Ring-fused thiophene compound, and composition for wavelength conversion film formation use which contains same

Abstract

A ring-fused thiophene compound represented by formula (1) is provided as a novel ring-fused thiophene compound suitable as a phosphor for a wavelength conversion film. (Ar1 and Ar2 each independently represent an aromatic ring which may have a substituent or a heteroarimatic ring which may have a substituent; R1 to R4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or the like; a case where all of R1 to R4 simultaneously represent hydrogen atoms is excluded; R1 and R2 may be bound to each other to form a ring in conjunction with a nitrogen atom adjacent thereto; R3 and R4 may be bound to each other to form a ring in conjunction with a nitrogen atom adjacent thereto; one or both of R1 and R2 may be bound to Ar1 to form a ring in conjunction with a nitrogen atom adjacent thereto; one or both of R3 and R4 may be bound to Ar2 to form a ring in conjunction with a nitrogen atom adjacent thereto; and one of Y1 and Y2 represents -SO2- and the other represents -S- or -SO2-.)

Description

Fused thiophene compound and wavelength conversion film-forming composition containing the same

[0001] The present invention relates to a fused ring thiophene compound and a composition for forming a wavelength conversion film containing the same.

[0002] Micro LED displays are expected to be the next generation display following LCDs and OLED displays, as they offer high contrast and brightness, and have a wide range of applications, including large screens and transparent displays. Micro LED displays typically have a tiny LED chip placed in each pixel. While the RGB-LED method, which uses three color LEDs, presents challenges with this method, including the complexity of LED light emission control and the low performance of the red LED. Wavelength conversion methods, which can solve these challenges, are gaining attention. Wavelength conversion methods use only blue LED chips, extracting red and green light using wavelength conversion materials, offering the advantage of being able to produce the three primary colors using only blue LED chips.

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

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

[0005] However, with the recent development of display technology, wavelength conversion film-forming compositions are being required to further improve the wavelength conversion efficiency and durability of wavelength converting materials in order to improve display performance.

[0006] Furthermore, Patent Document 11 discloses a fused thiophene compound having a specific structure, which is a fluorescent dye for staining intracellular lipid droplets. The fused thiophene compound has excellent light resistance and has maximum absorption and fluorescence wavelengths in the visible light region, and is therefore expected to be used as a wavelength conversion material, but there is room for further improvement in conversion efficiency.

[0007] JP 2002-348568 A JP 2007-273440 A JP 2002-317175 A JP 2001-164245 A JP 2011-241160 A JP 2014-136771 A JP 2006-89724 A JP 2011-149028 A International Publication No. 2020 / 189678 International Publication No. 2019 / 181698 JP 2018-145422 A

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel ring-fused thiophene compound suitable as a phosphor for a wavelength conversion film, and a composition for forming a wavelength conversion film, which contains the ring-fused thiophene compound and gives a wavelength conversion film having excellent wavelength conversion efficiency and durability.

[0009] As a result of intensive investigations to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by including a novel ring-fused thiophene compound as the phosphor in a composition for forming a wavelength conversion film containing a phosphor and a binder, and have completed the present invention.

[0010] That is, the present invention provides the following fused thiophene compound and a composition for forming a wavelength conversion film containing the same: 1. A fused thiophene compound represented by the following formula (1): (In the formula, Ar 1 and Ar 2 are each independently an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, 1 ~R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and R 1 ~R 4 All of R cannot be hydrogen atoms at the same time. 1 and R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 1 and R 2 Either one or both of 1 may bond to form a ring together with the adjacent nitrogen atom, and R 3 and R 4 Either one or both of 2 may be bonded to form a ring together with the adjacent nitrogen atom, 1 and Y 2 is -SO2-, and the other is -S- or -SO2-.) 2. The above Y 1 and Y 2 is a fused ring thiophene compound of 1, in which one ring is —SO— and the other is —S—. 3. The above Ar 1 and Ar 2is an aromatic ring optionally having a substituent or a heteroaromatic ring optionally having a substituent. 1 ~R 4 is an aryl group optionally having a substituent. 5. A composition for forming a wavelength conversion film, comprising (A) a phosphor consisting of the fused thiophene compound according to any one of (1) to (4) above, and (B) a binder. 6. The composition for forming a wavelength conversion film of (5), further comprising (C) light-scattering particles. 7. The composition for forming a wavelength conversion film of (6), wherein the (C) light-scattering particles are titanium oxide particles. 8. The composition for forming a wavelength conversion film of any one of (5) to (7), wherein the (B) binder comprises a resin. 9. The composition for forming a wavelength conversion film of any one of (5) to (7), wherein the (B) binder comprises a polymerizable monomer and a photopolymerization initiator. 10. The composition for forming a wavelength conversion film of any one of (5) to (7), wherein the (B) binder comprises an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator. 11. The composition for forming a wavelength conversion film of any one of (5) to (10), wherein the content of the (A) phosphor is 0.1 mass % or more of the solid content. 12. 12. The composition for forming a wavelength-converting film of any one of 6 to 11, wherein the content of the (C) light-scattering particles is 1 mass % or more based on the solid content. 13. The composition for forming a wavelength-converting film of any one of 5 to 12, wherein the haze value of a film formed from the composition is 18% or more.

[0011] According to the present invention, a novel ring-fused thiophene compound suitable as a phosphor for a wavelength conversion film can be provided, and a composition for forming a wavelength conversion film can be provided that gives a wavelength conversion film having excellent wavelength conversion efficiency and durability by using the ring-fused thiophene compound.

[0012] The present invention will be described in more detail below. The fused thiophene compound of the present invention is a fused thiophene compound represented by the following formula (1).

[0013]

[0014] In the formula, Ar 1 and Ar 2 are each independently an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, and R 1~R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and R 1 ~R 4 All of R cannot be hydrogen atoms at the same time. 1 and R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 1 and R 2 Either one or both of 1 may bond to form a ring together with the adjacent nitrogen atom, and R 3 and R 4 Either one or both of 2 may bond to the adjacent nitrogen atom to form a ring, and Y 1 and Y 2 is -SO2- on the one hand and -S- or -SO2- on the other hand.

[0015] Ar 1 and Ar 2 Examples of the aromatic ring represented by the formula (I) include a benzene ring as a monocyclic aromatic hydrocarbon ring, and a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a pyrene ring, and a triphenylene ring as a polycyclic aromatic hydrocarbon ring.

[0016] Ar 1 and Ar 2 The aromatic ring represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a heteroaryl group, a cyano group, and a nitro group, which will be described later. When the aromatic ring has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0017] Ar 1 and Ar 2Examples of the heteroaromatic ring represented by the formula (I) include a pyrrole ring, a thiophene ring, a furan ring, an imidazole ring, a pyrazole ring, a thiazole ring, an oxazole ring, a pyridine ring, and a pyrazine ring as monocyclic heteroaromatic rings, and examples of the polycyclic heteroaromatic rings include an indole ring, an isoindole ring, a benzimidazole ring, a quinoline ring, an isoquinoline ring, and a quinoxaline ring.

[0018] Ar 1 and Ar 2 The heteroaromatic ring represented by the formula (I) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a heteroaryl group, a cyano group, and a nitro group, which will be described later. When the heteroaromatic ring has a substituent, the number of the substituents is, for example, preferably 1 to 6, and more preferably 1 to 3.

[0019] Among them, Ar 1 and Ar 2 From the viewpoint of increasing the maximum absorption wavelength and maximum fluorescence wavelength and further improving light resistance, the aromatic ring is preferably a substituted or unsubstituted aromatic ring, and more preferably a substituted or unsubstituted monocyclic aromatic hydrocarbon ring.

[0020] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0021] The alkyl group may be either linear or branched, and specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and an alkyl group having 1 to 6 carbon atoms is preferred.

[0022] The alkyl group may have a substituent. Examples of the substituent include the halogen atoms described above, the cycloalkyl group described below, the aryl group described below, the heteroaryl group described below, a cyano group, and a nitro group. When the alkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0023] Examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups, and cycloalkyl groups having 4 to 8 carbon atoms are preferred.

[0024] The cycloalkyl group may have a substituent. Examples of the substituent include the halogen atoms, the alkyl groups, the aryl groups described below, the heteroaryl groups described below, a cyano group, and a nitro group. When the cycloalkyl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0025] Examples of the halogenated alkyl group include a trifluoromethyl group and a pentafluoroethyl group.

[0026] The aryl group may be any of a monocyclic aryl group, a fused ring aryl group, and a polycyclic aryl group. Specific examples of the monocyclic aryl group include a phenyl group; specific examples of the fused ring aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, and a triphenylenyl group; and specific examples of the polycyclic aryl group include aryl groups having 6 to 18 carbon atoms such as a biphenyl group and a terphenyl group, with an aryl group having 6 to 14 carbon atoms being preferred.

[0027] The aryl group may have a substituent. Examples of the substituent include the halogen atoms, alkyl groups, aryl groups, heteroaryl groups described below, cyano groups, and nitro groups. When the aryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0028] The heteroaryl group may be either a monocyclic heteroaryl group or a fused-ring heteroaryl group. Examples of the monocyclic heteroaryl group include a pyrrolyl group, a thienyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an oxazolyl group, a pyridyl group, and a pyrazyl group. Examples of the fused-ring heteroaryl group include an indolyl group, an isoindolyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, and a quinoxalyl group.

[0029] The heteroaryl group may have a substituent. Examples of the substituent include the halogen atom, the alkyl group, the aryl group, the heteroaryl group, a cyano group, and a nitro group. When the heteroaryl group has a substituent, the number of the substituents is preferably 1 to 6, and more preferably 1 to 3.

[0030] Among them, R 1 and R 2 As the aryl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group is preferable, a substituted or unsubstituted aryl group is more preferable, and an unsubstituted aryl group is even more preferable.

[0031] The above R 1 and R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom. 1 and R 2 However, examples of the ring formed by bonding together with the adjacent nitrogen atoms include the following groups.

[0032]

[0033] In addition, the above R 1 and R 2 is R 1 and R 2 Either one or both of 1 may be bonded to form a ring together with the adjacent nitrogen atom. 1 and R 2 Either one or both of 1 Examples of the ring formed by bonding with the adjacent nitrogen atom include the following groups:

[0034]

[0035] Also, R 3 and R 4 As the aryl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group is preferable, a substituted or unsubstituted aryl group is more preferable, and an unsubstituted aryl group is even more preferable.

[0036] The above R 3 and R 4may be bonded to each other to form a ring together with the adjacent nitrogen atom. 3 and R 4 However, examples of the ring formed by bonding together with the adjacent nitrogen atoms include, for example, R 1 and R 2 Specific examples of the ring formed by bonding together with the adjacent nitrogen atoms include the groups shown above.

[0037] In addition, the above R 3 and R 4 is R 3 and R 4 Either one or both of 2 may be bonded to form a ring together with the adjacent nitrogen atom. 3 and R 4 Either one or both of 2 Examples of the ring formed by bonding with the adjacent nitrogen atom include, for example, R 1 and R 2 Either one or both of 1 and bonded to the adjacent nitrogen atom to form a ring.

[0038] In the compound represented by the above formula (1), -NR 1 R 2 Ar of a group represented by 1 and -NR 3 R 4 Ar of a group represented by 2 The bonding position to Ar is not particularly limited. 1 and Ar 2 is a benzene ring, the compound represented by the following formula (1') is likely to be formed.

[0039]

[0040] In the formula, Y 1 and Y 2 is the same as above. 1 ~R 4are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and R 1 ~R 4 All of R cannot be hydrogen atoms at the same time. 1 and R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 1 and R 2 may be bonded to the adjacent benzene ring to form a ring together with the adjacent nitrogen atom, and R 3 and R 4 Either one or both of may be bonded to the adjacent benzene ring to form a ring together with the adjacent nitrogen atom.

[0041] In the above formula (1), Y 1 and Y 2 is -SO2- on the one hand and -S- or -SO2- on the other hand. 1 and Y 2 In consideration of the wavelength conversion efficiency of the wavelength conversion film to be obtained, it is preferable that one of the groups is —SO— and the other is —S—. 1 and Y 2 When the compound represented by the formula (1) is used as a red light emitting material, Y 1 and Y 2 are both preferably —SO2—.

[0042] As a fused thiophene compound that satisfies the above conditions, a compound represented by the following formula (1-1) is preferred.

[0043] (In the formula, Ar 1 , Ar 2 , R 1 ~R 4 , Y 1and Y 2 is the same as above.)

[0044] Furthermore, compounds represented by the following formulae (1-1A) and (1-2A) are more preferred.

[0045] (In the formula, Ar 1 and Ar 2 is the same as above. 1a ~R 4a are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group.

[0046] Preferred specific examples of the compound represented by the above formula (1) include compounds represented by the following formulae (1-1B) and (1-2B).

[0047]

[0048] Furthermore, the fused thiophene compound represented by formula (1) may exist as a solvate, and both of these solvates are encompassed within the scope of the present invention. The solvate is not particularly limited as long as it is a solvate of the fused thiophene compound represented by formula (1) and a solvent. Examples of solvents that may form solvates include dichloromethane, chloroform, acetonitrile, diethyl ether, ethyl acetate, methanol, ethanol, cyclohexane, toluene, acetone, N,N-dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran.

[0049] The compound represented by the above formula (1) not only has excellent light resistance but also has excellent conversion efficiency, and is suitable as a wavelength conversion material for display applications as a phosphor.

[0050] The compound represented by the above formula (1) can be synthesized by referring to a known method, for example, by the same procedure as the method described in paragraph

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

[0051] The composition for forming a wavelength conversion film of the present invention is characterized by containing (A) a phosphor composed of a fused thiophene compound represented by the above formula (1) and (B) a binder. In the following description, the solid content means components other than the solvent that constitute the composition for forming a wavelength conversion film.

[0052] The content of the phosphor of the component (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the solid content, in consideration of the wavelength conversion efficiency of the wavelength conversion film obtained. On the other hand, the upper limit of the content of the phosphor of the component (A) is not particularly limited, but in consideration of the decrease in fluorescence quantum yield when the phosphor is highly concentrated, the content is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, and even more preferably 5% by mass or less, based on the solid content.

[0053] Furthermore, the composition for forming a wavelength conversion film of the present invention may contain, as a phosphor, a phosphor other than the fused thiophene compound represented by the above formula (1), as long as the effects of the present invention are not impaired. Examples of the other phosphors include cyanine dyes such as 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; pyridine dyes such as 1-ethyl-2-[4-(p-dimethylaminophenyl)-1,3-butadienyl]-pyridium-perchlorate; rhodamine dyes such as rhodamine B and rhodamine 6G; red-converting phosphors such as oxazine dyes; coumarin dyes 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-converting phosphors such as naphthalimide dyes such as Solvent Yellow 11 and Solvent Yellow 116. Further, examples include red-converting phosphors or green-converting phosphors such as fused ring thiophene compounds described in JP 2018-145422 A.

[0054] When other phosphors are contained, the content thereof is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably no phosphor is contained (0% by mass) in the solid content.

[0055] The binder (B) may be selected from known resins used as binders in compositions for forming wavelength conversion films.

[0056] The resin can be appropriately selected from resins used as base resins in wavelength-converting film-forming compositions. Examples include polyolefin resins such as polystyrene (PS), polyethylene (PE), polypropylene (PP), polyester, polyimide, polyamide, and polymethylpentene; acrylic resins such as polymethyl methacrylate (PMMA), methyl methacrylate-methacrylic acid copolymer, and benzyl methacrylate-methacrylic acid copolymer; ethylene-vinyl acetate copolymer (EVA); polyvinyl butyrate (PVB); and cellulose ester resins such as triacetyl cellulose (TAC) and nitrocellulose. The resin may be an alkali-soluble resin, as described below, or may contain both an alkali-soluble resin and another resin. Among these, acrylic resins are preferred, and methyl methacrylate-methacrylic acid copolymers are more preferred. Each of the resins above may be a commercially available product, or those obtained by the reaction of unsaturated double bond groups may be synthesized according to a conventional method, such as radical polymerization using a polymerization initiator.

[0057] The average molecular weight of the resin is not particularly limited, but the weight average molecular weight (Mw) is usually 5,000 to 100,000, and preferably 10,000 to 50,000. In the present invention, the average molecular weight is a polystyrene-equivalent value determined by gel permeation chromatography.

[0058] The binder (B) may be a mixture of a polymerizable monomer and a photopolymerization initiator, which are polymerized after film formation. These may also be used in combination with the resin described above. The polymerizable monomer is not particularly limited as long as it is used together with a photopolymerization initiator and polymerizes upon irradiation with light, but an ethylenically unsaturated monomer is preferred. In the present invention, the ethylenically unsaturated monomer may be any of a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher functional monomer.

[0059] Examples of the monofunctional monomer include a mono(meth)acrylate represented by the following formula (M1), a mono(meth)acrylamide compound represented by the following formula (M2), and an amide compound represented by the following formula (M3).

[0060]

[0061] In formula (M1), R m1 represents a hydrogen atom or a methyl group, and R m2 represents a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The hydrocarbon group may be linear, branched, or cyclic. From the viewpoints of excellent ejection stability in the inkjet method and an excellent effect of improving external quantum efficiency, the R m2 The number of carbon atoms is preferably not more than 10. The hydrocarbon group may be substituted, for example, may have an ether bond.

[0062] In formula (M2), R m1 is the same as above. m3 and R m4 are each independently a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The hydrocarbon group may be linear, branched, or cyclic. m3 and R m4 may be bonded to each other to form a ring. In view of excellent ejection stability in the ink jet method and an excellent effect of improving external quantum efficiency, m3 and R m4 The total number of carbon atoms is preferably not more than 10. The hydrocarbon group may be substituted, for example, may have an ether bond.

[0063] In formula (M3), R m5 represents a hydrogen atom or a methyl group, and R m6 represents a monovalent hydrocarbon group having an ethylenically unsaturated group. The hydrocarbon group may be linear, branched, or cyclic. From the viewpoints of excellent ejection stability in the ink-jet method and an excellent effect of improving external quantum efficiency, the Rm6 The number of carbon atoms is preferably not more than 10. The hydrocarbon group may be substituted, for example, may have an ether bond.

[0064] Specific examples of the mono(meth)acrylate represented by the formula (M1) include methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, amyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, nonyl(meth)acrylate, dodecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, cyclohexyl(meth)acrylate, methoxyethyl(meth)acrylate, butoxyethyl(meth)acrylate, phenoxyethyl(meth)acrylate, nonylphenoxyethyl(meth)acrylate, glycidyl(meth)acrylate, and dimethylaminoethyl(meth)acrylate. acrylate, diethylaminoethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, and the like.

[0065] Specific examples of the mono(meth)acrylamide compound represented by the formula (M2) above include 4-(meth)acryloylmorpholine, (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, and N,N-diisopropyl(meth)acrylamide.

[0066] Specific examples of the amide compound represented by the formula (M3) include N-vinylformamide, N-vinylacetamide, N-allylformamide, and N-allylacetamide.

[0067] In the present invention, among the above-mentioned monofunctional monomers, ethoxyethoxyethyl (meth)acrylate, N-vinylformamide, 4-(meth)acryloylmorpholine, N,N-dimethylacrylamide, and N,N-diethyl(meth)acrylamide are preferably used.

[0068] From the viewpoint of easily improving the ejection stability in the inkjet method, the monofunctional monomer preferably has a viscosity of 10,000 mPa·s or less, more preferably 8,000 mPa·s or less, even more preferably 5,000 mPa·s or less, and even more preferably 1,000 mPa·s or less. In this specification, the viscosity of a monomer having an ethylenically unsaturated group, such as a monofunctional monomer, is the viscosity at 25°C measured, for example, with an EMS viscometer. However, when a mixture of multiple monomers is used, a monomer with a high viscosity can be suitably used by combining it with a monomer with a low viscosity. Furthermore, when a solvent is added, a monomer with a high viscosity can also be suitably used.

[0069] Examples of the bifunctional monomer include a di(meth)acrylate represented by the following formula (M4) and a di(meth)acrylamide compound represented by the following formula (M5).

[0070]

[0071] In formula (M4), a plurality of R m7 each independently represents a hydrogen atom or a methyl group, R m8 represents a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The divalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less. The divalent hydrocarbon group may be substituted, and may have, for example, an ether bond.

[0072] In formula (M5), a plurality of R m9 each independently represents a hydrogen atom or a methyl group, and a plurality of R m10 are each independently a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The monovalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoints of excellent ejection stability in the inkjet method and an excellent effect of improving external quantum efficiency, the R m10 The number of carbon atoms in R is preferably 7 or less. The monovalent hydrocarbon group may be substituted, for example, may have an ether bond. m11 represents a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The divalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less. The divalent hydrocarbon group may be substituted, and may have, for example, an ether bond.

[0073] Specific examples of the di(meth)acrylate represented by the formula (M4) include 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, (Meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, di(meth)acrylate in which two hydroxyl groups of tris(2-hydroxyethyl)isocyanurate are substituted with (meth)acryloyloxy groups, di(meth)acrylate in which two hydroxyl groups of a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol are substituted with (meth)acryloyloxy groups, bisphenol A Examples of such a di(meth)acrylate include a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, and two hydroxyl groups of the diol are substituted with (meth)acryloyloxy groups; a triol obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, and two hydroxyl groups of the triol are substituted with (meth)acryloyloxy groups; and a di(meth)acrylate obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of bisphenol A, and two hydroxyl groups of the diol are substituted with (meth)acryloyloxy groups.

[0074] Specific examples of the di(meth)acrylamide compound represented by formula (M5) include N,N-[oxybis(2,1-ethanediyloxy-3,1-propanediyl)]bisacrylamide, etc. Commercially available di(meth)acrylamide compounds may be used, and specific examples thereof include FOM-03008 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

[0075] In the present invention, among the above-mentioned bifunctional monomers, dipropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate are preferably used.

[0076] As the bifunctional monomer, from the viewpoint of easily improving the ejection stability in the inkjet method, it is preferable that the bifunctional monomer has a viscosity of preferably 10,000 mPa·s or less, more preferably 8,000 mPa·s or less, even more preferably 5,000 mPa·s or less, and even more preferably 1,000 mPa·s or less. The above viscosity is the viscosity at 25°C. However, when a mixture of multiple monomers is used, a high-viscosity monomer can be suitably used by combining it with a low-viscosity monomer. Furthermore, when used with the addition of a solvent, a high-viscosity monomer can also be suitably used.

[0077] Examples of tri- or higher functional monomers include tri(meth)acrylates, tetra(meth)acrylates, and penta(meth)acrylates represented by the following formula (M6), and tri(meth)acrylamide compounds and tetra(meth)acrylamide compounds represented by the following formula (M7).

[0078]

[0079] In formula (M6), a plurality of R m12 each independently represents a hydrogen atom or a methyl group, R m13represents a trivalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The trivalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the number of carbon atoms in the hydrocarbon group is preferably 10 or less, more preferably 5 or less. The trivalent hydrocarbon group may be substituted, and may have, for example, an ether bond.

[0080] In formula (M7), a plurality of R m14 each independently represents a hydrogen atom or a methyl group, and a plurality of R m15 are each independently a hydrogen atom or a monovalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The monovalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoints of excellent ejection stability in the inkjet method and an excellent effect of improving external quantum efficiency, the R m15 The number of carbon atoms in R is preferably 7 or less. The monovalent hydrocarbon group may be substituted, for example, may have an ether bond. m16 are each independently a divalent hydrocarbon group (excluding those containing an ethylenically unsaturated group). The divalent hydrocarbon group may be linear, branched, or cyclic. From the viewpoint of excellent ejection stability and an excellent effect of improving external quantum efficiency, the number of carbon atoms in the divalent hydrocarbon group is preferably 10 or less. The divalent hydrocarbon group may be substituted, and may have, for example, an ether bond.

[0081] Specific examples of the tri(meth)acrylate represented by the formula (M6) include glycerin tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate.

[0082] Specific examples of the tetra(meth)acrylate include pentaerythritol tetraacrylate and ditrimethylolpropane tetraacrylate.

[0083] Specific examples of the penta(meth)acrylate include dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

[0084] Specific examples of the tri(meth)acrylamide compound represented by formula (M7) include N,N-bis(2-acrylamidoethyl)acrylamide, etc. Commercially available products may be used as the tri(meth)acrylamide compound, and specific examples thereof include FOM-03007 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0085] Specific examples of the tetra(meth)acrylamide compound include N-[tris(3-acrylamidopropoxymethyl)methyl]acrylamide, N,N-1,2-ethanediylbis{N-[2-(acryloylamino)ethyl]acrylamide}, etc. Commercially available tetra(meth)acrylamide compounds may be used, and specific examples thereof include FOM-03006 and FOM-03009 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0086] In the present invention, among the above-mentioned trifunctional or higher functional monomers, glycerin tri(meth)acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferably used.

[0087] The trifunctional monomer preferably has a viscosity of 10,000 mPa·s or less, more preferably 8,000 mPa·s or less, even more preferably 5,000 mPa·s or less, and even more preferably 1,000 mPa·s or less, in order to easily improve the ejection stability in the inkjet method. The above viscosity is measured at 25°C. However, when a mixture of multiple monomers is used, a high-viscosity monomer can be suitably used by combining it with a low-viscosity monomer. Furthermore, when a solvent is added, a high-viscosity monomer can also be suitably used.

[0088] As the photopolymerization initiator, a photoradical polymerization initiator, a photocationic polymerization initiator, etc. can be used. In consideration of compatibility with general production methods for wavelength conversion members, it is preferable to use a photoradical polymerizable compound. On the other hand, in terms of being able to form a cured film (a cured product of the wavelength conversion film-forming composition) without being inhibited by oxygen in the curing process, it is preferable to use a photocationic polymerizable compound.

[0089] As the photoradical polymerization initiator, a molecular cleavage type or hydrogen abstraction type photoradical polymerization initiator is preferably used.

[0090] Examples of molecular cleavage type photoradical polymerization initiators include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide. Other molecular cleavage type photoradical polymerization initiators that may be used in combination include, for example, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

[0091] Examples of the hydrogen abstraction type photoradical polymerization initiator include benzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4'-methyl-diphenyl sulfide. A molecular cleavage type photoradical polymerization initiator and a hydrogen abstraction type photoradical polymerization initiator may be used in combination.

[0092] The photoradical polymerization initiator can also be obtained as a commercially available product. Examples of such commercially available products include acylphosphine oxide compounds such as Omnirad (registered trademark; the same applies hereinafter) TPO-H, Omnirad TPO-L, and Omnirad 819 manufactured by IGM Resin; alkylphenone compounds such as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG; intramolecular hydrogen abstraction compounds such as Omnirad MBF and Omnirad 754; and Irgacure (registered trademark; the same applies hereinafter) manufactured by BASF Japan Ltd. OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, TR-PBG-304 and TR-PBG-305 manufactured by Changzhou Strong Electronic New Materials Co., Ltd., and NCI-831 and NCI-930 manufactured by ADEKA Corporation.

[0093] In addition to these, the oxime ester compounds include oxime ester compounds such as those described in JP-T-2004-534797, JP-A-2000-80068, WO 2012 / 45736, WO 2015 / 36910, JP-A-2006-36750, JP-A-2008-179611, WO 2009 / 131189, WO 2012-526185, WO 2012-519191, WO 2006 / 18973, WO 2008 / 78678, and WO 2011-132215.

[0094] When a photoradical polymerization initiator is used as the photopolymerization initiator, a chain transfer agent may be used in combination. By using a chain transfer agent, the reaction rate of the photoradical reaction can be increased.

[0095] Chain transfer agents are defined on pages 683-684 of the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005). Examples of chain transfer agents include compounds having SH, PH, SiH, and GeH groups in the molecule. These donate hydrogen to low-activity radical species to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds (e.g., 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) are particularly preferred, with polyfunctional thiol compounds being particularly preferred. Polyfunctional thiols may be compounds having two or more thiol (SH) groups. Examples of polyfunctional thiol compounds include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate (PETP), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), Karenz (registered trademark, the same applies hereinafter) MT BD1, Karenz MT PE1, Karenz MT NR1 (all manufactured by Showa Denko K.K.), and the like.

[0096] Examples of the photocationic polymerization initiator include polyarylsulfonium salts such as triphenylsulfonium hexafluoroantimonate and triphenylsulfonium hexafluorophosphate; and polyaryliodonium salts such as diphenyliodonium hexafluoroantimonate and p-nonylphenyliodonium hexafluoroantimonate.

[0097] The cationic photopolymerization initiator can also be obtained as a commercially available product. Examples of such commercially available products include sulfonium salt-based cationic photopolymerization initiators such as CPI-100P manufactured by San-Apro Co., Ltd., Omnicat (registered trademark; the same applies hereinafter) 270 manufactured by IGM Resin, and Irgacure 290 manufactured by BASF Japan; and iodonium salt-based cationic photopolymerization initiators such as Omnicat 250 manufactured by IGM Resin.

[0098] The content of the photopolymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to 100% by mass of the polymerizable monomer, from the viewpoint of the curability of the composition. The upper limit of the content is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of film-forming property and the transparency, heat resistance, and light resistance of the cured film.

[0099] When the polymerizable monomer and the photopolymerization initiator are blended, an alkali-soluble resin may be further blended in. By blending an alkali-soluble resin in the composition for forming a wavelength conversion film of the present invention, it becomes possible to use it as a composition for forming a resist film.

[0100] In the present invention, the alkali-soluble resin is a resin having an alkali-soluble group, specific examples of which include a phenolic hydroxy group, a carboxy group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid group, a boronic acid group, and an active methylene group.

[0101] An active methylene group refers to a methylene group (-CH2-) that has a carbonyl group adjacent to it and is reactive with nucleophilic reagents.

[0102] The active methylene group is more preferably a group represented by the following formula (b1).

[0103] (In the formula, R b represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.

[0104] In the above formula (b1), R bExamples of the alkyl group represented by include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferred. Specific examples of such alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups. Of these, methyl, ethyl, and n-propyl groups are preferred.

[0105] In the above formula (b1), R b Examples of the alkoxy group represented by include alkoxy groups having 1 to 20 carbon atoms, and preferably alkoxy groups having 1 to 5 carbon atoms. Specific examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, and t-butoxy groups. Of these, methoxy, ethoxy, and n-propoxy groups are preferred.

[0106] Specific examples of the group represented by formula (b1) include, but are not limited to, groups represented by the following formulae (b1-1) to (b1-5): In the structural formula, dashed lines represent bonds.

[0107]

[0108] Among the above alkali-soluble groups, alkali-soluble resins having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxy group and having a number average molecular weight of 2,000 to 50,000 are preferred.

[0109] As described above, the alkali-soluble resin preferably has a number-average molecular weight in the range of 2,000 to 50,000, but if the number-average molecular weight is 50,000 or less, development residues are less likely to be generated and the required sensitivity can be obtained, while if the number-average molecular weight is 2,000 or more, film loss in exposed areas is less likely to occur during development and sufficient curability can be obtained.

[0110] The alkali-soluble resin may have the above structure, and there are no particular limitations on the types of main chain skeleton and side chains of the polymer constituting the resin.

[0111] Examples of the alkali-soluble resin include acrylic resins, polyhydroxystyrene resins, polyimide precursors, polyimides, and polyesters.

[0112] In the present invention, an alkali-soluble resin made of a copolymer obtained by polymerizing a plurality of types of monomers can also be used. Furthermore, the alkali-soluble resin may be a blend of a plurality of types of alkali-soluble resins.

[0113] The alkali-soluble resin may be an acrylic polymer, which is an acrylic resin. In the present invention, the term "acrylic polymer" refers to a resin obtained by the polymerization reaction of a monomer having an unsaturated double bond group, resulting in the reaction of the unsaturated double bond group portion. Examples of alkali-soluble acrylic polymers include copolymers formed from monomers exhibiting alkali solubility, i.e., monomers having at least one alkali-soluble group selected from the above-mentioned group, and at least one monomer selected from the group of monomers copolymerizable with these monomers, as essential structural units. The number-average molecular weight of the alkali-soluble resin is preferably 2,000 to 50,000. A number-average molecular weight of 50,000 or less reduces the likelihood of residue formation.

[0114] The above-mentioned "monomer having at least one selected from alkali-soluble groups" includes a monomer having a carboxy group, a phenolic hydroxy group, and a monomer having an imide group. These monomers are not limited to those having one carboxy group or one phenolic hydroxy group, but may also have multiple carboxy groups or one phenolic hydroxy group.

[0115] Specific examples of the above-mentioned monomers are listed below, but are not limited to these. Examples of monomers having a carboxy 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.

[0116] Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenyl methacrylate.

[0117] Examples of the monomer having an imide group include maleimide.

[0118] In the production of the alkali-soluble acrylic polymer, the ratio of the monomer having an alkali-soluble group and an unsaturated double bond group to all the monomers used in the production of the alkali-soluble acrylic polymer is preferably 5 to 90 mol %, more preferably 10 to 60 mol %, and most preferably 10 to 40 mol %. When 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.

[0119] The alkali-soluble acrylic polymer may be copolymerized with a monomer having a hydroxyalkyl group and an unsaturated double bond group in order to further stabilize the pattern shape after curing.

[0120] 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, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

[0121] In the production of the alkali-soluble acrylic polymer, the ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass. When the ratio of the monomer having a hydroxyalkyl group and an unsaturated double bond group is 10% by mass or more, the effect of stabilizing the pattern shape of the copolymer is obtained. When this ratio is 60% by mass or less, the content of the alkali-soluble group falls within an appropriate range, and sufficient properties such as developability are obtained.

[0122] The alkali-soluble acrylic polymer may be further copolymerized with an N-substituted maleimide compound in order to increase the Tg of the copolymer.

[0123] Specific examples of the N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. From the viewpoint of transparency, those not having an aromatic ring are preferred, and from the viewpoints of developability, transparency, and heat resistance, those having an alicyclic skeleton are more preferred, with cyclohexylmaleimide being even more preferred.

[0124] The ratio of N-substituted maleimide in the production of the alkali-soluble acrylic polymer is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 40% by mass. When the ratio of N-substituted maleimide is 10% by mass or more, the Tg of the copolymer becomes high, and therefore the Tg of the finally obtained wavelength conversion film also becomes high, and sufficient heat resistance and light resistance are obtained. When the ratio is 60% by mass or less, sufficient transparency is obtained.

[0125] In the present invention, the alkali-soluble acrylic polymer may also be a copolymer containing a monomer other than the above-mentioned monomers (hereinafter referred to as "other monomers") as a constituent unit. Specifically, the other monomer may be any monomer copolymerizable with at least one selected from the group consisting of the above-mentioned monomers having a carboxy group and the monomers having a phenolic hydroxy group, and is not particularly limited as long as it does not impair the properties of the alkali-soluble acrylic polymer. Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds. Specific examples of the other monomers are listed below, but are not limited to these.

[0126] Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, and methoxytriethylene glycol acrylate. 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-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, and the like.

[0127] Specific examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, and methoxytriethylene glycol methacrylate. Examples of the methacrylate include 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, and poly(ethylene glycol) ethyl ether methacrylate.

[0128] 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.

[0129] 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-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0130] The styrene compound may be a styrene having no hydroxy group, specific examples of which include styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

[0131] 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 even more preferably 20% by mass or less. When the ratio of the other monomers is 80% by mass or less, the effects of the present invention can be sufficiently obtained.

[0132] The method for obtaining the alkali-soluble acrylic polymer is not particularly limited, but can be, for example, by polymerizing a monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a group that generates a carboxylic acid upon the action of heat or acid, and a phenolic hydroxyl group upon the action of heat or acid; a monomer having a hydroxyalkyl group; and, optionally, a monomer having at least one group selected from a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, or a blocked isocyanate group, and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, or a blocked isocyanate group, at a temperature of 50 to 110°C in a solvent containing, optionally, other copolymerizable monomers; and, optionally, a polymerization initiator. The solvent used in this process is not particularly limited, as long as it dissolves the monomers that constitute the alkali-soluble acrylic polymer and the alkali-soluble acrylic polymer. Specific examples include the following solvents.

[0133] 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, and 3-methyl-2-pentanone. Examples of suitable solvents include ethanol, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, and butyl lactate are preferred from the viewpoints of good film-forming properties and high safety. These may be used alone or in combination of two or more.

[0134] The alkali-soluble acrylic polymer thus obtained is usually in the form of a solution dissolved in a solvent.

[0135] Furthermore, the solution of the specific copolymer obtained as described above can be reprecipitated by adding diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a powder of the specific copolymer. This procedure can remove polymerization initiators and unreacted monomers coexisting with the specific copolymer, resulting in a purified powder of the specific copolymer. If the specific copolymer cannot be sufficiently purified in a single procedure, the obtained powder can be redissolved in a solvent and the above procedure can be repeated. In the present invention, the powder of the specific copolymer may be used as is, or the powder may be redissolved in an appropriate solvent, such as the solvent used in the polymerization reaction, and used in the form of a solution.

[0136] In addition, as the alkali-soluble resin, polyimide precursors such as polyamic acid, polyamic acid ester, and partially imidized polyamic acid, and polyimides such as carboxylic acid group-containing polyimides can also be used, and the type of these resins is not particularly limited as long as they are alkali-soluble.

[0137] The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensation of (a) a tetracarboxylic dianhydride and (b) a diamine compound.

[0138] The (a) tetracarboxylic acid dianhydride is not particularly limited, and specific examples thereof include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride; and 1,2-dimethyl-1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Examples of the dianhydride include alicyclic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetracarboxylic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butane tetracarboxylic dianhydride. These may be used alone or in combination of two or more.

[0139] The (b) diamine compound is not particularly limited, and specific examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, phenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-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 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-3,3'-dihydroxy-5,Diamine compounds having a phenolic hydroxy group, such as 5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, 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; Examples of the diamine compound include 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. Further, 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,Examples of diamine compounds include 4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-toluyl)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, and 2,2'-bis(trifluoromethyl)benzidine. These may be used alone or in combination of two or more.

[0140] When the polyamic acid is produced from (a) a tetracarboxylic dianhydride and (b) a diamine compound, the compounding ratio of the two compounds, i.e., the total number of moles of (b) a diamine compound / the total number of moles of (a) a tetracarboxylic dianhydride, is preferably 0.7 to 1.2. As in a normal polycondensation reaction, the closer this molar ratio is to 1, the greater the degree of polymerization of the polyamic acid produced and the greater the molecular weight.

[0141] Furthermore, when polymerization is carried out using an excess diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting them with a carboxylic acid anhydride. Examples of such carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

[0142] In the production of polyamic acid, the reaction temperature for the reaction between a diamine compound and a tetracarboxylic dianhydride can be selected from the range of typically -20 to 150°C, preferably -5 to 100°C. To obtain a high-molecular-weight polyamic acid, the reaction temperature is appropriately selected from the range of 5 to 40°C and the reaction time from 1 to 48 hours. To obtain a low-molecular-weight, partially imidized polyamic acid with high storage stability, it is more preferable to select a reaction temperature from 40 to 90°C and a reaction time from 10 hours or more. Furthermore, when protecting the terminal amino groups with an acid anhydride, the reaction temperature can be selected from the range of -20 to 150°C, preferably -5 to 100°C.

[0143] The reaction of the diamine compound with the tetracarboxylic dianhydride can be carried out in a solvent, and examples of the solvent that can be used 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, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Examples of suitable solvents include 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, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These may be used alone or in combination of two or more. Furthermore, even if a solvent does not dissolve polyamic acid, it may be mixed with the above solvent to the extent that the polyamic acid produced by the polymerization reaction does not precipitate.

[0144] The polyamic acid solution thus obtained can be used as it is for preparing a negative-type photosensitive resin composition. Alternatively, the polyamic acid can be recovered and used by precipitation and isolation in a poor solvent such as water, methanol, or ethanol.

[0145] The alkali-soluble resin may be any polyimide. The polyimide used in the present invention is a polyimide precursor such as the polyamic acid described above that has been chemically or thermally imidized to 50% or more.

[0146] The polyimide preferably has a group selected from a carboxy group and a phenolic hydroxy group to impart alkali solubility. Methods for introducing the carboxy group or the phenolic hydroxy group into the polyimide include a method using a monomer having a carboxy group or a phenolic hydroxy group, a method of capping the amine end with an acid anhydride having a carboxy group or a phenolic hydroxy group, and a method of imidizing a polyimide precursor such as a polyamic acid to an imidization rate of 99% or less.

[0147] Such polyimides can be obtained by synthesizing a polyimide precursor such as the polyamic acid described above, followed by chemical imidization or thermal imidization. Chemical imidization is typically carried out by adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting the solution at room temperature to 100°C. Thermal imidization is typically carried out by heating a polyimide precursor solution at a temperature of 180 to 250°C while dehydrating it.

[0148] Furthermore, as the alkali-soluble resin, a phenol novolac resin can also be used.

[0149] Furthermore, polyester polycarboxylic acids can also be used as the alkali-soluble resin. Polyester polycarboxylic acids can be obtained from acid dianhydrides and diols by the method described in International Publication No. 2009 / 051186. Examples of acid dianhydrides include the above-mentioned (a) tetracarboxylic dianhydrides. Examples of diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol; alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; and aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0150] The alkali-soluble resin of the present invention is preferably a copolymer further having a self-crosslinking group or a group reactive with at least one group selected from the group consisting of a hydroxy group, a carboxy group, an amide group, and an amino group (hereinafter also referred to as a crosslinking group).

[0151] Specific examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a blocked isocyanate group.

[0152] Specific examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group.

[0153] When such a self-crosslinking group or crosslinkable group is contained in the alkali-soluble resin, the content thereof is preferably 0.1 to 0.9 per repeating unit in the alkali-soluble resin, and from the viewpoints of developability and solvent resistance, it is more preferably 0.1 to 0.8.

[0154] When the alkali-soluble resin further has a repeating unit having at least one selected from the crosslinkable group and the self-crosslinkable group, for example, in the case of an alkali-soluble acrylic polymer, it is sufficient to copolymerize an unsaturated compound that has radical polymerizability and further has at least one selected from the crosslinkable group and the self-crosslinkable group.

[0155] Specific examples of the radically polymerizable unsaturated compound having an N-alkoxymethyl group include N-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, and N-methylolacrylamide.

[0156] Specific examples of the radically polymerizable monomer having a hydroxymethylamide group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

[0157] Specific examples of the radically polymerizable monomer further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

[0158] Specific examples of radically polymerizable unsaturated compounds further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate are preferred. These may be used alone or in combination of two or more.

[0159] Examples of the radically polymerizable unsaturated compound further having an oxetane group include (meth)acrylic acid esters having an oxetane group. Specific examples of such monomers include 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, and 2-(acryloyloxymethyl)-4-trifluoromethyloxetane. Among these, 3-(methacryloyloxymethyl)-3-ethyl-oxetane and 3-(acryloyloxymethyl)-3-ethyl-oxetane are preferred.

[0160] Specific examples of the radically polymerizable monomer further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0161] Specific examples of the radically polymerizable monomer having a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

[0162] In the alkali-soluble resin of the present invention, the content of the structural unit derived from an unsaturated compound having radical polymerizability and having at least one group selected from the above-mentioned crosslinkable group and the above-mentioned self-crosslinkable group is preferably 10 to 70 mass %, more preferably 20 to 60 mass %, of all repeating units contained in the alkali-soluble resin. When the content of this structural unit is 10 mass % or more, the heat resistance and surface hardness of the cured film are improved. On the other hand, when the content of this structural unit is 70 mass % or less, the storage stability of the radiation-sensitive resin composition is improved.

[0163] When the alkali-soluble resin of the present invention is used in combination with the aforementioned polymerizable monomer, it is preferable that the alkali-soluble resin has a substituent reactive with the polymerizable monomer. The method for obtaining an alkali-soluble resin having a substituent reactive with the polymerizable monomer is not particularly limited as long as it can produce a resin with stable properties. Examples include a method of copolymerizing a monomer having a substituent reactive with the polymerizable monomer, and a method of synthesizing an alkali-soluble resin without a substituent reactive with the polymerizable monomer, followed by adding a compound having a substituent reactive with the polymerizable monomer by thermal reaction. When the alkali-soluble resin is an alkali-soluble acrylic polymer, the former method may result in a reaction of the substituent reactive with the polymerizable monomer during the polymerization process, leading to gelation, so the latter synthesis method is preferred.

[0164] Specifically, for example, a method can be used in which glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, or the like is added to an alkali-soluble acrylic polymer synthesized using a monomer that is radically polymerizable and further has a carboxyl group or a phenolic hydroxyl group. In this case, by reducing the molar ratio of the monomer to be added relative to the carboxyl group or phenolic hydroxyl group in the resin, a substituent reactive with the polymerizable monomer can be introduced while maintaining the alkali-solubility of the resin derived from the carboxyl group or phenolic hydroxyl group. Another example can be used in which a monomer having a substituent reactive with a polymerizable monomer capable of thermally reacting with the thermally reactive group in the resin is added to an alkali-soluble acrylic polymer obtained by copolymerizing a monomer that is radically polymerizable and further has a thermally reactive group. Specifically, a method can be used in which (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, or the like is added to an alkali-soluble acrylic polymer copolymerized with glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, or the like. In the alkali-soluble resin of the present invention, the proportion of repeating units having a substituent reactive with a polymerizable monomer is preferably 5 to 60 mass %, more preferably 10 to 50 mass %, and even more preferably 10 to 40 mass %, of all repeating units contained in the alkali-soluble resin. When the content of this structural unit is 5 mass % or more, the heat resistance and chemical resistance of the cured film are improved. On the other hand, when the content of this structural unit is 60 mass % or less, the pattern formability of the radiation-sensitive resin composition is improved.

[0165] In the present invention, the alkali-soluble resin may be a mixture of a plurality of types of alkali-soluble resins.

[0166] When the alkali-soluble resin is used, the content thereof is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to 100% by mass of the total of the polymerizable monomer and the alkali-soluble resin, from the viewpoint of film-forming properties, and the upper limit of the content thereof is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of pattern-forming properties.

[0167] The content of the binder (B) is preferably 70 to 99.9 mass % of the solid content, more preferably 85 to 99.9 mass %, and even more preferably 90 to 99 mass %.

[0168] The composition for forming a wavelength conversion film of the present invention may further contain (C) light-scattering particles, which have the function of scattering light that has entered the wavelength conversion film within the film, thereby essentially extending the optical path length within the wavelength conversion film and improving the light absorptance, and of scattering again light that has been reflected at the interface of the wavelength conversion film and returned to the wavelength conversion film, thereby improving the luminous efficiency.

[0169] The light-scattering particles can be appropriately selected depending on the purpose, and may be organic or inorganic fine particles. Among these, inorganic fine particles with a high refractive index are preferred in terms of enhancing the scattering performance of the particles.

[0170] 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.

[0171] Examples of the inorganic fine particles include inorganic oxide particles made of at least one oxide selected from silicon, zirconium, titanium, indium, zinc, antimony, cerium, niobium, tungsten, etc. Specific examples of the inorganic oxide particles include SiO2, ZrO2, TiO2 (hereinafter sometimes referred to as titanium oxide particles), BaTiO3, In2O3, ZnO, Sb2O3, ITO, CeO2, Nb2O5, and WO3. Of these, TiO2, BaTiO3, ZrO2, CeO2, and Nb2O5 are preferred, with TiO2 being more preferred. Furthermore, among TiO2, rutile type is preferred over anatase type because it has lower catalytic activity, resulting in higher film durability, and also has a higher refractive index.

[0172] These particles may be surface-treated. When surface treatment is performed, specific examples of the surface treatment material include different inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, organosiloxanes, and organic acids such as stearic acid. These surface treatment materials may be used alone or in combination.

[0173] The average particle diameter of the light-scattering particles is greater than 50 nm and less than 200 nm. From the viewpoint of wavelength conversion efficiency, the lower limit of the average particle diameter is preferably 60 nm or more, more preferably 70 nm or more. In consideration of patterning characteristics in addition to the viewpoint of wavelength conversion efficiency, an average particle diameter of more than 100 nm is more preferable from the viewpoint of low total light reflectance at i-line (365 nm). If the average particle diameter is too large, sedimentation tends to occur, so from the viewpoint of storage stability of the composition, the upper limit of the average particle diameter is preferably 190 nm or less, more preferably 180 nm or less. The average particle diameter of the light-scattering particles is the average particle diameter determined by observation with a transmission electron microscope.

[0174] Commercially available light-scattering particles may be used, and specific examples of titanium oxide particles include, but are not limited to, PT-401M (rutile type, average particle diameter 70 nm), PT-401L (rutile type, average particle diameter 130 nm), and PT-501R (rutile type, average particle diameter 180 nm). Note that the average particle diameter of the light-scattering particles exemplified above may vary by ±10 nm.

[0175] In consideration of wavelength conversion efficiency, the content of the (C) light scattering particles is preferably 0.1 to 20 mass % of the solid content, more preferably 0.2 to 15 mass %, and even more preferably 0.3 to 10 mass %.

[0176] Furthermore, the composition for forming a wavelength conversion film of the present invention may contain, in addition to the components (A) and (B), various known additives, such as a component (C), a light stabilizer, an antioxidant, a surfactant, a polymer dispersant, a flame retardant, a clarifying agent, an ultraviolet absorber, a crosslinking agent, and a filler, as necessary.

[0177] The surfactant is preferably a fluorine-based surfactant, more preferably a nonionic fluorine-based surfactant. Specific examples thereof include, but are not limited to, the Ftergent series manufactured by Neos Corporation, such as 212M, 215M, 250, 222F, FTX-218, and DFX-18. When a surfactant is used, the amount thereof is not particularly limited, but is preferably 0.01 to 1 mass %, more preferably 0.01 to 0.5 mass %, of the solid content of the composition for forming a wavelength conversion film.

[0178] The polymer dispersant is a polymer compound having a weight-average molecular weight of 750 or more and having functional groups that have affinity for light-scattering particles. The polymer dispersant has the function of dispersing the light-scattering particles. The polymer dispersant adsorbs to the light-scattering particles via the functional groups that have affinity for the light-scattering particles, and disperses the light-scattering particles in the composition due to electrostatic and / or steric repulsion between the polymer dispersants. The polymer dispersant is preferably bonded to the surface of the light-scattering particles and adsorbed to the light-scattering particles, but may be free in the composition for forming a wavelength conversion film.

[0179] The functional group having an affinity for light-scattering particles includes an acidic functional group, a basic functional group, and a nonionic functional group. The acidic functional group has a dissociable proton and may be neutralized with a base such as an amine or hydroxide ion, while the basic functional group may be neutralized with an acid such as an organic acid or an inorganic acid.

[0180] Examples of the acidic functional group include a carboxy group (-COOH), a sulfo group (-SO3H), a sulfate group (-OSO3H), a phosphonic acid group (-PO(OH)2), a phosphoric acid group (-OPO(OH)2), a phosphinic acid group (-PO(OH)-), and a mercapto group (-SH).

[0181] Examples of basic functional groups include primary amino groups, secondary amino groups, tertiary amino groups, ammonium groups, and imino groups, as well as nitrogen-containing heterocyclic groups such as pyridine, pyrimidine, pyrazine, imidazole, and triazole.

[0182] Examples of the nonionic functional group include a hydroxy group, an ether group, a thioether group, a sulfinyl group (—SO—), a sulfonyl group (—SO—), a carbonyl group, a formyl group, an ester group, a carbonate ester group, an amide group, a carbamoyl group, a ureido group, a thioamide group, a thioureido group, a sulfamoyl group, a cyano group, an alkenyl group, an alkynyl group, a phosphine oxide group, and a phosphine sulfide group.

[0183] The polymeric dispersant may be a polymer (homopolymer) of a single monomer or a copolymer (copolymer) of multiple types of monomers. The polymeric dispersant may be a random copolymer, a block copolymer, or a graft copolymer. When the polymeric dispersant is a graft copolymer, it may be a comb-shaped graft copolymer or a star-shaped graft copolymer. Specific examples of polymeric dispersants include acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyethers, phenolic resins, silicone resins, polyurea resins, amino resins, epoxy resins, polyethyleneimines, polyallylamine, polyimides, and the like.

[0184] As the polymer dispersant, commercially available products can be used, such as the DISPERBYK series and BYK series manufactured by BYK, the Efka series manufactured by BASF, the Solsperse series manufactured by Lubrizol Corporation, the AJISPER PB series manufactured by Ajinomoto Fine-Techno Co., Ltd., the TEGO series manufactured by Evonik Chemicals, and the DISPARLON series manufactured by Kusumoto Chemicals Co., Ltd.

[0185] Specific examples of the commercially available products include DISPERBYK-130, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, and DISPERBYK-1, all manufactured by BYK. 84, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2020, DISPERBYK-2022, DISPER BYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164; EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4061, EFKA4080, EFKA4300, EFKA4310, EFKA4320, EFKA4330, EFKA4340, EFKA4560, EFKA4585, EFKA5207, EFKA1501, EFKA1502, EFKA1503, and EFKA PX-4701 manufactured by BASF;Solsperse 3000, Solsperse 9000, Solsperse 13240, Solsperse 13650, Solsperse 13940, Solsperse 11200, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, and Solsperse 280 manufactured by Lubrizol 00, Solsperse 32000, Solsperse 32500, Solsperse 32550, Solsperse 32600, Solsperse 33000, Solsperse 34750, Solsperse 35100, Solsperse 35200, Solsperse 36000, Solsperse 37500, Solsperse 38500, Solsperse 39000, Solsperse 41000, Solsperse 54000, Solsperse 71000 and Solsperse 76500; Examples of such dispersants include Ajisper PB821, Ajisper PB822, Ajisper PB881, PN411, and PA111 manufactured by Ajinomoto Fine-Techno Co., Ltd.; TEGO Dispers 650, TEGO Dispers 660C, TEGO Dispers 662C, TEGO Dispers 670, TEGO Dispers 685, TEGO Dispers 700, TEGO Dispers 710, and TEGO Dispers 760W manufactured by Evonik Chemicals; and Disparlon AQ-320, Disparlon AQ-330, Disparlon AQ-340, Disparlon AQ-360, and Disparlon AQ-380 manufactured by Kusumoto Chemicals Co., Ltd.

[0186] When a polymer dispersant is used, the amount of the polymer dispersant to be added is not particularly limited, but is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on the light scattering particles.

[0187] Furthermore, the wavelength conversion film-forming composition of the present invention may contain a solvent, if necessary. Specific examples thereof include aromatic or halogenated aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene; aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ethyl acetate, n-hexyl acetate, ethyl lactate, γ-butyrolactone, and propylene carbonate. ester-based solvents such as diisopropyl malonate; halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, 1,2-dichloroethane, and chloroform; amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; alcohol-based solvents such as methanol, ethanol, isopropanol, n-propanol, cyclohexanol, diacetone alcohol, and 2-benzooxyethanol; ethylene glycol monoethyl ether, ... Examples of suitable organic solvents include glycol ether solvents such as ethylene glycol monobutyl ether, ethylene glycol diglycidyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; glycol solvents such as ethylene glycol, propylene glycol, hexylene glycol, 3-octylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol; nitrile solvents such as acetonitrile; and sulfur-containing solvents such as dimethyl sulfoxide.These may be used alone or in combination of two or more.

[0188] When the composition for forming a wavelength-converting film contains a solvent, the solids concentration of the composition for forming a wavelength-converting film cannot be generally defined because it varies depending on the intended thickness of the wavelength-converting film, the coating method, etc., but is usually 10 to 70 mass %, preferably 10 to 60 mass %.

[0189] The upper limit of the viscosity of the wavelength-converting film-forming composition at 25°C is 10,000 mPa s or less, preferably 1,000 mPa s or less. In consideration of storage stability, the lower limit is preferably 5 mPa s or more, more preferably 10 mPa s or more. In the present invention, viscosity refers to a value measured with an EMS viscometer.

[0190] The composition for forming a wavelength conversion film of the present invention can be prepared by mixing the above-mentioned components (A) and (B), the component (C) used if necessary, other additives such as a surfactant, and a solvent in any order.

[0191] The wavelength-converting film can be obtained by, for example, applying the wavelength-converting film-forming composition of the present invention to a substrate, evaporating the solvent by heating or the like as necessary, and then irradiating with active energy rays (e.g., ultraviolet light) as necessary. Examples of the application method include methods using a reverse roll coater, blade coater, slit die coater, direct gravure coater, offset gravure coater, kiss coater, natural roll coater, air knife coater, roll blade coater, bar bar roll blade coater, two-stream coater, rod coater, wire bar coater, applicator, dip coater, curtain coater, spin coater, knife coater, inkjet, etc.

[0192] Heating can be carried out using a general heating device such as an oven, a hot plate, etc. The heating conditions are not particularly limited as long as a film can be formed, but heating at 60 to 200°C for 5 minutes to 2 hours is preferred, and heating at 80 to 200°C for 15 minutes to 1 hour is more preferred. Heat curing may also be carried out in stages.

[0193] The ultraviolet light irradiation is not particularly limited as long as it can form a film, but light sources such as mercury lamps, metal halide lamps, xenon lamps, and LEDs can be used, and light from which light other than the target exposure wavelength has been removed can be irradiated by combining a bandpass filter as needed. The wavelength of the irradiated light is preferably 200 to 440 nm, and particularly preferably includes light with a wavelength of 300 to 400 nm. The exposure dose is 10 to 4,000 mJ / cm. 2 is preferred.

[0194] The heating step and the ultraviolet light exposure step may be combined in any order, for example, heating may be performed before ultraviolet light irradiation, ultraviolet light irradiation may be performed before heating, or heating may be performed after ultraviolet light irradiation, and then heating may be performed again.

[0195] The thickness of the wavelength conversion film is not particularly limited, but is usually 1 to 1,000 μm, preferably 3 to 500 μm, and more preferably 5 to 100 μm. The haze of the wavelength conversion film is not particularly limited, but is preferably 18% or more, more preferably 30% or more, and more preferably 40% or more, from the viewpoint of scattering incident light within the film and thereby increasing the amount of light that can be absorbed by the phosphor. The upper limit of the haze value is not particularly limited, but is usually about 95%. In the present invention, the haze value is a value measured in accordance with ASTM D1003-61. In the present invention, the haze value can be measured, for example, on a 10 μm-thick film formed from a composition containing 6.7% by mass of titanium oxide particles.

[0196] The substrate may be appropriately selected from those used as base substrates for forming this type of film, but a glass substrate or polymer plate having a transmittance of 50% or more for light in the visible region of 400 to 800 nm is preferred. Specific examples of glass include soda-lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Specific examples of polymers include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

[0197] In the present invention, when a coating film is formed using a composition containing an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator (negative-type photosensitive resin composition), a mask having a predetermined pattern is attached to the resulting coating film, which is then irradiated with light such as ultraviolet light and developed with an alkaline developer, whereby the unexposed areas are washed out, and the remaining patterned film is heated at 80 to 140°C for 0.5 to 10 minutes as necessary, thereby obtaining a relief pattern with a sharp edge.

[0198] 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 aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants known for use in developers can also be added to these developers.

[0199] Among the above, an aqueous solution of 0.1 to 2.58 mass % tetraethylammonium hydroxide is generally used as a developer for photoresists, and the composition of the present invention can also be developed satisfactorily using this alkaline developer without causing problems such as swelling.

[0200] The developing method may be any of the puddle method, dipping method, and swing immersion method, etc. The developing time is usually 15 to 180 seconds.

[0201] After development, the photosensitive resin film is washed with running water and then air-dried using compressed air or compressed nitrogen or by spinning, thereby removing moisture from the substrate and obtaining a patterned film. In the above, the washing time is usually about 20 to 120 seconds.

[0202] Subsequently, the pattern-forming film thus obtained is post-baked for thermal curing, thereby obtaining a film having a good relief pattern and excellent heat resistance, transparency, flattening properties, low water absorption, chemical resistance, etc. The pattern-forming film can be heated using a hot plate, an oven, or the like.

[0203] A typical post-baking method involves treating the film at a heating temperature selected from the range of 140 to 270° C. for 5 to 30 minutes on a hot plate or for 30 to 90 minutes in an oven. Post-baking under these conditions allows a cured film having a good pattern shape to be obtained.

[0204] The wavelength converting film obtained from the composition of the present invention has excellent wavelength conversion efficiency and durability, and can therefore be suitably used as a wavelength converting film (color converting film) for displays such as micro LED displays, organic EL displays, and liquid crystal displays, as well as for lighting.

[0205] The present invention will be described in more detail below with reference to synthesis examples, preparation examples, working examples and comparative examples, but the present invention is not limited to the following examples.

[0206] The molecular weight of the polymer was measured using a GPC system manufactured by JASCO Corporation as the apparatus and Shodex (registered trademark) KF-804L and 803L as columns under the following conditions: Column oven: 40°C, Flow rate: 1 mL / min, Eluent: tetrahydrofuran.

[0207] The abbreviations used in the following examples are as follows: MMA: methyl methacrylate MAA: methacrylic acid AIBN: α,α'-azobisisobutyronitrile CPN: cyclopentanone A11: 3-(2-benzothiazolyl)-7-(diethylamino)coumarin (Coumarin 6, manufactured by Tokyo Chemical Industry Co., Ltd.) A12: a compound represented by the following formula (X1) B2: HDDA (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Ltd.) B3: NDDA (1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Ltd.) B4: Irgacure OXE02 (manufactured by BASF) B5: KAYARAD DPHA (dipentaerythritol polyacrylate, manufactured by Nippon Kayaku Co., Ltd., polymerizable monomer) C1: titanium oxide particles PT-401L (rutile type, average particle size 130 nm, manufactured by Ishihara Sangyo Kaisha, Ltd.) D1: Megafac (registered trademark) R-40 (manufactured by DIC Corporation) D2: Ftergent DFX-18 (manufactured by Neos Corporation) D3: DISPARLON AQ-330 (manufactured by Kusumoto Chemicals Co., Ltd.) D4: DISPARLON AQ-320 (Kusumoto Chemicals Co., Ltd.)

[0208] <Analysis method> 1 H-NMR spectra were measured using a nuclear magnetic resonance spectrometer AVANCE III HD (manufactured by Bruker). Chemical shift values ​​are expressed in ppm, and deuterated tetrahydrofuran and deuterated chloroform were used as solvents. 1For H-NMR spectra, signals derived from residual protons in the solvent were used, with tetrahydrofuran set as the internal standard at δ 1.77, 3.62 ppm, and chloroform set as the internal standard at δ 7.26 ppm. Benzo[b]benzo[4,5]thieno[2,3-d]thiophene was purchased from BLD Pharmatech. Bromine, iodine, tris(dibenzylideneacetone)dipalladium(0) (Pd(dba)), diphenylamine (PhNH), sodium tert-butoxide (t-BuONa), and metachloroperbenzoic 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-BuPHBF) was purchased from Fujifilm Wako Pure Chemical Industries, Ltd. Thin-layer chromatography (TLC) was performed using a glass plate coated with 0.25 mm of silica gel 60F-254 (Merck). Silica gel column chromatography was performed using silica gel 60N spherical neutral (Kanto Chemical Co., Ltd.) as the packing material.

[0209] [1] Preparation of polymer solution [Synthesis Example 1] Synthesis of acrylic polymer B1 80.0 g of MMA, 20.0 g of MAA, and 2.5 g of AIBN were dissolved in 190.0 g of CPN, and the mixture was allowed to react at 90° C. for 20 hours to obtain a solution containing acrylic polymer B1 (solid content concentration: 30% by mass). The obtained acrylic polymer had an Mn of 9,900 and an Mw of 17,300.

[0210] [2] Synthesis of fluorescent dyes [Synthesis Example 2] 2,7-dibromobenzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 2)

[0211] A bromo group was introduced into Compound 1 using bromine to obtain Compound 2 in a yield of 28%. Specifically, the synthesis was carried out as follows.

[0212] Bromine (14.2 g, 89.0 mmol) was dissolved in dichloromethane (500 mL) and cooled to 0°C. To this solution, 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 (1,000 mL) were added dropwise over 1 hour. This mixture was stirred at room temperature for 62 hours. 1,000 mL of methanol was added, and the precipitated white solid was collected by suction filtration, washed with saturated aqueous sodium thiosulfate (100 mL), water (500 mL), and methanol (500 mL), and dried under reduced pressure at 50°C for 5 hours to obtain 15.0 g of a white solid. Tetrahydrofuran (1,500 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 collected by suction filtration and dried under reduced pressure at 50° C. for 5 hours to obtain Compound 2 as a white solid in a yield of 28% (4.68 g, 11.8 mmol). 1 H-NMR (500MHz, Tetrahydrofuran-d8): δ 8.29 (d, J HH =2.0Hz, 2H), 7.92(d, J HH =8.5Hz, 2H), 7.67(dd, J HH =8.5Hz, 2.0Hz, 2H).

[0213] [Synthesis Example 3] N 2 , N 2 , N 7 , N 7 -Tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 3)

[0214] A diphenylamino group was introduced into compound 2 by Buchwald-Hartwig coupling reaction to obtain compound 3 in a yield of 26%. Specifically, the synthesis was carried out as follows.

[0215] Under a N2 gas atmosphere, 2,7-dibromobenzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 2; 4.68 g, 11.8 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3; 238 mg, 0.260 mmol), tri-tert-butylphosphonium tetrafluoroborate (tert-Bu3PHBF4; 281 mg, 0.968 mmol), diphenylamine (Ph2NH; 11.9 g, 70.5 mmol), and 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. The combined organic layer was dehydrated over anhydrous sodium sulfate, and the filtrate was concentrated under reduced pressure. Concentrate (developing solvent: hexane; f The crude product (hexane → hexane / chloroform = 5 / 1 → hexane / chloroform = 2 / 1 → hexane / chloroform = 1 / 1 → chloroform) was purified by silica gel column chromatography (hexane → hexane / chloroform = 5 / 1 → hexane / chloroform = 2 / 1 → hexane / chloroform = 1 / 1 → chloroform). Hexane (300 mL) was added to the purified product, and the precipitated light green solid was collected by suction filtration to obtain compound 3 as a light green solid in a yield of 26% (1.75 g, 3.04 mmol). 1 H-NMR (500MHz, CDCl3): δ 7.66 (d, J HH =8.5Hz, 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).

[0216] [Synthesis Example 4] 2,7-bis(diphenylamino)benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (Compound 4) (A1)

[0217] Compound 3 was oxidized with m-CPBA to give compound 4 in a yield of 33%. Specifically, the synthesis was carried out as follows.

[0218] N 2 , N 2 , N7 , N 7 1.75 g, 3.04 mmol) of 1,3-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). To this was slowly added metachloroperbenzoic acid (m-CPBA (30% by mass water content); 1.65 g, 6.70 mmol) 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 layer for dehydration, and the filtrate was concentrated under reduced pressure. The concentrate (developing 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) to obtain Compound 4 (A1) as an orange solid in a yield of 33% (607 mg, 1.00 mmol). 1 H-NMR (500MHz, CDCl8): δ 7.78 (d, J HH =8.5Hz, 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).

[0219] [Synthesis Example 5] 4,4'-(benzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diyl)bis(N,N-diphenylaniline) (Compound 5)

[0220] A diphenylaminophenyl group was introduced into Compound 2 by a coupling reaction to obtain Compound 5 in a yield of 43%. Specifically, the synthesis was carried out as follows.

[0221] Under a N2 gas atmosphere, 2,7-dibromobenzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 2; 100 mg, 0.251 mmol), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4; 14.5 mg, 0.126 mmol), 4-(diphenylamino)phenylboronic acid (218 mg, 0.754 mmol), and sodium carbonate (133 mg, 1.26 mmol) were dissolved in a mixed solvent of 1,4-dioxane (5 mL) and water (1 mL). The mixture was heated to 90°C and stirred for 18 hours. After adding cold water, the mixture was extracted three times with ethyl acetate. Anhydrous sodium sulfate was added to the combined organic layer for dehydration, and the filtrate was concentrated under reduced pressure. The concentrate (developing solvent: hexane / chloroform = 1 / 1; R f =0.8) was purified by silica gel column chromatography (hexane / chloroform=10 / 1→hexane / chloroform=3 / 1→hexane / chloroform=1 / 1) to obtain Compound 5 as a yellow solid in a yield of 43% (78.0 mg, 0.107 mmol). 1 H-NMR (500MHz, CDCl3): δ 8.10 (s, 2H), 7.91 (d, J HH =8.5Hz, 2H), 7.68(dd, J HH =8.5Hz, 1.5Hz, 2H), 7.58-7.56 (m, 4H), 7.30-7.27 (m, 8H), 7.19-7.15 (m, 12H), 7.07-7.04 (m, 4H).

[0222] [Synthesis Example 6] 2,7-bis[4-(diphenylamino)phenyl]benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (Compound 6) (A2)

[0223] N 2 , N 2 , N 7 , N 7Compound 6 (A2) was obtained as an orange solid in a yield of 14% (11.0 mg, 0.0145 mmol) in substantially the same manner as in Synthesis example 4, except that 4,4'-(benzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diyl)bis(N,N-diphenylaniline) (Compound 5) was used instead of 1,4-tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 3). 1 H-NMR (500MHz, CDCl3): δ 8.07-8.05 (m, 2H), 7.97 (d, J HH =1.5Hz, 1H), 7.78-7.74 (m, 2H), 7.54-7.49 (m, 5H), 7.32-7.27 (m, 8H), 7.17-7.14 (m, 12H), 7.10-7.05 (m, 4H).

[0224] [Synthesis Example 7] 2,7-bis(diphenylamino)benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5,10,10-tetraoxide (Compound 7) (A3)

[0225] Compound 3 obtained in Synthesis Example 2 was oxidized with m-CPBA to obtain compound 7 (A3) in a yield of 7.2%. Specifically, the synthesis was carried out as follows.

[0226] N 2 , N 2 , N 7 , N 7 1,3-Tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 3; 100 mg, 0.174 mmol) was dissolved in 1,2-dichloroethane (10 mL). To this was added metachloroperbenzoic acid (m-CPBA (30% by mass water content); 450 mg, 1.83 mmol). The temperature was raised to 70°C and the mixture was stirred for 29 hours. A saturated aqueous solution of sodium bicarbonate was added, and the mixture was extracted three times with chloroform. Anhydrous sodium sulfate was added to the combined organic layer for dehydration, and the filtrate was concentrated under reduced pressure. The concentrate (developing solvent: hexane / ethyl acetate = 2 / 1; R f=0.5) was purified by silica gel column chromatography (hexane / chloroform=1 / 1→chloroform) to obtain Compound 7 (A3) as a red solid in a yield of 7.2% (8.00 mg, 0.00125 mmol). 1 H-NMR (500MHz, CDCl3): δ 7.38-7.33 (m, 12H), 7.22-7.19 (m, 4H), 7.16 (d, J HH =7.5Hz, 8H), 7.10(dd, J HH =8.5Hz, 2.0Hz, 2H).

[0227] [Synthesis Example 8] N 2 , N 7 -di(naphthalen-1-yl)-N 2 , N 7 -diphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 8)

[0228] An N-phenyl-1-naphthylamino group was introduced into Compound 2 obtained in Synthesis Example 2 by Buchwald-Hartwig coupling reaction to obtain Compound 8 in an 87% yield. Specifically, the synthesis was carried out as follows.

[0229] Under a N gas atmosphere, 2,7-dibromobenzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 2; 500 mg, 1.26 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd(dba); 25.4 mg, 0.0280 mmol), tri-tert-butylphosphonium tetrafluoroborate (tert-BuPHBF; 30.0 mg, 0.103 mmol), N-phenyl-1-naphthylamine (605 mg, 2.76 mmol), and sodium tert-butoxide (t-BuONa; 400 mg, 4.16 mmol) were dissolved in degassed o-xylene (5 mL). The mixture was heated to 140 °C and stirred for 6 hours. Water (5 mL) was added and the mixture was stirred for 1 hour. The precipitated brown solid was collected by suction filtration and washed with water (5 mL) and hexane (5 mL) to obtain Compound 8 (developing solvent: hexane; R f = 0.1) was obtained as a brown solid in 87% yield (736 mg, 1.09 mmol). 1H-NMR (500MHz, CDCl3): δ 7.96 (d, J HH =8.5Hz, 2H), 7.90(d, J HH =8.5Hz, 2H), 7.79(d, J HH =8.5Hz, 2H), 7.58(d, J HH =8.5Hz, 2H), 7.50-7.44 (m, 6H), 7.37-7.34 (m, 4H), 7.24-7.20 (m, 4H), 7.16 (dd, J HH =8.5Hz, 2.0Hz, 2H), 7.07(d, J HH =7.5Hz, 4H), 6.98-6.95(m, 2H).

[0230] [Synthesis Example 9] 2,7-bis(naphthalen-1-yl(phenyl)amino)benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (Compound 9) (A4)

[0231] N 2 , N 2 , N 7 , N 7 -tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 3) instead of N 2 , N 7 -di(naphthalen-1-yl)-N 2 , N 7 Compound 9 (A4) was obtained as an orange solid in a yield of 8.8% (18.4 mg, 0.0260 mmol) by substantially the same reaction as in Synthesis example 4, except that -diphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 8) was used. 1 H-NMR (500MHz, CDCl3): δ 7.92-7.80 (m, 6H), 7.73 (d, J HH =9.0Hz, 1H), 7.53-7.46 (m, 4H), 7.44-7.40 (m, 1H), 7.38-7.33 (m, 3H), 7.31-7. 28 (m, 4H), 7.24-7.18 (m, 5H), 7.12-7.09 (m, 4H), 7.03-7.00 (m, 1H), 6.87 (dd, J HH =8.5Hz, 2.0Hz, 1H).

[0232] [Synthesis Example 10] 2,7-di(9H-carbazol-9-yl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 10)

[0233] Compound 10 was obtained as a brown solid in a yield of 81% (580 mg, 1.02 mmol) by substantially the same reaction as in Synthesis Example 8, except that carbazole was used instead of N-phenyl-1-naphthylamine. 1 H-NMR (500MHz, CDCl3): δ 8.20-8.14 (m, 8H), 7.72 (dd, J HH =8.0Hz, 1.5Hz, 2H), 7.51-7.44 (m, 8H), 7.35-7.32 (m, 4H).

[0234] [Synthesis Example 11] 2,7-di(9H-carbazol-9-yl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (Compound 11) (A5)

[0235] N 2 , N 2 , N 7 , N 7 Compound 11 (A5) was obtained as an orange solid in a yield of 56% (119 mg, 0.197 mmol) in substantially the same manner as in Synthesis example 4, except that 2,7-di(9H-carbazol-9-yl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene (Compound 10) was used instead of 1,4-tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 3). 1 H-NMR (500MHz, CDCl3): δ 8.30 (d, J HH =8.5Hz, 1H), 8.19-8.16 (m, 5H), 8.09 (d, J HH =2.0Hz, 1H), 7.89(dd, J HH =8.5Hz, 2.0Hz, 1H), 7.83-7.80 (m, 2H), 7.53-7.46 (m, 8H), 7.38-7.33 (m, 4H).

[0236] [Synthesis Example 12] N 2 , N 2 , N 7 , N7 -Tetrakis[4-(tert-butyl)phenyl]benzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 12)

[0237] Compound 12 was obtained as a yellow-green solid in a yield of 81% (487 mg, 0.609 mmol) by substantially the same reaction as in Synthesis Example 8, except that bis(4-tert-butylphenyl)amine was used instead of N-phenyl-1-naphthylamine. 1 H-NMR (500MHz, Tetrahydrofuran-d8): δ 7.70-7.69 (m, 2H), 7.60 (s, 2H), 7.34 (d, J HH =7.5Hz, 8H), 7.20-7.17 (m, 2H), 7.07 (d, J HH =7.5Hz, 8H), 1.35(S, 36H).

[0238] [Synthesis Example 13] 2,7-bis{bis[4-(tert-butyl)phenyl]amino}benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (Compound 13) (A6)

[0239] N 2 , N 2 , N 7 , N 7 -tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 3) instead of N 2 , N 2 , N 7 , N 7 Compound 13 (A6) was obtained as an orange solid in a yield of 5.9% (6.10 mg, 0.00734 mmol) by substantially the same reaction as in Synthesis example 4, except that 1-tetrakis[4-(tert-butyl)phenyl]benzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 12) was used. 1 H-NMR (500MHz, CDCl3): δ 7.74 (d, J HH =8.5Hz, 1H), 7.40 (s, 1H), 7.36-7.28 (m, 9H), 7.22-7.20 (m, 1H), 7.14 (d, J HH=8.5Hz, 1H), 7.09-7.03 (m, 9H), 1.33-1.32 (m, 36H).

[0240] [Synthesis Example 14] N 2 , N 2 , N 7 , N 7 -tetra-meta-tolylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 14)

[0241] Compound 14 was obtained as a yellow solid in a yield of 50% (236 mg, 0.374 mmol) by substantially the same reaction as in Synthesis Example 8, except that di-meta-tolylamine was used instead of N-phenyl-1-naphthylamine. 1 H-NMR (500MHz, CDCl3): δ 7.64 (d, J HH =8.5Hz, 2H), 7.50 (s, 2H), 7.18-7.15 (m, 6H), 6.95-6.92 (m, 8H), 6.86 (d, J HH =7.5Hz, 4H), 2.27(s, 12H).

[0242] [Synthesis Example 15] 2,7-bis(di-meta-tolylamino)benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (Compound 15) (A7)

[0243] N 2 , N 2 , N 7 , N 7 -tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 3) instead of N 2 , N 2 , N 7 , N 7 Compound 15 (A7) was obtained as an orange solid in a yield of 23% (56.2 mg, 0.0848 mmol) by substantially the same reaction as in Synthesis example 4, except that 1,3-tetra-meta-tolylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 14) was used. 1 H-NMR (500MHz, CDCl3): δ 7.77 (d, J HH=8.5Hz, 1H), 7.39 (s, 1H), 7.30 (s, 1H), 7.24-7.17 (m, 7H), 7.07-7.05 (m, 1H), 6.99-6.89 (m, 11H), 2.30-2.28 (m, 12H).

[0244] [Synthesis Example 16] N 2 , N 2 , N 7 , N 7 -tetra-para-tolylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 16)

[0245] Compound 16 was obtained as a yellow solid in a yield of 69% (326 mg, 0.517 mmol) by substantially the same reaction as in Synthesis Example 8, except that di-para-tolylamine was used instead of N-phenyl-1-naphthylamine. 1 H-NMR (500MHz, CDCl3): δ 7.60 (d, J HH =6.5Hz, 2H), 7.47 (s, 2H), 7.15-7.02 (m, 18H), 2.33 (s, 12H).

[0246] [Synthesis Example 17] 2,7-bis(di-para-tolylamino)benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (Compound 17) (A8)

[0247] N 2 , N 2 , N 7 , N 7 -tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 3) instead of N 2 , N 2 , N 7 , N 7 Compound 17 (A8) was obtained as an orange solid in a yield of 37% (127 mg, 0.192 mmol) by substantially the same reaction as in Synthesis example 4, except that 1,4-tetra-para-tolylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 16) was used. 1 H-NMR (500MHz, CDCl3): δ 7.73 (d, J HH=8.5Hz, 1H), 7.35 (s, 1H), 7.27 (s, 1H), 7.18-7.09 (m, 10H), 7.05-7.00 (m, 9H), 2.35-2.33 (m, 12H).

[0248] [Synthesis Example 18] N 2 , N 2 , N 7 , N 7 -tetra-ortho-tolylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 18)

[0249] Compound 18 was obtained as a yellow solid in a yield of 25% (120 mg, 0.190 mmol) by substantially the same reaction as in Synthesis Example 8, except that di-ortho-tolylamine was used instead of N-phenyl-1-naphthylamine. 1 H-NMR (500MHz, CDCl3): δ 7.55 (d, J HH =9.0Hz, 2H), 7.22(d, J HH =7.5Hz, 4H), 7.18-7.10 (m, 12H), 7.00-6.98 (m, 2H), 6.83 (d, J HH =8.5Hz, 2H), 2.04(s, 12H).

[0250] [Synthesis Example 19] 2,7-bis(di-ortho-tolylamino)benzo[b]benzo[4,5]thieno[2,3-d]thiophene 5,5-dioxide (Compound 19) (A9)

[0251] N 2 , N 2 , N 7 , N 7 -tetraphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (compound 3) instead of N 2 , N 2 , N 7 , N 7 Compound 19 (A9) was obtained as an orange solid in a yield of 37% (23.0 mg, 0.0347 mmol) by substantially the same reaction as in Synthesis example 4, except that 1,4-tetra-ortho-tolylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene-2,7-diamine (Compound 18) was used.1 H-NMR (500MHz, CDCl3): δ 7.70 (d, J HH =8.5Hz, 1H), 7.26-7.23 (m, 3H), 7.20-7.11 (m, 10H), 7.04-6.96 (m, 6H), 6.86 (d, J HH =8.5Hz, 1H), 6.65(d, J HH =9.0Hz, 1H), 2.10-2.03(m, 12H).

[0252] [Synthesis Example 20] Fluorescent dye compound A10 Fluorescent dye compound A10 represented by the following formula was obtained according to the synthesis method described in ACS Materials Lett. 2021, 3, 42-49.

[0253] [3] Preparation of Light-Scattering Particle Dispersion [Preparation Example 1] Preparation of Light-Scattering Particle Dispersion 1 To a 50 ml glass vial, acrylic polymer solution B1 was added in an amount of 50% by weight (solids content) relative to light-scattering particles C1, and CPN was further added to adjust the solids concentration to 30% by weight. Zirconia balls with a diameter of 1 mm were then added to the container, and ball milling was performed by stirring for 48 hours using a mix rotor VMR-5R manufactured by AS ONE Corporation, to obtain light-scattering particle dispersion 1. The particle size distribution of the resulting dispersion was measured using a Nanotrac UPA (manufactured by Microtrac). The solvent of the dispersion was used as the dilution solution, and the 50% cumulative diameter (D50) of the particles in the dispersion was calculated on a volume basis using Microtrac DMS analysis software manufactured by Nikkiso Co., Ltd., based on the scattering occurring when the diluted sample was irradiated with laser light. The result was 181 nm.

[0254] [Preparation Example 2] Preparation of Light-Scattering Particle Dispersion 2 143.3 g of B3 and 80.0 g of C1 were added to a 500 ml polystyrene bottle, and then 26.7 g of D3 diluted to 30% with B3 was added while stirring with a disperser. The mixture was stirred with a disperser at 1,000 rpm for 30 minutes to obtain a slurry. The mass of D3 added relative to C1 was 10% by mass. Next, the entire slurry was transferred to a slurry tank, and then, using a Labo Ministar DMS65 bead mill manufactured by Ashizawa Finetech Co., Ltd., the mixture was subjected to five passes at a liquid feed rate of 40 ml / min and a disk peripheral speed of 8 m / s, with the mixture filled with 60% by volume of zirconia beads having a diameter of 0.2 mm. Light-scattering particle dispersion 2 was obtained. The particle size distribution of the resulting dispersion was measured using a Nanotrac UPA (manufactured by Microtrac). B3 was used as the dilution solution, and the 50% cumulative diameter (D50) of the particles in the dispersion solution was calculated on a volume basis from the scattering that occurred when the diluted sample was irradiated with laser light using analytical software Microtrac DMS manufactured by Nikkiso Co., Ltd., and was found to be 134 nm.

[0255] [Preparation Example 3] Preparation of Light-Scattering Particle Dispersion 3 Particle dispersant D4 was added to a 500 ml polystyrene bottle in an amount of 20% by weight (solids content) relative to the light-scattering particles C1, and CPN was further added to adjust the solids concentration to 30% by weight. A slurry was obtained by dispersing and stirring at 1,000 rpm for 30 minutes. The entire slurry was then transferred to a slurry tank, and the resulting mixture was subjected to 10 passes using a Labo Ministar DMS65 bead mill manufactured by Ashizawa Finetech Co., Ltd., filled with 60% by volume of zirconia beads having a diameter of 0.2 mm. The mixture was then subjected to a liquid feed rate of 60 ml / min and a disk peripheral speed of 8 m / s to obtain a light-scattering particle dispersion 3. The particle size distribution of the resulting dispersion was measured using a Nanotrac UPA (manufactured by Microtrac). CPN was used as the dilution liquid, and the 50% cumulative diameter (D50) of the particles in the dispersion liquid was calculated on a volume basis from the scattering that occurred when laser light was irradiated onto the diluted sample using analysis software Microtrac DMS manufactured by Nikkiso Co., Ltd., and was found to be 185 nm, and the volume average particle diameter was 191 nm.

[0256] [4] Preparation and Evaluation of Compositions for Forming Wavelength-Converting Films [Examples 1 to 9, Comparative Example 1] Preparation and Evaluation of Compositions for Forming Wavelength-Converting Films (1) Preparation of Compositions for Forming Wavelength-Converting Films Compositions for forming wavelength-converting films were prepared by mixing the components according to the compositions shown in Table 1 and filtering the resulting mixtures using a PTFE filter with a pore size of 0.2 μm. The composition ratios in Table 1 represent the ratios based on the solid content.

[0257]

[0258] (2) Evaluation 1: Evaluation of Light Resistance The wavelength-converting film-forming compositions of Examples 1 to 9 and Comparative Example 1 were applied to quartz substrates using a spin coater, and then pre-baked on a hot plate at 100°C for 120 seconds, followed by post-baking at 160°C for 30 minutes to obtain three substrates each with a coating film sample having a thickness of 1 μm. These are referred to as Substrates A, B, and C. Next, Substrate A was exposed to light in a nitrogen atmosphere, and Substrate B was exposed to light in the air using a blue LED light (manufactured by CCS Inc., emission peak wavelength 450 nm, illuminance 2.1 mW / cm). 2 ), and the LED light was turned on to irradiate the substrates for 20 hours. During this time, Substrate C was stored in the atmosphere in a light-shielded state. Thereafter, using a fluorescence spectrometer (F-7000 manufactured by Hitachi, Ltd.), the fluorescence spectra of all the substrates were measured by excitation at a predetermined excitation wavelength. The value obtained by dividing the peak intensity of the fluorescence spectrum of Substrate A by the peak intensity of the fluorescence spectrum of Substrate C was taken as the fluorescence intensity maintenance rate in a nitrogen atmosphere, and the value obtained by dividing the peak intensity of the fluorescence spectrum of Substrate B by the peak intensity of the fluorescence spectrum of Substrate C was taken as the fluorescence intensity maintenance rate in the atmosphere. The evaluation results are shown in Table 2.

[0259]

[0260] As shown in Table 2, Examples 1 to 9, which satisfy the requirements of the present invention, exhibited higher fluorescence intensity maintenance rates after light irradiation in a nitrogen atmosphere and superior light resistance compared to Comparative Example 1, which used a dye that does not satisfy the requirements of the present invention. Furthermore, Examples 1 to 3 and 5 to 9 also exhibited higher fluorescence intensity maintenance rates after light irradiation even in air and superior light resistance compared to Comparative Example 1.

[0261] [Examples 10 to 15, Comparative Examples 2 to 10] (1) Preparation of compositions for forming wavelength conversion films The components were mixed according to the compositions shown in Tables 3 and 4. The resulting mixtures were filtered using a polytetrafluoroethylene (PTFE) filter with a pore size of 5.0 μm to prepare compositions for forming wavelength conversion films. The composition ratios in Tables 3 and 4 represent mass ratios of the solid contents.

[0262]

[0263]

[0264] (2) Evaluation of Film Properties The resin compositions of Examples 10 to 12 and Comparative Examples 2 to 6 were applied to a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100°C for 120 seconds, followed by post-baking at 160°C for 30 minutes to obtain coating film samples with a film thickness of 10 μm. In addition, each composition of Example 13 and Comparative Example 7 was applied using a spin coater, and then exposed to 2000 mJ / cm using a UV-LED exposure device (emission peak wavelength 365 nm) manufactured by CCS Inc. 2 The resin compositions of Examples 14 and 15 and Comparative Examples 8 to 10 were applied to a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100°C for 120 seconds. The coating film was then exposed to ultraviolet light at a wavelength of 365 nm at a light intensity of 3 mW / cm using a Canon Inc. PLA-600FA ultraviolet irradiation device. 2 of ultraviolet light at 500 mJ / cm 2 Then, post-baking was carried out at 160° C. for 30 minutes to obtain a coating sample having a film thickness of 10 μm.

[0265] The haze value of the obtained coating film sample was measured using a turbidity meter NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with the measurement method of ASTM D 1003-61. Next, the coating film sample was placed on a blue LED light (emission peak wavelength 450 nm) manufactured by CCS Co., Ltd., the LED light was turned on, and the light emitted through the coating film sample was measured using a spectroradiometer USR-45 manufactured by Ushio Inc., and the result was designated as (I). Similarly, the light emitted from only the LED light, excluding the coating film sample, was measured in the same manner, and the result was designated as (II). From the obtained spectral irradiance spectrum, the number of photons of light with a wavelength of 480 nm or less in Result (II) was designated as the "excitation light photon number." Similarly, the number of photons of light with a wavelength of 480 nm or less in Result (I) was designated as the "transmitted light photon number." Similarly, the number of photons of light with a wavelength of 480 nm or more in Result (I) was designated as the "emission photon number." The "blue light absorptance" and "conversion efficiency" were calculated using the following formulas: Blue light absorptance = (number of excitation light photons - number of transmitted light photons) / number of excitation light photons Conversion efficiency = number of emitted light photons / number of excitation light photons

[0266] (3) Evaluation of Light Fastness Three coating film samples each prepared under the same conditions as those used in (2) above were irradiated for 100 hours with light at a wavelength of 450 nm using a blue LED exposure device manufactured by CCS Inc. in the atmosphere or in a nitrogen atmosphere in a glove box manufactured by VAC. The blue light absorptance and conversion efficiency of the coating film samples after light irradiation were measured in the same manner as in Evaluation 1. The value obtained by dividing the blue light absorptance after light irradiation by the blue light absorptance before light irradiation was taken as the "maintenance rate" of blue light absorptance, and the value obtained by dividing the conversion efficiency after light irradiation by the conversion efficiency before light irradiation was taken as the "maintenance rate" of conversion efficiency.

[0267] The results of the evaluations (2) and (3) above are shown in Tables 5 and 6.

[0268]

[0269]

[0270] As shown in Tables 5 and 6, in Examples 10 to 15 using the phosphor of the present invention, the retention rate of conversion efficiency after the light resistance test was good not only under a nitrogen atmosphere but also in air, compared to Comparative Examples 2 to 10.

Claims

1. A composition for forming a wavelength conversion film, comprising: a phosphor made of a fused thiophene compound represented by the following formula (1); and (B) a binder: 【Chemistry 1】 (In the formula, Ar 1 and Ar 2 each independently represents an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent, R 1 ~R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and R 1 ~R 4 Not all of these can be hydrogen atoms at the same time. R 1 and R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 1 and R 2 Either one or both of 1 may bond to form a ring together with the adjacent nitrogen atom, and R 3 and R 4 Either one or both of 2 may be bonded to form a ring together with the adjacent nitrogen atom, Y 1 and Y 2 is one side -SO 2 -, and the other is -S- or -SO 2 - is.)

2. Above Y 1 and Y 2 is one side -SO 2 2. The composition for forming a wavelength conversion film according to claim 1, wherein the other is - and the other is -S-.

3. The above Ar 1 and Ar 2 2. The composition for forming a wavelength conversion film according to claim 1, wherein is an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent.

4. The above R 1 ~R 4 The composition for forming a wavelength conversion film according to claim 1 , wherein is an aryl group which may have a substituent.

5. The composition for forming a wavelength-converting film according to claim 1 , further comprising (C) light-scattering particles.

6. 6. The composition for forming a wavelength conversion film according to claim 5, wherein the (C) light-scattering particles are titanium oxide particles.

7. The composition for forming a wavelength conversion film according to claim 1 , wherein the binder (B) contains a resin.

8. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the binder (B) contains a polymerizable monomer and a photopolymerization initiator.

9. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the binder (B) comprises an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator.

10. 2. The composition for forming a wavelength conversion film according to claim 1, wherein the content of the phosphor (A) is 0.1 mass % or more based on the solid content.

11. 6. The composition for forming a wavelength conversion film according to claim 5, wherein the content of the light-scattering particles (C) is 1% by mass or more based on the solid content.

12. 52. The composition for forming a wavelength conversion film according to claim 51, wherein a film formed from the composition has a haze value of 18% or more.

13. A fused ring thiophene compound represented by the following formula (1): 【Chemistry 2】 (wherein Ar 1 and Ar 2 each independently represent an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent; R 1 to R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, and R 1 to R 4 are not all hydrogen atoms at the same time; R 1 and R 2 may be bonded to each other to form a ring together with the adjacent nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring together with the adjacent nitrogen atom, either or both of R 1 and R 2 may be bonded to Ar 1 to form a ring together with the adjacent nitrogen atom, either or both of R 3 and R 4 may be bonded to Ar 2 to form a ring together with the adjacent nitrogen atom, One of Y 1 and Y 2 is —SO 2 —, and the other is —S—.

14. The fused thiophene compound according to claim 13, wherein Ar 1 and Ar 2 are an aromatic ring which may have a substituent or a heteroaromatic ring which may have a substituent.

15. The fused ring thiophene compound according to claim 13, wherein R 1 to R 4 are aryl groups which may have a substituent.

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