyl group include a monocyclic hydrocarbon group and a cross-linked hydrocarbon ring group.

[0287] Examples of the monocyclic hydrocarbon group include a group formed by removing one hydrogen atom from a monocyclic hydrocarbon ring such as a cyclohexyl ring, and a group formed by removing one hydrogen atom from a monocyclic hydrocarbon ring in which one or two or more hydrogen atoms in the ring are substituted with an aliphatic hydrocarbon group.

[0288] Examples of the crosslinked hydrocarbon ring group include a group formed by removing one hydrogen atom from a cycloalkyl ring of a crosslinked hydrocarbon ring such as a norbornyl ring, and a group formed by removing one hydrogen atom from a crosslinked hydrocarbon ring in which one or more hydrogen atoms in the ring are substituted with an aliphatic hydrocarbon group.

[0289] Specific examples of the above-mentioned monocyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, methylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tetramethylcyclohexyl, pentamethylcyclohexyl, ethylcyclohexyl and methylcycloheptyl, among which cyclopentyl, cyclohexyl and cycloheptyl are preferred.

[0290] Specific examples of the crosslinked hydrocarbon ring group include bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, bicyclo[4.3.1]decyl, bicyclo[3.3.1]nonyl, bornyl, bornenyl, norbornyl, norbornyl, 6,6-dimethylbicyclo[3.1.1]heptyl, tricyclobutyl, and adamantyl.

[0291] As X b1 The alkyl group having a cycloalkyl ring represented by may be a group in which the above cycloalkyl group and the above straight-chain or branched alkyl group are combined. For example, a group in which one or more hydrogen atoms in a straight-chain or branched alkyl group are substituted by the above cycloalkyl group, a group in which one or more methylene groups in a straight-chain or branched alkyl group are substituted by a group obtained by removing one hydrogen atom from the above cycloalkyl group, a group in which one or more hydrogen atoms in the above cycloalkyl group are substituted by the above straight-chain or branched alkyl group, and the like.

[0292] Specific examples thereof include cycloalkylene groups (including cycloalkylidene groups) such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene and cyclohexylidene.

[0293] Examples of the alkenylene group in the alkenylene group in which a part or all of the carbon-carbon double bond is epoxidized (hereinafter sometimes referred to as "epoxidized alkenylene group") include straight-chain or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene, propenylene, 1-butenylene, 2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, and octenylene.

[0294] In the present invention, X b1It is preferably a linking group, preferably a divalent hydrocarbon group, an ester bond, or a group in which a plurality of these are linked, and particularly preferably a group in which a divalent hydrocarbon group and an ester bond are linked.

[0295] In addition, in the present invention, X b1 The divalent hydrocarbon group represented is preferably an alkylene group formed by removing one hydrogen atom from a straight-chain or branched alkyl group having 1 to 18 carbon atoms, more preferably an alkylene group formed by removing one hydrogen atom from a straight-chain or branched alkyl group having 1 to 8 carbon atoms, further preferably an alkylene group formed by removing one hydrogen atom from a straight-chain alkyl group having 1 to 5 carbon atoms, and still more preferably an alkylene group formed by removing one hydrogen atom from a straight-chain alkyl group having 1 to 3 carbon atoms.

[0296] In the present invention, preferred examples of the compound having two or more cyclohexene oxide structures include compounds represented by the following formulae (B1-1) to (B1-2).

[0297] [Chemistry 29]

[0298]

[0299] As the alicyclic epoxy compound, a compound represented by the following formula (B2) can also be preferably used.

[0300] [Chemistry 30]

[0301]

[0302] (Where Z b1 represents an alkylene group having 6 to 30 carbon atoms and having a cycloalkyl ring.

[0303] As Z b1 The alkylene group having 1 to 30 carbon atoms and having a cycloalkyl ring represented by b1 The same groups as those represented by the alkylene group having a cycloalkyl ring.

[0304] In the present invention, Z b1 From the viewpoint of obtaining a cured product having a steeper absorption peak in a desired wavelength range, an alkylene group having 13 to 20 carbon atoms and having two cycloalkyl rings is preferred, and a group represented by the following formula (B3) is more preferred.

[0305] [Chemistry 31]

[0306]

[0307] (Where R b2 and R b3 represents a hydrogen atom or a methyl group, and * represents a bonding site. )

[0308] Specific examples of the alicyclic epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl)methyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 4-epoxycyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, and the like. In the present invention, from the viewpoint of obtaining a cured product having excellent light absorption in a desired wavelength region, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate are preferred among these.

[0309] In addition, a compound including both an aliphatic ring and an aromatic ring belongs to an alicyclic epoxy compound.

[0310] In addition, as the above-mentioned alicyclic epoxy compound, a compound having a structure in which a cycloalkyl ring derived from an epoxycycloalkyl ring and an ethylene group are directly bonded with a single bond as a structural unit and a structure in which epoxy groups of the epoxycycloalkyl ring are polymerized as a main chain structure, such as a 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (hereinafter sometimes referred to as "alicyclic epoxy compound A").

[0311] As the alicyclic epoxy compound, a commercially available product can be used, and specific examples thereof include those described in Japanese Patent No. 6103653 and the like.

[0312] The above-mentioned alicyclic epoxy compounds may be used alone or in combination of two or more. For example, it is also preferred to use a compound having two or more cyclohexene oxide structures and an alicyclic epoxy compound A in combination. This is because a cured product having excellent light absorption in a desired wavelength region can be obtained.

[0313] The content of the alicyclic epoxy compound can be any amount that can obtain a cured product with excellent film-forming properties and curing properties, and is preferably 0 parts by mass or more, more preferably 2 parts by mass or more, further preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and most preferably 20 parts by mass or more, based on 100 parts by mass of the cationic curable compound.

[0314] In addition, when the content of the epoxy compound is 90 parts by mass or less in 100 parts by mass of the cationically curable compound, the content of the above-mentioned alicyclic epoxy compound is preferably 0 to 80 parts by mass, more preferably 10 to 60 parts by mass, further preferably 15 to 35 parts by mass, and further preferably 20 to 25 parts by mass in 100 parts by mass of the cationically curable compound.

[0315] By setting the content in the above range, a cured product having excellent film-forming properties can be obtained. In addition, the above composition can obtain a cured product having good curing properties.

[0316] Specific examples of the above-mentioned aromatic epoxy compounds include polyglycidyl ethers of polyphenols having at least one aromatic ring or their oxyalkylene adducts, such as bisphenol A, bisphenol F, or glycidyl ethers of these compounds to which oxyalkylene is further added, phenol novolac-type 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 benzyl alcohol, benzyl alcohol, and benzyl butanol; polyglycidyl esters of polyacid 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, styrene oxide, or epoxides of divinylbenzene, etc.

[0317] Among them, it is preferred to contain at least one selected from polyglycidyl ethers of phenols, polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, polyglycidyl ethers of polyphenols, polyglycidyl esters of benzoic acid, and polyglycidyl esters of polyacids, and in particular, polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups are preferred, because a cured product having excellent light absorption in a desired wavelength region can be obtained.

[0318] In addition, specific examples of the above-mentioned aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyols or their oxyalkylene adducts, polyglycidyl esters of aliphatic long-chain polyacids, homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate and other vinyl monomers, and the like.

[0319] As the polyglycidyl ether of the above-mentioned aliphatic polyol or its oxyalkylene adduct, the diglycidyl ether of the aliphatic diol compound is preferred, and the compound represented by the following formula (B4) is particularly preferred. By using the above-mentioned compound, the light absorption of the above-mentioned composition in the required wavelength region becomes excellent, and its cured product becomes good in adhesion with the substrate. In addition, the above-mentioned composition forms a cured product having a steeper absorption peak in the required wavelength range.

[0320] [Chemistry 32]

[0321]

[0322] (Where Z b2 represents a linear or branched alkylene group having 1 to 30 carbon atoms.

[0323] As Z b2 The linear or branched alkylene group having 1 to 30 carbon atoms represented by Z may be exemplified by the group consisting of b1 The same groups as those represented by the linear or branched alkylene group having 1 to 30 carbon atoms. In addition, one or two or more methylene groups of the alkylene group having 1 to 30 carbon atoms may be replaced by -O-.

[0324] In addition, when the methylene group in the above-mentioned alkylene group is replaced by -O-, the methylene group is replaced by -O- under the condition that the oxygen atom in the above-mentioned alkylene group is not adjacent.

[0325] Regarding the above Z b2 In terms of obtaining a cured product having a steeper absorption peak in a desired wavelength range, a branched alkylene group is preferred. This is because, by having the above structure, the above composition can obtain a cured product having a steeper absorption peak in a desired wavelength range.

[0326] Regarding the above Z b2 From the viewpoint of obtaining a cured product having a steeper absorption peak in the desired wavelength range, a linear or branched alkylene group having 2 to 30 carbon atoms is preferred, a linear or branched alkylene group having 3 to 28 carbon atoms is more preferred, and a linear or branched alkylene group having 4 to 26 carbon atoms is further preferred. b2In the case of an alkylene group in which the methylene group is not replaced by -O-, the number of carbon atoms is preferably 4 to 10, and more preferably 4 to 8. b2 In the case of an alkylene group in which a methylene group is replaced by -O-, Z b2 The alkylene group is preferably an alkylene group having 10 to 26 carbon atoms and having a structure in which hydroxyl groups at both terminals are removed from polyalkylene glycol, more preferably an alkylene group having 10 to 26 carbon atoms and having a structure in which hydroxyl groups at both terminals are removed from polyethylene glycol or polypropylene glycol, and still more preferably an alkylene group having 15 to 24 carbon atoms and having a structure in which hydroxyl groups at both terminals are removed from polyethylene glycol or polypropylene glycol. This is because the above composition can obtain a cured product having a steeper absorption peak in a desired wavelength range.

[0327] Specific examples of diglycidyl ethers of aliphatic diol compounds represented by the above formula (B4) include diglycidyl ethers 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, cyclohexane dimethylol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, and the like.

[0328] As for the above-mentioned aliphatic epoxy compounds, representative aliphatic epoxy compounds include glycidyl ethers of polyols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerol, 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 polyol such as propylene glycol, trimethylolpropane, and glycerol; 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 epoxystearate, butyl epoxystearate, and epoxidized polybutadiene.

[0329] In addition, the aliphatic epoxy resin may be a resin containing no aliphatic ring and no aromatic ring.

[0330] As the aromatic and aliphatic epoxy compounds, commercially available products can be used, and specific examples thereof include compounds described in Japanese Patent No. 6103653 and the like.

[0331] The content of the epoxy compound can be any amount that can obtain a cured product having excellent light absorption in a desired wavelength region, for example, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more in 100 parts by mass of the cationic curable compound. By making the content within the above range, a cured product having excellent film-forming properties and curability can be obtained.

[0332] [Oxetane compounds]

[0333] The oxetane compound may be a compound having an oxetane structure and not containing an epoxy structure.

[0334] Specific examples of such oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-(methyl)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-oxetanylmethoxy)methyl]benzene, -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, 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 ) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) 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-methylene) propanediyl bis (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-oxetanylmethyl) ether, tricyclodecanediyl dimethylene (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 tetra(3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetra(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether , caprolactone modified dipentaerythritol penta(3-ethyl-3-oxetanyl methyl) ether, di(trimethylolpropane)tetra(3-ethyl-3-oxetanyl methyl) ether, EO modified bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, PO modified bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, EO modified bisphenol F(3-ethyl-3-oxetanyl methyl) ether, etc. ,

[0335] In the present invention, a preferred oxetane compound includes a compound represented by the following formula (B5) (3-ethyl-3-{[(3-ethyl-3-oxetanyl)methoxy]methyl}oxetane).

[0336] [Chemistry 33]

[0337]

[0338] The content of the oxetane compound is preferably 1 to 100 parts by mass, more preferably 25 to 95 parts by mass, further preferably 50 to 90 parts by mass, and further preferably 60 to 80 parts by mass, based on 100 parts by mass of the cationic curable compound. By making the content within the above range, a cured product with excellent film-forming properties and curability can be obtained.

[0339] As the cationic curable compound, other compounds such as a thiirane compound and a thietane compound can also be used.

[0340] Other compounds that can be used as such a cationic curable compound, such as cyclic lactone compounds, cyclic acetal compounds, cyclic sulfide compounds, spirocyclic orthoester compounds, and vinyl compounds such as vinyl ether compounds and ethylenically unsaturated compounds, can be the same as those described in Japanese Patent No. 6103653 and the like.

[0341] [N-Alkoxymethylol compounds]

[0342] N-alkoxymethylol compounds are crosslinking compounds having two or more substituents selected from alkoxymethyl and hydroxymethyl groups, and undergo crosslinking reaction by dehydration condensation reaction when exposed to high temperature during thermal curing. Examples of such compounds include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine and the like.

[0343] Specific examples of the alkoxymethylated glycoluril 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-imidazolidinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0344] As N-alkoxymethylol compounds, commercially available products can be used. Specific examples thereof include glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174), methylated urea-formaldehyde resins (trade names: UFR (registered trademark) 65), butylated urea-formaldehyde resins (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea-formaldehyde / formaldehyde-based resins manufactured by DIC Co., Ltd. (highly condensed type, trade names: BECKAMINE (registered trademark) J-300S, P-955, N), and the like.

[0345] Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like.

[0346] As the alkoxymethylated benzoguanamine, commercially available products can be used. Specific examples thereof include those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (trade names: NIKALAC (registered trademark) BX-4000, BX-37, BL-60, BX-55H).

[0347] Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like.

[0348] As the alkoxymethylated melamine, commercially available products can be used. Specific examples thereof include methoxymethyl-type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl-type melamine compounds (trade names: Mycoat (registered trademark) 506, 508), 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, MX-035) manufactured by Sanwa Chemical, and butoxymethyl-type melamine compounds (trade names: NIKALAC (registered trademark) MX-45, MX-410, MX-302), and the like.

[0349] In addition, it can be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atoms of such an amino group are substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound as described in U.S. Patent No. 6,323,310 can be cited. The above-mentioned melamine compound can use a commercial product, and as a specific example thereof, a trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec (Strain)) can be cited, and as a commercial product of the above-mentioned benzoguanamine compound, a trade name: Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec (Strain)) can be cited.

[0350] Furthermore, as the N-alkoxymethylol compound, a polymer produced from an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylmethacrylamide, or N-butoxymethylmethacrylamide, can also be used.

[0351] Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropylmethacrylate, etc. The weight average molecular weight (Mw) of such polymers is preferably 1,000 to 50,000, more preferably 1,500 to 20,000, and even more preferably 2,000 to 10,000.

[0352] [Alkali-soluble resin having at least one cation-curable functional group in the side chain]

[0353] In the alkali-soluble resin having at least one cation-curable functional group in the side chain (cation-curable alkali-soluble resin), examples of the “cation-curable functional group” include an epoxy group, an oxetanyl group, and an N-alkoxymethyl group.

[0354] The cation-curable functional group can be introduced into the cation-curable alkali-soluble resin by using an unsaturated compound having the cation-curable functional group.

[0355] As unsaturated compounds having a cationically curable functional group, (3-ethyloxetane-3-yl)methyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, N-(butoxymethyl)acrylamide, etc. These compounds can use commercial products, and specific examples thereof include OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and M100 (manufactured by Daicel Corporation).

[0356] The content of the cation-curable functional group in the cation-curable alkali-soluble resin is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin, and more preferably 0.1 to 0.6 from the viewpoint of solvent resistance.

[0357] The term "alkali-soluble resin" refers to a resin having an alkali-soluble group. Specific examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid group, a boric acid group, and an active methylene group.

[0358] The so-called active methylene refers to the methylene (-CH 2 -) has a carbonyl group and a methylene group reactive toward a nucleophile at an adjacent position.

[0359] As the active methylene group, a group represented by the following formula (b1) is more preferable.

[0360] [Chemistry 34]

[0361]

[0362] (Where R b4 represents an alkyl group, an alkoxy group, or a phenyl group, and a dotted line represents a bonding end. )

[0363] In the above formula (b1), R b4 The alkyl group represented by , for example, includes an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms. Specific examples of such an alkyl group include methyl, ethyl, n-propyl, isopropyl, etc. Among these, methyl, ethyl and n-propyl are preferred.

[0364] In the above formula (b1), Rb4 The alkoxy group represented by , for example, includes alkoxy groups having 1 to 20 carbon atoms, preferably alkoxy groups having 1 to 5 carbon atoms. Specific examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc. Among these, methoxy, ethoxy and n-propoxy are preferred.

[0365] Specific examples of the group represented by the formula (b1) include groups represented by the following formulae (b1-1) to (b1-5), but the group is not limited thereto. In the structural formula, the dotted line represents a bonding end.

[0366] [Chemistry 35]

[0367]

[0368] Among the above-mentioned alkali-soluble groups, it is preferred to have at least one organic group selected from a phenolic hydroxyl group and a carboxyl group.

[0369] The alkali-soluble resin may have the above-mentioned structure and at least one cation-curable functional group in a side chain, and the main chain skeleton of the polymer constituting the resin is not particularly limited.

[0370] Examples of the alkali-soluble resin include acrylic resins, polyhydroxystyrene resins, polyimide precursors, polyimide, and polyester.

[0371] In the present invention, an alkali-soluble resin including a copolymer obtained by polymerizing a plurality of monomers can also be used. Furthermore, the alkali-soluble resin may be a blend of a plurality of alkali-soluble resins.

[0372] As the alkali-soluble resin, an acrylic polymer as an acrylic resin can be used. In the present invention, the acrylic polymer refers to a resin obtained by partially reacting an unsaturated double bond group by a polymerization reaction of a monomer having an unsaturated double bond group.

[0373] Examples of the alkali-soluble acrylic polymer include copolymers having, as essential structural units, an alkali-soluble monomer, that is, a monomer having at least one selected from the above-mentioned alkali-soluble group and at least one selected from monomers copolymerizable with these monomers.

[0374] The above-mentioned "monomer having at least one selected from alkali-soluble groups" includes monomers having a carboxyl group, and monomers having a phenolic hydroxyl group and an imide group. These monomers are not limited to having one carboxyl group or phenolic hydroxyl group, and may have multiple groups.

[0375] Specific examples of the above monomers are listed below, but the monomers are not limited to these.

[0376] Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

[0377] Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenyl methacrylate.

[0378] Examples of the monomer having an imide group include maleimide and the like.

[0379] In the production of the above-mentioned alkali-soluble acrylic polymer, the ratio of the monomer having an alkali-soluble group and an unsaturated double bond group is preferably 5 to 90 mol%, more preferably 10 to 60 mol%, and most preferably 10 to 40 mol% of all the monomers used in the production of the alkali-soluble acrylic polymer. If the ratio of the monomer having an alkali-soluble group and an unsaturated double bond group is 10 mass % or more, sufficient alkali solubility can be obtained.

[0380] The alkali-soluble acrylic polymer may be further copolymerized with a monomer having a hydroxyalkyl group and an unsaturated double bond group in order to further stabilize the pattern shape after curing.

[0381] Specific examples of monomers having a hydroxyalkyl group and an unsaturated double bond group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, and the like.

[0382] The ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group in the manufacture of the above-mentioned alkali-soluble acrylic polymer is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 20 to 40% by mass. If the ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group is 10% by mass or more, the stabilization effect of the pattern shape of the copolymer is obtained. If the ratio is 60% by mass or less, the content of the alkali-soluble group becomes an appropriate range, and sufficient properties such as developability are obtained.

[0383] The alkali-soluble acrylic polymer may be further copolymerized with an N-substituted maleimide compound from the viewpoint of increasing Tg of the copolymer.

[0384] Specific examples of N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. From the viewpoint of transparency, it is preferred that the compound does not have an aromatic ring, and from the perspective of transparency and heat resistance, it is more preferred that the compound has an alicyclic skeleton, and cyclohexylmaleimide is further preferred.

[0385] The ratio of N-substituted maleimide in the manufacture of the above-mentioned alkali-soluble acrylic polymer is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and further preferably 20 to 40% by mass. If the ratio of N-substituted maleimide is 10% by mass or more, since the Tg of the copolymer increases, the Tg of the wavelength conversion film finally obtained also increases, and sufficient heat resistance and light resistance are obtained. If the ratio is 60% by mass or less, sufficient transparency is obtained.

[0386] In addition, in the present invention, the alkali-soluble acrylic polymer may be a copolymer containing monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as structural units. As for other monomers, specifically, as long as they are monomers copolymerizable with at least one selected from the above-mentioned monomers having a carboxyl group and a monomer having a phenolic hydroxyl group, there is no particular limitation as long as the properties of the alkali-soluble acrylic polymer are not impaired. Specific examples of such monomers include acrylate compounds, methacrylate compounds, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds.

[0387] Specific examples of the other monomers are listed below, but the invention is not limited to these.

[0388] Specific examples of the above-mentioned acrylate compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenyl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecanyl acrylate, 8-ethyl-8-tricyclodecanyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether acrylate, and the like.

[0389] Specific examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracenyl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether methacrylate, and the like.

[0390] Specific examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.

[0391] Specific examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0392] Examples of the styrene compound include styrenes having no hydroxyl group, and specific examples thereof include styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

[0393] In the production of the alkali-soluble acrylic polymer, the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 20% by mass or less. If the ratio of the other monomers is 80% by mass or less, the effects of the present invention can be fully obtained.

[0394] There is no particular limitation on the method for obtaining the above-mentioned alkali-soluble acrylic polymer. For example, the alkali-soluble acrylic polymer can be obtained by performing a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which the following substances coexist: a monomer having at least one selected from a carboxyl group, a phenolic hydroxyl group, a carboxylic acid generated by heat or acid, and a phenolic hydroxyl group generated by heat or acid; a monomer having a hydroxyalkyl group; an unsaturated compound having the above-mentioned cationic curable functional group; other copolymerizable monomers as required; and a polymerization initiator as required. At this time, the solvent used is not particularly limited as long as it is a solvent that dissolves the monomers constituting the alkali-soluble acrylic polymer and the alkali-soluble acrylic polymer. As specific examples, the following solvents can be cited.

[0395] Examples of the solvent used in the above reaction include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, ethoxyethyl acetate, hydroxyethyl acetate, 2-hydroxy-3-methylbutyric acid methyl ester, 3-methoxymethyl propionate, 3-methoxyethyl propionate, 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-Methylpyrrolidone etc. Among these, from the viewpoint that film coating is good and safety is high, more preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate etc. These can be used alone 1 kind, also can be used in combination of 2 or more kinds.

[0396] The alkali-soluble acrylic polymer obtained in this way is usually in the state of a solution dissolved in a solvent.

[0397] In addition, the solution of the specific copolymer obtained as described above is put into diethyl ether, water, etc. under stirring to make it reprecipitate, and the generated precipitate is filtered, washed, and then dried at room temperature or heated under normal pressure or reduced pressure to prepare a powder of the specific copolymer. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a refined powder of the specific copolymer is obtained. In the case where it cannot be fully refined by one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

[0398] In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in an appropriate solvent, for example, the solvent used in the above-mentioned polymerization reaction, and used in the state of a solution.

[0399] As the alkali-soluble resin, polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, and polyimides such as polyimide containing a carboxylic acid group can be used. Any type of these can be used without particular limitation as long as they are alkali-soluble.

[0400] The polyamic acid as a polyimide precursor can generally be obtained by polycondensing (x) tetracarboxylic dianhydride and (y) a diamine compound.

[0401] The tetracarboxylic dianhydride (x) is not particularly limited. Specific examples thereof include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl Alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0402] The diamine compound (y) is also not particularly limited. Specific examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-phthalic acid, 2,5-diamino-1,4-phthalic acid, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethylbiphenyl, and 4,4′-diamino-3,3′-dicarboxyphenyl. Amino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane; 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxyphenyl) ether, bis(4-amino-3,5-dihydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl) methane, bis(4-amino-3-hydroxyphenyl) methane, bis(4-amino-3,5-dihydroxyphenyl) methane, bis(3-amino-4-hydroxyphenyl) sulfone, bis(4-amino-3-hydroxyphenyl) sulfone, bis(4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino diamine compounds having a phenolic hydroxyl group such as bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane and 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane;Diamine compounds having a thiophenol group such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl) ether, and 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane; and diamine compounds having a sulfonic acid group such as 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3',5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3 , 3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-toluoyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine and other diamine compounds. These may be used alone or in combination of two or more. ;

[0403] When the polyamic acid is prepared from (x) tetracarboxylic dianhydride and (y) diamine compound, the mixing ratio of the two compounds, i.e., the total mole number of the (y) diamine compound / the total mole number of the (x) tetracarboxylic dianhydride, is preferably 0.7 to 1.2. As in a conventional polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the generated polyamic acid and the greater the molecular weight.

[0404] Moreover, when the diamine compound is used excessively for polymerization, the terminal amino group of the remaining polyamic acid can be reacted with the carboxylic anhydride to protect the terminal amino group.

[0405] Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene dicarboxylic anhydride, hydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

[0406] In the production of polyamic acid, the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride can be generally selected from -20 to 150°C, preferably from -5 to 100°C. When a high molecular weight polyamic acid is to be obtained, the reaction temperature is appropriately selected from the range of 5 to 40°C and the reaction time is 1 to 48 hours. When a low molecular weight, highly stable, partially imidized polyamic acid is to be obtained, the reaction temperature is more preferably selected from 40 to 90°C and the reaction time is 10 hours or more.

[0407] The reaction temperature when protecting the terminal amino group with an acid anhydride can be any temperature from -20 to 150°C, preferably from -5 to 100°C.

[0408] The reaction of the diamine compound and the tetracarboxylic dianhydride can be carried out in a solvent. Examples of the solvent that can be used at this time include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate Ethyl ester, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, pimelinketone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone etc.These can be used alone one kind, also can be used in combination of two or more.And then, even if the solvent of insoluble polyamic acid, in the scope that the polyamic acid generated by polyreaction does not separate out, also can be used in combination in above-mentioned solvent.

[0409] In addition, any polyimide can be used as the alkali-soluble resin. The polyimide used in the present invention is a product obtained by chemically or thermally imidating 50% or more of the polyimide precursor such as the polyamic acid described above.

[0410] The polyimide preferably has a group selected from a carboxyl group and a phenolic hydroxyl group in order to impart alkali solubility.

[0411] Examples of methods for introducing a carboxyl group or a phenolic hydroxyl group into a polyimide include a method of using a monomer having a carboxyl group or a phenolic hydroxyl group, a method of capping the amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxyl group, and a method of making the imidization rate 99% or less when imidizing a polyimide precursor such as a polyamic acid.

[0412] Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.

[0413] As a method of chemical imidization, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting them at room temperature to 100° C. is generally used. As a method of thermal imidization, a method of superheating a polyimide precursor solution at a temperature of 180 to 250° C. while dehydrating the solution is generally used.

[0414] Moreover, as the above-mentioned alkali-soluble resin, a phenol novolac resin can be further used.

[0415] In addition, polyester polycarboxylic acid can also be used as the alkali-soluble resin. Polyester polycarboxylic acid can be obtained from acid dianhydride and diol by the method described in International Publication No. 2009 / 051186.

[0416] Examples of the acid dianhydride include the above-mentioned (x) tetracarboxylic dianhydride.

[0417] Examples of the diol include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol; alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; and aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0418] In the present invention, the cation-curable alkali-soluble resin may be a mixture of a plurality of cation-curable alkali-soluble resins.

[0419] The cationic curable alkali-soluble resin preferably has a number average molecular weight in the range of 2000 to 50000. If the number average molecular weight is 50000 or less, it is difficult to generate development residues and the desired sensitivity can be obtained. On the other hand, if the number average molecular weight is 2000 or more, it is difficult to reduce the film of the exposed part during development and sufficient curability can be obtained.

[0420] The (B) cation curable compound may be used alone or in combination of two or more.

[0421] (C) Photoacid generator

[0422] The photoacid generator is a catalyst that generates an acid by irradiation with light and causes cationic polymerization of epoxy groups and oxetane groups by the action of the acid.

[0423] 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.

[0424] Examples of the onium salt compound include sulfonium salts, iodonium salts, phosphonium salts, and selenonium salts. Specific examples thereof include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; polyaryliodonium salts such as diphenyliodonium hexafluoroantimonate and p-nonylphenyliodonium hexafluoroantimonate.

[0425] Specific examples of preferred sulfonium salts in the present invention include sulfonium salts represented by the following formula.

[0426] [Chemistry 36]

[0427]

[0428] The above-mentioned onium salt compounds can also be obtained as commercial products. Examples of such commercial products include CPI-100P and CPI-310FG manufactured by San-Apro (Strain), Omnicat (registered trademark, hereinafter the same) 270 manufactured by IGM resin, Irgacure 290 manufactured by BASF Japan, and the like; aromatic sulfonium salt-based photocationic polymerization initiators such as ADEKAARKLS SP-606 manufactured by ADEKA; and iodonium salt-based photocationic polymerization initiators such as Omnicat 250 manufactured by IGM resin.

[0429] The above-mentioned sulfonium salt (photoacid generator) may be dissolved in advance in a solvent that does not inhibit polymerization or cross-linking reaction in order to facilitate dissolution in the cationically polymerizable compound.

[0430] 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; polyols such as 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, and their derivatives; cyclic hydrocarbons such as dioxane; Ethers; 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-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene, etc.

[0431] When a solvent is used, the amount of the solvent used is preferably 15 to 1000 parts by mass, more preferably 30 to 500 parts by mass, based on 100 parts by mass of the sulfonium salt (photoacid generator). The solvents may be used alone or in combination of two or more.

[0432] Examples of the metallocene complex compound include (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) hexafluorophosphate and the like.

[0433] Examples of the iron arene complex compound include bis(η 5 -cyclopentadienyl)(η 6 -isopropylbenzene) iron (II) hexafluorophosphate, etc.

[0434] Examples of the disulfone compounds include aromatic disulfone compounds such as diphenyl disulfone, and sulfonimide compounds and derivatives thereof such as N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)-1,8-naphthalene dicarboximide, N-(trifluoromethanesulfonyloxy)-2-alkyl-1,8-naphthalene dicarboximide, N-(trifluoromethanesulfonyloxy)-3-alkyl-1,8-naphthalene dicarboximide, and N-(trifluoromethanesulfonyloxy)-4-alkyl-1,8-naphthalene dicarboximide. Among these, sulfonimide compounds and derivatives thereof are preferred, and N-(trifluoromethanesulfonyloxy)-1,8-naphthalene dicarboximide and derivatives thereof are more preferred.

[0435] Examples of the 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)pentane-3-one.

[0436] Examples of triazine compounds include halogenated alkyl triazinyl aromatic hydrocarbons such as 1-methoxy-4-(3,5-bis(trichloromethyl)triazinyl)benzene, 1,2-methylenedioxy-4-(3,5-bis(trichloromethyl)triazinyl)benzene, and 1-methoxy-4-(3,5-bis(trichloromethyl)triazinyl)naphthalene; and halogenated alkyl triazinyl aromatic hydrocarbons such as 1-methoxy-4-[2-(3,5-bis(trichloromethyl)triazinyl)vinyl]benzene, 1,2-dimethoxy-4-[2-(3,5-bis(trichloromethyl)triazinyl)vinyl]benzene and 1-methoxy-2-[2-(3,5-bis(trichloromethyl)triazinyl)vinyl]benzene.

[0437] Examples of the acetophenone derivative compound include 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexyl phenyl ketone.

[0438] Examples of the diazomethane compound include bis(cyclohexylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, and bis(p-toluenesulfonyl)diazomethane.

[0439] The content of the photoacid generator (C) is preferably 0.1 to 49% by mass, more preferably 0.1 to 20% by mass, further preferably 0.2 to 10% by mass, and further preferably 0.3 to 5% by mass based on the solid content, from the viewpoint of film-forming properties and transparency, heat resistance and light resistance of the cured film.

[0440] The photoacid generator (C) may be used alone or in combination of two or more.

[0441] (D) an alkali-soluble resin having a reactive functional group for reacting with the cationically curable compound in a side chain and having no cationically curable functional group

[0442] In the present invention, when one or more selected from a compound having an epoxy group (however, excluding alkali-soluble resins), a compound having an oxetane group (however, excluding alkali-soluble resins), and an N-alkoxymethylol compound is used as the (B) cationic curable compound, by further combining (D) an alkali-soluble resin having a reactive functional group for reacting with the cationic curable compound in a side chain and having no cationic curable functional group (hereinafter referred to as "alkali-soluble resin containing a reactive functional group"), pattern formation by photolithography can be achieved, and the composition can be used as a resist film-forming composition.

[0443] Examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amide group, and a hydroxyl group is preferred.

[0444] The reactive functional group can be introduced into the alkali-soluble resin containing the reactive functional group by using an unsaturated compound having the reactive functional group.

[0445] Specific examples of the unsaturated compound having a reactive functional group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, p-hydroxystyrene, α-methyl p-hydroxystyrene, N-hydroxy Phenylmaleimide, N-hydroxyphenylacrylamide, N-hydroxyphenylmethacrylamide, p-hydroxyphenyl acrylate, p-hydroxyphenyl methacrylate, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, acrylamide, methacrylamide, N-methylacrylamide, and the like.

[0446] The content of the reactive functional group in the alkali-soluble resin containing a reactive functional group is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin, and more preferably 0.1 to 0.5 from the viewpoint of developability and solvent resistance.

[0447] The "alkali-soluble resin" in the reactive functional group-containing alkali-soluble resin includes the same alkali-soluble resins as those in the cationic curable alkali-soluble resin of the component (B), and acrylic polymers as acrylic resins can be used.

[0448] As the alkali-soluble acrylic polymer, a copolymer including, as essential structural units, a monomer exhibiting alkali solubility, that is, a monomer having at least one selected from the above-mentioned alkali-soluble group and at least one selected from monomers copolymerizable with these monomers can be used.

[0449] The method for obtaining the above-mentioned alkali-soluble acrylic polymer is not particularly limited, and for example, it can be obtained by polymerizing it at a temperature of 50 to 110° C. in a solvent in which the following substances coexist: a monomer having at least one selected from a carboxyl group, a phenolic hydroxyl group, a group that generates a carboxylic acid by the action of heat or acid, and a group that generates a phenolic hydroxyl group by the action of heat or acid; a monomer having a hydroxyalkyl group; an unsaturated compound having the above-mentioned reactive functional group; other copolymerizable monomers as required; and a polymerization initiator as required. At this time, the solvent used is not particularly limited as long as it is a solvent that dissolves the monomers constituting the alkali-soluble acrylic polymer and the alkali-soluble acrylic polymer. As specific examples, the following solvents can be cited.

[0450] The content of the cation-curable functional group is preferably 0.1 to 0.9 per one repeating unit in the alkali-soluble resin, and more preferably 0.1 to 0.8 from the viewpoint of developability and solvent resistance.

[0451] The solution containing the reactive functional group-containing alkali-soluble resin can be used directly for the preparation of the negative photosensitive resin composition. Alternatively, the reactive functional group-containing alkali-soluble resin can be precipitated in a poor solvent such as water, methanol, ethanol, etc., and recovered for use.

[0452] In the present invention, the reactive functional group-containing alkali-soluble resin may be a mixture of a plurality of reactive functional group-containing alkali-soluble resins.

[0453] The number average molecular weight of the alkali-soluble resin containing a reactive functional group is preferably in the range of 2000 to 50000. If the number average molecular weight is 50000 or less, it is difficult to generate development residues and the required sensitivity can be obtained. On the other hand, if the number average molecular weight is 2000 or more, the photodegradation of the organic phosphor can be suppressed.

[0454] The above-mentioned (D) alkali-soluble resin having a reactive functional group may be used alone or in combination of two or more.

[0455] About the content of (B) component and (D) component

[0456] The content of the cationic curable compound (B) is preferably 1% by mass or more in the solid content from the viewpoint of obtaining a cured product having excellent light absorption in a desired wavelength range.

[0457] When component (D) is not contained, from the viewpoint of improving the light absorption of the obtained cured product in the desired wavelength region, its content is more preferably 50 to 99.8% by mass, further preferably 70 to 99.5% by mass, and further preferably 80 to 99.2% by mass in the solid content.

[0458] When the component (D) is contained, the content thereof is more preferably 1 to 20% by mass, further preferably 3 to 15% by mass, and further preferably 5 to 10% by mass in the solid content from the viewpoint of film-forming properties and pattern-forming properties.

[0459] The content of the above-mentioned (D) alkali-soluble resin containing a reactive functional group is generally 0 to 98.8% by mass of the solid component. From the viewpoint of film-forming properties and pattern-forming properties, it is preferably 30 to 98.8% by mass of the solid component, more preferably 50.0 to 95.0% by mass, further preferably 60.0 to 90.0% by mass, and further preferably 70.0 to 85.0% by mass.

[0460] When the components (B) and (D) are contained, the content ratio of the two components is preferably 0:100 to 50:50, more preferably 5:95 to 15:85, in terms of mass ratio, from the viewpoint of film-forming property and pattern-forming property.

[0461] When the above-mentioned (D) alkali-soluble resin containing a reactive functional group is used, a compound having a particle dispersing effect can also be used as the (F) polymer dispersant described later. It should be noted that in the present invention, among the alkali-soluble resin containing a reactive functional group, the compound containing the two definitions of the (F) polymer dispersant belongs to the (D) alkali-soluble resin containing a reactive functional group.

[0462] (E) Light scattering particles

[0463] The composition for forming a wavelength conversion film of the present invention may further contain (E) light scattering particles. The light scattering particles have the following functions: by scattering light entering the wavelength conversion film in the film, the optical path length in the wavelength conversion film is substantially extended, the light absorptivity is improved, and the light reflected at the interface of the wavelength conversion film and returned to the wavelength conversion film is rescattered, thereby improving the luminous efficiency.

[0464] The light scattering particles can be appropriately selected according to the purpose, and may be organic fine particles or inorganic fine particles. Among them, inorganic fine particles having a large refractive index are preferred from the perspective of improving the scattering performance of the particles.

[0465] The light scattering particles can be appropriately selected according to the purpose, and may be organic fine particles or inorganic fine particles. Among them, inorganic fine particles having a large refractive index are preferred from the perspective of improving the scattering performance of the particles.

[0466] 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.

[0467] Examples of the inorganic fine particles include inorganic oxide particles containing at least one oxide selected from silicon, zirconium, titanium, indium, zinc, antimony, cerium, niobium, tungsten, and the like. Specifically, examples of the inorganic oxide particles include SiO 2 、ZrO 2 、TiO 2 (hereinafter sometimes referred to as titanium oxide particles), BaTiO 3 、In 2 O 3 , ZnO, Sb 2 O 3 、ITO、CeO 2 , Nb 2 O 5 and WO 3 Among these, TiO 2 、BaTiO 3 、ZrO 2 、CeO 2 and Nb 2 O 5 , more preferably TiO 2 In addition, TiO 2 Among them, the rutile type is preferred because it has lower catalytic activity than the anatase type and thus improves the durability of the film and also has a higher refractive index.

[0468] These particles may be those subjected to surface treatment.

[0469] When surface treatment is performed, specific materials for surface treatment include different inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, organic acids such as organosiloxane and stearic acid, etc. These surface treatment materials can be used alone or in combination.

[0470] The average particle size of the light scattering particles is greater than 50nm and less than 200nm. From the viewpoint of wavelength conversion efficiency, the lower limit of the average particle size is preferably more than 60nm, more preferably more than 70nm. In addition to the viewpoint of wavelength conversion efficiency, if patterning characteristics are considered, from the viewpoint of the low total light reflectance under i-rays (365nm), the average particle size more than 100nm is more preferably used. If the upper limit of the average particle size is too large, it becomes easy to precipitate, therefore from the viewpoint of the storage stability of the composition, preferably less than 190nm, more preferably less than 180nm. It should be noted that the average particle size of the light scattering particles is the average particle size obtained by transmission electron microscope observation.

[0471] Light scattering particles can use commercial products, for example, as specific examples of titanium oxide particles, can list PT-401M (rutile type, average particle size 70nm), PT-401L (rutile type, average particle size 130nm), PT-501R (rutile type, average particle size 180nm) etc., but are not limited to these. It should be noted that the average particle size of the exemplified light scattering particles can have a deviation of ± 10nm.

[0472] The content of the light scattering particles (E) is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and even more preferably 0.3 to 10% by mass in the solid content in consideration of wavelength conversion efficiency.

[0473] In addition, the wavelength conversion film forming composition of the present invention may contain various known additives such as (D) component, (E) component, (F) polymer dispersant, (G) surfactant, (H) antioxidant, (I) curing aid, light stabilizer, flame retardant, transparent agent, ultraviolet absorber, crosslinking agent, filler, etc. in addition to the above-mentioned (A), (B) and (C) components as needed.

[0474] (F) The polymer dispersant is a polymer compound having a weight average molecular weight of 750 or more and having a functional group having an affinity for the (E) light scattering particles. The polymer dispersant has the function of dispersing the light scattering particles. The polymer dispersant is adsorbed on the light scattering particles via the functional group having an affinity for the light scattering particles, and the light scattering particles are dispersed in the composition by utilizing electrostatic repulsion and / or steric repulsion between the polymer dispersants. The polymer dispersant is preferably bound to the surface of the light scattering particles and adsorbed on the light scattering particles, but may be free in the wavelength conversion film forming composition.

[0475] Functional groups having affinity for the (E) light scattering particles include acidic functional groups, basic functional groups, and nonionic functional groups. Acidic functional groups have dissociative protons and can be neutralized by bases such as amines and hydroxide ions, while basic functional groups can be neutralized by acids such as organic acids and inorganic acids.

[0476] Examples of the acidic functional group include carboxyl (-COOH), sulfone (-SO 3 H), sulfate (-OSO 3 H), phosphonic acid group (-PO(OH) 2 ), phosphate group (-OPO(OH) 2 ), phosphinate group (-PO(OH)-), mercapto group (-SH), etc.

[0477] Examples of the basic functional group include a primary amino group, a secondary amino group, a tertiary amino group, an ammonium group, an imino group, and a nitrogen-containing heterocyclic group such as pyridine, pyrimidine, pyrazine, imidazole, and triazole.

[0478] Examples of the nonionic functional group include a hydroxyl group, an ether group, a thioether group, a sulfinyl group (-SO-), a sulfonyl group (-SO 2 -), carbonyl, formyl, ester, carbonate, amide, carbamoyl, urea, thioamide, thiourea, sulfamoyl, cyano, alkenyl, alkynyl, phosphine oxide, phosphine sulfide, etc.

[0479] (F) The polymer dispersant may be a polymer (homopolymer) of a single monomer or a copolymer (copolymer) of multiple monomers. In addition, the polymer dispersant may be any of a random copolymer, a block copolymer or a graft copolymer. In addition, when the polymer dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer. Specific examples of the polymer dispersant include acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyethers, phenolic resins, silicone resins, polyurea resins, amino resins, epoxy resins, polyethylene imine, polyallylamine, polyimide, etc.

[0480] As the (F) polymer dispersant, commercially available products may be used, for example, DISPERBYK series and BYK series manufactured by BYK, Efka series manufactured by BASF, Solsperse series manufactured by Lubrizol, Ajisper PB series manufactured by Ajinomoto Fine-Techno Co., Ltd., TEGO series manufactured by Evonik, and DISPARLON series manufactured by Kusumoto Chemicals Co., Ltd.

[0481] 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, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, and DISPERBYK-190. PERBYK-2020, DISPERBYK-2022, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164; manufactured by BASF EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4061, EFKA4080, EFKA4300, EFKA4310, EFKA43 20. EFKA4330, EFKA4340, EFKA4560, EFKA4585, EFKA5207, EFKA1501, EFKA1502, EFKA1503 and EFKA PX-4701;Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 11200, Solsperse13940, Solsperse 16000, Solsperse 17000, Solsperse manufactured by Lubrizol 18000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, 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., Ltd.; TEGO Dispers650 and TEGO manufactured by Evonik Corporation Dispers660C, TEGO Dispers662C, TEGO Dispers670, TEGO Dispers685, TEGO Dispers700, TEGO Dispers710 and TEGO Dispers760W; and DISPARLON AQ-320, DISPARLON AQ-330, DISPARLON AQ-340, DISPARLON AQ-360, DISPARLONAQ-380, etc. manufactured by Kusumoto Chemicals Co., Ltd.;

[0482] When the (F) polymer dispersant is used, the amount thereof is not particularly limited, but is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on 100% by mass of the (E) light scattering particles.

[0483] In addition, the above-mentioned (F) polymer dispersant may be used alone or in combination of two or more.

[0484] As the (G) surfactant, a fluorine-based surfactant is preferred, and a nonionic fluorine-based surfactant is more preferred.

[0485] Specific examples thereof include FTERGENT series, 212M, 215M, 250, 222F, FTX-218, and DFX-18 manufactured by Neos Corporation, but are not limited to these.

[0486] When the (G) surfactant is used, the amount thereof is not particularly limited, but is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.5% by mass, based on the solid content of the wavelength conversion film-forming composition.

[0487] (H) As the antioxidant, hindered phenol-based antioxidants, phenol-based antioxidants, and the like are exemplified.

[0488] As the (H) antioxidant, commercially available products may be used, and examples thereof include Irganox 1010 manufactured by BASF Japan Co., Ltd. and ADK STAB AO-80 manufactured by ADEKA Corporation, but the antioxidant is not limited thereto.

[0489] When an antioxidant is used, the amount thereof is not particularly limited, but is preferably 0.1 to 5.0% by mass, more preferably 0.3 to 1.5% by mass, based on the solid content of the wavelength conversion film-forming composition.

[0490] (J) an alkali-soluble resin having no reactive functional group for reacting with the cationically curable compound and no cationically curable functional group in a side chain

[0491] In the present invention, when one or more selected from a compound having an epoxy group (however, excluding alkali-soluble resins), a compound having an oxetane group (however, excluding alkali-soluble resins), and an N-alkoxymethylol compound is used as the (B) cationic curable compound, by further combining (D) an "alkali-soluble resin containing a reactive functional group" and / or (J) an alkali-soluble resin having no reactive functional group for reacting with the cationic curable compound in a side chain and having no cationic curable functional group (hereinafter referred to as "alkali-soluble resin not containing a reactive functional group"), pattern formation by photolithography can be achieved, and the composition can be used as a resist film-forming composition.

[0492] (J) As the alkali-soluble resin containing no reactive functional group, copolymers of methyl methacrylate and methacrylic acid, etc. are mentioned.

[0493] When (J) an alkali-soluble resin having no reactive functional group is used, the amount thereof is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the solid content of the wavelength conversion film-forming composition.

[0494] When the above-mentioned (J) alkali-soluble resin not containing reactive functional groups is used, a compound having a particle dispersing effect can also be used as (F) a polymer dispersant. It should be noted that in the present invention, a compound including both the (J) alkali-soluble resin containing reactive functional groups and the (F) polymer dispersant is included in the (J) alkali-soluble resin not containing reactive functional groups.

[0495] Furthermore, the wavelength conversion film forming composition of the present invention may contain a solvent as needed. 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, dioxane, and 1,2-dimethoxyethane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone (CPN); ester solvents such as ethyl acetate, n-hexyl acetate, ethyl lactate, γ-butyrolactone, propylene carbonate, and diisopropyl malonate; halogenated hydrocarbon solvents such as dichloromethane, 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; methanol, ethanol, isopropanol, n-propanol, cyclopentanone, and the like. Alcohol solvents such as hexanol, diacetone alcohol, and 2-benzoylethanol; 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 (PGMEA); glycol solvents such as ethylene glycol, propylene glycol, hexanediol, 3-octanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol; nitrile solvents such as acetonitrile; organic solvents such as sulfur-containing solvents such as dimethyl sulfoxide. These may be used alone or in combination of two or more.

[0496] When the wavelength conversion film-forming composition contains a solvent, the solid content concentration of the wavelength conversion film-forming composition varies depending on the thickness of the target wavelength conversion film, the coating method, etc. and cannot be generally specified, but is usually 10 to 70% by mass, preferably 20 to 60% by mass.

[0497] The upper limit of the viscosity of the wavelength conversion film-forming composition at 25° C. is 10000 mPa·s or less, preferably 1000 mPa·s or less. The lower limit is preferably 5 mPa·s or more, more preferably 10 mPa·s or more, in consideration of storage stability.

[0498] In addition, in the present invention, the viscosity means a value measured by an EMS viscometer.

[0499] The wavelength conversion film-forming composition of the present invention can be prepared by mixing the above-mentioned components (A), (B) and (C), components (D) to (J) as needed, other additives such as a light stabilizer, and a solvent in any order.

[0500] The wavelength conversion film can be obtained by applying the wavelength conversion film-forming composition of the present invention onto a substrate, for example, evaporating the solvent by heating or the like as needed, and irradiating with active energy rays (eg, ultraviolet light) as needed.

[0501] Examples of the coating method include a reverse roll coater, a knife coater, a slot die coater, a direct gravure coater, an offset gravure coater, a lick coater, a natural roll coater, an air knife coater, a roll knife coater, a reverse roll knife coater, a two stream coater, a rod coater, a wire bar coater, a coater, a dip coater, a curtain coater, a spin coater, a blade coater, an inkjet, and the like.

[0502] Heating can be performed using a common heating device such as an oven or a hot plate.

[0503] The heating conditions are not particularly limited as long as a film can be formed, but heating is preferably performed at 60 to 200° C. for 5 minutes to 2 hours, and more preferably at 80 to 200° C. for 15 minutes to 1 hour. In addition, heat curing may be performed in stages.

[0504] As for the irradiation of ultraviolet light, there is no particular limitation as long as a film can be formed. A light source such as a mercury lamp, a metal halide lamp, a xenon lamp, or an LED can be used, and a bandpass filter can be combined as needed to irradiate light that removes light other than the target exposure wavelength. The wavelength of the irradiated light is preferably 200 to 440 nm, and light containing a wavelength of 300 to 400 nm is particularly preferred. The exposure amount is preferably 10 to 4000 mJ / cm 2 .

[0505] The above-mentioned heating step and ultraviolet light exposure step can be combined in any order. For example, ultraviolet light exposure can be performed after heating, ultraviolet light exposure can be performed after heating, or ultraviolet light exposure can be performed after heating, and then heating can be performed.

[0506] The thickness of the wavelength conversion film is not particularly limited, but is usually 1 to 1000 μm, preferably 3 to 500 μm, and more preferably 5 to 100 μm.

[0507] There is no particular restriction on the haze of the wavelength conversion film. From the viewpoint of increasing the amount of light that can be absorbed by the phosphor by scattering the incident light in the film, it is preferably 18% or more, more preferably 30% or more, and further preferably 40% or more. There is no particular restriction on the upper limit of the haze value, but it is usually about 95%. It should be noted that in the present invention, the haze value is a value measured in accordance with ASTM D1003-61. In addition, in the present invention, as the measurement conditions of the above-mentioned haze value, for example, the conditions for measuring a film with a thickness of 10 μm formed from a composition having a titanium oxide particle content of 6.7% by mass can be cited.

[0508] The substrate may be appropriately selected from substrates used as base substrates for forming such films, and is preferably a glass substrate or a polymer plate having a transmittance of 50% or more for light in the visible region of 400 to 800 nm.

[0509] Specific examples of glass include soda-lime glass, glass containing barium / strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.

[0510] Specific examples of the polymer include polycarbonate, acryl, polyethylene terephthalate, polyether sulfide, and polysulfone.

[0511] In the present invention, when a coating film is formed using a composition (negative photosensitive resin composition) which is a combination of (B) a cationic curable compound selected from a compound having an epoxy group (but excluding alkali-soluble resins), a compound having an oxetane group (but excluding alkali-soluble resins), and an N-alkoxymethylol compound, and (E) an alkali-soluble resin containing a reactive functional group, and further contains (A) an organic phosphor and (C) a photoacid generator, a mask having a predetermined pattern is attached to the obtained coating film, and light such as ultraviolet rays is irradiated, and development is performed with an alkaline developer to wash away the unexposed portion, and the remaining patterned film is heated at 80 to 140° C. for 0.5 to 10 minutes as necessary to obtain a relief pattern with a clear end surface.

[0512] Examples of the alkaline developer include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and alkaline aqueous solutions such as aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, a known surfactant used in a developer may be added to these developers.

[0513] In the above, a 0.1-2.58 mass % aqueous solution of tetraethylammonium hydroxide is generally used as a developer for photoresists. In the composition of the present invention, this alkaline developer can also be used to achieve good development without causing problems such as swelling.

[0514] As a developing method, any method such as a flooding method, a dipping method, a shaking dipping method, etc. can be used. The developing time in this case is usually 15 to 180 seconds.

[0515] After development, the photosensitive resin film is washed with running water, and then air-dried with compressed air or compressed nitrogen or by spin drying to remove moisture on the substrate, thereby obtaining a film having a pattern formed thereon. In the above, the washing time is usually about 20 to 120 seconds.

[0516] Next, the obtained patterned film is post-baked for thermal curing, thereby obtaining a film having excellent heat resistance, transparency, planarization, low water absorption, chemical resistance, etc. and having a good relief pattern. A hot plate, an oven, etc. can be used for heating the patterned film.

[0517] As a method of post-baking, generally, there is a method of treating at a heating temperature selected from the range of 140 to 270° C. on a hot plate for 5 to 30 minutes, and in an oven for 30 to 90 minutes. By post-baking under such conditions, a cured film having a good pattern shape can be obtained.

[0518] The wavelength conversion film obtained using the composition of the present invention has excellent wavelength conversion efficiency and durability, 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, and lighting.

[0519] Example

[0520] The present invention will be described in more detail below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0521] [Molecular weight determination]

[0522] The molecular weight of the polymer in this example was measured under the following conditions using a GPC system manufactured by JASCO Corporation as an apparatus and Shodex (registered trademark) KF-804L and 803L as columns.

[0523] Column oven: 40°C

[0524] Flow rate: 1mL / min

[0525] Eluent: Tetrahydrofuran

[0526] The meanings of the abbreviations used in the present examples are as follows.

[0527] MMA: Methyl methacrylate

[0528] MAA: Methacrylic acid

[0529] OXE-30: (3-ethyloxetane-3-yl)methyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

[0530] MI: Maleimide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0531] ·St: Styrene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0532] ·M100: 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Corporation)

[0533] ·HEMA: 2-Hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0534] ·CHMI: IMILEX-C (N-cyclohexylmaleimide, manufactured by Nippon Shokubai Co., Ltd.)

[0535] ·AIBN: α, α'-azobisisobutyronitrile

[0536] ·PGMEA: Propylene glycol monomethyl ether acetate

[0537] ·CPN: Cyclopentanone

[0538] [(A) Component: organic phosphor]

[0539] A-1: a compound represented by the following formula (A3), FL 305 (manufactured by BASF Corporation)

[0540] [Chemistry 37]

[0541]

[0542] A-2: Organic phosphor represented by the above formula (A1-7), synthetic product (refer to Synthesis Example 1)

[0543] A-3: Organic phosphor represented by the above formula (A2-4), synthetic product (refer to Synthesis Example 2)

[0544] A-4: Organic phosphor represented by the above formula (A4-4), synthetic product (see Synthesis Example 3)

[0545] [Component (B): Cationic curable compound]

[0546] · B1-1: Epoxy compound, CELLOXIDE 8010 (manufactured by Daicel Corporation)

[0547] · B1-2: Epoxy compound, CELLOXIDE 2021P (manufactured by Daicel Corporation)

[0548] · B1-3: Epoxy compound, EPOLEAD GT-401 (manufactured by Daicel Corporation)

[0549] · B1-4: Oxetane compound, Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)

[0550] · B1-5: N-alkoxymethylol compound, PL-LI (manufactured by MIDORI Chemical Co., Ltd.)

[0551] B1-6: Cationic curing alkali-soluble resin, synthetic product (refer to Synthesis Example 4)

[0552] B1-7: Cationic curing alkali-soluble resin, synthetic product (refer to Synthesis Example 5)

[0553] B1-8: Cationic curing alkali-soluble resin, synthetic product (refer to Synthesis Example 6)

[0554] · B1-9: Epoxy compound, DENACOL EX-212L (manufactured by NAGASE CHEMTEX Co., Ltd.)

[0555] B2-1: 1,6-Hexanediol diacrylate, VISCOAT#230 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), radical curable compound (comparative product)

[0556] B2-2: 1,9-nonanediol diacrylate, VISCOAT#260 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), radical curable compound (comparative product)

[0557] B2-3: Bisphenol A EO-modified diacrylate, ARONIX M-211B (manufactured by Toagosei Co., Ltd.), radical curable compound (comparative product)

[0558] B2-4: dipentaerythritol polyacrylate, A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), radical curable compound (comparative product)

[0559] B2-5: ethoxylated bisphenol A diacrylate, NK-ESTER A-BPE-4 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), radical curable compound (comparative product)

[0560] [Component (C): photoacid generator]

[0561] · C1-1: Aromatic sulfonium salt, CPI-310FG (manufactured by San-Apro Co., Ltd.)

[0562] C2-1: Omnirad 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, manufactured by IGM Resins BV), photoradical initiator (comparative product)

[0563] C2-2: Irgacure OXE02 (ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(o-acetoxime), manufactured by BASF Japan Co., Ltd.), photoradical initiator (comparative product)

[0564] [Component (D): Alkali-soluble resin containing reactive functional groups]

[0565] D-1: Synthetic product (refer to Synthesis Example 7)

[0566] [(E) ingredient: light scattering particles]

[0567] · E-1: Titanium oxide particles, PT-401L (rutile type, average particle size 130 nm, manufactured by Ishihara Sangyo Co., Ltd.)

[0568] [Component (F): polymer dispersant]

[0569] ·F-1: Polyether phosphate, AQ-320 (manufactured by Kusumoto Chemicals Co., Ltd.)

[0570] ·F-2: Polyether phosphate, AQ-330 (manufactured by Kusumoto Chemicals Co., Ltd.)

[0571] [(G) ingredient: surfactant]

[0572] ·G-1: FTERGENT DFX-18 (manufactured by Neos Corporation)

[0573] [(H) ingredient: antioxidant]

[0574] H-1: Irganox 1010 (pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), manufactured by BASF Japan Co., Ltd.)

[0575] H-2: ADK STAB AO-80 (3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, manufactured by ADEKA Corporation)

[0576] [(I) Component: Curing Aid]

[0577] ·I-1: Karenz MT (registered trademark) PE1 (pentaerythritol tetrakis (3-mercaptobutyrate), manufactured by RESONAC Co., Ltd.)

[0578] [Component (J): Alkali-soluble resin containing no reactive functional group]

[0579] J-1: Acrylic acid polymer, synthetic product (refer to Synthesis Example 8)

[0580] [Solvent]

[0581] S1: PGMEA / CPN mixed solvent (weight ratio 70 / 30)

[0582] ·S2:CPN (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0583] [Synthesis Example 1] Synthesis of A-2

[0584] According to the synthesis method described in ACS Materials Lett. 2021, 3, 42-49, an organic phosphor A-2 represented by the following formula (A1-7) was obtained.

[0585] [Chemistry 38]

[0586]

[0587] [Synthesis Example 2] Synthesis of A-3

[0588] (1) Synthesis of 2,7-dibromobenzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 2)

[0589] [Chemistry 39]

[0590]

[0591] A bromine group was introduced into compound 1 using bromine to obtain compound 2 in a yield of 28%. Specifically, the synthesis was performed as follows.

[0592] Bromine (14.2 g, 89.0 mmol) was dissolved in dichloromethane (500 mL) and cooled to 0°C. Benzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 1; 10.0 g, 41.6 mmol) and iodine (211 mg, 0.832 mmol) dissolved in dichloromethane (1000 mL) were added dropwise over 1 hour. The mixture was stirred at room temperature for 62 hours. 1000 mL of methanol was added, and the precipitated white solid was recovered by suction filtration, washed with saturated sodium thiosulfate aqueous solution (100 mL), water (500 mL), and methanol (500 mL) in this order, and dried under reduced pressure at 50°C for 5 hours to obtain 15.0 g of a white solid. Tetrahydrofuran (1500 mL) was added to the obtained white solid (15.0 g), and the mixture was stirred at room temperature for 15 hours. The white solid in tetrahydrofuran was recovered by suction filtration and dried under reduced pressure at 50°C for 5 hours to obtain Compound 2 as a white solid with a yield of 28% (4.68 g, 11.8 mmol). 1 H-NMR measurement results.

[0593] 1 H-NMR (500 MHz, tetrahydrofuran-d 8 )δ8.29(d,J HH =2.0 Hz, 2H), 7.92 (d, J HH =8.5 Hz, 2H), 7.67 (dd, J HH =8.5Hz, 2.0Hz, 2H)

[0594] (2)N 2 , N 2 , N 7 , N 7 -Synthesis of tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 3)

[0595] [Chemistry 40]

[0596]

[0597] In compound 2, a diphenylamino group was introduced by Buchwald-Hartwig coupling reaction to obtain compound 3 in a yield of 26%. Specifically, the synthesis was performed as follows.

[0598] In N 2 2,7-Dibromobenzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 2; 4.68 g, 11.8 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba) 3; 238 mg, 0.260 mmol), tri-tert-butylphosphonium tetrafluoroborate (tert-Bu 3 PHB 4 ; 281 mg, 0.968 mmol), diphenylamine (Ph 2 NH; 11.9 g, 70.5 mmol), sodium tert-butoxide (t-BuONa; 7.48 g, 77.9 mmol) were dissolved in degassed o-xylene (50 mL). The mixture was heated to 140°C and stirred for 15 hours. After adding cold water, the mixture was extracted three times with ethyl acetate. Anhydrous sodium sulfate was added to the combined organic layers, the mixture was dehydrated, and the filtrate was concentrated under reduced pressure. The concentrate (elution solvent hexane; R f =0.1) was purified by silica gel column chromatography (hexane → hexane / chloroform = 5 / 1 → hexane / chloroform = 2 / 1 → hexane / chloroform = 1 / 1 → chloroform) and concentrated under reduced pressure. Hexane (300 mL) was added to the concentrate, and the precipitated light green solid was recovered by suction filtration to obtain compound 3 as a light green solid with a yield of 26% (1.75 g, 3.04 mmol). 1 H-NMR measurement results.

[0599] 1 H-NMR (500 MHz, CDCl 8 )δ7.66(d,J HH =8.5 Hz, 2H), 7.55 (d, J HH =2.0Hz, 2H), 7.30-7.26 (m, 8H), 7.19 (dd, J HH =8.5Hz, 2.0Hz, 2H), 7.15-7.13(m, 8H), 7.06-7.03(m, 4H)

[0600] (3) Synthesis of 2,7-bis(diphenylamino)benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (organic phosphor A-3)

[0601] [Chemistry 41]

[0602]

[0603] The organic phosphor A-3 represented by the above formula (A2-4) was obtained at a yield of 33% by oxidizing the compound 3 using m-CPBA. Specifically, the synthesis was performed as follows.

[0604] Make N 2 , N 2 , N 7 , N 7-Tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 3; 1.75 g, 3.04 mmol) was dissolved in chloroform (175 mL). Meta-chloroperbenzoic acid (m-CPBA; 1.65 g, 6.70 mmol) was slowly added thereto at 0°C. The mixture was returned to room temperature and stirred for 5 hours. Saturated sodium bicarbonate was added and the mixture was extracted three times with chloroform. Anhydrous sodium sulfate was added to the combined organic layers, the mixture was dehydrated, and the filtrate was concentrated under reduced pressure. The concentrate (elution solvent: hexane / ethyl acetate = 3 / 1; R f =0.5) was purified by silica gel column chromatography (hexane → hexane / chloroform = 1 / 1 → hexane / chloroform = 1 / 2 → chloroform) and concentrated under reduced pressure. As a result, organic phosphor A-3 was obtained as an orange solid with a yield of 33% (607 mg, 1.00 mmol). 1 H-NMR measurement results.

[0605] 1 H-NMR (500 MHz, CDCl 8 )δ7.78(d,J HH =8.5 Hz, 1H), 7.44 (d, J HH =2.0Hz, 1H), 7.36-7.28(m, 9H), 7.24(dd, J HH =8.5Hz, 2.0Hz, 1H), 7.20-7.07(m, 14H)

[0606] [Synthesis Example 3] 3,9-Perylene dicarboxylic acid bis[2-(2-isobutoxyethoxy)ethyl] ester (organic phosphor A-4)

[0607] [Chemistry 42]

[0608]

[0609] Toluene (4 mL) was added to solvent Green 5 (mixture of isomers of diisobutyl perylene dicarboxylate) (1.06 g, 2.34 mmol), diethylene glycol monoisobutyl ether (0.93 g, 5.73 mmol), and titanium tetraisopropoxide (1.35 g, 4.75 mmol), and the mixture was heated to 130°C, and stirred for 2 hours while removing the distillate. After the reaction solution was cooled to room temperature, cold water was added, and the generated insoluble matter was removed by filtration, and the filtrate was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the organic layer, dehydrated, and anhydrous sodium sulfate was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 1.29 g of a mixture of 1-substituted and 2-substituted bodies. Diethylene glycol monoisobutyl ether (1.86 g, 11.5 mmol), titanium tetraisopropoxide (0.67 g, 2.37 mmol), and anisole (6 mL) were added thereto again, and the mixture was heated to 170°C, and stirred for 3 hours while removing the distillate. After the reaction solution was cooled to room temperature, cold water was added, the generated insoluble matter was removed by filtration, and the filtrate was extracted with ethyl acetate. Anhydrous sodium sulfate was added to the organic layer, dehydrated, and anhydrous sodium sulfate was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 1.48 g of a crude product. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 3 / 1), and a mixture containing compound A-4 represented by formula (A4-4) and isomers of compound A-4 was obtained as a yellow-orange solid with a yield of 62% (0.92 g, 1.46 mmol) with a production ratio of (compound A-4): (isomers of compound A-4) = 0.9:1.1 (isomers of compound A-4 are estimated to be derived from the raw material).

[0610] 1 H-NMR (500 MHz, CDCl 3 ): δ8.94-8.97(m, 0.92H), 8.85-8.88(m, 1.08H), 8.30-8.36(m, 2H), 8.21-8.28(m, 4H), 7.63-7.69(m, 2H), 4.56-4.62(m, 4H), 3.93(t, J HH =5Hz, 4H), 3.75(t, J HH =5Hz, 4H), 3.64(t, J HH =5 Hz, 4H), 3.25 (d, J HH =7Hz, 4H), 1.88(m, 2H), 0.90(d, 12H).

[0611] 〈Analysis Method〉

[0612] 1 H-NMR spectra were measured using a nuclear magnetic resonance device AVANCE III HD (manufactured by Bruker). Chemical shift values ​​were expressed in ppm, and deuterated tetrahydrofuran and deuterated chloroform were used as solvents.1 In the H-NMR spectrum, the signal of the residual proton from the solvent was used as the internal standard, and tetrahydrofuran was set to δ1.77, 3.62 ppm, or chloroform was set to δ7.26 ppm. Benzo[b]benzo[4,5]thieno[2,3-d]thiophene was purchased from BLD Pharmatech. Bromine, iodine, tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba) 3 ), diphenylamine (Ph 2 NH), sodium tert-butyl alcohol (t-BuONa), and m-chloroperbenzoic acid (m-CPBA) were purchased from Tokyo Chemical Industry Co., Ltd. Dichloromethane, methanol, tetrahydrofuran, o-xylene, chloroform, hexane, ethyl acetate, sodium thiosulfate, anhydrous sodium sulfate, and sodium bicarbonate were purchased from Junsei Chemical Co., Ltd. Tri-tert-butylphosphonium tetrafluoroborate (tert-Bu 3 PHB 4 ) was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. Thin layer chromatography (TLC) was performed using a glass plate coated with 0.25 mm silica gel 60F-254 (Merck). Silica gel chromatography was performed using silica gel 60N spherical neutral (Kanto Chemical Co., Ltd.) as a filler.

[0613] (B) Synthesis of cationic curable alkali-soluble resin

[0614] [Synthesis Example 4] Synthesis of B1-6

[0615] An acrylic polymer B1-6 solution (solid content concentration: 35 mass %) was obtained by dissolving 60.0 g of MMA, 20.0 g of MAA, 20.0 g of OXE-30 and 2.5 g of AIBN in 190.0 g of CPN and reacting at 90° C. for 20 hours. The obtained acrylic polymer B1-6 had an Mn of 6,700 and an Mw of 12,500.

[0616] [Synthesis Example 5] Synthesis of B1-7

[0617] An acrylic polymer B1-7 solution (solid content concentration: 35 mass %) was obtained by dissolving 24.1 g of MI, 25.9 g of St, 50.0 g of M100 and 3.0 g of AIBN in 191.1 g of CPN and reacting at 90° C. for 20 hours. The obtained acrylic polymer B1-7 had an Mn of 7,400 and an Mw of 12,600.

[0618] [Synthesis Example 6] Synthesis of B1-8

[0619] An acrylic polymer B1-8 solution (solid content concentration: 35 mass %) was obtained by dissolving 24.1 g of MI, 25.9 g of St, 50.0 g of OXE-30 and 3.0 g of AIBN in 191.1 g of CPN and reacting at 90° C. for 20 hours. The obtained acrylic polymer B1-8 had an Mn of 6,300 and an Mw of 11,500.

[0620] (D) Synthesis of Alkali-Soluble Resin Containing Reactive Functional Groups

[0621] [Synthesis Example 7] Synthesis of D-1

[0622] 35.3 g of CHMI, 25.5 g of HEMA, 25.7 g of MMA, 13.5 g of MAA, and 6.4 g of AIBN were dissolved in 160.0 g of PGMEA and reacted at 80° C. for 20 hours. The solution after the reaction was concentrated using a rotary evaporator to obtain an acrylic polymer D-1 solution (solid content concentration 45.2% by mass). The Mn of the obtained acrylic polymer D-1 was 4100 and the Mw was 8565.

[0623] (E) Preparation of light scattering particle dispersion

[0624] [Preparation Example 1] Preparation of Light Scattering Particle Dispersion Liquid 1 (CPN Dispersion Liquid of E-1)

[0625] In a 50mL glass vial, an acrylic polymer J-1 solution (refer to Synthesis Example 8 described later) in an amount of 50% by mass relative to the light scattering particles E-1 was added, and then CPN was added to adjust the solid content concentration to 30% by mass. Then, a zirconia ball with a diameter of 1 mm was added to the container, and a mixing rotor VMR-5R manufactured by AS ONE (strain) was used to stir for 48 hours, thereby performing ball milling to obtain a light scattering particle dispersion 1. Nanotrac UPA (manufactured by Microtrac) was used to measure the particle size distribution of the obtained dispersion. The diluent used the solvent of the dispersion, and according to the scattering generated when the diluted sample was irradiated with laser, the analytical software Microtrac DMS manufactured by Nikkiso (strain) was used to calculate the 50% cumulative diameter (D50) of the particles in the dispersion based on the volume standard, and the result was 181nm.

[0626] [Preparation Example 2] Preparation of Light Scattering Particle Dispersion Liquid 2 (OXT-221 Dispersion Liquid of E-1)

[0627] Light scattering particle dispersion 2 was prepared in the same manner as in Preparation Example 1, except that F-1 in an amount of 10% by mass was used in place of the acrylic polymer J-1 solution in an amount of 50% by mass relative to E-1 in terms of solid content ratio, and B1-4 was used in place of CPN. The particle size distribution of the obtained dispersion was measured using Nanotrac UPA (manufactured by Microtrac). CPN was used as the diluent, and the 50% cumulative diameter (D50) of the particles in the dispersion based on volume was calculated using the analysis software MicrotracDMS manufactured by Nikkiso (Strain) based on the scattering generated when the diluted sample was irradiated with laser light, and the result was 225 nm.

[0628] [Preparation Example 3] Preparation of Light Scattering Particle Dispersion Liquid 3 (VISCOAT #260 Dispersion Liquid of E-1)

[0629] After adding 143.3 g of B2-2 and 80.0 g of E-1 into a 500 mL styrene bottle, 26.7 g of F-2 diluted to 30% by mass with B2-2 was added under stirring in a disperser, and the disperser was stirred at 1000 rpm for 30 minutes to obtain a slurry. The added mass of F-2 relative to E-1 was 10% by mass.

[0630] Next, after the entire amount of the slurry was transferred to a slurry tank, a bead mill device LABSTAR Mini DMS65 manufactured by Ashizawa Finetech (Strain) was used, and in a state filled with 60% by volume of zirconia beads with a diameter of 0.2 mm, a liquid feeding rate of 40 mL / min and a disk peripheral speed of 8 m / s were used to perform 5 passes to obtain a light scattering particle dispersion 3. Nanotrac UPA (manufactured by Microtrac) was used to measure the particle size distribution of the obtained dispersion. B2-2 was used as the diluent, and the 50% cumulative diameter (D50) of the particles in the dispersion based on the volume was calculated using the analysis software MicrotracDMS manufactured by Nikkiso (Strain) based on the scattering generated when the diluted sample was irradiated with laser light, and the result was 134 nm.

[0631] (J) Synthesis of Alkali-Soluble Resin Containing No Reactive Functional Group

[0632] [Synthesis Example 8] Synthesis of J-1

[0633] An acrylic polymer J-1 solution (solid content concentration: 35 mass %) was obtained by dissolving 80.0 g of MMA, 20.0 g of MAA, and 2.5 g of AIBN in 190.0 g of CPN and reacting them at 90° C. for 20 hours. The obtained acrylic polymer J-1 had an Mn of 9,900 and an Mw of 17,078.

[0634] [Examples 1 to 34, Comparative Examples 1 to 8] Preparation and Evaluation of Compositions for Forming Wavelength Conversion Films

[0635] (1) Preparation of wavelength conversion film-forming composition

[0636] The wavelength conversion film-forming composition was prepared by mixing the components in the compositions shown in Tables 1 to 5 and filtering the obtained mixture using a polytetrafluoroethylene (PTFE) filter having a pore size of 5.0 μm. The composition ratios in Tables 1 to 5 represent mass ratios based on solid content.

[0637] [Table 1]

[0638]

[0639] [Table 2]

[0640]

[0641] [Table 3]

[0642]

[0643] [Table 4]

[0644]

[0645] [Table 5]

[0646]

[0647] (2) Evaluation 1: Conversion efficiency evaluation (absolute evaluation)

[0648] The wavelength conversion film-forming compositions of Examples 1 to 34 and Comparative Examples 1 to 8 were applied onto a quartz substrate using a spin coater and pre-baked on a hot plate at 110° C. for 120 seconds to obtain a coating sample having a film thickness of 10 μm. Then, a UV-LED exposure device (peak emission wavelength 365 nm) manufactured by CCS Corporation was used to irradiate the sample with 2000 mJ / cm 2 The samples were exposed to ultraviolet light and then post-baked once or twice under the conditions shown in Table 6 to obtain coating samples with a film thickness of 10 μm.

[0649] [Table 6]

[0650]

[0651] Next, the coating sample was placed on a blue LED lamp (peak emission wavelength 450 nm) manufactured by CCS Co., Ltd., the LED lamp was turned on, and the light emitted through the coating sample was measured using a spectroradiometer USR-45 manufactured by USHIO Electric Co., Ltd., and the result was set as (1).

[0652] Similarly, the light emitted only from the LED lamp without the coating sample is measured, and this is referred to as result (2). From the obtained spectral irradiance spectrum, the number of photons of light with a wavelength of 480 nm or less in result (2) is referred to as the "number of photons of excitation light". Similarly, the number of photons of light with a wavelength of 480 nm or less in result (1) is referred to as the "number of photons of transmitted light". Similarly, the number of photons of light with a wavelength of more than 480 nm in result (1) is referred to as the "number of photons of emitted light".

[0653] The "blue light absorption rate" and "conversion efficiency" were calculated according to the following formula.

[0654] Blue light absorption rate = (number of excitation light photons - number of transmitted light photons) ÷ number of excitation light photons Conversion efficiency = number of luminescent photons ÷ number of excitation light photons

[0655] The evaluation criteria are as follows. The obtained results are shown in Tables 8 to 12.

[0656] <Judgment Criteria>

[0657] A: Conversion efficiency is greater than 40%

[0658] B: Conversion efficiency is greater than 35% and less than 40%

[0659] C: Conversion efficiency is below 35%

[0660] (3) Light resistance evaluation (relative evaluation)

[0661] For the coating film sample produced under the same conditions as those used in (3) above, light with a wavelength of 450 nm was irradiated for 100 hours using a blue LED exposure device manufactured by CCS (Strain) in a nitrogen atmosphere in a glove box manufactured by VAC. For the coating film sample after light irradiation, the blue light absorptivity and conversion efficiency were measured in the same manner as in Evaluation 1. The value obtained by dividing the conversion efficiency after light irradiation by the conversion efficiency before light irradiation was set as the conversion efficiency "maintenance rate".

[0662] Furthermore, the conversion efficiency "maintenance rate" was evaluated relative to the comparative example as shown in Table 7. The evaluation criteria were as follows. The obtained results are shown in Tables 8 to 12.

[0663] <Judgment Criteria>

[0664] A: The conversion efficiency maintenance rate is greater than that of the comparative example.

[0665] B: The conversion efficiency maintenance rate is lower than the conversion efficiency maintenance rate of the reference comparative example

[0666] [Table 7]

[0667]

[0668] (4) Evaluation of patterning characteristics

[0669] For Examples 2 to 6, 8, 29, and 34, each composition was applied on a silicon substrate using a spin coater, and then pre-baked on a hot plate at 100° C. for 120 seconds to form a coating film with a film thickness of 11 μm. Then, the coating film was irradiated with 2 J / cm2 using an ultraviolet irradiation device PLA-600FA manufactured by Canon Co., Ltd. through an i-ray transmission filter and a photomask having a 100 μm square light transmission portion provided at 100 μm intervals. 2 The light intensity at 365 nm of the exposure is 2.9 mW / cm 2 of ultraviolet rays. Secondly, the substrate was heated on a hot plate at a temperature of 120°C for 10 minutes. After immersing the coating in a 2.38 mass % tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 120 seconds, it was washed with ultrapure water for 30 seconds. Then, it was heated on a hot plate at a temperature of 180°C for 30 minutes to obtain a coating sample with a pattern formed. For Examples 2 to 6, 8, 29, and 34, no coating was found on the substrate in the light-shielding portion during ultraviolet irradiation, the film was removed by development treatment, and the coating was maintained in the exposed portion.

[0670] [Table 8]

[0671]

[0672] [Table 9]

[0673]

[0674] [Table 10]

[0675]

[0676] [Table 11]

[0677]

[0678] [Table 12]

[0679]

[0680] As shown in Tables 8 to 12, Examples 1 to 34 satisfying the essential features of the present invention all had higher conversion efficiency maintenance rates in Evaluation 2 than Comparative Examples 1 to 8.

Claims

1. A wavelength conversion film-forming composition comprising (A) an organic phosphor, (B) a cationically curable compound, and (C) a photoacid generator.

2. The composition for forming a wavelength conversion film according to claim 1, wherein The (A) organic phosphor is at least one selected from condensed ring thiophene compounds and perylene derivatives.

3. The composition for forming a wavelength conversion film according to claim 2, wherein The perylene derivative is a perylene derivative represented by the following formula (A3), [Chemistry 1] 4. The composition for forming a wavelength conversion film according to claim 2, wherein The perylene derivative is a perylene derivative represented by the following formula (A4), [Chemistry 2] In the formula, R A and R B are each independently a group represented by the following formula (a4-1) or (a4-2), [Chemistry 3] G 1 O or NR 43 , A 1 is ethylene or propylene, n is an integer from 1 to 10, R 41 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, or a heteroarylcarbonyl group which may have a substituent, R 43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, The dotted line is the bonding end. [Chemistry 4] G 2 O or NR 43 , L 2 is a single bond or an alkylene group which may have a substituent, R 42 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, a heteroarylcarbonyl group which may have a substituent, or OR 44 , R 43 is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, R 44 is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, an alkylcarbonyl group which may have a substituent, an alkenylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, or a heteroarylcarbonyl group which may have a substituent, G 2 NR 43 And L 2 When it is a single bond, R 42 and R 43 may bond to each other to form a ring together with the nitrogen atom, L 2 When it is a single bond, R 42 Not an OR 44 , L 2 When it is an alkylene group which may have a substituent, R 42 Not a hydrogen atom, R 42 When L is an alkyl group which may have a substituent, 2 is a single bond, The dotted line is the bonding end. Among them, R is not included A and R B is a group represented by the formula (a4-2), L 2 is a single bond, and R 42 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

5. The composition for forming a wavelength conversion film according to claim 1, wherein The (B) cationic curable compound is one or more selected from a compound having an epoxy group which does not include an alkali-soluble resin, a compound having an oxetane group which does not include an alkali-soluble resin, an N-alkoxymethylol compound, and an alkali-soluble resin having at least one cationic curable functional group in a side chain.

6. The composition for forming a wavelength conversion film according to claim 1, wherein The (B) cationic curable compound is one or more selected from a compound having an epoxy group which does not include an alkali-soluble resin, a compound having an oxetane group which does not include an alkali-soluble resin, and an N-alkoxymethylol compound. The composition further contains (D) an alkali-soluble resin having a reactive functional group for reacting with the cationically curable compound in a side chain and having no cationically curable functional group.

7. The composition for forming a wavelength conversion film according to claim 6, wherein The reactive functional group is a hydroxyl group.

8. The composition for forming a wavelength conversion film according to claim 1, wherein The (C) photoacid generator is one or more selected from onium salt compounds, metallocene complex compounds, iron arene complex compounds, disulfone compounds, sulfonic acid derivative compounds, triazine compounds, acetophenone derivative compounds, and diazomethane compounds.

9. The composition for forming a wavelength conversion film according to claim 8, wherein The (C) photoacid generator is an onium salt compound. 10 . The composition for forming a wavelength conversion film according to claim 1 , further comprising (E) light scattering particles.

11. The composition for forming a wavelength conversion film according to claim 10, wherein The (E) light scattering particles are titanium oxide particles.

12. The composition for forming a wavelength conversion film according to claim 10, wherein The content of the (E) light scattering particles is 1 mass % or more in the solid content.

13. The composition for forming a wavelength conversion film according to claim 1, wherein The content of the (A) organic phosphor is 0.1 mass % or more in the solid content. The composition for forming a wavelength conversion film according to claim 1 , which is a composition for forming a wavelength conversion film for a display. 15 . A wavelength conversion film obtained from the wavelength conversion film-forming composition according to claim 1 .

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