Hardened film, method for manufacturing hardened film, and display device

Abstract

This invention provides a hardened film and a method for manufacturing the hardened film. The hardened film is a hardened film containing a quantum dot hardened composition and has strong resistance to deformation and breakage. This invention provides a hardened film and a manufacturing method. The hardened film is a hardened film containing a quantum dot (A) and a photopolymerizable compound (B) hardened composition and has a Martens hardness greater than 0.10 GPa. The manufacturing method is a method for manufacturing a hardened film containing a quantum dot (A) and a photopolymerizable compound (B), and includes an exposure step of irradiating the film of the hardened composition with light, and a thermal curing step of thermally curing the film of the hardened composition. When the exposure amount in the exposure step is set as X (mJ / cm²), the thermal curing temperature in the thermal curing step is set as Y (°C), and the thermal curing time is set as Z (hr), equation (1) is satisfied: X×Y×Z²≧6500.

Description

[Technical Field]

[0001] The present invention relates to a hardened film and a display device including the hardened film. [Previous Technology]

[0002] Patent Document 1 discloses a composition for forming a hardened film comprising an adhesive polymer, a polymerizable compound, and semiconductor quantum dots, and a hardened film formed from the composition. [Prior Art Documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-025165 [Summary of the Invention]

[0004] [The problem that the invention aims to solve]

[0005] One object of the present invention is to provide a hardened film and a method for manufacturing the hardened film, said hardened film being a hardened film comprising a quantum dot composition, and exhibiting strong resistance to deformation and breakage. Another object of the present invention is to provide a display device including said hardened film. [Means for Solving the Problem]

[0006] The present invention provides a hardened film, a method for manufacturing the hardened film, and a display device as shown below. [1] A hardened film is a hardened film comprising a hardening composition of quantum dots (A) and a photopolymerizable compound (B), wherein the hardened film has a Martens hardness greater than 0.10 GPa. [2] The hardened film as described in [1], wherein the hardening composition further comprises a photopolymerization initiator (C). [3] The hardened film as described in [1] or [2], wherein the hardening composition further comprises a resin (D). [4] The hardened film as described in any one of [1] to [3], wherein the hardening composition further comprises a light scattering agent (E). [5] A method for manufacturing a curing film, comprising a curing composition including quantum dots (A) and a photopolymerizable compound (B), and comprising: an exposure step of irradiating the film of the curing composition with light; and a thermal curing step of thermally curing the film of the curing composition, wherein when the exposure amount in the exposure step is set to X (mJ / cm2), the thermal curing temperature in the thermal curing step is set to Y (°C), and the thermal curing time is set to Z (hr), the following equation (1) is satisfied: X×Y×Z2≧6500 (1). [6] The manufacturing method of [5] wherein the thermal curing step is performed in a vacuum atmosphere. [7] A display device comprising a curing film as described in any one of [1] to [4]. [Effects of the Invention]

[0007] A hardening film, a method for manufacturing the hardening film, and a display device including the hardening film may be provided, wherein the hardening film is a hardening film containing a quantum dot hardening composition and has strong resistance to deformation and damage.

Implementation Method

[0009] <<Curing Film>> The curing film of the present invention (hereinafter also simply referred to as "curing film") is a curing film of a curing composition, which can be formed by curing the curing composition. The curing composition contains at least quantum dots (A) and a photopolymerizable compound (B). The curing film formed from the curing composition containing quantum dots (A) can emit light of a different wavelength than the irradiated light when irradiated with ultraviolet or visible light. Therefore, the curing film containing quantum dots (A) can be used as a wavelength conversion film.

[0010] The hardened film, as measured by the method described in the following examples, has a Marvin hardness greater than 0.10 GPa. The Marvin hardness of the hardened film is preferably 0.12 GPa or higher, more preferably 0.15 GPa or higher, even more preferably 0.20 GPa or higher, even more preferably 0.22 GPa or higher, particularly preferably 0.24 GPa or higher, and most preferably 0.25 GPa or higher. Marvin hardness is a hardness that includes both plastic deformation and elastic deformation of the hardened film; it is a characteristic value that includes not only the hardness and deformation difficulty of the hardened film but also its flexibility. A hardened film with a Marvin hardness greater than 0.10 GPa can improve the deformation resistance and breakage resistance of the hardened film. When the hardened film is used as a wavelength conversion film (especially as a hardened pattern), deformation or breakage of the film can be prevented during the manufacture or use of the device containing the film.

[0011] The hardened film can also have high abrasion resistance. The abrasion resistance of the hardened film can be evaluated by pencil hardness. Specifically, the pencil hardness measured by the method described in the following embodiments is, for example, 3B or higher, preferably 2B or higher, more preferably H or higher, even more preferably 2H or higher, even more preferably 3H or higher, and particularly preferably 4H or higher. According to the hardened film with a pencil hardness of 2B or higher, damage to the surface of the hardened film during the manufacturing process of the display device is less likely to occur, and the reduction in emitted light intensity caused by surface damage or the deterioration of the hardened film during long-term use can be suppressed. According to the present invention, a hardened film with a pencil hardness of 2B or higher and high emitted light intensity can also be provided.

[0012] The martensitic hardness of the hardened film is preferably 0.35 GPa or less, more preferably 0.32 GPa or less, even more preferably 0.30 GPa or less, and particularly preferably 0.28 GPa or less. If the martensitic hardness of the hardened film is too high, the emitted light intensity may decrease when the hardened film is used as a wavelength conversion film. It is believed that the decrease in emitted light intensity is caused, for example, by extinction due to the shrinkage of the hardened film, resulting in the interparticle distance of the quantum dots (A) in the hardened film becoming closer. In a preferred embodiment, the martensitic hardness of the hardened film is greater than 0.10 GPa, and the emitted light intensity measured by the method described in the following examples is 1000 μW or more. In another preferred embodiment, the martensitic hardness of the hardened film is 0.20 GPa or more, and the emitted light intensity measured by the method described in the following examples is 1000 μW or more. In another preferred embodiment, the hardened film has a Martens hardness greater than 0.10 GPa, a pencil hardness of 2B or higher, and an emitted light intensity of 1000 μW or higher. The emitted light intensity is preferably 1100 μW or higher, more preferably 1200 μW or higher, and even more preferably 1300 μW or higher.

[0013] The hardening film of the present invention is not particularly limited, and can be preferably manufactured by the method described in the "Method for Manufacturing Hardening Film" described later.

[0014] <Curing composition> The curing composition includes quantum dots (A) and photopolymerizable compounds (B).

[0015] [1] Quantum dot (A) Quantum dot (A) is a semiconductor particle with a particle size of more than 1 nm and less than 100 nm, and is a particle that uses the band gap of semiconductor to absorb ultraviolet light or visible light to emit light. Examples of quantum dots (A) include: CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgST e. CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSe Compounds of Group 12 and Group 16 elements such as S, HgZnSeTe, and HgZnSTe; compounds of Group 13 and Group 15 elements such as GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, and InAlPAs; and compounds of Group 14 and Group 16 elements such as PdS and PbSe.

[0016] In cases where the quantum dot (A) contains S or Se, quantum dots with surfaces modified by metal oxides or organic materials may be used. By using surface-modified quantum dots, the removal of S or Se by reactive components contained in or potentially contained in the curing composition can be prevented.

[0017] Quantum dots (A) can be combined with the aforementioned compounds to form a core-shell structure. Examples of such combinations include particles with a CdSe core and a ZnS shell, particles with an InP core and a ZnSeS shell, etc.

[0018] The energy state of a quantum dot (A) depends on its size, thus the emission wavelength can be freely selected by changing the particle size. For example, in the case of quantum dots composed solely of CdSe, the peak wavelengths of the fluorescence spectra for particle sizes of 2.3 nm, 3.0 nm, 3.8 nm, and 4.6 nm are 528 nm, 570 nm, 592 nm, and 637 nm, respectively. Furthermore, the light emitted from the quantum dot (A) has a narrow spectral width; by combining this light with steep peaks, the displayable color gamut can be expanded in display devices including hardened films formed from hardening components. Moreover, the quantum dot (A) has high responsiveness, allowing for efficient utilization of light emitted from a light source.

[0019] The curing composition may contain only one type of quantum dot that emits light of a specific wavelength by means of light emitted from a light source, or it may combine two or more types of quantum dots that emit light of different wavelengths. Examples of the specific wavelength of light include red light, green light, and blue light.

[0020] Relative to the total amount of solid components in the curing composition, the content of quantum dots (A) in the curing composition is, for example, 1% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 50% by mass or less, further preferably 20% by mass or more and 50% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less. In this specification, the total amount of solid components refers to the sum of the components contained in the curing composition excluding the solvent (I). The content of each component in the solid components of the curing composition can be determined by known analytical methods such as liquid chromatography or gas chromatography. The content of each component in the solid components of the curing composition can be calculated from the formulation used in the preparation of the curing composition.

[0021] [2] Ligand (H) The curing composition may contain a compound (hereinafter also referred to as "ligand") having the ability to coordinate with the quantum dot (A). The ligand is, for example, an organic compound having a polar group that exhibits the ability to coordinate with semiconductor particles. The curing composition may contain one or more ligands.

[0022] The polar group is preferably at least one group selected from the group consisting of thiol groups (-SH), carboxyl groups (-COOH), and amino groups (-NH2). Polar groups selected from this group are advantageous in terms of improving the coordination ability to semiconductor particles. High coordination ability can help improve the color uniformity of the cured film and / or improve the pattern formation of the cured composition. In particular, from the viewpoint of obtaining a cured film with excellent emitted light characteristics, the polar group is more preferably at least one group selected from the group consisting of thiol groups and carboxyl groups. The ligand may have one or more polar groups.

[0023] The ligand may be, for example, an organic compound represented by the following formula (I). XA-RX (I) Wherein, XA is the polar group, and RX is a monovalent hydrocarbon group that may contain heteroatoms (N, O, S, halogen atoms, etc.). The hydrocarbon group may have one or more unsaturated bonds such as carbon-carbon double bonds. The hydrocarbon group may have a straight-chain, branched-chain, or cyclic structure. The number of carbon atoms in the hydrocarbon group may be, for example, 1 or more and 40 or less, or 1 or more and 30 or less. The methylene group contained in the hydrocarbon group may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc.

[0024] The base RX may also contain a polar base. For a specific example of such a polar base, please refer to the description of the polar base XA.

[0025] Specific examples of ligands having a carboxyl group as a polar group XA include: formic acid, acetic acid, propionic acid, and other saturated or unsaturated fatty acids. Specific examples of saturated or unsaturated fatty acids include: saturated fatty acids such as butyric acid, valeric acid, hexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, docosahexaenoic acid, and lignoceric acid; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, icosenoic acid, erucic acid, and nervonic acid; and linolenic acid, α-linolenic acid, γ-linolenic acid, stearidonic acid, dihomeno-γ-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenaline. Polyunsaturated fatty acids such as docosatraenoic acid (docosatetraenoic acid).

[0026] Specific examples of ligands having a thiol group or an amino group as a polar group XA include ligands formed by replacing the carboxyl group of the ligands having a carboxyl group as a polar group XA as illustrated above with a thiol group or an amino group.

[0027] As preferred examples of the ligands represented by the formula (I), compounds (J-1) and (J-2) can be listed.

[0028] [Compound (J-1)] Compound (J-1) is a compound having a first functional group and a second functional group. The first functional group is a carboxyl group (-COOH), and the second functional group is a carboxyl group or a thiol group (-SH). Because compound (J-1) has a carboxyl group and / or a thiol group, it can be a ligand with the ability to coordinate with quantum dots (A). The hardening composition may contain only one compound (J-1) or may contain two or more compounds.

[0029] By including compound (J-1) in the curing composition, the development speed of the curing composition can be significantly accelerated, and the emitted light intensity of the cured film formed by the curing composition can be increased. This is believed to be because the carboxyl and thiol groups present in compound (J-1) can impart high developability to the curing composition based on alkaline developing solutions, and can be well-coordinated with quantum dots (A) to improve the dispersibility of quantum dots (A) in the curing composition. In particular, the carboxyl groups have a greater effect on improving developability based on alkaline developing solutions, and the thiol groups have a greater effect on improving the dispersibility of quantum dots (A).

[0030] Furthermore, the term "emitted light intensity" as used in this specification refers to the intensity of light emitted from the hardened film, which can be measured as brightness. For example, "emitted light intensity" may include the following two light intensities: the intensity of light emitted from the side of the incident light incident on the hardened film from the side opposite to the light source on the opposing main surface of the hardened film (e.g., incident light from the light source of the backlight unit incident on the hardened film is emitted towards the display side), and the intensity of light extracted by the excitation light incident on the hardened film from the quantum dot (A) inside the hardened film (internal emission) when the excitation light incident on the hardened film from the light source extracts the fluorescence (internal emission) emitted by the quantum dot (A) inside the hardened film from the hardened film to one side of the opposing main surface of the hardened film (e.g., the display side in the case where the display is arranged above the hardened film in the backlight unit).

[0031] Accelerating the development speed of the curing components can also help increase the intensity of emitted light from the cured film. This is believed to be because it can inhibit the penetration of water into the cured film during the development step.

[0032] An example of compound (J-1) is the compound represented by the following formula (J-1a). Compound (J-1) may also be the acid anhydride of the compound represented by formula (J-1a).

[0033] [Chemical 1][In the formula, RB represents a divalent hydrocarbon group; when multiple RBs are present, they may be the same or different; the hydrocarbon group may have more than one substituent; when multiple substituents are present, they may be the same or different, and they may bond to each other to form a ring together with the atoms they are bonded to; the -CH2- contained in the hydrocarbon group may be substituted to at least one of -O-, -S-, -SO2-, -CO- and -NH-. p represents an integer from 1 to 10.]

[0034] Examples of divalent hydrocarbon groups represented by RB include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Chain hydrocarbon groups include linear or branched alkyl diesters, typically with 1 to 50 carbon atoms, preferably 1 to 20, and more preferably 1 to 10. Alicyclic hydrocarbon groups include monocyclic or polycyclic cycloalkyl diesters, typically with 3 to 50 carbon atoms, preferably 3 to 20, and more preferably 3 to 10. Aromatic hydrocarbon groups include monocyclic or polycyclic aromatic diesters, typically with 6 to 20 carbon atoms.

[0035] Examples of substituents that may be present in the hydrocarbon group include: alkyl groups with 1 to 50 carbon atoms, cycloalkyl groups with 3 to 50 carbon atoms, aryl groups with 6 to 20 carbon atoms, carboxyl groups, amino groups, halogen atoms, etc. Preferably, the substituents that may be present in the hydrocarbon group are carboxyl groups, amino groups, or halogen atoms.

[0036] Where the -CH2- group contained in the hydrocarbon group is substituted with at least one of -O-, -CO- and -NH-, the substitution of -CH2- is preferably at least one of -CO- and -NH-, more preferably -NH-. p is preferably 1 or 2.

[0037] As a compound represented by formula (J-1a), for example, compounds represented by formulas (1-1) to (1-9) can be listed below.

[0038] [Chemical 2]

[0039] Specific examples of compounds represented by formula (J-1a) can be shown by chemical names, such as: mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercaptobutyric acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetylglycine, 3-methoxybutyl 3-mercaptopropionic acid, 3-mercapto-2-methylpropionic acid, etc. Among these, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0040] Another example of compound (J-1) is a polycarboxylic acid compound, preferably a compound (J-1b) formed by substituting -SH in formula (J-1a) with a carboxyl group (-COOH).

[0041] As compounds (J-1b), the following compounds can be listed for example: succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanedioic acid, octadecanoic acid, nonadecanedioic acid, dodecanoic acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenic acid, sebacic acid, hexafluorosecanedioic acid, acetylenic acid dicarboxylic acid, trans-torsinolic acid, 1,3-adamantane dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, 1,1-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, cis-1,3-cyclohexane dicarboxylic acid or trans-1,3-cyclohexane dicarboxylic acid, cis-1 4-Cyclohexanedicarboxylic acid or trans-1,4-cyclohexanedicarboxylic acid, 1,1-cyclopentanediacetic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, 2,3-norbornanedicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, phthalic acid, 3-fluorophthalic acid, isophthalic acid, tetrafluoroisophthalic acid, terephthalic acid, tetrafluoroterephthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,1'-ferrocenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,5-furandicarboxylic acid, diphenylcarboxylic acid Ketone-2,4'-dicarboxylic acid monohydrate, benzophenone-4,4'-dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 2,3-pyridine dicarboxylic acid, 2,4-pyridine dicarboxylic acid, 3,5-pyridine dicarboxylic acid, 2,5-pyridine dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 3,4-pyridine dicarboxylic acid, pyrazole-3,5-dicarboxylic acid monohydrate, 4,4'-stilbene dicarboxylic acid, anthraquinone-2,3-dicarboxylic acid, 4-(carboxymethyl)benzoic acid, chelidonic acid monohydrate, azobenzene-4,4'-dicarboxylic acid, azobenzene-3,3'-dicarboxylic acid, chlorobridged acid, 1H-imidazolium-4,5-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane 1,10-bis(4-carboxyphenoxy)decane, dipropylmalonic acid, dithiodiethanolic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiodibutyric acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl ether, ethylene glycol bis(4-carboxyphenyl) ether, 3,4-ethyldioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropylidene diphenoxyacetic acid, 1,3-propanone dicarboxylic acid, methylene disalicylic acid, 5,5'-thiodisalicylic acid, tris(2-carboxyethyl)isocyanurate, tetrafluorosuccinic acid, α,α,α',α'-tetramethyl-1,3-phenylenediamine, 1,3,5-benzenetricarboxylic acid, etc.

[0042] From the viewpoint of accelerating the development speed of the curing composition and increasing the emitted light intensity of the cured film, the molecular weight of compound (J-1) is preferably 3000 or less, more preferably 2000 or less, even more preferably 1000 or less, even more preferably 800 or less, and particularly preferably 500 or less. The molecular weight of compound (J-1) is generally 100 or more.

[0043] The molecular weight may be either the number average molecular weight or the weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are the number average molecular weight and weight average molecular weight converted from standard polystyrene, respectively, determined by gel permeation chromatography (GPC).

[0044] When the curing composition includes quantum dots (A) and compound (J-1), the content ratio of compound (J-1) to quantum dots (A) in the curing composition, by mass ratio, is preferably 0.001 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, and even more preferably 0.02 or more and 0.1 or less. If this content ratio is within this range, it may be advantageous from the viewpoint of accelerating the development speed of the curing composition and increasing the emitted light intensity of the cured film.

[0045] When the curing composition contains compound (J-1), from the viewpoint of accelerating the development speed of the curing composition and increasing the emitted light intensity of the cured film, the content of compound (J-1) in the curing composition is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, further preferably 0.2% by mass or more and 8% by mass or less, even more preferably 0.2% by mass or more and 5% by mass or less, and particularly preferably 0.5% by mass or more and 4% by mass or less.

[0046] [Compound (J-2)] Compound (J-2) is different from compound (J-1). It is a compound containing a polyalkylene glycol structure and having a polar group at the molecule's end. The molecule's end is preferably the end of the longest carbon chain in compound (J-2) (the carbon atom in the carbon chain may be replaced by other atoms such as oxygen atoms). The curing composition may contain only one compound (J-2) or may contain two or more. Furthermore, compounds containing a polyalkylene glycol structure and having the first functional group and the second functional group belong to compound (J-1).

[0047] From the viewpoint of accelerating the development speed of the curing composition and increasing the intensity of emitted light from the curing film, the curing composition may contain compound (J-1) or compound (J-2), or may contain both compound (J-1) and compound (J-2).

[0048] The polyalkylene glycol structure refers to the structure represented by the following formula (n is an integer greater than or equal to 2).

[0049] [Chemical 3]

[0050] In the formula, RC is an alkyl group, such as alkyl ethyl, alkyl propyl, etc. As a specific example of compound (J-2), polyalkylene glycol compounds represented by the following formula (J-2a) can be listed.

[0051] [Chemical 4]

[0052] In formula (J-2a), X is a polar group, Y is a monovalent group, and ZC is a divalent or trivalent group. n is an integer greater than or equal to 2. m is 1 or 2. RC is an alkyl group.

[0053] The polar group X is preferably selected from at least one group chosen from the group consisting of thiol groups (-SH), carboxyl groups (-COOH), and amino groups (-NH2). Polar groups selected from this group are advantageous in improving the coordination ability to the quantum dot (A). In particular, from the viewpoint of improving the emitted light intensity of the hardened film, the polar group X is more preferably selected from at least one group chosen from the group consisting of thiol groups and carboxyl groups.

[0054] Base Y is a monovalent base. There are no particular restrictions on base Y; examples include monovalent hydrocarbon groups that can have substituents (N, O, S, halogen atoms, etc.). The -CH2- contained in this hydrocarbon group can be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc.

[0055] The hydrocarbon group has, for example, 1 or more and 12 or less carbon atoms. The hydrocarbon group may also have an unsaturated bond. Examples of the group Y include: alkyl groups having a straight-chain, branched-chain, or cyclic structure with 1 or more and 12 or less carbon atoms; alkoxy groups having a straight-chain, branched-chain, or cyclic structure with 1 or more and 12 or less carbon atoms. The alkyl group and alkoxy group preferably have 1 or more and 8 or less carbon atoms, more preferably 1 or more and 6 or less, and even more preferably 1 or more and 4 or less carbon atoms. The -CH2- group contained in the alkyl group and alkoxy group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. Preferably, the group Y is a straight-chain or branched-chain alkoxy group with 1 or more and 4 or less carbon atoms, more preferably a straight-chain alkoxy group with 1 or more and 4 or less carbon atoms.

[0056] The base Y may contain a polar group. Such a polar group may be selected from at least one group chosen from the group consisting of thiols (-SH), carboxyl groups (-COOH), and amino groups (-NH2). As described above, compounds containing a polyalkylene glycol structure and having both the first and second functional groups belong to compound (J-1). Preferably, the polar group is disposed at the end of the base Y.

[0057] The ZC group is a divalent or trivalent group. There are no particular restrictions on the ZC group, and examples include divalent or trivalent hydrocarbon groups that may contain heteroatoms (N, O, S, halogen atoms, etc.). The number of carbon atoms in the hydrocarbon group is, for example, 1 or more and 24 or less. The hydrocarbon group may also have unsaturated bonds.

[0058] Examples of divalent ZC groups include: alkyl groups having a linear, branched, or cyclic structure with 1 or more and 24 or less carbon atoms; and alkenyl groups having a linear, branched, or cyclic structure with 1 or more and 24 or less carbon atoms. Preferably, the alkyl and alkenyl groups have 1 or more and 12 or less carbon atoms, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less carbon atoms. The -CH2- group contained in the alkyl and alkenyl groups may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -C(=O)-NH-, -NH-, etc. Examples of trivalent ZC groups include groups formed by removing one hydrogen atom from the divalent ZC groups described above.

[0059] The ZC base may have a branched structure. The ZC base having a branched structure may also have a polyalkylene glycol structure different from the polyalkylene glycol structure represented by the formula (J-2a) in a branched chain that is different from the branched chain containing the polyalkylene glycol structure represented by the formula (J-2a).

[0060] Wherein, the ZC is preferably a straight-chain or branched alkyl group having 1 or more and 6 or less carbon atoms, and more preferably a straight-chain alkyl group having 1 or more and 4 or less carbon atoms.

[0061] RC is an alkyl group, preferably a straight-chain or branched alkyl group having 1 or more and 6 or fewer carbon atoms, and more preferably a straight-chain alkyl group having 1 or more and 4 or fewer carbon atoms.

[0062] In formula (J-2a), n is an integer greater than or equal to 2, preferably greater than or equal to 2 and less than 540, more preferably greater than or equal to 2 and less than 120, and even more preferably greater than or equal to 2 and less than 60.

[0063] The molecular weight of compound (J-2) may be, for example, 150 or more and 10,000 or less. From the viewpoint of accelerating the development speed of the curing composition and increasing the intensity of emitted light from the curing film, it is preferred to be 150 or more and 5,000 or less, and more preferably 150 or more and 4,000 or less.

[0064] The molecular weight may be either the number average molecular weight or the weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are the number average molecular weight and weight average molecular weight converted from standard polystyrene, respectively, determined by gel permeation chromatography (GPC).

[0065] When the curing composition includes quantum dots (A) and compound (J-2), the content ratio of compound (J-2) to quantum dots (A) in the curing composition, by mass ratio, is preferably 0.001 or more and 2 or less, more preferably 0.01 or more and 1.5 or less, and even more preferably 0.1 or more and 1 or less. If this content ratio is within this range, it may be advantageous from the viewpoint of accelerating the development speed of the curing composition and increasing the emitted light intensity of the cured film.

[0066] When the curing composition contains compound (J-2), from the viewpoint of accelerating the development speed of the curing composition and increasing the emitted light intensity of the curing film, the content of compound (J-2) in the curing composition is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and more preferably 2% by mass or more and 10% by mass or less.

[0067] When the curing composition includes compound (J-1) and compound (J-2), the content ratio of compound (J-2) to compound (J-1) in the curing composition, by mass ratio, is preferably 1 or more and 50 or less, more preferably 5 or more and 40 or less, and even more preferably 10 or more and 25 or less. If this content ratio is within this range, it may be advantageous from the viewpoint of accelerating the development speed of the curing composition and increasing the emitted light intensity of the cured film.

[0068] The curing composition may further include compounds other than compounds (J-1) and (J-2), namely, compounds (J-3) that have the ability to coordinate with quantum dots (A). Examples of compounds (J-3) include organic acids, organic amine compounds, thiols, etc.

[0069] [3] Photopolymerizable compound (B) The curing component includes one or more photopolymerizable compounds (B). The photopolymerizable compound (B) is a compound that can be polymerized by active free radicals, acids, etc. generated from the photopolymerization initiator (C) described later. Examples of photopolymerizable compounds (B) include photoradical polymers that are cured by light irradiation and free radical polymerization reactions, and photocationic polymers that are cured by light irradiation and cationic polymerization reactions. The photopolymerizable compound (B) is preferably a photoradical polymer.

[0070] The weight average molecular weight of the photopolymerizable compound (B) is, for example, 150 or more and 3000 or less, preferably 150 or more and 2900 or less, and more preferably 250 or more and 1500 or less.

[0071] Examples of photoradical polymerizable compounds include compounds with polymerizable vinyl unsaturated bonds, among which (meth)acrylate compounds are preferred. Examples of (meth)acrylate compounds include: monofunctional (meth)acrylate monomers having one (meth)acryloxy group (hereinafter also referred to as "Compound (B-1)"); difunctional (meth)acrylate monomers having two (meth)acryloxy groups (hereinafter also referred to as "Compound (B-2)"); and polyfunctional (meth)acrylate monomers having three or more (meth)acryloxy groups (hereinafter also referred to as "Compound (B-3)"). In this specification, "(meth)acrylate" refers to acrylates and / or methacrylates. The same applies to "(meth)acrylyl", "(meth)acrylic acid", etc.

[0072] As a compound (B-1), examples include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, dodecyl methacrylate (laurate methacrylate), hexadecyl methacrylate, octadecyl methacrylate, cyclohexyl methacrylate, methoxyethyl methacrylate, butoxyethyl methacrylate, phenoxyethyl methacrylate, nonylphenoxyethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Esters, isobornyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, phenyl methacrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, 2-(2-ethyleneoxyethoxy)ethyl methacrylate, ω-carboxy-polycaprolactone monoacrylate, ethyl carbitol methacrylate ((meth)acrylate ethoxyethoxyethyl methacrylate), 3,3,5-trimethylcyclohexyl methacrylate, etc.

[0073] As a compound (B-2), examples include: 1,3-butanediol 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, neopentanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentanediol hydroxypentanoate di(meth)acrylate, tri... Di(meth)acrylates containing two hydroxyl groups substituted with (meth)acryloxy groups of (2-hydroxyethyl)isocyanurate, di(meth)acrylates containing two hydroxyl groups substituted with (meth)acryloxy groups of a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, di(meth)acrylates containing two hydroxyl groups substituted with (meth)acryloxy groups of a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, di(meth)acrylates containing two hydroxyl groups substituted with (meth)acryloxy groups of a triol obtained by adding 3 or more moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane, di(meth)acrylates containing two hydroxyl groups substituted with (meth)acryloxy groups of a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, etc.

[0074] As compounds (B-3), examples include: triglyceride (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tri(2-(meth)acryloxyethyl)iso Cyanourea ester, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate succinate monoester, dipentaerythritol pentaacrylate succinate monoester, pentaerythritol triacrylate maleate monoester, dipentaerythritol pentaacrylate maleate monoester, etc.

[0075] Examples of photocationically polymerizable compounds include compounds having at least one oxetane ring (4-membered cyclic ether) in the molecule (hereinafter also referred to as "oxetane compounds"), compounds having at least one ethylene oxide ring (3-membered cyclic ether) in the molecule (hereinafter also referred to as "epoxide compounds"), and vinyl ether compounds.

[0076] As oxetane compounds, examples include: 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetane-butyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, di[(3-ethyl-3-oxetane-butyl)methyl] ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenolic varnish oxetane, etc. These oxetane compounds are readily available commercially, and as commercially available products, they are all sold under trade names by Toa Synthetic (Co., Ltd.), such as "Aron Oxetane (registered trademark) OXT-101", "Aron Oxetane (registered trademark) OXT-121", "Aron Oxetane (registered trademark) OXT-211", "Aron Oxetane (registered trademark) OXT-221", and "Aron Oxetane (registered trademark) OXT-121", etc.

[0077] As epoxides, examples include: aromatic epoxides, glycidyl ethers of polyols having alicyclic rings, aliphatic epoxides, alicyclic epoxides, etc.

[0078] As aromatic epoxy compounds, examples include: bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol S; phenolic varnish type epoxy resins such as phenolic varnish epoxy resin, cresolic varnish epoxy resin and hydroxybenzaldehyde phenolic varnish epoxy resin; and multifunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone and epoxidized polyethylene phenol.

[0079] Examples of glycidyl ethers of polyols having alicyclic rings include: glycidyl ethers obtained by selectively hydrogenating the aromatic ring of an aromatic polyol under pressure in the presence of a catalyst. Examples of aromatic polyols include: bisphenol-type compounds such as bisphenol A, bisphenol F, and bisphenol S; phenolic varnish-type resins such as phenol-formaldehyde resin, cresol-formaldehyde resin, and hydroxybenzaldehyde-formaldehyde resin; and polyfunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxybenzophenone, and polyvinylphenol. Glycidyl ethers can be prepared by reacting epichlorohydrin with alicyclic polyols obtained by hydrogenating the aromatic ring of these aromatic polyols. Among these glycidyl ethers of polyols having alicyclic rings, diglycidyl ethers of hydrogenated bisphenol A are preferred.

[0080] Examples of aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyols or their alkylene oxide adducts. Specifically, examples include: diglycidyl ether of 1,4-butanediol; diglycidyl ether of 1,6-hexanediol; triglycidyl ether of glycerol; trimethylolpropane triglycidyl ether; diglycidyl ether of polyethylene glycol; diglycidyl ether of propylene glycol; diglycidyl ether of neopentyl glycol; and polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyols such as ethylene glycol, propylene glycol, or glycerol.

[0081] Alicyclic epoxy compounds are compounds that have at least one ethylene oxide ring formed together with a carbon atom of an alicyclic ring within the molecule. Examples include: "Celloxide" series and "Cyclomer" (all manufactured by Daicel Inc.), "Cyracure UVR" series (manufactured by Dow Chemical Company), etc.

[0082] As vinyl ether compounds, examples include: 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, trimethylolpropane trivinyl ether, etc.

[0083] The photopolymerizable compound (B) is preferably a polyfunctional (meth)acrylate monomer (compound (B-3)) having three or more (meth)acryloxy groups within its molecule. By including compound (B-3) in the curing composition, the heat resistance and mechanical strength of the curing composition and the cured film can be improved, and it is also advantageous in improving the emitted light intensity of the cured film. In addition, by including compound (B-3) in the curing composition, the curability of the curing composition can be improved.

[0084] As compound (B-3), examples include compounds (B-3a) having three or more (meth)acryloxy groups and having acidic functional groups, and compounds (B-3b) having three or more (meth)acryloxy groups and not having acidic functional groups. The photopolymerizable compound (B) preferably includes at least one of compounds (B-3a) and (B-3b), and may also include two or more compounds (B-3a), two or more compounds (B-3b), or at least one of compounds (B-3a) and at least one of compounds (B-3b).

[0085] Preferably, the curing composition includes compound (B-3a) as a photopolymerizable compound. By including compound (B-3a) in the curing composition, the aggregation of quantum dots (A) can be suppressed, the dispersion of quantum dots (A) can be improved, and as a result, the emitted light intensity of the cured film obtained from the curing composition can be improved. In addition, by including compound (B-3a) in the curing composition, the curability of the curing composition can be improved. Furthermore, by including compound (B-3a) in the curing composition, the heat resistance of the curing composition and the cured film can be improved. In one embodiment, from the viewpoint of improving the development speed of the curing composition, the photopolymerizable compound (B) includes compound (B-3b) at least 50% by mass relative to the total amount of photopolymerizable compound (B) contained in the curing composition. In another embodiment, from the viewpoint of improving the solvent resistance (residual film rate) of the cured film, the photopolymerizable compound (B) includes both compound (B-3a) and compound (B-3b).

[0086] Examples of acidic functional groups include carboxyl groups, sulfonic acid groups, and phosphate groups. Among these, carboxyl groups are preferred.

[0087] The number of (meth)acryloxy groups in one molecule of compound (B-3) is, for example, 3 or more and 6 or less, preferably 3 or more and 5 or less, and more preferably 3. The number of acidic functional groups in one molecule of compound (B-3a) is 1 or more, preferably 1. When there are 2 or more acidic functional groups, the individual acidic functional groups may be different or the same, but it is preferred that at least one carboxyl group is present.

[0088] As a compound (B-3a), examples include compounds formed by esterifying a compound having three or more (meth)acrylic acid groups, such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, with a dicarboxylic acid. Examples of such compounds include compounds formed by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid, compounds formed by monoesterifying dipentaerythritol penta(meth)acrylate with succinic acid, compounds formed by monoesterifying pentaerythritol tri(meth)acrylate with maleic acid, and compounds formed by monoesterifying dipentaerythritol penta(meth)acrylate with maleic acid. Preferably, the compound formed by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid is preferred.

[0089] Commercially available products containing compound (B-3a) include, for example, "Aronix M-510" manufactured by Toa Synthetic Co., Ltd., whose main component is a dicarboxylic acid anhydride adduct of pentaerythritol tri(meth)acrylate, and "Aronix M-520D" manufactured by Toa Synthetic Co., Ltd., whose main component is a dicarboxylic acid anhydride adduct of dipentaerythritol penta(meth)acrylate. These commercially available products have a carboxyl group as an acidic functional group.

[0090] When the photopolymerizable compound (B) includes compound (B-3) (preferably compound (B-3a)), from the viewpoint of improving the curability of the curable composition, the heat resistance of the curable film and the intensity of emitted light, the content of compound (B-3) relative to the total amount of photopolymerizable compound (B) is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, more preferably 50% by mass or less, more preferably 40% by mass or less, and especially preferably 30% by mass or less.

[0091] When the photopolymerizable compound (B) includes compound (B-3) (preferably compound (B-3a)), from the viewpoint of improving the curability of the curable composition, the heat resistance of the curable film, and the intensity of emitted light, the content of compound (B-3) relative to the total amount of the curable composition or the total amount of the solid component of the curable composition is preferably 0.1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 40% by mass or less, further preferably 2% by mass or more and 30% by mass or less, further preferably 5% by mass or more and 20% by mass or less, and especially preferably 5% by mass or more and 15% by mass or less.

[0092] When the photopolymerizable compound (B) includes compound (B-3) (preferably compound (B-3a)), the content of compound (B-3) is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, more preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and preferably 110 parts by mass or less, more preferably 100 parts by mass or less, more preferably 85 parts by mass or less, and more preferably 70 parts by mass or less, relative to 100 parts by mass or less of quantum dots (A).

[0093] The photopolymerizable compound (B) is preferably a (meth)acrylate monomer (hereinafter also referred to as "compound (B-4)") containing a vinyl ether group and a (meth)acrylyl group (preferably (meth)acryloxy) within the same molecule. By including compound (B-4) in the curing composition, the aggregation of quantum dots (A) can be suppressed, and the dispersion of semiconductor particles (A) can be improved. As a result, the emitted light intensity of the cured film obtained from the curing composition can be improved. In addition, by including compound (B-4) in the curing composition, the viscosity of the curing composition can be reduced, and the coatability can be improved. Compound (B-4) may be any one of compounds (B-1) to (B-3).

[0094] The compound (B-4) preferably has 1 or more and 4 or less vinyl ether groups, more preferably 1 or more and 2 or less, and especially preferably 1. The compound (B-4) preferably has 1 or more and 4 or less (meth)acrylic groups, more preferably 1 or more and 2 or less, and especially preferably 1.

[0095] As compounds (B-4), examples include: 2-ethoxyethyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 1-ethoxypropyl (meth)acrylate, 1-methyl-2-ethoxyethyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate, 3-ethoxybutyl (meth)acrylate, 2-ethoxybutyl (meth)acrylate, 1-methyl-3-ethoxypropyl (meth)acrylate, 2-methyl-3-ethoxypropyl (meth)acrylate, 1-methyl-2-ethoxypropyl (meth)acrylate, 1,1-Dimethyl-2-ethyleneoxyethyl ester, 6-ethyleneoxyhexyl (meth)acrylate, 4-ethyleneoxycyclohexyl (meth)acrylate, (4-ethyleneoxymethylcyclohexyl)methyl (meth)acrylate, (3-ethyleneoxymethylcyclohexyl)methyl (meth)acrylate, (2-ethyleneoxymethylcyclohexyl)methyl (meth)acrylate, (4-ethyleneoxymethylphenyl)methyl (meth)acrylate, (3-ethyleneoxymethylphenyl)methyl (meth)acrylate, 2-ethyleneoxymethylphenyl (meth)acrylate, 2-(2-ethyleneoxy)methyl acrylate 2-(2-ethyleneoxyethoxy)ethyl acrylate, 2-(2-ethyleneoxyethoxy)propyl acrylate, 2-(2-ethyleneoxyisopropoxy)propyl acrylate, 2-(2-ethyleneoxyethoxy)isopropyl acrylate, 2-(2-ethyleneoxyisopropoxy)isopropyl acrylate, 2-{2-(2-ethyleneoxyethoxy)ethoxy}ethyl acrylate, 2-{2-(2-ethyleneoxyisopropoxy)ethoxy}ethyl acrylate, 2-{2-(2-ethyleneoxyisopropoxy)ethoxy}ethyl acrylate, 2-(ethyleneoxyisopropoxy)ethyl acrylate 2-(2-Ethyleneoxyisopropoxy)isopropoxy}ethyl acrylate, 2-(2-(2-Ethyleneoxyethoxy)ethoxy}propyl acrylate, 2-(2-(2-Ethyleneoxyethoxy)isopropoxy}propyl acrylate, 2-(2-Ethyleneoxyisopropoxy)ethoxy}propyl acrylate, 2-(2-(2-Ethyleneoxyisopropoxy)isopropoxy}propyl acrylate, 2-(2-(2-Ethyleneoxy)ethoxy}isopropyl acrylate, 2-(2-Ethyleneoxyethoxy)isopropoxy}propyl acrylate (Methoxy)isopropoxy}isopropyl ester, (meth)acrylate 2-{2-(2-ethyleneoxyisopropoxy)ethoxy}isopropyl ester, (meth)acrylate 2-{2-(2-ethyleneoxyisopropoxy)ethoxy}isopropyl ester, (meth)acrylate 2-[2-{2-(2-ethyleneoxyethoxy)ethoxy}ethoxy]ethyl ester, (meth)acrylate 2-[2-{2-(2-ethyleneoxyisopropoxy)ethoxy}ethoxy]ethyl ester, (meth)acrylate 2-(2-[2-{2-(2-ethyleneoxyethoxy)ethoxy}ethoxy]ethoxy)ethyl ester, etc.

[0096] As compound (B-4), it is preferably (meth)acrylate vinyloxy C1-6 alkyl ester or (meth)acrylate (vinyloxy C1-4 alkoxy) C1-4 alkyl ester, more preferably (meth)acrylate (vinyloxy C1-4 alkoxy) C1-4 alkyl ester, and especially preferably (meth)acrylate 2-(2-vinyloxyethoxy)ethyl ester.

[0097] When the photopolymerizable compound (B) includes compound (B-4), from the viewpoints of reducing the viscosity of the curing composition and increasing the emitted light intensity of the curing film, the content of compound (B-4) relative to the total amount of photopolymerizable compound (B) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, and preferably 85% by mass or less, even more preferably 75% by mass or less, even more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less.

[0098] When the photopolymerizable compound (B) contains compound (B-4), from the viewpoint of reducing the viscosity of the curing composition and increasing the emitted light intensity of the curing film, the content of compound (B-4) is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, further preferably 10% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 35% by mass or less.

[0099] When the photopolymerizable compound (B) contains compound (B-4), the content of compound (B-4) is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, more preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and preferably 110 parts by mass or less, more preferably 100 parts by mass or less, more preferably 85 parts by mass or less, and more preferably 70 parts by mass or less, relative to 100 parts by mass or less of quantum dots (A).

[0100] The photopolymerizable compound (B) is preferably a monofunctional (meth)acrylate monomer (compound (B-1)) having an intramolecular (meth)acryloxy group. By including compound (B-1) in the curing composition, the viscosity of the curing composition can be reduced and the coatability can be improved.

[0101] From the viewpoint of suppressing degassing of the self-curing film caused by heat load or pressure reduction in the subsequent step (formation of the barrier layer, etc.) of forming the color conversion layer of the display device described later, the curing component is preferably a polymeric compound containing a volatility of 10% by mass or less when heated at 80°C for 1 hour. From the same viewpoint, the photopolymeric compound (B) is more preferably a compound containing compound (B-1), i.e., a compound containing a volatility of 10% by mass or less when heated at 80°C for 1 hour. This volatility is preferably 8% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and may also be 0.01% by mass or more or 0.1% by mass or more. The volatility when heated at 80°C for 1 hour can be determined in the following order: Weigh 5 g of the photopolymeric compound (B) onto an aluminum cup, and then set it on a heating plate at 80°C for 1 hour. The amount of vaporization (mass%) is calculated from the initial weight (W0) and the weight after 1 hour (W1) using the following formula: Amount of vaporization (mass%) = 100 × (W0 - W1) / W0

[0102] From the viewpoint of obtaining a hardened film with good emitted light intensity, the curing component is preferably a polymeric compound, that is, a polymeric compound whose homopolymer has a glass transition temperature of -50°C or higher. Similarly, from the same viewpoint, the photopolymeric compound is more preferably a compound (B-1) whose homopolymer has a glass transition temperature of -50°C or higher. This glass transition temperature is preferably -30°C or higher, more preferably -20°C or higher, and may be 0°C or higher, or 200°C or lower. This glass transition temperature can be a value found in a catalog, a general property table, or can be measured using a commercially available differential scanning calorimeter.

[0103] From the viewpoint of obtaining a hardened film with good emitted light intensity, the hardening component is preferably a compound containing a hydrocarbon group, which is a compound (B-1) and whose group bonded to (meth)acryloxy group is free of heteroatoms such as oxygen and nitrogen atoms. This hydrocarbon group is more preferably a chain hydrocarbon group or an alicyclic hydrocarbon group.

[0104] When the photopolymerizable compound (B) contains compound (B-1), from the viewpoint of reducing the viscosity of the curable composition, the content of compound (B-1) relative to the total amount of photopolymerizable compound (B) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, and preferably 75% by mass or less, even more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 50% by mass or less.

[0105] When the photopolymerizable compound (B) contains compound (B-1), from the viewpoint of reducing the viscosity of the curing composition, the content of compound (B-1) is preferably 5% by mass or more and 50% by mass or less, more preferably 8% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and more preferably 15% by mass or more and 35% by mass or less, relative to the total amount of the curing composition or the total amount of the solid component of the curing composition.

[0106] Relative to the total amount of solid components in the curing composition, the content of the photopolymerizable compound (B) in the curing composition is, for example, 5% by mass or more and 70% by mass or less, preferably 7% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and even more preferably 13% by mass or more and 40% by mass or less. When the content of the photopolymerizable compound (B) is within the above range, the solvent resistance (residual film rate) of the cured film tends to be improved.

[0107] From the viewpoint of improving the development speed of the curing composition, the content of photopolymerizable compound (B) is preferably 13% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to the total amount of solid components in the curing composition.

[0108] [4] Photopolymerization initiator (C) The curing composition may contain one or more photopolymerization initiators (C). The photopolymerization initiator (C) is a compound that can initiate polymerization by generating active free radicals, acids, etc. through the action of light or heat.

[0109] The photopolymerization initiator (C) is preferably an oxime compound having the first molecular structure represented by the following formula (1). Hereinafter, the oxime compound is also referred to as "oxime compound (1)".

[0110] [Chemistry 5]

[0111] From the viewpoint of increasing the intensity of emitted light from the hardened film, it may be advantageous to contain an oxime compound (1) as a photopolymerization initiator (C). One reason for this effect is speculated to be that, due to the unique molecular structure of the oxime compound (1), the absorption wavelength of the oxime compound (1) changes significantly before and after the oxime compound (1) required to initiate photopolymerization, thus the oxime compound (1) has a high photoradical polymerization initiation ability.

[0112] In formula (1), R1 represents R11, OR11, COR11, SR11, CONR12R13 or CN. R11, R12 and R13 independently represent hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 30 carbon atoms or heterocyclic groups with 2 to 20 carbon atoms. The hydrogen atoms of the groups represented by R11, R12 or R13 may be substituted with OR21, COR21, SR21, NR22Ra23, CONR22R23, -NR22-OR23, -N(COR22)-OCOR23, -C(=N-OR21)-R22, -C(=N-OCOR21)-R22, CN, halogen atoms or COOR21. R21, R22, and R23 independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms. The hydrogen atom of the group represented by R21, R22, or R23 may be substituted with CN, a halogen atom, a hydroxyl group, or a carboxyl group. When the group represented by R11, R12, R13, R21, R22, or R23 has an alkyl extension moiety, the alkyl extension moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR24-, -NR24CO-, -NR24COO-, -OCONR24-, -SCO-, -COS-, -OCS-, or -CSO-. R24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. When the group represented by R11, R12, R13, R21, R22, or R23 has an alkyl moiety, the alkyl moiety may be branched or cyclic. Furthermore, R12 and R13, and R22 and R23, may each form a ring together. * indicates a bond with a molecular structure other than the first molecular structure of the oxime compound (1), i.e., a second molecular structure.

[0113] The alkyl groups with 1 to 20 carbon atoms represented by R11, R12, R13, R21, R22, R23 and R24 in formula (1) can be exemplified by, for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, dibutyl, tributyl, pentyl, isopentyl, tripentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, etc.

[0114] The aryl groups represented by R11, R12, R13, R21, R22, R23 and R24 in formula (1) with 6 to 30 carbon atoms can be exemplified by: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracene, phenanthryl, phenyl substituted with one or more of the alkyl groups, biphenyl, naphthyl, anthracene and the like.

[0115] The aralkyl groups represented by R11, R12, R13, R21, R22, R23 and R24 in formula (1) with 7 to 30 carbon atoms can be exemplified by, for example: benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, etc.

[0116] The heterocyclic groups represented by R11, R12, R13, R21, R22, R23 and R24 in formula (1) having 2 to 20 carbon atoms can be listed as follows: pyridinyl, pyrimidinyl, furanyl, thiopheneyl, tetrahydrofuranyl, dioxacyclopentyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidyl, pyrazolidyl, tetrahydrothiazolyl, isotetrahydrothiazolyl, oxazolidyl, isoxazolidyl, piperidinyl, piperazinyl, morpholinyl, etc., preferably 5-membered to 7-membered heterocyclic groups.

[0117] In formula (1), R12 and R13 and R22 and R23 can form a ring together, meaning that R12 and R13 and R22 and R23 can form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached. Examples of rings that R12 and R13 and R22 and R23 can form together in formula (1) include: cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactone ring, etc., preferably 5-membered to 7-membered rings.

[0118] The halogen atoms that can be substituents in formula (1) include: fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.

[0119] In formula (1), R1 is preferably R11, more preferably an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms, and especially preferably an alkyl group having 1 to 6 carbon atoms.

[0120] An example of a second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by formula (2) below. The second molecular structure refers to the molecular structure portion other than the first molecular structure possessed by the oxime compound (1). The bond represented by "*" in formula (2) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (2), the benzene ring with "-*" in formula (2) is directly bonded to the carbonyl group with "-*" in formula (1).

[0121] [Chemistry 6]

[0122] In formula (2), R2 and R3 independently represent R11, OR11, SR11, COR11, CONR12R13, NR12COR11, OCOR11, COOR11, SCOR11, OCSR11, COSR11, CSOR11, CN, or a halogen atom. When multiple R2s are present, they may be the same or different. When multiple R3s are present, they may be the same or different. R11, R12, and R13 have the same meaning as described above. s and t independently represent integers from 0 to 4. L represents a sulfur atom, CR31R32, CO, or NR33. R31, R32, and R33 independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an aralkyl group with 7 to 30 carbon atoms. When the group represented by R31, R32 or R33 has an alkyl moiety, the alkyl moiety may be branched chain or cyclic, and R31, R32 and R33 may each independently form a ring with an adjacent benzene ring. R4 represents a hydroxyl group, a carboxyl group or a group represented by the following formula (2-1).

[0123] [Chemical 7] (In formula (2-1), L1 represents -O-, -S-, -NR22-, -NR22CO-, -SO2-, -CS-, -OCO- or -COO-; R22 represents the same meaning as described above; L2 represents a group formed by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group formed by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, a group formed by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms, or a group formed by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms; When the group represented by L2 has an alkyl group, the alkyl group may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR22-, -NR22COO-, -OCONR22-, -SCO-, -COS-, -OCS-, or -CSO-. The alkyl group may be branched or cyclic. R4a represents OR41, SR41, CONR42R43, NR42COR43, OCOR41, COOR41, SCOR41, OCSR41, COSR41, CSOR41, CN, or a halogen atom. When multiple R4a are present, they may be the same or different. R41, R42 and R43 independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, or an aralkyl group with 7 to 30 carbon atoms. When the group represented by R41, R42 and R43 has an alkyl part, the alkyl part can be branched chain or cyclic. R42 and R43 can form a ring together; v represents an integer from 1 to 3) * represents a bond with the first molecular structure of the oxime compound (1).

[0124] The examples of alkyl groups with 1 to 20 carbons, aryl groups with 6 to 30 carbons, and aralkyl groups with 7 to 30 carbons represented by R11, R12, R13, R21, R22, R23, R24, R31, R32 and R33 in formula (2) and R22, R41, R42 and R43 in formula (2-1) are the same as the examples of R11, R12, R13, R21, R22, R23 and R24 in formula (1).

[0125] The examples of heterocyclic groups with 2 to 20 carbons represented by R11, R12, R13, R21, R22, R23, R24 in formula (2) and R22 in formula (2-1) are the same as the examples of R11, R12, R13, R21, R22, R23 and R24 in formula (1).

[0126] In formula (2), R31, R32, and R33 can each independently form a ring with an adjacent benzene ring, meaning that R31, R32, and R33 can each independently form a ring with an adjacent benzene ring and the nitrogen atom to which they are attached. The examples of rings formed by R31, R32, and R33 with an adjacent benzene ring in formula (2) are the same as the examples of rings formed by R12 and R13 and R22 and R23 together in formula (1).

[0127] In the formula (2-1), L2 represents a group formed by removing v hydrogen atoms from an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms, or a heterocyclic group with 2 to 20 carbon atoms.

[0128] As a group formed by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, for example, when v is 1, the following can be listed: methylene, ethyl, propyl, methyl ethyl, butyl, 1-methyl propyl, 2-methyl propyl, 1,2-dimethyl propyl, 1,3-dimethyl propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 4-methyl butyl, 2,4-dimethyl butyl, 1,3-dimethyl butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, decadecyl, ethane-1,1-diyl, propane-2,2-diyl, etc.

[0129] As a group formed by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, for example, when v is 1, examples include: 1,2-epenylphenyl, 1,3-epenylphenyl, 1,4-epenylphenyl, 2,6-epenylnaphthyl, 1,4-epenylnaphthyl, 2,5-dimethyl-1,4-epenylphenyl, diphenylmethane-4,4'-diyl, 2,2-diphenylpropane-4,4'-diyl, diphenyl sulfide-4,4'-diyl, diphenyl arbutin-4,4'-diyl, etc.

[0130] As a group formed by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms, for example, when v is 1, the group represented by formula (A) and the group represented by formula (b) below can be listed.

[0131] [Chemical 8] [In formulas (a) and (b), L3 and L5 represent alkyl groups having 1 to 10 carbon atoms, and L4 and L6 represent single bonds or alkyl groups having 1 to 10 carbon atoms]

[0132] Examples of alkyl groups having 1 to 10 carbon atoms include: methylene, ethyl, propyl, methyl ethyl, butyl, 1-methyl propyl, 2-methyl propyl, 1,2-dimethyl propyl, 1,3-dimethyl propyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 4-methyl butyl, 2,4-dimethyl butyl, 1,3-dimethyl butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.

[0133] As a group formed by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms, for example, when v is 1, the following divalent heterocyclic groups can be listed: 2,5-pyridinidyl, 2,6-pyridinidyl, 2,5-pyrimidineidyl, 2,5-thiopheneidyl, 3,4-tetrahydrofuranidyl, 2,5-tetrahydrofuranidyl, 2,5-furanidyl, 3,4-thiazolidyl, 2,5-benzofuranidyl, 2,5-benzothiapheneidyl, N-methylindole-2,5-diyl, 2,5-benzothiazolidyl, 2,5-benzoxazoleidyl, etc.

[0134] As examples of halogen atoms represented by R2 and R3 in formula (2) and R4a in formula (2-1), fluorine atoms, chlorine atoms, bromine atoms and iodine atoms can be listed.

[0135] From the viewpoint of solubility in solvent (I) and / or development speed of hardening components, a preferred example of the structure represented by formula (2) is the structure represented by formula (2a) below.

[0136] [Chemical 9][In formula (2a), L' represents a sulfur atom or NR50, R50 represents a linear, branched, or cyclic alkyl group with 1 to 20 carbon atoms, and R2, R3, R4, s, and t have the same meaning as described above.]

[0137] For the same viewpoint described above, another preferred example of the structure represented by equation (2) is the structure represented by equation (2b) below.

[0138] [Chemical 10] In formula (2b), R44 represents a hydroxyl group, a carboxyl group or a group represented by the following formula (2-2).

[0139] [Chemical 11] (In formula (2-2), L11 represents -O- or *-OCO-, * represents a bond with L12, L12 represents an alkyl group with 1 to 20 carbon atoms, which can be interrupted by 1 to 3 -O-, R44a represents OR55 or COOR55, R55 represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms)

[0140] R44 is preferably the base represented by formula (2-2). In this case, it is advantageous in terms of the solubility of the oxime compound (1) in the solvent (I) and the development speed of the curing composition.

[0141] The number of carbon atoms in the alkyl group represented by L12 is preferably 1 to 10, more preferably 1 to 4. R44a is preferably a hydroxyl or carboxyl group, more preferably a hydroxyl group.

[0142] There is no particular limitation on the method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (2). For example, it can be manufactured by the method described in Japanese Patent Application Publication No. 2011-132215.

[0143] Another example of a second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by formula (3) below. The bond represented by "*" in formula (3) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (3), the benzene ring with "-*" in formula (3) is directly bonded to the carbonyl group with "-*" in formula (1).

[0144] [Chemical 12]

[0145] In formula (3), R5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. When the group represented by R5 has an alkyl moiety, the alkyl moiety may be branched or cyclic. The hydrogen atom of the group represented by R5 may be substituted with R21, OR21, COR21, SR21, NR22R23, CONR22R23, -NR22-OR23, -N(COR22)-OCOR23, NR22COR21, OCOR21, COOR21, -C(=N-OR21)-R22, -C(=N-OCOR21)-R22, SCOR21, OCSR21, COSR21, CSOR21, hydroxyl, nitro, CN, halogen atom, or COOR21. R21, R22, and R23 have the same meaning as described above. The hydrogen atom of the group represented by R21, R22, or R23 may be substituted with a CN, a halogen atom, a hydroxyl group, or a carboxyl group. When the group represented by R21, R22, or R23 has an alkyl moiety, the alkyl moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR24-, -NR24CO-, -NR24COO-, -OCONR24-, -SCO-, -COS-, -OCS-, or -CSO-. R24 has the same meaning as described above. When the group represented by R21, R22, or R23 has an alkyl moiety, the alkyl moiety may be branched or cyclic; furthermore, R22 and R23 may form a ring together. R6, R7, R8, and R9 independently represent R61, OR61, SR61, COR62, CONR63, R64, NR65, COR61, OCOR61, COOR62, SCOR61, OCSR61, COSR62, CSOR61, hydroxyl, nitro, CN, or halogen atom, respectively. R61, R62, R63, R64, and R65 independently represent hydrogen atom, alkyl group with 1 to 20 carbon atoms, aryl group with 6 to 30 carbon atoms, arylalkyl group with 7 to 30 carbon atoms, or heterocyclic group with 2 to 20 carbon atoms, respectively. The hydrogen atoms of the groups represented by R61, R62, R63, R64, or R65 may be substituted with OR21, COR21, SR21, NR22Ra23, CONR22R23, -NR22-OR23, -N(COR22)-OCOR23, -C(=N-OR21)-R22, -C(=N-OCOR21)-R22, CN, halogen atoms, or COOR21. R6 and R7, R7 and R8, and R8 and R9 may form rings together. * indicates a bond with the first molecular structure of the oxime compound (1).

[0146] The examples of alkyl groups with 1 to 20 carbons, aryl groups with 6 to 30 carbons, aralkyl groups with 7 to 30 carbons, and heterocyclic groups with 2 to 20 carbons represented by R5, R21, R22, R23, R24, R61, R62, R63, R64 and R65 in formula (3) are the same as those for R11, R12, R13, R21, R22, R23 and R24 in formula (1).

[0147] The fact that R22 and R23 can form a ring together in Equation (3) means that R22 and R23 can form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected. The examples of the rings that R22 and R23 can form together in Equation (3) are the same as the examples of the rings that R12 and R13 and R22 and R23 can form together in Equation (1).

[0148] As examples of halogen atoms represented by R6, R7, R8 and R9 in formula (3), halogen atoms that can replace hydrogen atoms of R5, R21, R22, R23, R61, R62, R63, R64 and R65, fluorine atoms, chlorine atoms, bromine atoms and iodine atoms can be listed.

[0149] In view of the solubility in solvent (I) and / or the development speed of the curing components, in a preferred form, R5 is the base represented by the following formula (3-1).

[0150] [Chemical 13] [In Formula (3-1), Z represents a group formed by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, a group formed by removing one hydrogen atom from an aryl group having 6 to 30 carbon atoms, a group formed by removing one hydrogen atom from an aralkyl group having 7 to 30 carbon atoms, or a group formed by removing one hydrogen atom from a heterocyclic group having 2 to 20 carbon atoms. When the group represented by Z has an alkyl extension moiety, the alkyl extension moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR24-, -NR24COO-, -OCONR24-, -SCO-, -COS-, -OCS-, or -CSO-. The alkyl extension moiety may be branched or cyclic. R21, R22, and R24 have the same meaning as described above.]

[0151] For the same purpose as described above, Z in formula (3-1) is preferably methylene, ethyl, or phenyl. For the same purpose as described above, R21 and R22 in formula (3-1) are preferably alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 30 carbon atoms, more preferably methyl, ethyl, or phenyl.

[0152] In another preferred form, R7 is nitro, which is the same as described above.

[0153] There is no particular limitation on the method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (3). For example, it can be manufactured by the method described in Japanese Patent Application Publication No. 2000-80068 and Japanese Patent Application Publication No. 2011-178776.

[0154] Another example of a second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by formula (4) below. The bond represented by "*" in formula (4) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (4), the benzene ring with "-*" in formula (4) is directly bonded to the carbonyl group with "-*" in formula (1).

[0155] [Chemical 14]

[0156] In formula (4), R71 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. When the group represented by R71 has an alkyl moiety, the alkyl moiety may be branched or cyclic. The hydrogen atom of the group represented by R71 may be substituted with R21, OR21, COR21, SR21, NR22R23, CONR22R23, -NR22-OR23, -N(COR22)-OCOR23, NR22COR21, OCOR21, COOR21, -C(=N-OR21)-R22, -C(=N-OCOR21)-R22, SCOR21, OCSR21, COSR21, CSOR21, hydroxyl, nitro, CN, halogen atom, or COOR21. R21, R22, and R23 have the same meaning as described above. The hydrogen atom of the group represented by R21, R22, or R23 may be substituted with a CN, a halogen atom, a hydroxyl group, or a carboxyl group. When the group represented by R21, R22, or R23 has an alkyl moiety, the alkyl moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR24-, -NR24CO-, -NR24COO-, -OCONR24-, -SCO-, -COS-, -OCS-, or -CSO-. R24 has the same meaning as described above. When the group represented by R21, R22, or R23 has an alkyl moiety, the alkyl moiety may be branched or cyclic; furthermore, R22 and R23 may form a ring together. R72, R73, and the three R74s independently represent R61, OR61, SR61, COR62, CONR63, R64, NR65, COR61, OCOR61, COOR62, SCOR61, OCSR61, COSR62, CSOR61, hydroxyl, nitro, CN, or halogen atom, respectively. R61, R62, R63, R64, and R65 independently represent hydrogen atom, alkyl group with 1 to 20 carbon atoms, aryl group with 6 to 30 carbon atoms, arylalkyl group with 7 to 30 carbon atoms, or heterocyclic group with 2 to 20 carbon atoms, respectively. The hydrogen atoms of the groups represented by R61, R62, R63, R64, or R65 may be substituted with OR21, COR21, SR21, NR22Ra23, CONR22R23, -NR22-OR23, -N(COR22)-OCOR23, -C(=N-OR21)-R22, -C(=N-OCOR21)-R22, CN, halogen atoms, or COOR21. R72 and R73, as well as the two R74 groups, may form rings together. * indicates a bond with the first molecular structure of the oxime compound (1).

[0157] The examples of alkyl groups with 1 to 20 carbons, aryl groups with 6 to 30 carbons, aralkyl groups with 7 to 30 carbons, and heterocyclic groups with 2 to 20 carbons represented by R71, R21, R22, R23, R24, R61, R62, R63, R64 and R65 in formula (4) are the same as the examples of R11, R12, R13, R21, R22, R23 and R24 in formula (1).

[0158] The fact that R22 and R23 can form a ring together in Equation (4) means that R22 and R23 can form a ring together with the nitrogen atom, carbon atom or oxygen atom they are connected to. The examples of the rings that R22 and R23 can form together in Equation (4) are the same as the examples of the rings that R12 and R13 and R22 and R23 can form together in Equation (1).

[0159] As examples of halogen atoms represented by R72, R73 and R74 in formula (4), and halogen atoms that can replace hydrogen atoms of R71, R21, R22, R23, R61, R62, R63, R64 and R65, the following can be listed: fluorine atom, chlorine atom, bromine atom and iodine atom.

[0160] There is no particular limitation on the method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (4), for example, it can be manufactured by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0161] Another example of a second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by formula (5) below. The bond represented by "*" in formula (5) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (5), the pyrrole ring with "-*" in formula (5) is directly bonded to the carbonyl group with "-*" in formula (1).

[0162] [Chemical 15]

[0163] In formula (5), R81 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. When the group represented by R81 has an alkyl moiety, the alkyl moiety may be branched or cyclic. The hydrogen atom of the group represented by R81 may be substituted with R21, OR21, COR21, SR21, NR22R23, CONR22R23, -NR22-OR23, -N(COR22)-OCOR23, NR22COR21, OCOR21, COOR21, -C(=N-OR21)-R22, -C(=N-OCOR21)-R22, SCOR21, OCSR21, COSR21, CSOR21, hydroxyl, nitro, CN, halogen atom, or COOR21. R21, R22, and R23 have the same meaning as described above. The hydrogen atom of the group represented by R21, R22, or R23 may be substituted with a CN, a halogen atom, a hydroxyl group, or a carboxyl group. When the group represented by R21, R22, or R23 has an alkyl moiety, the alkyl moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR24-, -NR24CO-, -NR24COO-, -OCONR24-, -SCO-, -COS-, -OCS-, or -CSO-. R24 has the same meaning as described above. When the group represented by R21, R22, or R23 has an alkyl moiety, the alkyl moiety may be branched or cyclic; furthermore, R22 and R23 may form a ring together. R82, R83, R84, R85, and R86 independently represent R61, OR61, SR61, COR62, CONR63, R64, NR65, COR61, OCOR61, COOR62, SCOR61, OCSR61, COSR62, CSOR61, hydroxyl, nitro, CN, or halogen atom, respectively. R61, R62, R63, R64, and R65 independently represent hydrogen atom, alkyl group with 1 to 20 carbon atoms, aryl group with 6 to 30 carbon atoms, arylalkyl group with 7 to 30 carbon atoms, or heterocyclic group with 2 to 20 carbon atoms, respectively. The hydrogen atoms of the groups represented by R61, R62, R63, R64, or R65 may be substituted with OR21, COR21, SR21, NR22Ra23, CONR22R23, -NR22-OR23, -N(COR22)-OCOR23, -C(=N-OR21)-R22, -C(=N-OCOR21)-R22, CN, halogen atoms, or COOR21. R83 and R84, R84 and R85, and R85 and R86 may form rings together. * indicates a bond with the first molecular structure of the oxime compound (1).

[0164] The examples of alkyl groups with 1 to 20 carbons, aryl groups with 6 to 30 carbons, aralkyl groups with 7 to 30 carbons, and heterocyclic groups with 2 to 20 carbons represented by R81, R21, R22, R23, R24, R61, R62, R63, R64 and R65 in formula (5) are the same as the examples of R11, R12, R13, R21, R22, R23 and R24 in formula (1).

[0165] The fact that R22 and R23 can form a ring together in Equation (5) means that R22 and R23 can form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached. The examples of the rings that R22 and R23 can form together in Equation (5) are the same as the examples of the rings that R12 and R13 and R22 and R23 can form together in Equation (1).

[0166] As examples of halogen atoms represented by R82, R83, R84, R85 and R86 in formula (5), and halogen atoms that can replace hydrogen atoms of R81, R21, R22, R23, R61, R62, R63, R64 and R65, the following can be listed: fluorine atom, chlorine atom, bromine atom and iodine atom.

[0167] There is no particular limitation on the method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (5), for example, it can be manufactured by the method described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0168] Another example of a second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by formula (6) below. The bond represented by "*" in formula (6) is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (6), the benzene ring with "-*" in formula (6) is directly bonded to the carbonyl group with "-*" in formula (1).

[0169] [Chemical 16]

[0170] In formula (6), the four R91, R92, R93, R94, R95, R96 and R97 independently represent R61, OR61, SR61, COR62, CONR63, R64, NR65, COR61, OCOR61, COOR62, SCOR61, OCSR61, COSR62, CSOR61, hydroxyl, nitro, CN or halogen atom. R61, R62, R63, R64 and R65 independently represent hydrogen atom, alkyl group with 1 to 20 carbon atoms, aryl group with 6 to 30 carbon atoms, arylalkyl group with 7 to 30 carbon atoms or heterocyclic group with 2 to 20 carbon atoms. The hydrogen atoms of the groups represented by R61, R62, R63, R64, or R65 may be substituted with OR21, COR21, SR21, NR22Ra23, CONR22R23, -NR22-OR23, -N(COR22)-OCOR23, -C(=N-OR21)-R22, -C(=N-OCOR21)-R22, CN, halogen atoms, or COOR21. R21, R22, and R23 have the same meaning as described above. R92 and R93, R94 and R95, R95 and R96, and R96 and R97 may form rings together. * indicates a bond with the first molecular structure of the oxime compound (1).

[0171] The examples of alkyl groups with 1 to 20 carbons, aryl groups with 6 to 30 carbons, aralkyl groups with 7 to 30 carbons, and heterocyclic groups with 2 to 20 carbons represented by R21, R22, R23, R61, R62, R63, R64 and R65 in formula (6) are the same as the examples of R11, R12, R13, R21, R22 and R23 in formula (1).

[0172] In Equation (6), R22 and R23 can form a ring together, meaning that R22 and R23 can form a ring together with the nitrogen atom, carbon atom, or oxygen atom they are connected to. The examples of rings that R22 and R23 can form together in Equation (6) are the same as the examples of rings that R12 and R13 and R22 and R23 can form together in Equation (1).

[0173] As examples of halogen atoms represented by R91, R92, R93, R94, R95, R96 and R97 in formula (6), and halogen atoms that can replace hydrogen atoms of R21, R22, R23, R61, R62, R63, R64 and R65, the following can be listed: fluorine atom, chlorine atom, bromine atom and iodine atom.

[0174] There is no particular limitation on the method of manufacturing the oxime compound (1) having the second molecular structure represented by formula (6), for example, it can be manufactured by the method described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0175] The photopolymerization initiator (C) may further include other photopolymerization initiators besides the oxime compound (1). Examples of other photopolymerization initiators include oxime compounds other than the oxime compound (1), benzyl ketone compounds, biimidazole compounds, triazine compounds, and acetyphosphine compounds.

[0176] Oxime compounds other than oxime compound (1) can be listed as oxime compounds having a partial structure represented by the following formula (d1). * indicates a bond.

[0177] [Chemistry 17]

[0178] Examples of oxime compounds having a partial structure represented by formula (d1) include: N-benzoyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di-di-2-yl ... Compounds including: (oxacyclopentylmethyloxy)benzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetyoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-one-2-imine; compounds described in Japanese Patent Application Publication No. 2011-132215, International Publication No. 2008 / 78678, International Publication No. 2008 / 78686, and International Publication No. 2012 / 132558. You can also use commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA).

[0179] The oxime compound having the partial structure represented by formula (d1) is preferably selected from at least one of the group consisting of N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, more preferably N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine.

[0180] A benzyl ketone compound is a compound having a partial structure represented by formula (d4) or a partial structure represented by formula (d5). In these partial structures, the benzene ring may have substituents.

[0181] [Chemistry 18]

[0182] Examples of compounds having the structure represented by formula (d4) include 2-methyl-2-morpholino-1-(4-methylmercaptophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]butane-1-one. Commercially available products such as OMNIRAD 369, OMNIRAD 907, and OMNIRAD 379 (manufactured by IGM Resins) can also be used.

[0183] Examples of compounds having the structure represented by formula (d5) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc. In terms of sensitivity, compounds having the structure represented by formula (d4) are preferred as benzyl ketone compounds.

[0184] As a biimidazole compound, for example, compounds represented by formula (d6) can be listed.

[0185] [Chemical 19] [In formula (d6), RE~RJ represent aryl groups with 6 to 10 carbon atoms that may have substituents.]

[0186] Examples of aryl groups having 6 to 10 carbon atoms include phenyl, toluene, xylene, ethylphenyl, and naphthyl, with phenyl being preferred. Examples of substituents include halogen atoms and alkoxy groups having 1 to 4 carbon atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with chlorine being preferred. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, with methoxy being preferred.

[0187] Examples of biimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Application Publication No. 06-75372, Japanese Patent Application Publication No. 06-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)biimidazole, etc. Imidazole compounds containing phenyl group (phenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g., see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), and imidazole compounds in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group (e.g., see Japanese Patent Publication No. 7-10913, etc.). Preferably, these are compounds represented by the formulas below or mixtures thereof.

[0188] [Chemical 20]

[0189] Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. Among these, 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine is preferred.

[0190] Examples of phosphine compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0191] Other examples of photopolymerization initiators other than oxime compounds (1) include, for example: benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthroquinone, 2-ethylanthraquinone, and camphorquinone; and 10-butyl-2-chloroacridone, benzoin, methyl phenylglyoxylate, and titanium decene compounds.

[0192] Other photopolymerization initiators besides oxime compound (1) may be used alone or in combination with two or more photopolymerization initiators. When other photopolymerization initiators besides oxime compound (1) are used together with oxime compound (1), the other photopolymerization initiator may be an oxime compound other than oxime compound (1), a benzyl ketone compound, a biimidazole compound, a triazine compound, or a phenylphosphine compound, etc.

[0193] When the curable composition contains a photopolymerization initiator (C), the content of the photopolymerization initiator (C) in the curable composition is preferably 0.1 parts by mass or more and 300 parts by mass or less, more preferably 0.1 parts by mass or more and 200 parts by mass or less, relative to 100 parts by mass of the photopolymerizable compound (B). When the content of the photopolymerization initiator (C) is within the aforementioned range, the productivity of the curable film tends to increase.

[0194] [5] Resin (D) The curing component may further include resin (D). Resin (D) may further include one or more resins. Examples of resin (D) include resins [K1] to resins [K4]. Resin [K1]: a copolymer of at least one (A) (hereinafter also referred to as "(A)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a monomer (c) (which is different from (A)) (hereinafter also referred to as "(c)") capable of copolymerizing with (A); Resin [K2]: a resin obtained by reacting a monomer (b) (hereinafter also referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms with an ethylene unsaturated bond, and a copolymer of (A) and (c); Resin [K3]: a resin obtained by reacting a copolymer of (A) and (b) with (c); Resin [K4]: a resin obtained by reacting a copolymer of (A) and (b) with (c), and then reacting it with a carboxylic anhydride.

[0195] As (a), examples include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, succinic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid. Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, and other bicyclic unsaturated compounds containing carboxyl groups; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene anhydride and other unsaturated dicarboxylic acid anhydrides; unsaturated mono[(meth)acrylic acid alkyl] esters of di- or higher polycarboxylic acids, such as succinate mono[2-(meth)acrylic acid oxyethyl] ester and phthalate mono[2-(meth)acrylic acid oxyethyl] ester; unsaturated (meth)acrylates containing hydroxyl and carboxyl groups in the same molecule, such as (meth)acrylate α-(hydroxymethyl) ester. Of these, from the viewpoint of copolymerization reactivity or the solubility of the obtained resin (D) in alkaline aqueous solution, (meth)acrylic acid, maleic anhydride, etc. are preferred.

[0196] (b) For example, a monolith having a cyclic ether structure having 2 to 4 carbon atoms (e.g., selected from at least one of the group consisting of an ethylene oxide ring, an oxobutane ring, and a tetrahydrofuran ring) and an ethylene unsaturated bond. (b) Preferably, a monolith having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acrylic acid oxy group.

[0197] As in (b), examples include: (meth)acrylate glycidyl ester, (meth)acrylate β-methylglycidyl ester, (meth)acrylate β-ethylglycidyl ester, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4- Monomers of bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, etc., containing ethylene oxide rings and vinyl unsaturated bonds; Monomers of 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, etc., having an oxetane ring and an ethylene-like unsaturated bond; Monomers of tetrahydrofurfuryl acrylate (e.g., Biscoat V#150, manufactured by Osaka Organic Chemicals Co., Ltd.), tetrahydrofurfuryl methacrylate, etc., having a tetrahydrofuran ring and an ethylene-like unsaturated bond; etc. Regarding the aspect that the reactivity of resins [K2] to [K4] is high and unreacted residues are not easily left during the manufacture of (b), as (b), it is preferable to be a monolith having an ethylene oxide ring and an ethylene unsaturated bond.

[0198] As (c), examples include: methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.02,6]decane-8-yl methacrylate (in this art, it is commonly referred to as "( Dicyclopentyl methacrylate; also sometimes called tricyclodecyl methacrylate, tricyclo[5.2.1.02,6]decen-8-yl methacrylate (commonly known as dicyclopentenyl methacrylate in this technical field), dicyclopentyloxyethyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, allyl methacrylate, propargyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, etc.; hydroxyl-containing methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid. Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5, 6-Dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1].[1] Bicyclic unsaturated compounds such as hepta-2-ene; dicarbonyl amide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimido-3-maleimide benzoate, N-succinimido-4-maleimide butyrate, N-succinimido-6-maleimide hexanoate, N-succinimido-3-maleimide propionate, and N-(9-acridyl)maleimide; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; etc. Among these, from the viewpoint of copolymerization reactivity and the heat resistance of resin (D), styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc., are preferred.

[0199] The ratio of structural units derived from each of the components in resin [K1] is preferably as follows among all structural units constituting resin [K1]: structural units derived from (A): 2 mol% or more and 60 mol% or less; structural units derived from (c): 40 mol% or more and 98 mol% or less; more preferably structural units derived from (A): 10 mol% or more and 50 mol% or less; structural units derived from (c): 50 mol% or more and 90 mol% or less. When the ratio of structural units in resin [K1] is within the range described, it tends to have excellent storage stability of the curable composition, developability of the cured film, and solvent resistance.

[0200] The resin [K1] can be manufactured, for example, by referring to the method described in the literature "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Chemical Dojin Publishing Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the references described in that literature.

[0201] Specifically, the following method can be used: A specified amount of (A) and (c), the polymerization initiator, and the solvent are placed into a reaction vessel. For example, nitrogen is used to replace the oxygen, thereby creating a deoxygenated environment. The mixture is then stirred while being heated and kept at a constant temperature. There are no particular limitations on the polymerization initiator and solvent used here; those commonly used in this field can be used. For example, as a polymerization initiator, examples include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile) etc.) or organic peroxides (benzoyl peroxide, etc.). As a solvent, any solvent that dissolves the monomers can be used; examples include solvents (I) contained in the curing composition and solvents described later.

[0202] The obtained copolymer can be used directly from the reaction solution, or from a concentrated or diluted solution, or from a solid (powder) obtained by methods such as reprecipitation. If the solvent (I) described later is used as the solvent during polymerization, the reaction solution can be used directly in the preparation of the curable composition, thus simplifying the manufacturing steps of the curable composition.

[0203] Resin [K2] can be manufactured by adding a cyclic ether of (b) having 2 to 4 carbon atoms to a carboxylic acid and / or carboxylic anhydride in (A) to the copolymer of (A) and (c) in the same manner as described in the method for manufacturing resin [K1]. In this case, the ratio of structural units derived from each is preferably the same as the ratio described for resin [K1].

[0204] Next, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a portion of the carboxylic acid and / or carboxylic anhydride derived from (A) in the copolymer. After producing the copolymer of (A) and (c), the environment inside the flask is replaced with air instead of nitrogen, and the reaction is carried out in the presence of (b), a reaction catalyst for the carboxylic acid or carboxylic anhydride and the cyclic ether (e.g., an organophosphorus compound, a metal complex, an amine compound, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.), for example, at a temperature above 60°C and below 130°C for 1 to 10 hours, thereby producing resin [K2].

[0205] Compared to (a) 100 mol, the amount used in (b) is preferably 5 mol or more and 80 mol or less, and more preferably 10 mol or more and 75 mol or less. By setting it within this range, the storage stability of the curing composition, the developability of the curing film, and the balance between the solvent resistance, heat resistance and mechanical strength of the curing film tend to become better.

[0206] Examples of organophosphorus compounds used as reaction catalysts include triphenylphosphine. Examples of amine compounds used as reaction catalysts include aliphatic tertiary amine compounds or aliphatic quaternary ammonium salt compounds; specific examples include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, and tetrabutylammonium chloride. From the viewpoint of the developability of the cured film and the intensity of the emitted light from the cured film, organophosphorus compounds are preferred as reaction catalysts.

[0207] The amount of reaction catalyst used is preferably 0.001 parts by mass or more and 5 parts by mass or less, relative to the total amount of 100 parts by mass of (a), (b) and (c). The amount of polymerization inhibitor used is preferably 0.001 parts by mass or more and 5 parts by mass or less, relative to the total amount of 100 parts by mass of (a), (b) and (c).

[0208] The charging method, reaction temperature, and time, among other reaction conditions, can be appropriately adjusted taking into account the heat generated by the manufacturing equipment or polymerization. Furthermore, similar to polymerization conditions, the charging method or reaction temperature can be appropriately adjusted taking into account the heat generated by the manufacturing equipment or polymerization.

[0209] Regarding resin [K3], as a first stage, copolymers of (b) and (c) are obtained in the same manner as those for resin [K1]. Similarly, the obtained copolymer can be used directly from the reaction solution, or from a concentrated or diluted solution, or taken out in solid (powder) form by methods such as reprecipitation.

[0210] Relative to the total number of moles of all structural units constituting the copolymer, the ratios of structural units derived from (b) and (c) are preferably: structural units derived from (b): 5 mol% or more and 95 mol% or less, structural units derived from (c): 5 mol% or more and 95 mol% or less, more preferably structural units derived from (b): 10 mol% or more and 90 mol% or less, structural units derived from (c): 10 mol% or more and 90 mol% or less.

[0211] The resin [K3] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (A) with the cyclic ether derived from (b) in the copolymer of (b) and (c) under the same conditions as those for manufacturing the resin [K2]. The amount of (A) used in reaction with the copolymer is preferably 5 mol or more and 80 mol or less relative to 100 mol of (b).

[0212] Resin [K4] is a resin obtained by further reacting a carboxylic anhydride with resin [K3]. The carboxylic anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride. Examples of carboxylic anhydrides include: maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxylic bicyclo[2.2.1]hept-2-ene anhydride, etc. The amount of carboxylic anhydride used is preferably 0.5 mol or more and 1 mol or less, relative to the amount used in (A) of 1 mol.

[0213] As resins [K1], [K2], [K3] and [K4], examples include: (meth)acrylate benzyl ester / (meth)acrylate copolymer, styrene / (meth)acrylate copolymer and other resins [K1]; Resins such as benzyl methacrylate / (meth)acrylate copolymer with glycidyl methacrylate, resins such as tricyclodecyl methacrylate / styrene / (meth)acrylate copolymer with glycidyl methacrylate, and resins such as tricyclodecyl methacrylate / (meth)acrylate / benzyl methacrylate / (meth)acrylate copolymer with glycidyl methacrylate [K2]; resins such as (meth)acrylate and (meth)acrylate / (meth)acrylate copolymer with glycidyl methacrylate, and resins such as (meth)acrylate and (meth)acrylate / (meth)acrylate copolymer with glycidyl methacrylate [K3]; resins such as (meth)acrylate and (meth)acrylate / (meth)acrylate copolymer with glycidyl methacrylate to obtain a resin, and then reacting the obtained resin with tetrahydrophthalic anhydride [K4], etc. The resin (D) is preferably at least one selected from the group consisting of resin [K2], resin [K3] and resin [K4].

[0214] As another example of resin (D), the alkali-soluble resin described in Japanese Patent Application Publication No. 2018-123274 can be cited. As such an alkali-soluble resin, a polymer (hereinafter also referred to as "resin (Da)") having double bonds in its side chains and containing structural units (α) represented by formula (I) and (β) represented by formula (II) in its main chain can be cited. The acid group can be introduced into the resin (Da) by including structural units (γ) derived from an acid-containing monomer (e.g., (meth)acrylic acid). Preferably, the resin (Da) contains structural units (α), (β), and (γ) on its main backbone.

[0215] [Chemical 21] [In the formula, RA and RB may be the same or different, representing hydrogen atoms or hydrocarbon groups with 1 to 25 carbon atoms. n represents the average number of repeating units of the structural unit represented by formula (I), and is a number greater than 1.]

[0216] [Chemical 22][In the formula, RC, whether the same or different, represents a hydrogen atom or a methyl group. RD, whether the same or different, represents a straight-chain or branched-chain hydrocarbon group with 4 to 20 carbon atoms. m represents the average number of repeating units of the structural unit represented by formula (II), and is a number greater than 1.]

[0217] In the resin (Da), from the viewpoint of the heat resistance or storage stability of the resin (Da), the content of structural unit (α) relative to 100% by mass of all monolithic units providing the main chain backbone of the resin (Da) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 1% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. In Formula (I), n represents the average number of repeating units of the structural unit (α) in the resin (Da), and n can be set such that the content of the structural unit (α) is within the aforementioned range.

[0218] From the viewpoint of solvent resistance of the cured film, relative to 100% by mass of all monolithic units of the main chain backbone of the resin (Da), the content of structural unit (β) is, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 75% by mass or less. In Formula (II), m represents the average number of repeating units of structural unit (β) in the resin (Da), and m can be set such that the content of structural unit (β) is within the aforementioned range.

[0219] From the viewpoint of the solubility of resin (Da) relative to alkaline substances or the solubility of resin (Da) relative to solvent (I), the content of structural unit (γ) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 2% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 45% by mass or less, relative to the total amount of all monolithic units providing the main chain skeleton of resin (Da) 100% by mass.

[0220] The resin (D) may include one or more of the group consisting of the resins [K1], [K2], [K3], [K4] and the alkali-soluble resins described in Japanese Patent Application Publication No. 2018-123274.

[0221] As a further example of resin (D), polyalkylene glycol compounds can be cited. Examples of polyalkylene glycol compounds include polyethylene glycol and polypropylene glycol. Polyalkylene glycol compounds are advantageous in improving the dispersibility of quantum dots (A) in curable components.

[0222] The weight-average molecular weight (Mw) of the resin (D) as determined by gel permeation chromatography (GPC) based on standard polystyrene is preferably 9000 or less. With the resin (D) possessing the aforementioned Mw, there is a tendency to improve the development speed of the hardened film and obtain a hardened film with high emitted light intensity. For example, the Mw of the resin (D) based on standard polystyrene is 1000 or more and 9000 or less; from the viewpoint of development speed and emitted light intensity of the hardened film, it is preferably 2000 or more and 8500 or less, and more preferably 3000 or more and 8500 or less. To ensure that the Mw of the resin (D) falls within the aforementioned range, the reaction conditions, such as the selection of raw materials used, the method of addition, the reaction temperature, and the reaction time, can be appropriately combined and adjusted.

[0223] The molecular weight distribution of the resin (D) [weight average molecular weight (Mw) / number average molecular weight (Mn)] as determined by GPC is, for example, 1.0 or more and 6.0 or less, and from the viewpoint of the developability of the hardened film, it is preferably 1.2 or more and 4.0 or less.

[0224] The acid value of the resin (D), based on the solid content, is preferably 90 mgKOH / g or higher and 150 mgKOH / g or lower. When the acid value is less than 90 mgKOH / g, the solubility of the hardened film in the alkaline developer decreases, and residues may remain on the substrate. When the acid value exceeds 150 mgKOH / g, the possibility of peeling off the hardened pattern obtained by development (described later) increases.

[0225] From the viewpoint of the developability of the hardened film, the acid value of the resin (D) is preferably 95 mgKOH / g or more and 140 mgKOH / g or less, and more preferably 100 mgKOH / g or more and 130 mgKOH / g or less.

[0226] The acid value is a value determined as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (D), and can be determined, for example, by titration using an aqueous solution of potassium hydroxide.

[0227] The resin (D) may contain a double bond equivalent of, for example, 300 g / eq or more and 2000 g / eq or less, preferably 500 g / eq or more and 1500 g / eq or less. By containing a resin with a double bond equivalent of 300 g / eq or more and 2000 g / eq or less, the resin (D) tends to easily prevent matting during the step of creating the hardened pattern described later. When the resin (D) contains a resin with a double bond equivalent of more than 2000 g / eq, the resin (D) tends to have a decreased ability to effectively protect the quantum dots (A). When the resin (D) contains a resin with a double bond equivalent of less than 300 g / eq, it does not dissolve during development, and the hardened pattern tends to be easily peeled off. Examples of resins with a double bond equivalent of 300 g / eq or more and 2000 g / eq or less include (meth)acrylic resins. The resin (D) preferably contains a (meth)acrylic resin.

[0228] When the curable composition contains resin (D), the content of resin (D) in the curable composition is, for example, 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 65% by mass or less, and more preferably 15% by mass or more and 45% by mass or less, relative to the total amount of solid components in the curable composition. When the content of resin (D) is within the aforementioned range, the quantum dots (A) are easily dispersed, and in the step of manufacturing the curable pattern described later, there is a tendency to easily maintain a high intensity of emitted light.

[0229] When the curing composition includes resin (D), the mass ratio (solid content ratio) of resin (D) to photopolymerizable compound (B) is, for example, 1 or more. From the viewpoint of the developability of the curing film, it is preferably 1.2 or more and 7.0 or less, more preferably 1.5 or more and 6.0 or less, and even more preferably 1.7 or more and 5.5 or less.

[0230] [6] Light scattering agent (E) The curing composition may further contain one or more light scattering agents (E). The curing film formed from the curing composition may exhibit light scattering properties. By including the light scattering agent (E) in the curing film, the transmittance and viewing angle characteristics of the curing film can be controlled, or the intensity of emitted light from the curing film can be increased.

[0231] As a light scattering agent (E), inorganic particles such as metal or metal oxide particles and glass particles can be included. Preferably, metal oxide particles are preferred as they do not cause absorption due to coloration and only have a scattering effect. Examples of metal oxides include TiO2, SiO2, BaTiO3, and ZnO. For efficient light scattering, TiO2 particles are preferred. Generally, these inorganic particles are difficult to disperse directly in a solvent; therefore, dispersants described later are usually used.

[0232] The particle size of the light scattering agent (E) is, for example, about 0.03 μm or more and about 20 μm or less. From the viewpoint of improving light scattering ability and improving dispersibility in the curable composition, it is preferably 0.05 μm or more and about 1 μm or less, and more preferably 0.05 μm or more and about 0.5 μm or less.

[0233] As a light scattering agent (E), a light scattering agent that has been pre-dispersed in part or all of the solvent (I) using a dispersant can be used. Commercially available dispersants can be used. Examples of commercially available dispersants include: DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, and 2001 manufactured by BYK-Chemie Japan. 2020, 2025, 2050, 2070, 2095, 2150, 2155; ANTI-TERRA-U, U100, 203, 204, 250; BYK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc. The SOLSPERSE series manufactured by Lubrizol Corporation of Japan includes models such as 3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, and 76500. BASF manufactures EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc.; Ajinomoto Precision Technology. Fine-Techno manufactures Ajisper PA111, PB711, PB821, PB822, PB824, etc.

[0234] When the curable composition contains a light scattering agent (E), the content of the light scattering agent (E) in the curable composition is, for example, 0.001% by mass or more and 50% by mass or less relative to the total amount of solid components in the curable composition. From the viewpoints of the developability of the curable film, the viewpoints of improving light scattering energy and improving the emitted light intensity of the curable film, it is more preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 10% by mass or less, and even more preferably 3% by mass or more and 8% by mass or less.

[0235] [7] Antioxidant (F) The hardening component may contain one or more antioxidants (F). As an antioxidant (F), there are no particular limitations on the antioxidants commonly used in industry, such as phenolic antioxidants, phosphorus antioxidants, phosphorus / phenolic complex antioxidants and sulfur antioxidants.

[0236] Phosphorus / phenol complex antioxidants can be compounds having one or more phosphorus atoms and phenol structures in their molecules. From the viewpoint of the developability of the hardened film and the intensity of emitted light, antioxidant (F) is preferably a phosphorus / phenol complex antioxidant.

[0237] As phenolic antioxidants, examples include: Irganox 1010 (registered trademark: pentaerythritol tetratetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF), Irganox 1076 (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox 1330 (3,3',3'',5,5',5''-hexa-tert-butyl-α,α',α''-(trimethylbenzene-2,4,6-triyl)tri-p-cresol, manufactured by BASF), and Irganox 3114 (Irganox... 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF (s.). Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-dimethyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF (s.). Irganox 1035: thiodiethyl bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF (s.). Irganox 1135: Irganox 1035. 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 alkyl ester of phenylpropionic acid, manufactured by BASF (s.). Irganox 1520L (4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF (s.). Irganox 3125 (Irganox 3125, manufactured by BASF (s.). Irganox 565 (2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tertiary butylaniline)-1,3,5-triazine, manufactured by BASF (s.). Adekastab (registered trademark) AO-80. AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid)-1,1-dimethylethyl)-2,4,8,10-tetraoxazolo(5,5) Undecane, manufactured by ADEKA (stock), Sumilizer (registered trademark) BHT, Sumilizer GA-80, Sumilizer GS (all manufactured by Sumitomo Chemical (stock), Cyanox 1790 (registered trademark, manufactured by Cytec (stock), Vitamin E (manufactured by Eisai (stock), etc.)

[0238] As phosphorus-based antioxidants, examples include: Irgafos 168 (a registered trademark: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF), Irgafos 12 (a mixture of tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxane-6-yl]oxy]ethyl]amine, manufactured by BASF), and Irgafos 38 (a mixture of tris[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxane-6-yl]oxy]ethyl]amine, manufactured by BASF). 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite (manufactured by BASF), Adekastab (registered trademark) 329K, Adekastab PEP36, Adekastab PEP-8 (and above, manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston (registered trademark) 618, Weston 619G (and above, manufactured by GE), Ultranox 626 (manufactured by GE), etc.

[0239] As a phosphorus / phenol complex antioxidant, examples include Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphazenecycloheptane) (manufactured by Sumitomo Chemical Co., Ltd.).

[0240] As sulfur-based antioxidants, examples include: dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, or distearate thiodipropionate, and β-alkyl mercaptopropionate compounds of polyols such as tetra[methylene(3-dodecylthio)propionate]methane.

[0241] When the curing composition contains an antioxidant (F), from the viewpoint that the content of antioxidant (F) in the curing composition is 1 part by mass or more relative to 100 parts by mass of resin (D), it is more preferably 2 parts by mass or more, more preferably 3 parts by mass or more, more preferably 5 parts by mass or more, particularly preferably 7 parts by mass or more, and from the viewpoint that 50 parts by mass or less, for example, is more preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 25 parts by mass or less.

[0242] [8] Leveling Agent (G) The curing composition may contain one or more leveling agents (G). By containing leveling agents (G), the flatness of the cured film can be improved. Examples of leveling agents (G) include silicone surfactants, fluorinated surfactants, and silicone surfactants with fluorine atoms. These may also have polymerizable groups on their side chains. From the viewpoint of the developability and emitted light intensity of the cured film, fluorinated surfactants are preferred as leveling agents (G).

[0243] As silicone-based surfactants, examples include surfactants with intramolecular siloxane bonds. Specifically, examples include: Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, and Toray silicone SH8400 (trade name: Toray Dow Corning). KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

[0244] As fluorinated surfactants, examples include surfactants with intramolecular fluorocarbon chains. Specific examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac F575, Megafac R30, and Megafac (…). Megafac RS-718-K (manufactured by DIC Corporation), Eftop EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics & Chemicals Corporation), Surflon S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Corporation), and E5844 (manufactured by Daikin Fine Chemicals Research Institute Corporation), etc.

[0245] As silicone-based surfactants containing fluorine atoms, examples include surfactants with intramolecular siloxane bonds and fluorocarbon chains. Specifically, examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC).

[0246] When the curing composition contains a leveling agent (G), the content of the leveling agent (G) in the curing composition, relative to the total amount of the curing composition, is, for example, 0.001% by mass or more and 1.0% by mass or less, preferably 0.005% by mass or more and 0.75% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, and even more preferably 0.05% by mass or more and 0.5% by mass or less. If the content of the leveling agent (G) is within the aforementioned range, the flatness of the cured film can be improved.

[0247] Furthermore, the curing composition may also include, as needed, photopolymerization initiators, polymerization inhibitors, fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and other additives known in the art.

[0248] [9] Solvent (I) The curing composition may further contain one or more solvents (I). The solvent (I) is not particularly limited as long as it dissolves the photopolymerizable compound (B), and solvents commonly used in the field may be used. Examples include: ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH but not -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. When the curing composition further contains a photopolymerization initiator (C) and / or a resin (D), the solvent (I) is preferably for dissolving these.

[0249] As ester solvents, examples include: methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone, etc.

[0250] As an ether solvent, examples include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methyl anisole, etc.

[0251] As an ether ester solvent, examples include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate, etc.

[0252] As ketone solvents, examples include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

[0253] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of acetamide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0254] The solvent (I) is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, toluene, or a mixture of two or more of these, more preferably containing propylene glycol monomethyl ether acetate.

[0255] The solvent (I) is a component other than the solid component of the curable composition. The solvent contained in the quantum dot (A), resin (D), light scattering agent (E), etc. is also included in the solvent (I).

[0256] <Method for manufacturing a curable composition> A curable composition may be manufactured by a method including steps of mixing specified components and other components to be used as needed. The method for manufacturing a curable composition may further include a step of preparing a resin (D).

[0257] The curable composition of the first embodiment (hereinafter also referred to as "curable composition M") includes a resin (D). Curable composition M includes quantum dots (A), a photopolymerizable compound (B) and a resin (D), and preferably further includes a photopolymerization initiator (C). In order to improve the coatability of the composition and the flatness of the composition layer during coating, curable composition M preferably includes a solvent (I).

[0258] Relative to the total amount of solid components in the curing composition, the content of photopolymerizable compound (B) in the curing composition M is, for example, 5% by mass or more and 50% by mass or less, preferably 7% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 35% by mass or less, even more preferably 13% by mass or more and 30% by mass or less, and even more preferably 15% by mass or more and 30% by mass or less.

[0259] The content of solvent (I) in curing composition M is, for example, 40% by mass or more and 95% by mass or less, preferably 45% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 80% by mass or less, relative to the total amount of curing composition M.

[0260] The curable composition of the second embodiment (hereinafter also referred to as "curable composition N") does not contain resin (D). Curable composition N contains quantum dots (A) and photopolymerizable compounds (B), and preferably further contains a photopolymerization initiator (C). Curable composition N may contain solvent (I), but preferably does not contain solvent (I) or contains it in a low proportion.

[0261] Relative to the total amount of solid components in the curing composition, the content of photopolymerizable compound (B) in the curing composition N is, for example, 10% by mass or more and 70% by mass or less, preferably 15% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 45% by mass or less, even more preferably 25% by mass or more and 40% by mass or less, and even more preferably 30% by mass or more and 40% by mass or less.

[0262] Relative to the total amount of curable component N, the content of solvent (I) in curable component N is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and may be 0% by mass or more, or may be 0.5% by mass or more. By reducing the content of solvent (I), the film thickness control during the formation of the cured film becomes easier, and manufacturing costs and the burden of solvent on the earth's environment and working environment can be reduced. Curable component N is suitable for use as ink for inkjet printers.

[0263] <<Method for Manufacturing a Hardened Film>> The manufacturing method of the present invention is a method for manufacturing a hardened film of a hardened composition containing at least quantum dots (A) and a photopolymerizable compound (B). The manufacturing method of the present invention is suitable as a method for manufacturing a hardened film having high martensitic hardness, and is suitable as a method for manufacturing a hardened film of a hardened composition containing quantum dots (A) and a photopolymerizable compound (B), wherein the martensitic hardness is greater than 0.10 GPa. Regarding the preferred range of martensitic hardness of the hardened film obtained by the manufacturing method of the present invention, the description in the <<Hardened Film>> is cited.

[0264] The manufacturing method of the present invention includes the following steps: an exposure step of irradiating a film (hereinafter also referred to as "composition layer") of a curable composition comprising quantum dots (A) and a photopolymerizable compound (B) with light, and a thermal curing step of thermally curing the composition layer. Preferably, the thermal curing step is performed after the exposure step.

[0265] The method for manufacturing the curing film may include steps other than those described above. Examples of such steps include: a coating step of applying a curable composition to a substrate, or an ejection step of ejecting a curable composition into a region defined by a dam in a substrate having a dam formed, a drying step of drying the composition layer formed by the coating or ejection step, and a development step of performing a development step on the composition layer after the exposure step. The curing film may be formed on the entire surface of the substrate, or it may be formed as a curing pattern on a portion of the substrate surface. In this specification, a curing pattern is a type of curing film, referring to a curing film formed in a patterned manner.

[0266] The curing composition used to form the curing film includes quantum dots (A) and photopolymerizable compounds (B), examples of which are the curing compositions described in the <Curing Compositions>.

[0267] The coating step is the step of coating a curable composition onto a substrate to form a composition layer. Examples of coating methods include spin coating, slot coating, and slot spin coating. The ejection step can be, for example, a step of selectively ejecting and adhering the curable composition to the area defined by the dike using an inkjet method.

[0268] Examples of substrates include quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass coated with silicon dioxide; or resin sheets such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and substrates formed with aluminum, silver, or silver / copper / palladium alloy films. Glass substrates and silicon substrates are preferred.

[0269] The substrate may also be a substrate that has undergone a pretreatment that can adjust the wettability of the substrate surface. Examples of pretreatments include solvent washing such as alcohol or acetone, acid treatment, alkali treatment, plasma treatment, and corona treatment. By selecting an appropriate pretreatment for the substrate to which the curable film is to be deposited, the coatability of the curable composition can be improved compared to an untreated substrate.

[0270] When the curable composition contains solvent (I), it is preferable to perform a drying step to remove volatile components such as solvent (I) from the composition layer after the coating step. The drying step may include heat drying (pre-baking) treatment, or it may include vacuum drying treatment, or both. The temperature for heat drying is preferably 30°C or higher and 120°C or lower, more preferably 50°C or higher and 110°C or lower. The heating time is preferably 10 seconds or higher and 60 minutes or lower, more preferably 30 seconds or higher and 30 minutes or lower. In the case of vacuum drying, it is preferable to perform it at a pressure of 50 Pa or higher and 150 Pa or lower, and at a temperature range of 20°C or higher and 25°C or lower.

[0271] The thickness of the composition layer after the coating step, spraying step, or drying step is not particularly limited. It can be appropriately selected according to the thickness of the target hardened film. For example, it can be 1 μm or more and 20 μm or less, preferably 1.5 μm or more and 18 μm or less, more preferably 2 μm or more and 14 μm or less, and even more preferably 2 μm or more and 12 μm or less. The thickness of the finally obtained hardened film can also be the same as described above.

[0272] Next, an exposure step is performed on the composition layer after the coating step, the spraying step, or the drying step. The exposed composition layer is cured by polymerization of the photopolymerizable compound (B) contained in the composition layer. As the light source for exposure, a light source that generates light with a wavelength of 250 nm or more and 450 nm or less is preferred. When the curing composition contains a photopolymerization initiator (C), light around 436 nm, around 408 nm, or around 365 nm can be selectively extracted from the light of that wavelength using a bandpass filter, depending on the absorption wavelength of the photopolymerization initiator (C). Examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0273] From the viewpoint of increasing the Martens hardness of the obtained hardened film, the exposure amount X in the exposure step is preferably 50 mJ / cm² or more, more preferably 80 mJ / cm² or more, even more preferably 100 mJ / cm² or more, and even more preferably 150 mJ / cm² or more. The exposure amount X is usually 1000 mJ / cm² or less, preferably 800 mJ / cm² or less, and even more preferably 700 mJ / cm² or less. When the exposure amount X in the exposure step is 1000 mJ / cm² or less, excessive shrinkage of the hardened film can be prevented, thus preventing the approach of quantum dots (A) in the film caused by the shrinkage of the hardened film, thereby preventing a decrease in the intensity of emitted light.

[0274] The exposure amount X is the exposure amount at a wavelength of 365 nm, which can be measured using an ultraviolet cumulative photometer (UIT-250, manufactured by Ushio Electric Co., Ltd.).

[0275] As an example of a method for forming a hardened pattern as a hardened film, photolithography can be cited. Photolithography is a method of exposing and developing a constituent layer through a photomask used to form the target hardened pattern. At this time, in order to uniformly irradiate the exposed surface with parallel light, or to accurately align the photomask with the substrate on which the constituent layer is formed, it is preferable to use an exposure device such as a mask aligner and a stepper.

[0276] By subjecting the composition layer after the exposure step to a developing solution for development, the unexposed portions of the composition layer dissolve in the developing solution and are removed, thereby imparting a pattern to the composition layer. Examples of developing solutions include aqueous solutions or organic solvents of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the alkaline compound in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. Examples of organic solvents include those similar to the solvent (I). The developing solution may contain a surfactant. The developing method may be any one of the following: immersion method, dipping method, or spray method. Furthermore, the substrate can be tilted at any angle during development.

[0277] The composition layer after the exposure step or the development step is heat-cured (post-baked) in the heat curing step. By means of the heat curing step, the polymerization of photopolymerizable compounds (B) and the like can be further carried out.

[0278] From the viewpoint of increasing the Martens hardness of the obtained hardened film, the heat curing temperature Y in the heat curing step is preferably 90°C or higher, more preferably 100°C or higher, even more preferably 120°C or higher, and even more preferably 150°C or higher. The heat curing temperature Y is usually 250°C or lower, preferably 240°C or lower, and even more preferably 235°C or lower. When the heat curing temperature Y in the heat curing step is 250°C or lower, excessive shrinkage of the hardened film can be prevented, thus preventing the approach of quantum dots (A) in the film caused by the shrinkage of the hardened film, and preventing a decrease in the intensity of emitted light.

[0279] From the viewpoint of increasing the Martens hardness of the obtained hardened film, the heat curing time Z in the heat curing step is preferably 0.1 hr or more, more preferably 0.2 hr or more, further preferably 0.4 hr or more, and even more preferably 0.5 hr or more. The heat curing time Z is usually 2 hr or less, preferably 1.5 hr or less, and more preferably 1.2 hr or less.

[0280] The thermosetting step can be carried out in an atmospheric atmosphere or in a vacuum atmosphere. From the viewpoint of increasing the martensitic hardness of the obtained cured film and improving the intensity of emitted light from the cured film, the thermosetting step is preferably carried out in a vacuum atmosphere. A vacuum atmosphere refers to a pressure range of 150 Pa or less, preferably 120 Pa or less, more preferably 100 Pa or less, and may also be 50 Pa or more.

[0281] Other examples of methods for forming a hardened pattern as a form of hardened film include inkjet printing and printing. As a method for forming a hardened pattern by inkjet printing, for example, a method is described in which, after forming a dam on a substrate, a curable component is selectively attached to the area defined by the dam on the substrate by inkjet printing, and the curable component is hardened by exposure in an exposure step and / or by thermal curing in a thermal curing step. As a method for forming the dam, photolithography and inkjet printing are examples, but inkjet printing is preferred.

[0282] The exposure amount X (mJ / cm2) in the exposure step, the heat curing temperature Y (°C) in the heat curing step, and the heat curing time Z (hr) satisfy the following equation (1): X×Y×Z2≧6500 (1). By performing the exposure step and the heat curing step in a manner that satisfies equation (1), a curing film with high martensite hardness can be manufactured, and a curing film with a martensite hardness greater than 0.10 GPa can be manufactured. Hereinafter, X×Y×Z2 is also referred to as the P value.

[0283] From the viewpoint of manufacturing a hardened film with high martensitic hardness, the P value is preferably 7000 or more, more preferably 8000 or more, even more preferably 10000 or more, even more preferably 15000 or more, particularly preferably 17500 or more, and especially more preferably 20000 or more. From the viewpoint of suppressing the decrease in emitted light intensity of the hardened film, the P value is preferably 150000 or less, more preferably 140000 or less, and even more preferably 120000 or less. In addition, when the P value is within the above range, the dispersibility of quantum dots (A) or light scattering agents (E) in the hardened film is improved, and thus it is easy to obtain a hardened film with small deviation in emitted light intensity.

[0284] <<Display Device>> The hardened film has the function of converting the wavelength of the irradiated light, and therefore can be used as a color conversion layer (wavelength conversion film) in a display device. Examples of such display devices include those described in Japanese Patent Application Publication Nos. 2006-309219, 2006-310303, 2013-15812, 2009-251129, and 2014-2363. The hardened film of the present invention is useful as a color conversion layer (wavelength conversion film) in display devices, particularly liquid crystal display devices, organic electroluminescence (EL) display devices, or inorganic EL display devices. [Example]

[0285] Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "parts" in the examples refer to mass percentage and mass parts.

[0286] [Determination of Margravimetric Hardness of Hardened Film] For the hardened film formed on the substrate, a Berkovich pyramid indenter was installed on an ultra-microhardness testing machine (Elionix, ENT-2100) to perform a load-unload test and determine the load / indentation curve. The test temperature was set to room temperature. Here, the maximum test load was set to 6 mN, and the load was unloaded to 0 mN without holding time. The test data was processed using ENT-Win ver.7.50 (Elionix) to determine the indentation hardness and margravimetric hardness (GPa).

[0287] [Measurement of the intensity of emitted light from the hardened film] A narrow-pointing-angle sensing backlight (OPF series; manufactured by OPTEX FA) equipped with an LED lamp with an emission wavelength of 444 nm and a scratch-resistant cover was prepared as a backlight source. The backlight source was placed with the scratch-resistant cover facing upwards, and an optical fiber for detecting the emitted light was installed at a height of 4 cm above the surface of the scratch-resistant cover. A reference glass substrate (Eagle 2000; manufactured by Corning) was placed on the surface of the scratch-resistant cover of the backlight source. The backlight source was lit in this state, and the light intensity of the backlight source was adjusted so that the total emitted beam (μW) of the backlight source exceeded that of the reference glass substrate (Eagle 2000; manufactured by Corning) by 5000 μW.

[0288] Next, a substrate having a hardened film is disposed on the surface of the reference glass substrate. With the backlight illuminated in this state, the emitted light intensity (unit: μW) is measured as the cumulative emission beam in the range of wavelengths from 485 nm to 780 nm, excluding light emitted from the hardened film. The emitted light intensity is measured using a spectrometer (manufactured by Ocean Optics).

[0289] 〔Determination of Pencil Hardness of Hardened Film〕 The pencil hardness of the surface of the hardened film formed on the substrate was determined using a TRIBORGEAR reciprocating abrasion tester (model: 30, manufactured by HEIDON Co., Ltd.) according to the pencil hardness test specified in Japanese Industrial Standard (JIS) K5600-5-4:1999 "General Test Methods for Coatings - Part 5: Mechanical Properties of Coatings - Section 4: Scratch Hardness (Pencil Method)". The load used in the test was 500 g, and the speed was 40 mm / sec.

[0290] 〔Weight Average Molecular Weight〕 The weight average molecular weight (Mw) of resin (D1) was determined using the GPC method under the following conditions. Apparatus: K2479 (manufactured by Shimadzu Corporation) Column: Shimadzu Shim-pack GPC-80M Column temperature: 40℃ Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI Calibration standard materials: TSK Standard Polystyrene F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0291] 〔Acid Value〕 Accurately weigh 3 g of resin (D1) solution, dissolve it in a mixed solvent of 90 g acetone and 10 g water, use 0.1% KOH aqueous solution as titrant, determine the acid value of resin (D1) solution using an automatic titration device (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555), and calculate the acid value (AV) per 1 g of solid component based on the acid value of the solution and the solid component of the solution.

[0292] 〔Solid composition〕 Take about 1 g of resin (D1) solution in an aluminum cup, dry it at 180°C for 1 hour, and then determine its mass. Calculate the solid composition (mass %) of the resin (D1) solution based on the amount of mass reduction.

[0293] (Manufacturing Example 1: Preparation of Dispersion c of Quantum Dots (A1)) A toluene dispersion a of InP / ZnSeS quantum dots (A1) coordinated with oleic acid as a ligand (H2) was prepared. Dispersion a was distilled under reduced pressure to remove toluene. 70 parts of cyclohexyl acetate were added relative to 30 parts of solids to obtain dispersion b (30% solids). A specified amount of ligand (H1) was added to dispersion b, and the mixture was stirred at 80°C for 2 hours to obtain dispersion c of quantum dots (A1) containing ligand (H1) and ligand (H2).

[0294] (Manufacturing Example 2: Preparation of a dispersion of light scattering agent (E1)) 3 parts of DISPERBYK 21116 (manufactured by BYK-Chemie Japan) based on solid content were added to 70 parts of TiO2 nanoparticles, and propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") was added in a total amount of 100 parts by mass. The mixture was stirred using a paint shaker until it was fully dispersed, thereby obtaining a dispersion of light scattering agent (E1) (73% solid content).

[0295] (Manufacturing Example 3: Preparation of Resin (D1) Solution) In a flask including a stirrer, a reflux cooling tube with a thermometer, a dropping funnel, and a nitrogen inlet tube, 110 parts of PGMEA were added, and the mixture was stirred while being purged with nitrogen, and the temperature was raised to 80°C. A solution was obtained by dissolving 25 parts of dicyclopentyl methacrylate, 23 parts of methyl methacrylate, 19 parts of methacrylic acid, and 10 parts of 2,2'-azobis(2,4-dimethylpentanonitrile) in 110 parts of PGMEA, and then added dropwise to the flask using a dropping funnel. The mixture was stirred at 80°C for 3 hours. Next, 16 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts of triphenylphosphine were added to the flask, and the temperature was raised to 110°C and stirred for 8 hours. This allowed the carboxylic acid and epoxy groups in the polymer to react, thereby introducing polymerizable unsaturated bonds. Subsequently, 17 parts of 1,2,3,6-tetrahydrophthalic anhydride were added and the reaction was continued for 3 hours to introduce carboxylic acid groups into the side chains. The reaction solution was cooled to room temperature to obtain a resin (D1) solution. The resin (D1) had a weight-average molecular weight of 8400 converted from standard polystyrene, an acid value of 120 mgKOH / g, and a solid content of 40% by mass in the resin (D1) solution.

[0296] (Manufacturing Example 4: Preparation of Curable Composition 1) Curable composition 1 was prepared by mixing the dispersion c obtained in Manufacturing Example 1, the dispersion of the light scattering agent (E1) obtained in Manufacturing Example 2, the resin (D1) solution obtained in Manufacturing Example 3, and other components shown in Table 1 in specified amounts. Furthermore, in examples other than Example 3 described later, a curable film was formed from curable composition 1 using a dispersion c containing InP / ZnSeS quantum dots (Al) with a maximum peak wavelength of 530 nm and a full width at half maximum (FWHM) of 42 nm. In Example 3, a curable film was formed from curable composition 1 using a dispersion c containing InP / ZnSeS quantum dots (Al) with a maximum peak wavelength of 630 nm and a FWHM of 42 nm. The emission spectrum of quantum dots (A1) was measured using an absolute PL quantum yield measurement device ("C9920-02" manufactured by Hamamatsu Photonics, excitation light 450 nm, room temperature, atmospheric conditions), with a dispersion of quantum dots (A1) diluted to an absorbance of 0.4 at a wavelength of 450 nm as the measurement sample.

[0297] The composition of the obtained curable composition 1 is shown in Table 1. In Table 1, the components other than solvent (I) are the content converted from solid components (unit: parts by mass). The content of solvent (I) is in parts by mass. For example, quantum dots (A1) are prepared as a dispersion c of quantum dots (A1) in the preparation of curable composition 1, and the content shown in Table 1 is the amount of quantum dots (A1) contained in the dispersion itself. The solvent (I) in Table 1 includes the solvent contained in the dispersion or solution used in the preparation of curable composition 1.

[0298] [Table 1] Composition of hardening component 1 (by weight) Quantum dot (A) (A1) 21.1 Photopolymerizable compounds (B) (B1) 9.2 (B2) 12.2 Photopolymerization initiator (C) (C1) 1.9 Resin (D) (D1) 39.5 Light scattering agent (E) (E1) 5.0 Antioxidants (F) (F1) 3.5 Leveling agent (G) (G1) 0.1 Ligand (H) (H1) 0.6 (H2) 6.9 The total of the above 100.0 Solvent (I) (I1) 100.0 (I2) 86.0

[0299] The detailed information of the abbreviations of the components shown in Table 1 is as follows. 〔1〕Photopolymerizable compound (B1): M-510 (carboxyl-containing polyfunctional (meth)acrylate, manufactured by Toa Synthetic Co., Ltd. under the trade name "Aronix M-510", 100% solids). This compound is equivalent to the aforementioned photopolymerizable compound (B-3a). 〔2〕Photopolymerizable compound (B2): A-9550 (dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., 100% solids). This compound is equivalent to the aforementioned photopolymerizable compound (B-3b). 〔3〕Photopolymerization initiator (C1): The compound represented by the following formula. Manufactured by the method described in Japanese Patent Application Publication No. 2011-132215 (100% solids).

[0300] [Chemistry 23]

[0301] 〔4〕Antioxidant (F1): Sumilizer-GP (phosphorus / phenol complex antioxidant, manufactured by Sumitomo Chemical Co., Ltd., 100% solid content) 〔5〕Leveling agent (G1): F-575 (fluorinated leveling agent, manufactured by DIC Co., Ltd., 10% solid content, containing PGMEA) 〔6〕Ligand (H1): 3-mercaptopropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 100% solid content) 〔7〕Ligand (H2): Oleic acid 〔8〕Solvent (I1): PGMEA (propylene glycol monomethyl ether acetate) 〔9〕Solvent (I2): Cyclohexyl acetate

[0302] (Manufacturing Example 5: Preparation of Dried Quantum Dots (A1)) A toluene dispersion a of InP / ZnSeS quantum dots (A1) coordinated with oleic acid as a ligand (H2) was prepared. The toluene was removed by vacuum distillation of dispersion a to obtain dried quantum dots (A1).

[0303] (Manufacturing Example 6: Preparation of a dispersion of light scattering agent (E2)) 10 parts of DISPERBYK 21116 (manufactured by BYK-Chemie Japan) based on solid content were added to 60 parts of TiO2 nanoparticles, and PGMEA was added in a total amount of 100 parts. The mixture was stirred using a coating shaker until it was fully dispersed, thereby obtaining a dispersion of light scattering agent (E2) (70% solid content).

[0304] (Manufacturing Example 7: Preparation of Curable Composition 2) In the dried quantum dot (A1) obtained in Manufacturing Example 5, the prescribed amounts of photopolymerizable compound (B1), 2-(2-ethyleneoxyethoxy)ethyl acrylate (VEEA (registered trademark) manufactured by Nippon Shokubai Co., Ltd.), which is the photopolymerizable compound (B3), and ethyl methacrylate (Light Ester E manufactured by Kyoeisha Chemical Co., Ltd.), which is the photopolymerizable compound (B4), were added. The mixture was stirred using an ultrasonic cleaner and a touch mixer until the solids disappeared, thereby obtaining a quantum dot monomer dispersion. Photopolymerizable compound (B3) is equivalent to the photopolymerizable compound (B-4), and photopolymerizable compound (B4) is equivalent to the photopolymerizable compound (B-1).

[0305] A dispersion of light scattering agent (E2), a photopolymerization initiator, an antioxidant, and a leveling agent were added to the obtained dispersion in a manner consistent with the formulation described in Table 2, and the curable composition 2 was prepared by stirring with a touch mixer. Furthermore, in Example 6, a curable film was formed from InP / ZnSeS quantum dots (A-1) containing quantum dots with a maximum peak wavelength of 630 nm and a full width at half maximum (FWHM) of 42 nm.

[0306] The composition of the obtained curable composition 2 is shown in Table 2. In Table 2, the components other than solvent (I) are the content converted from solid components (unit: parts by mass). The content of solvent (I) is in parts by mass. The solvent (I) in Table 2 includes the solvent contained in the dispersion or solution used in the preparation of curable composition 2. In addition, the content of quantum dots (A) in Table 2 also includes ligands (H2).

[0307] [Table 2] Composition of hardening component 2 (by weight) Quantum dot (A) (A1) 29.1 Photopolymerizable compounds (B) (B1) 11.6 (B3) 11.6 (B4) 15.5 Photopolymerization initiator (C) (C2) 3.9 Light scattering agent (E) (E2) 5.8 Antioxidants (F) (F1) 19.4 Leveling agent (G) (G2) 0.1 The total of the above 97.0 Solvent (I) (I1) 3.0

[0308] The detailed information of the abbreviations of the components shown in Table 2 is as follows. 〔10〕Photopolymerization initiator (C2): OMNIRAD (registered trademark) 907 (manufactured by IGM Resins) 〔11〕Leveling agent (G2): Megafac (registered trademark) F-554 (manufactured by DIC)

[0309] <Example 1> The curable composition 1 obtained in Manufacturing Example 4 was coated onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) to achieve a film thickness of 10 μm by spin coating. A drying step (pre-baking) at 100°C for 3 minutes was then performed to form a film of the curable composition 1. An exposure step was performed on this film using an exposure machine (TME-150RSK; manufactured by Topcon) at an exposure dose of 200 mJ / cm² (based on 365 nm) under atmospheric conditions. After development, a heat curing step was performed at 180°C for 1 hour under a vacuum atmosphere (pressure: 100 kPa) (post-baking) to obtain a substrate with a cured film.

[0310] <Examples 2 to 5, Comparative Example 1> Except for the exposure amount X (mJ / cm2) in the exposure step, the heat curing temperature Y (°C), the heat curing time Z (hr) in the heat curing step, and the heat curing atmosphere as shown in Table 3, the drying step, exposure step, and heat curing step were performed in the same manner as in Example 1, thereby obtaining a substrate with a cured film.

[0311] <Example 6> Using the curable composition 2 obtained in Manufacturing Example 7, except that the exposure amount X (mJ / cm2) in the exposure step, the heat curing temperature Y (°C) in the heat curing step, the heat curing time Z (hr) and the heat curing atmosphere are as shown in Table 3, the drying step, the exposure step and the heat curing step are performed in the same way as in Example 1, thereby obtaining a substrate with a curable film.

[0312] The results of the P value, the measurement of the martensitic hardness, the measurement of the pencil hardness, and the measurement of the emitted light intensity are shown in Table 3.

[0313] [Table 3] Example Comparative example 1 2 3 4 5 6 1 dry step Drying conditions 100℃ / 3 minutes 100℃ / 3 minutes 100℃ / 3 minutes 100℃ / 3 minutes 100℃ / 3 minutes 25℃ / 10 minutes 100℃ / 3 minutes exposure step Exposure (mJ / cm) 2 ) 200 200 80 200 500 200 80 Thermosetting steps Thermosetting temperature (°C) 180 100 100 180 230 180 80 Heat curing time (hr) 1 1 1 1 1 0.5 1 Thermosetting atmosphere vacuum vacuum atmosphere atmosphere atmosphere atmosphere atmosphere p-value 36000 20000 8000 36000 115000 9000 6400 Mardull hardness (GPa) 0.26 0.24 0.20 0.24 0.30 0.22 0.10 Pencil hardness 4H 2H 2B 3H 5H 2B 4B Emitted light intensity (μW) 1462 1664 1966 1378 1025 1878 1639 [Simplified Explanation of the Diagram]

[0008] None

Claims

1. A hardening film comprising a hardening composition including quantum dots (A) and a photopolymerizable compound (B), wherein the hardening film has a Martens hardness greater than 0.10 GPa, and the photopolymerizable compound comprises 10% by mass or more and 45% by mass or less relative to the total amount of the hardening composition, and the hardening composition further comprises a photopolymerization initiator (C) and a light scattering agent (E).

2. The hardened film as claimed in claim 1, wherein, The curing component further comprises a resin (D).

3. A method for manufacturing a hardened film, comprising a hardened composition including quantum dots (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a light scattering agent (E), and further comprising: The exposure step involves irradiating the film of the curable composition with light; And a thermal curing step, wherein the film of the curable composition is thermally cured, and when the exposure amount at a wavelength of 365 nm in the exposure step is set to X (mJ / cm2), the thermal curing temperature in the thermal curing step is set to Y (°C), and the thermal curing time is set to Z (hr), the following equation (1) is satisfied: X×Y×Z2≧15000 (1).

4. The manufacturing method as described in claim 3, wherein, The thermosetting step is carried out in a vacuum atmosphere.

5. A display device comprising a hardened film as described in claim 1 or claim 2.