Photosensitive resin composition, cured film, substrate with the film, method for producing thesubstrate, and display device

Abstract

This invention provides a photosensitive resin composition with high wavelength conversion efficiency and low particle sedimentation during storage. The photosensitive resin composition comprises (A) a photocurable compound, (B) particles with an average particle size of 100 nm or more and 600 nm or less, a hollowness of 10% or more and 90% or less, and including metal oxides with a refractive index of 1.9 or more and 2.7 or less, (C) a photopolymerization initiator, and (F) quantum dots. The content of component (B) relative to the total mass of the solid components is 5% by mass or more and 70% by mass or less.

Description

[Technical Field]

[0001] This invention relates to a photosensitive resin composition, a hardened film, a substrate with a hardened film, a method for manufacturing the substrate with a hardened film, and a display device. [Previous Technology]

[0002] In display devices that display images or videos, a hardened film for wavelength conversion of light from a light source is sometimes used. As such a hardened film, a hardened film containing particles such as metal oxides can be used to scatter light in the hardened film (for example, Patent Document 1).

[0003] Regarding the aforementioned particles, Patent Document 2 describes that by using particles having an average particle diameter that is 8% or less of the thickness of the hardened film and a refractive index of 0.10 or more relative to the refractive index of the adhesive resin, the wavelength conversion efficiency of the wavelength conversion layer can be improved. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2020-129034 [Patent Document 2] Japanese Patent Application Publication No. 2016-159445 [Summary of the Invention]

[0005] [Problem to be solved by the invention] There is a need to further improve the wavelength conversion efficiency of the hardened film with wavelength conversion function. In addition, in the photosensitive resin composition used to make these hardened films, since the particles contained for light scattering have a high specific gravity, there is a problem that the particles tend to settle during storage, and frequent stirring or vibration is necessary to suppress particle settling.

[0006] This invention has been made in view of the above circumstances, and its object is to provide a photosensitive resin composition with high wavelength conversion efficiency and low particle sedimentation during storage, a hardened film made from the photosensitive resin composition, a substrate having the hardened film, a method for manufacturing the substrate having the hardened film, and a display device having the substrate having the hardened film. [Technical Means for Solving the Problem]

[0007] One aspect of the present invention for solving the aforementioned problem comprises a photosensitive resin composition including: (A) a photocurable compound, (B) particles having an average particle size of 100 nm or more and 600 nm or less, a hollowness of 10% or more and 90% or less, and comprising metal oxides with a refractive index of 1.9 or more and 2.7 or less, (C) a photopolymerization initiator, and (F) quantum dots. The content of component (B) relative to the total mass of the solid components is 5% by mass or more and 70% by mass or less.

[0008] Another aspect of the present invention relates to a hardened film formed by hardening the photosensitive resin composition.

[0009] Another aspect of the present invention relates to a substrate with a hardening film comprising the hardening film.

[0010] Another aspect of the present invention relates to a method for manufacturing a substrate with a hardened film, comprising: a step of coating the photosensitive resin composition onto a substrate; and a step of exposing the coated photosensitive resin composition to light. Another aspect of the present invention relates to a display device having the substrate with the hardened film. [Effects of the Invention]

[0011] The present invention provides a photosensitive resin composition with high wavelength conversion efficiency and low particle sedimentation during storage, a hardened film made from the photosensitive resin composition, a substrate with the hardened film, a method for manufacturing the substrate with the hardened film, and a display device having the substrate with the hardened film.

Implementation Method

[0012] 1. Photosensitive resin composition The photosensitive resin composition according to one embodiment of the present invention includes: (A) a photocurable compound, (B) particles with an average particle size of 100 nm or more and 600 nm or less, a hollowness of 10% or more and 90% or less, and comprising metal oxides with a refractive index of 1.9 or more and 2.7 or less, (C) a photopolymerization initiator, and (F) quantum dots.

[0013] 1-1. (A) Component (A) is a photocurable compound that is polymerized and cured by light irradiation. Component (A) imparts specified photosensitivity to the photosensitive resin composition.

[0014] (A) Component can be selected appropriately depending on the intended use of the photosensitive resin composition. For example, when patterning a hardened film by photolithography, component (A) preferably includes an alkali-soluble resin containing an unsaturated group (A1) for imparting alkali developability to the coating of the photosensitive resin composition, and preferably also includes a photopolymerizable compound having at least two vinyl unsaturated bonds (A2) for improving exposure sensitivity. Alternatively, when the photosensitive resin composition is applied to it in a fine pattern by inkjet printing and then cured, component (A) need only include at least a photopolymerizable compound having at least two vinyl unsaturated bonds (A2).

[0015] 1-1-1. (A1) Component (A1) is an alkali-soluble resin containing unsaturated groups. Component (A1) imparts solubility relative to alkali development to the coating of the photosensitive resin composition.

[0016] (A1) The preferred component has a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility in one molecule, more preferably having a polymerizable unsaturated group and a carboxyl group. (A1) The component is not particularly limited as long as it is the resin in question, and can be any type of resin. Because (A1) has a polymerizable unsaturated group, it imparts excellent photocurability to the photosensitive resin composition, and furthermore, its molecular weight increases during curing, thus acting as an adhesive. In addition, because (A1) has an acidic group, it improves the physical properties of the cured film, such as developability and patterning characteristics (pattern line width, pattern straightness).

[0017] (A1) The preferred component is an alkali-soluble resin containing unsaturated groups, obtained by further reacting an epoxy compound having two or more epoxy groups and the reaction product of (meth)acrylic acid with a polycarboxylic acid or its anhydride. In manufacturing the alkali-soluble resin containing unsaturated groups, a polyester is generated by reacting hydroxyl groups with a polycarboxylic acid. The preferred component (A1) is a low molecular weight resin with an average degree of polymerization of approximately 2 to 500. Furthermore, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, "(meth)acrylyl" is a general term for acrylyl and methacrylyl, and "(meth)acrylate" is a general term for acrylate and methacrylate; all refer to one or both of these.

[0018] Examples of epoxy compounds having two or more epoxy groups include: bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenolic varnish type epoxy compounds, o-cresol phenolic varnish type epoxy compounds, m-cresol phenolic varnish type epoxy compounds, p-cresol phenolic varnish type epoxy compounds, phenol aralkyl type epoxy compounds, and biphenyl type epoxy compounds (e.g., jER). YX4000: Manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the company), phenolic varnish compounds containing a naphthalene skeleton (e.g., NC-7000L: Manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, triphenol methane type epoxy compounds (e.g., EPPN-501H: Manufactured by Nippon Kayaku Co., Ltd.), tetraphenol ethane type epoxy compounds and other epoxy compounds with aromatic structures, glycidyl ethers of polyols, glycidyl esters of polycarboxylic acids, copolymers of methacrylic acid and glycidyl methacrylate, copolymers of monomers containing (meth)acrylic acid glycidyl ester as units, represented by copolymers of methacrylic acid and glycidyl methacrylate, hydrogenated bisphenol A diglycidyl ether (e.g., Ricarex). Rikaresin HBE-100: manufactured by New Japan Rika Co., Ltd., "Rikaresin" is a registered trademark of the company, and other epoxy compounds with glycidyl groups, 1,4-cyclohexanediethanol-bis(3,4-epoxycyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,1-spiro(3,4-epoxy)cyclohexyl-m-dioxane (e.g., Araldite CY175: manufactured by Huntsman, "Araldite" is a registered trademark of the company), bis(3,4-epoxycyclohexylmethyl) adipate (e.g., CYRACURE UVR-6128: Dow Chemical Co., Ltd.). Chemicals, Inc., 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g., Celloxide 2021P: manufactured by Daicel Inc., "Celloxide" is a registered trademark of the company), tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone of butanetetracarboxylate (e.g., EPOLEAD GT401: manufactured by Daicel Inc., "EPOLEAD" is a registered trademark of the company), epoxy compounds having an epoxycyclohexyl group (e.g., HiREM-1: manufactured by Shikoku Chemical Industry Co., Ltd.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Inc.), 2,Alicyclic epoxy compounds such as the 1,2-epoxy-4-(2-oxetanepropyl)cyclohexane adduct of 2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Inc.), epoxy-based polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the company), and epoxy compounds having a silicone backbone, etc.

[0019] Examples of other preferred resins for the composition (A1) include alkali-soluble resins as acrylic copolymers.

[0020] Examples of the acrylic copolymer include resins that are copolymers of (meth)acrylic acid, (meth)acrylate, etc., and have (meth)acrylic acid and carboxyl groups. Examples of the resin include alkali-soluble resins containing polymerizable unsaturated groups obtained by copolymerizing (meth)acrylates containing glycidyl (meth)acrylate in a solvent to obtain a copolymer, reacting (meth)acrylic acid with the obtained copolymer, and finally reacting a dicarboxylic acid or tricarboxylic acid anhydride. The copolymer may refer to: the copolymer disclosed in Japanese Patent Application Publication No. 2014-111722, which comprises 20 mol% to 90 mol% repeating units derived from glycerol ester, which is obtained by esterifying the hydroxyl groups at both ends of (meth)acrylic acid, and 10 mol% to 80 mol% repeating units derived from one or more polymeric unsaturated compounds that can copolymerize therewith, and has a number average molecular weight (Mn) of 2000 to 20000 and an acid value of 35 mgKOH / g to 120 mgKOH / g; and the polymer disclosed in Japanese Patent Application Publication No. 2018-141968, which comprises units derived from (meth)acrylate compounds and units having (meth)acrylic acid and dicarboxylic acid residues or tricarboxylic acid residues, has a weight average molecular weight (Mw) of 3000 to 50000, and an acid value of 30 mgKOH / g to 200 mgKOH / g, i.e., an alkali-soluble resin containing polymeric unsaturated groups.

[0021] From the viewpoint of further improving the heat resistance and solvent resistance of the hardened film, the (A1) component is preferably having a plurality of aromatic rings, more preferably having repeating units containing a fluorene structure, and even more preferably having repeating units containing a diarylfluorene skeleton. For example, the (A1) component is preferably a resin represented by the following general formula (1).

[0022] [Chemical 1] (In formula (1), R1, R2, R3 and R4 are independently hydrogen atoms, straight-chain or branched alkyl groups with 1 to 5 carbon atoms, halogen atoms or phenyl groups, R5 is a hydrogen atom or methyl group, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or direct bond, Y is a tetravalent carboxylic acid residue, Z are independently hydrogen atoms or substituents represented by general formula (2), and more than one is a substituent represented by general formula (2). The average value of n is 1 to 20)

[0023] [Chemical 2] (In formula (2), W is a divalent or trivalent carboxylic acid residue, m is 1 or 2, and * is the bonding site)

[0024] Next, the method for manufacturing the alkali-soluble resin represented by the general formula (1) will be described in detail.

[0025] First, an epoxy compound (a-1) having two epoxy groups in one molecule, represented by general formula (3) (hereinafter also simply referred to as "epoxide compound (a-1)"), is reacted with a monocarboxylic acid containing an unsaturated group (e.g., (meth)acrylic acid) to obtain an epoxy ester of (meth)acrylic acid. Furthermore, "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and "(meth)acrylyl" is a general term for acrylyl and methacrylyl, referring to one or both of these.

[0026] [Chemical 3] (In formula (3), R1, R2, R3 and R4 are respectively hydrogen atoms, straight-chain or branched alkyl groups with 1 to 5 carbon atoms, halogen atoms or phenyl groups, and X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or direct bond)

[0027] Epoxide (a-1) is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin.

[0028] Examples of the bisphenols include: bis(4-hydroxyphenyl)one, bis(4-hydroxy-3,5-dimethylphenyl)one, bis(4-hydroxy-3,5-dichlorophenyl)one, bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, bis(4-hydroxy-3,5-dichlorophenyl) ketone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dichlorophenyl) ketone ... 5-Dichlorophenyl)hexafluoropropane, bis(4-hydroxyphenyl)dimethylsilane, bis(4-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(4-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl) 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl) ether, bis(4-hydroxy-3,5-dimethylphenyl) ether, bis(4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis( Fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4'-biphenol, 3,3'-biphenol, etc. Among these, bisphenols having a fluorene-9,9-diyl group are preferred from the viewpoint of further improving adhesion. These can be used alone or in combination of two or more.

[0029] Examples of monocarboxylic acid compounds containing unsaturated groups include, in addition to acrylic acid and methacrylic acid, compounds formed by reacting monoanhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride with acrylic acid or methacrylic acid.

[0030] The reaction of the epoxy compound (a-1) with (meth)acrylic acid can be carried out using known methods. For example, Japanese Patent Application Publication No. 4-355450 discloses that a diol compound containing polymerizable unsaturated groups can be obtained by using about 2 moles of (meth)acrylic acid relative to 1 mole of an epoxy compound having two epoxy groups. In the present invention, the compound obtained by the reaction is a diol compound containing polymerizable unsaturated groups, and is a diol (d) containing polymerizable unsaturated groups represented by general formula (4) (hereinafter also simply referred to as "diol (d) represented by general formula (4)").

[0031] [Chemical 4] (In formula (4), R1, R2, R3 and R4 are respectively independent hydrogen atoms, straight-chain or branched alkyl groups with 1 to 5 carbon atoms, halogen atoms or phenyl groups, R5 is a hydrogen atom or a methyl group, and X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or direct bond)

[0032] When synthesizing the diol (d) represented by general formula (4), and subsequently reacting the polycarboxylic acid or its anhydride, and then reacting the monofunctional epoxy compound having a polymerizable unsaturated group that is reactive with the carboxyl group to produce the alkali-soluble resin represented by general formula (1), a catalyst is usually used in the solvent as needed to carry out the reaction.

[0033] Examples of solvents include: cellosol solvents such as ethyl cellosol acetate and butyl cellosol acetate; high-boiling-point ether or ester solvents such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone solvents such as cyclohexanone and diisobutyl ketone. Furthermore, there are no particular restrictions on the reaction conditions regarding the solvents, catalysts, etc., used. For example, it is preferable to use a solvent that does not have hydroxyl groups and has a boiling point higher than the reaction temperature as the reaction solvent.

[0034] In addition, a catalyst is preferably used in the reaction between the carboxyl group and the epoxy group. For example, Japanese Patent Application Publication No. 9-325494 discloses ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, as well as phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0035] Next, by reacting the diol (d) represented by general formula (4) obtained by reacting the epoxy compound (a-1) with (meth)acrylic acid, and the dicarboxylic acid or tricarboxylic acid or its monohydric anhydride (b), and the tetracarboxylic acid or its dianhydride (c), a base-soluble resin represented by general formula (1) having a carboxyl group and a polymerizable unsaturated group in one molecule can be obtained.

[0036] [Chemical 5] (In formula (1), R1, R2, R3 and R4 are independently hydrogen atoms, straight-chain or branched alkyl groups with 1 to 5 carbon atoms, halogen atoms or phenyl groups, R5 is a hydrogen atom or methyl group, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or direct bond, Y is a tetravalent carboxylic acid residue, Z are independently hydrogen atoms or substituents represented by general formula (2), and more than one is a substituent represented by general formula (2). The average value of n is 1 to 20)

[0037] [Chemical 6] (In formula (2), W is a divalent or trivalent carboxylic acid residue, m is 1 or 2, and * is the bonding site)

[0038] The acid component used to synthesize the alkali-soluble resin represented by general formula (1) is a polybasic acid component that can react with the hydroxyl group in the diol (d) molecule represented by general formula (4), and requires the use of a dicarboxylic acid or tricarboxylic acid or their monohydric anhydride (b) with a tetracarboxylic acid or its dianhydride (c). The carboxylic acid residues of the acid component can be either saturated or unsaturated hydrocarbon groups. In addition, these carboxylic acid residues may also contain bonds containing heteroelements such as -O-, -S-, and carbonyl groups.

[0039] As the dicarboxylic acid or tricarboxylic acid or the acid monoanhydride of these, chain hydrocarbon dicarboxylic acid or tricarboxylic acid, alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or the acid monoanhydride of these may be used.

[0040] Examples of the monoanhydrides of the chain-type dicarboxylic or tricarboxylic acids include: monoanhydrides of succinic acid, acetosuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citric acid, malic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, octanoic acid, diethylene glycol, etc., and monoanhydrides of dicarboxylic or tricarboxylic acids with any substituents.

[0041] Examples of monoanhydrides of alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include: monoanhydrides of cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methyl-3,6-methylenetetrahydrophthalic acid, norbornane dicarboxylic acid, chlorobridged acid, hexahydrotriphenylcarboxylic acid, etc., and monoanhydrides of dicarboxylic acids or tricarboxylic acids with any substituents.

[0042] Examples of monoanhydrides of aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include: monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, etc., and monoanhydrides of dicarboxylic acids or tricarboxylic acids with any substituents.

[0043] Among the monohydric anhydrides of dicarboxylic or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotriphenylamine, phthalic acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred. Furthermore, these monohydric anhydrides are preferred among dicarboxylic or tricarboxylic acids. The monohydric anhydrides of the dicarboxylic or tricarboxylic acids may be used alone or in combination with two or more.

[0044] In addition, as a tetracarboxylic acid or its acid dianhydride (c), a chain-type hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or the acid dianhydride of these can be used.

[0045] Examples of chain tetracarboxylic acids include: butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain tetracarboxylic acids with substituents such as alicyclic hydrocarbon groups or unsaturated hydrocarbon groups.

[0046] Examples of alicyclic tetracarboxylic acids include: cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acids with substituents such as chain hydrocarbon groups or unsaturated hydrocarbon groups.

[0047] Examples of aromatic hydrocarbon tetracarboxylic acids include: pyromellitic tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl tannic acid tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, etc.

[0048] Among the tetracarboxylic acids or their dianhydrides, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenyl ethertetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenyl ethertetracarboxylic acid are more preferred. Furthermore, among the tetracarboxylic acids or their dianhydrides, their dianhydrides are preferred. The tetracarboxylic acid or its dianhydride may be used alone or in combination with two or more.

[0049] There are no particular limitations on the reaction method of the diol (d) with the acid components (b) and (c), and known methods can be used. For example, Japanese Patent Application Publication No. 9-325494 discloses a method for reacting (meth)acrylate epoxy ester with tetracarboxylic acid dianhydride at a reaction temperature of 90°C to 140°C.

[0050] At this time, in order to make the end of the compound a carboxyl group, it is preferable to carry out the reaction in a molar ratio of (meth)acrylate epoxy ester (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monohydric anhydride (b), and tetracarboxylic acid dianhydride (c) such that (d):(b):(c) = 1.0:0.01 to 1.0:0.2 to 1.0.

[0051] For example, when using monohydric anhydride (b) and dianhydride (c), it is preferable to carry out the reaction in such a way that the molar ratio of the amount of acid component [(b) / 2+(c)] to diol (d) [[(b) / 2+(c)] / (d)] is greater than 0.5 and less than 1.0. If the molar ratio is greater than 0.5, since the end of the curing resin containing unsaturated groups represented by general formula (1) will not become anhydride, the increase in the content of unreacted dianhydride can be suppressed, thereby improving the long-term stability of the curing composition. In addition, if the molar ratio is less than 1.0, the increase in the amount of unreacted component in diol (d) containing polymerizable unsaturated groups can be suppressed, thereby improving the long-term stability of the curing composition. Furthermore, for the purpose of adjusting the acid value and molecular weight of the curing resin containing unsaturated groups represented by general formula (1), the molar ratios of each component of (b), (c) and (d) can be arbitrarily changed within the range stated.

[0052] Furthermore, the synthesis of diol (d) and the subsequent reactions of polycarboxylic acids or their anhydrides are usually carried out in a solvent using a catalyst as needed.

[0053] Examples of the solvents include: solvent-based solvents such as ethyl cellolytic acetate and butyl cellolytic acetate; high-boiling-point ether or ester-based solvents such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone-based solvents such as cyclohexanone and diisobutyl ketone. Furthermore, there are no particular limitations on the reaction conditions regarding the solvents, catalysts, etc., used; for example, it is preferable to use a solvent that does not have hydroxyl groups and has a boiling point higher than the reaction temperature as the reaction solvent.

[0054] Furthermore, the reaction between the epoxy group and the carboxyl or hydroxyl group is preferably carried out using a catalyst. As such catalysts, Japanese Patent Application Publication No. 9-325494 discloses ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, triphenylphosphine, and phosphine derivatives such as tris(2,6-dimethoxyphenyl)phosphine.

[0055] (A1) Component is preferably a compound with a weight average molecular weight (Mw) of 1,000 or more and 40,000 or less, more preferably a compound with a weight average molecular weight (Mw) of 2,000 or more and 20,000 or less. The higher the Mw of component (A1), the better the adhesion and flexibility of the hardened film, and the easier it is to adjust the crosslinking density. On the other hand, the lower the Mw of component (A1), the better the solubility of component (A1) in the solvent, and the better the compatibility with component (A2), thereby improving the whitening suppression, flatness and patternability of the hardened film.

[0056] From the same point of view, the (A1) component is preferably an acid value of 30 mgKOH / g or more and 200 mgKOH / g or less.

[0057] In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of each component can be set as styrene conversion values ​​obtained using gel permeation chromatography (GPC) (e.g., "HLC-8220GPC" (manufactured by Tosoh Corporation)). Additionally, the acid value can be set as a value obtained using a potentiometric titration apparatus (e.g., "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.)). For compounds such as monomers whose molecular weight can be calculated from their structure, the value calculated based on the structure can be set as the molecular weight of the compound.

[0058] In addition, (A1) ingredient can be used alone or in combination with two or more ingredients.

[0059] 1-1-2. (A2) Component (A2) is a photopolymerizable compound having at least two vinyl unsaturated bonds. Component (A2) improves the exposure sensitivity of the photosensitive resin composition and, during curing, forms a moderate cross-linked structure to improve the adhesion of the cured film to the substrate, and improves the developability (resolution, e.g., linearity of the pattern) of the cured film.

[0060] (A2) Specific examples of the ingredients include: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate Acrylic esters, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxy-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate and other (meth)acrylates, hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, and dendritic polymers with (meth)acrylic groups as compounds with vinyl double bonds, etc.

[0061] From the viewpoint of further improving the exposure sensitivity of the photosensitive resin composition and improving the adhesion by increasing the crosslinking density of the hardened film, component (A2) is preferably having three or more vinyl unsaturated bonds, and more preferably having five or more vinyl unsaturated bonds.

[0062] By the same viewpoint, the acrylic acid equivalent of component (A2) is preferably 50 or more and 300 or less, more preferably 80 or more and 200 or less. Furthermore, component (A2) does not have free carboxyl groups.

[0063] Furthermore, when forming a pattern by applying a photosensitive resin composition to the inkjet process, from the viewpoint of suppressing the increase in viscosity of the photosensitive resin composition, component (A2) is preferably having two vinyl unsaturated bonds. From the same viewpoint, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 3-methyl-1,5-pentanediol di(meth)acrylate are preferred as component (A2).

[0064] Furthermore, when the photosensitive resin composition includes a compound having two ethylene unsaturated bonds as component (A2), from the viewpoint of suppressing shape changes or shrinkage of the hardened film, a high molecular weight macromonomer such as a dendrimer can be used. Examples of such dendrimers include dendrimer acrylates, hyperbranched acrylic polymers, and hyperbranched acrylic oligomers, which are macromolecules formed by assembling branched molecules having acrylic groups into radially spherical shapes.

[0065] When forming a pattern using photolithography or the like, in order to impart alkaline developability to the coating of the photosensitive resin composition while improving the adhesion, straightness, fineness, and hardness of the cured film, it is preferable to use both component (A1) and component (A2). In this case, it is preferable that the content of component (A1) is 5% by mass or more and 70% by mass or less relative to the total mass of the solid components, and the content of component (A2) is 1% by mass or more and 20% by mass or less relative to the total mass of the solid components. The alkaline developability of the photosensitive resin composition tends to decrease depending on component (B). Therefore, it is preferable to have a higher amount of component (A1) that imparts alkaline developability to the cured film. On the other hand, by further increasing component (A2), the exposure sensitivity of the photosensitive resin composition, as well as the adhesion, straightness, fineness, and hardness of the cured film, can be further improved. The respective contents of components (A1) and (A2) can be adjusted by considering the balance of these properties while adding component (B) to ensure light scattering.

[0066] For example, relative to the total mass of the solid components, the content of component (A1) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, further preferably 10% by mass or more and 50% by mass or less, and particularly preferably 10% by mass or more and 40% by mass or less. Furthermore, relative to the total mass of the solid components, the content of component (A2) is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and further preferably 2% by mass or more and 10% by mass or less.

[0067] In addition, (A2) ingredient can be used alone or in combination with two or more ingredients.

[0068] Furthermore, when forming a pattern by applying a photosensitive resin composition to an inkjet printer, alkaline developability is not necessarily required. Therefore, from the viewpoint of suppressing the increase in viscosity of the photosensitive resin composition, the content of component (A1) relative to the total mass of the solid components is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 1% by mass or less. On the other hand, the content of component (A2) relative to the total mass of the solid components is preferably 30% by mass or more and 93% by mass or less, more preferably 35% by mass or more and 83% by mass or less, and even more preferably 40% by mass or more and 80% by mass or less.

[0069] 1-2. (B) Component (B) is a particle with an average particle size of 100 nm or more and 600 nm or less, a hollowness of 10% or more and 90% or less, and containing metal oxide particles with a refractive index of 1.9 or more and 2.7 or less. Component (B) causes light transmitted through the hardened film to scatter, allowing more light to irradiate Component (F), thereby improving the wavelength conversion efficiency of the hardened film.

[0070] If the average particle size of component (B) is 100 nm or more, the light scattering properties of the hardened film can be further improved. If the average particle size of component (B) is 600 nm or less, the properties of the hardened film, such as adhesion, straightness, fineness, and flatness, are less likely to be reduced. In addition, if the average particle size of component (B) is 600 nm or less, the ejection performance using inkjet printing is easily improved. From the above perspective, the average particle size of component (B) is preferably 100 nm or more and 450 nm or less, more preferably 150 nm or more and 400 nm or less.

[0071] If component (B) is a particle made of a metal oxide with a refractive index of 1.9 or higher and 2.7 or lower, then light passing through the hardened film can be appropriately refracted, further improving the light scattering property of the hardened film. From this point of view, the refractive index of the metal oxide used as component (B) is preferably 2.1 or higher and 2.7 or lower, more preferably 2.3 or higher and 2.7 or lower.

[0072] (B) The average particle size of the component can be determined using a particle size analyzer “FPAR-1000” with dynamic light scattering and by the accumulation method. In addition, the refractive index of the metal oxide can be measured using an Abbe refractometer with light at a wavelength of 589 nm.

[0073] Examples of metal oxides with a refractive index of 1.9 or higher and 2.7 or lower as component (B) include titanium oxide (TiO2), zirconium oxide (ZrO2), zinc oxide (ZnO), tin oxide (SnO2), antimony-doped tin oxide (ATO), indium tin oxide (ITO), barium titanate (BaTiO3), and niobium pentoxide (Sb2O5). Among these, titanium oxide and zirconium oxide are preferred in terms of both excellent light refractive and transmissive properties and easy isotropic scattering of light. Titanium oxide is more preferred.

[0074] (B) is a hollow particle with a hollowness of 10% or more and 90% or less. According to the present invention, hollow particles are more likely to scatter light isotropically and more likely to achieve a scattering state close to Lambert scattering. In particular, in particles containing materials with high refractive index, such as (B), the effect of isotropic scattering of light is significant by making them hollow. In addition, since hollow particles have higher transmittance than solid particles, light is more likely to pass through the interior of the hardened film and more likely to be distributed among the quantum dots dispersed in the hardened film.

[0075] Furthermore, in this specification, the term "hollow ratio" refers to the ratio of the volume of the voids inside the particle, calculated based on the hollow diameter of the particle, to the volume of the particle calculated based on its outer diameter. The outer diameter and hollow diameter of the particle can be measured by observation using an electron microscope.

[0076] Furthermore, particles containing materials with high refractive indices, such as component (B), are generally heavy and tend to settle during storage of photosensitive resin compositions. Therefore, to ensure uniform concentration of the photosensitive resin composition, it is necessary to periodically vibrate or stir it during storage. In contrast, hollow particles have a lower specific gravity and are less prone to settling, thus reducing the need for vibration and stirring during storage.

[0077] Relative to the total mass of the solid components, the content of component (B) is 5% by mass or more and 70% by mass or less, preferably 5% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and even more preferably 5% by mass or more and 35% by mass or less. By further increasing the amount of component (B), the light transmittance of the hardened film can be improved, and light can be scattered more isotropically. In order to suppress the reduction of properties such as adhesion, straightness, fineness and flatness of the hardened film caused by the decrease in the relative amount of other components, the content of component (B) is set to 70% by mass or less.

[0078] 1-3. (C) Component (C) is a photopolymerization initiator.

[0079] (C) The component is not particularly limited to any compound capable of initiating addition polymerization of a compound having polymerizable unsaturated bonds. Examples of components (C) include photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and acetylglucime compounds. Furthermore, in this specification, photopolymerization initiator is used to include sensitizers.

[0080] Examples of acetophenone compounds include: acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzodiazepine dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one, etc.

[0081] Examples of triazine compounds include: 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4 6-Bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(piperonyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, etc.

[0082] Examples of benzoin compounds include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-tert-butyl ether, etc.

[0083] Examples of benzophenone compounds include: benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(N,N-diethylamino)benzophenone, etc.

[0084] Examples of thioxanthone compounds include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0085] Examples of imidazole compounds include: 2-(o-chlorophenyl)-4,5-phenylimidazolium dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazolium dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolium dimer, 2,4,5-triarylimidazolium dimer, etc.

[0086] Examples of acetooxime compounds include: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-dicyclohepty-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl [9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantylmethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-one oxime-O-benzoate [9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-one oxime-O-acetate, 1-[ ... [9-Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-morpholinylmethane-1-ketooxime-O-acetate 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-tricyclodecanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-ketooxime-O-adamantanecarboxylate, 1-[4-( [phenyl-thio[sulfanyl]phenyl]octane-1,2-dione, 2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]acetone-O-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluorene-2-yl)acetyl oxime, acetone, 1-[7-(2-methyl] [9-[9-ethyl-6-(2-methylbenzoyl)-9H-fluoren-2-yl]-1-(O-acetylgoxime), acetone, 1-(9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetylgoxime, acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetylgoxime), 1,2-octyl Diene, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetylated oxime), 1-(4-phenylmercaptophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylmercaptophenyl)butane-1,Examples of photopolymerization initiators include 2-dione-2-oxime-O-acetate, 1-(4-methylmercaptophenyl)butane-1-one-oxime-O-acetate, and 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazolo-3-yl-O-acetylated oxime. The photopolymerization initiator can be used alone or in combination with two or more.

[0087] Among these, component (C) is preferably a acetooxime-based (including ketoxime) photopolymerization initiator. Since acetooxime-based photopolymerization initiators have high sensitivity, even in photosensitive resin compositions containing a large amount of acrylic acid equivalent (A2) component, sufficient photosensitivity can be ensured, and the developability (resolution) of the hardened film can be significantly improved.

[0088] Examples of acetylated photopolymerization initiators include: O-acetylated photopolymerization initiators represented by general formula (5) or general formula (6), 1-[4-(phenylmercapto)phenyl]octane-1,2-dione, 2-O-benzoacetylated oxime (Irgacure OXE-01, manufactured by BASF, "Irgacure" is a registered trademark of the company), acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetylated oxime) (Irgacure OXE-02, manufactured by BASF), etc.

[0089] [Chemical 7]

[0090] In formula (5), R6 and R7 are independently C1-C15 alkyl, C6-C18 aryl, C7-C20 arylalkyl, or C4-C12 heterocyclic groups, respectively, and R8 is C1-C15 alkyl, C6-C18 aryl, or C7-C20 arylalkyl. Here, the alkyl and aryl groups can be substituted with C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylyl, or halogen, and the extended alkyl portion can contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. In addition, the alkyl group can be any type of straight-chain, branched, or cyclic alkyl group.

[0091] [Chemical 8]

[0092] In formula (6), R9 and R10 are independently linear or branched alkyl groups having 1 to 10 carbon atoms, or cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl groups having 4 to 10 carbon atoms, or phenyl groups that may be substituted with alkyl groups having 1 to 6 carbon atoms. R11 is independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, wherein a portion of the -CH2- group in the alkyl or alkenyl group may be substituted with an -O- group. Furthermore, a portion of the hydrogen atoms in these R9 to R11 groups may also be substituted with halogen atoms.

[0093] In addition, from the viewpoint of preventing damage to the quantum dots ((F) component) during curing, it is preferable to cure the photosensitive resin composition by ultraviolet light on the long wavelength side. From the viewpoint of improving the efficiency of the effect brought by ultraviolet light on the long wavelength side, it is also preferable to use 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO, IGM Resins) or Omnirad 380 (IGM Resins).

[0094] In addition, as component (C), an active free radical generator or an acid generator may be used.

[0095] Examples of active free radical generators include: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzodiazepine, 9,10-phenanthroquinone, camphorquinone, methyl phenylglyoxylate, and titanium decene compounds.

[0096] Examples of acid generating agents include: 4-hydroxyphenyl dimethyl strontium p-toluenesulfonate, 4-hydroxyphenyl dimethyl strontium hexafluoroantimonate, 4-acetoxyphenyl dimethyl strontium p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl strontium hexafluoroantimonate, triphenyl strontium p-toluenesulfonate, triphenyl strontium hexafluoroantimonate, diphenyl strontium p-toluenesulfonate, diphenyl strontium hexafluoroantimonate, etc., as well as nitrobenzyl toluenesulfonates, benzoin toluenesulfonates, etc.

[0097] Furthermore, while it does not function as a photopolymerization initiator or sensitizer on its own, it can be used in combination with the aforementioned compound to add compounds that can enhance the ability of photopolymerization initiators or sensitizers. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of such amine compounds include: triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc.

[0098] Relative to the total 100 parts by mass of component (A), the content of component (C) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.2 parts by mass or more and 10 parts by mass or less. If the content of component (C) is 0.1 parts by mass or more, a suitable photopolymerization rate is achieved, thus ensuring sufficient sensitivity. In addition, if the content of component (C) is 30 parts by mass or less, linewidths faithful to the mask can be reproduced, and pattern edges can be made sharp. Furthermore, the content of component (C) can be set to a suitable range depending on the type of component (C) used.

[0099] In addition, (C) ingredient can be used alone or in combination with two or more ingredients.

[0100] 1-4. (D) and (E) components: The photosensitive resin composition may include (D) an epoxy compound and (E) a curing agent and a curing accelerator of the epoxy compound as any component. The photosensitive resin composition may include both a curing agent and a curing accelerator as component (E), or may include only either one.

[0101] Component (D) can improve the solvent resistance of the hardened film. Furthermore, when patterning the hardened film using photolithography, component (D) can harden the photosensitive resin composition through low-temperature (e.g., below 150°C) post-baking, thus improving the production efficiency of the hardened film. Additionally, component (E) can improve the curability of component (D), making it easier to harden even during low-temperature post-baking. In particular, component (F) has low heat resistance and sometimes deteriorates during high-temperature post-baking. In contrast, components (D) and (E) easily harden the photosensitive resin composition at low temperatures below 150°C, effectively suppressing the decrease in light conversion efficiency caused by the deterioration of component (F).

[0102] Examples of ingredients (D) include epoxy compounds having two or more epoxy groups as described in ingredient (A). Furthermore, these compounds may be used with only one of them, or with two or more in combination.

[0103] (D) The preferred components are bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, phenolic varnish type epoxy compounds, cresol phenolic varnish type epoxy compounds, and biphenyl type epoxy compounds, more preferably biphenyl type epoxy compounds. Biphenyl type epoxy compounds can take into account the mechanical strength or solvent resistance of the cured material that meets the required characteristics, as well as the patternability of the composition for microlens formation during photocuring, and can increase the degree of freedom in designing photosensitive resin compositions.

[0104] The epoxy equivalent of component (D) is preferably 100 g / eq or more and 500 g / eq or less, more preferably 100 g / eq or more and 400 g / eq or less, and even more preferably 100 g / eq or more and 250 g / eq or less. Furthermore, the number average molecular weight (Mn) of component (D) is preferably 100 or more and 5000 or less. If the epoxy equivalent of component (D) is 100 g / eq or more, the solvent resistance of the hardened film is improved. If the epoxy equivalent of component (D) is 500 g / eq or less, sufficient alkali resistance can be maintained even when an alkaline solution is used in a subsequent step. Furthermore, if the Mn of component (D) is 5000 or less, sufficient alkali resistance can be maintained even when an alkaline solution is used in a subsequent step.

[0105] In addition, the epoxy equivalent of component (D) can be determined by titration with a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) using a 1 / 10 N-perchloric acid solution.

[0106] In addition, (D) ingredient can be used alone or in combination with two or more ingredients.

[0107] Examples of curing agents as component (E) include: amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamine, Lewis acid complexes, etc., which contribute to the curing of epoxy resins.

[0108] Examples of polycarboxylic acid compounds include: polycarboxylic acids, anhydrides of polycarboxylic acids, and thermally decomposable esters of polycarboxylic acids. A polycarboxylic acid is a compound having two or more carboxyl groups in one molecule, such as: succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, etc. Examples of anhydrides of polycarboxylic acids include the anhydrides of the aforementioned compounds. These can be intermolecular anhydrides, but intramolecularly closed-ring anhydrides are generally used. Examples of thermally decomposable esters of polycarboxylic acids include tert-butyl esters, 1-(alkyloxy)ethyl esters, and 1-(alkylmercapto)ethyl esters of the compounds described above (wherein the alkyl group is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a branched or cyclic structure and may be substituted with any substituents). Additionally, polymers or copolymers having two or more carboxyl groups may also be used as polycarboxylic acid compounds, where the carboxyl groups may be anhydrides or thermally decomposable esters.

[0109] Furthermore, examples of the polymers or copolymers include: polymers or copolymers containing (meth)acrylic acid as a constituent (excluding the (A1) component), copolymers containing maleic anhydride as a constituent, and compounds formed by reacting tetracarboxylic dianhydride with a diamine or diol and opening the ring of the anhydride. Among these, the anhydrides of phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and phenyl-1,2,4-tricarboxylic acid are preferred. When a polycarboxylic acid compound is used as a curing agent for an epoxy compound, it is preferable to formulate the compound such that the carboxyl group of the polycarboxylic acid compound is 0.5 mol to 1.5 mol, more preferably 0.6 mol to 1.2 mol, relative to 1 mol of the epoxy group of the epoxy compound.

[0110] Examples of curing accelerators include: tertiary amines, quaternary ammonium salts, tertiary phosphine, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to the curing promotion of epoxy resins. Among these, 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene or salts thereof are preferred.

[0111] Relative to the total mass of the solid components, the content of components (D) and (E) is preferably 5% by mass or more and 35% by mass or less, more preferably 10% by mass or more and 30% by mass or less. Setting the content of components (D) and (E) to 5% by mass or more further improves the solvent resistance of the hardened film, particularly ensuring high solvent resistance even after post-baking at low temperatures. Setting the content of components (D) and (E) to 35% by mass or less further improves the adhesion of the hardened film to the substrate.

[0112] The content of the curing accelerator is preferably 0.01 parts by mass or more and 2 parts by mass or less when the content of component (D) is set to 100 parts by mass. If the amount of curing accelerator added is 0.01 parts by mass or more, the amount added can be adjusted according to the solvent resistance performance of the resin film pattern after heat curing, etc. In addition, if the amount of curing accelerator added is 2 parts by mass or less, the curing speed of the epoxy compound can be set to an appropriate range.

[0113] In addition, (E) ingredient can be used alone or in combination with two or more ingredients.

[0114] 1-5. (F) Component (F) Component is quantum dot.

[0115] Quantum dots are nanoparticles (e.g., particle diameter greater than 2 nm and less than 20 nm) that emit different wavelengths of light (e.g., red or green light) when illuminated with light of a specified wavelength (e.g., blue). The wavelength of the light emitted by a quantum dot varies depending on the particle size. Therefore, it is sufficient to have a size that matches the wavelength of the light to be emitted.

[0116] For example, component (F) may be a quantum dot that emits red light when irradiated with blue light, or a quantum dot that emits green light when irradiated with blue light. The quantum dot is not limited to these, and may be a quantum dot that emits red light, green light, and blue light when irradiated with light of a specified wavelength.

[0117] Furthermore, the photosensitive resin composition may also contain multiple quantum dots that emit different colors of light. For example, by including quantum dots that emit red light when illuminated by blue light and quantum dots that emit green light when illuminated by blue light, white light can be emitted from the hardened film when illuminated by blue light. Alternatively, by including three types of quantum dots that emit red, green, and blue light when illuminated by light of a specified wavelength, white light can also be emitted from the hardened film.

[0118] There is no particular limitation on the type of quantum dot; a semiconductor having the aforementioned properties can be used, which is a semiconductor containing a combination of atoms from groups II-VI, III-V, IV-VI, etc. Examples of such semiconductors include CdSe, CdTe, CdS, CdTe, ZnO, ZnS, ZnSe, InP, PbSe, and PbS.

[0119] (F) Component can be a core-shell type particle with these materials as the core and shell, and its surface can be further coated with resin, and it can also be modified with ligands having functional groups. Component (F) is preferably an average particle diameter of 1 nm or more and 40 nm or less.

[0120] Relative to the total mass of the solid components, the content of component (F) is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 50% by mass or less, and even more preferably 15% by mass or more and 40% by mass or less. By further increasing the content of component (F), the light conversion efficiency of the hardened film can be improved. In order to suppress the reduction of properties of the hardened film such as adhesion, straightness, fineness and flatness caused by the decrease in the relative amount of other components, the content of component (F) is set to 60% by mass or less.

[0121] 1-6. (G) The photosensitive resin composition may also contain (G) solvent. Examples of ingredients in

[0122] (G) include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α-terpineol or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and acetates such as ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. (G) Components may be used alone or in combination with two or more.

[0123] The content of component (G) varies depending on the target viscosity, and is preferably 30% by mass or more and 90% by mass or less relative to the total mass of the photosensitive resin composition. If the content of component (G) is 30% by mass or more, it can be set to a viscosity that makes it easy to coat the photosensitive resin composition onto the substrate; if it is 90% by mass or less, the drying time required after coating the photosensitive resin composition onto the substrate can be shortened.

[0124] 1-7. Other components The photosensitive resin composition may be formulated with (H) coupling agent, (I) surfactant, (J) thermal polymerization inhibitor and antioxidant, other resin components, plasticizer, filler, leveling agent, defoamer, ultraviolet absorber and viscosity modifier as needed.

[0125] Examples of coupling agents include silane coupling agents. As silane coupling agents, those having amino, isocyanate, urea, epoxy, vinyl, (meth)acrylate, or mercapto groups as reactive groups are preferred; more preferably, those having epoxy, isocyanate, or methacrylate groups as reactive groups are preferred. Specific examples of such coupling agents include 3-(glycidoxy)propyltrimethoxysilane, 3-acrylateoxypropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, and 3-ureopropyltriethoxysilane.

[0126] Examples of thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds, etc.

[0127] Examples of other resin components include: vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, and melamine resins, etc.

[0128] Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include: glass fiber, silicon dioxide, mica, alumina, etc.

[0129] Examples of leveling agents or defoamers include: silicone-based, fluorine-based, and acrylic-based compounds.

[0130] Examples of ultraviolet absorbers include: benzotriazole compounds, benzophenone compounds, triazine compounds, etc.

[0131] 1-8. Manufacturing method: The photosensitive resin composition can be obtained by mixing the components.

[0132] 2. Applications: The photosensitive resin composition described herein can be used to produce a hardened film with good light transmittance and high light conversion efficiency. Therefore, the photosensitive resin composition is suitable for use in the fabrication of wavelength conversion layers in image display devices and the like.

[0133] The hardening film can be made by the following steps: coating the photosensitive resin composition onto a substrate; and exposing the coated photosensitive resin composition to harden it.

[0134] The coating of the photosensitive resin composition can be performed by methods such as dip coating, spray coating, spin coating, roller coating, curtain coating, and screen printing. After coating to the desired thickness using these methods, the solvent is removed (pre-baking), thereby forming a coating film. Pre-baking is performed by heating using an oven, hot plate, etc. The heating temperature and heating time in pre-baking can be selected appropriately according to the solvent used; for example, it is sufficient to bake at a temperature of 60°C to 110°C (set to not exceed the heat resistance temperature of the substrate) for 1 to 3 minutes.

[0135] During exposure, a light shield exposes the coating to radiation, thereby exposing only the resist corresponding to the patterned area to light and causing it to photocur. Examples of radiation include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Among these, ultraviolet light with a wavelength of 250 nm or more and 450 nm or less is preferred. Ultraviolet irradiation can be performed using light sources such as ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, and far ultraviolet lamps. The radiation exposure dose is preferably 25 mJ / cm² or more and 3000 mJ / cm² or less.

[0136] The unexposed portions of the coating are removed by alkaline development. Alkaline development can be performed using an aqueous solution containing sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. A surfactant may also be added to the developer if necessary. The unexposed and uncured coating is removed by contacting the developer with the coating using methods such as spray development, immersion development, or puddle development. The preferred development temperature is 20°C to 35°C.

[0137] After alkaline development, the patterned hardened film is formally hardened by post-baking, improving adhesion to the substrate. Post-baking can be performed using known methods such as baking at a temperature of 180°C to 250°C for 20 to 60 minutes. In cases where a light-scattering hardened film pattern is formed on a substrate with a heat resistance temperature of 150°C or lower, it is preferable to perform heat treatment (post-baking) after development at a temperature of 80°C to 140°C (set to not exceed the heat resistance temperature of the substrate) for 20 to 90 minutes, and more preferably at a temperature of 90°C to 120°C for 30 to 60 minutes. When component (D) or component (E) is present, the photosensitive resin composition can be sufficiently hardened and adhered even at such low temperatures.

[0138] Alternatively, a patterned coating film can be formed by coating the photosensitive resin composition using an inkjet printing method. Then, the coating film can be exposed to radiation to harden it, thus creating a hardened film on the substrate. Furthermore, during exposure, the coating film can be exposed to radiation through a light mask, and the unexposed portions of the coating film can be removed subsequently by alkaline development. [Example]

[0139] Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.

[0140] First, the description will begin with the synthesis examples of the alkali-soluble resin as component A. However, unless otherwise stated, the evaluation of the resin in these synthesis examples will be carried out as follows. Regarding various measuring devices, if the same model is used, the name of the device manufacturer will be omitted from the second reference onwards. In addition, in [Experiment 1] and [Experiment 2], the glass substrates used in the fabrication of the substrates with the measuring hardened film were all glass substrates that underwent the same treatment.

[0141] [Solid Component Concentration] The solid component concentration is calculated using the following formula: Based on the weight [W1 (g)] of 1 g of the resin solution obtained in the synthesis example after immersion in a glass filter [weight: W0 (g)] and weighing, and the weight [W2 (g)] after heating at 160°C for 2 hours. Solid component concentration (wt%) = 100 × (W2 - W0) / (W1 - W0)

[0142] [Epoxy Equivalent] After dissolving the resin solution in dioxane, add a tetraethylammonium bromide acetic acid solution, and use a potentiometric titration apparatus "COM-1600" (manufactured by Hiranuma Industrial Co., Ltd.) to titrate with 1 / 10 N-perchloric acid solution to determine the equivalent.

[0143] [Acid Value] The acid value is determined by dissolving the resin solution in dioxane, using a potentiometric titration apparatus "COM-1600", and titrating with a 1 / 10 N-KOH aqueous solution.

[0144] [Molecular weight] The molecular weight was determined using a gel permeation chromatograph (GPC) “HLC-8220GPC” (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40℃, speed: 0.6 ml / min), and the weight average molecular weight (Mw) was calculated by using it as a conversion value to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0145] In addition, the abbreviations used in the following synthesis examples are as follows: AA: Acrylic acid; BPFE: Bisphenol fluorene-type epoxy compound (the reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxetane); BPDA: 3,3',4,4'-Biphenyltetracarboxylic acid dianhydride; THPA: Tetrahydrophthalic anhydride; TEAB: Tetraethylammonium bromide; PGMEA: Propylene glycol monomethyl ether acetate.

[0146] [Synthesis Example 1] BPFE (114.4 g, 0.23 mol), AA (33.2 g, 0.46 mol), PGMEA (157 g), and TEAB (0.48 g) were charged into a 500 ml four-necked flask equipped with a reflux condenser and stirred at 100°C–105°C for 20 hours to carry out the reaction. Subsequently, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask and stirred at 120°C–125°C for 6 hours to obtain a alkali-soluble resin (A1-1) containing polymerizable unsaturated groups. The obtained resin solution had a solids content of 56.5% by mass, an acid value (converted from solids content) of 103 mgKOH / g, and a Mw of 3600 obtained by GPC analysis.

[0147] [Synthesis Example 2] The BPFE of Synthesis Example 1 was replaced with BPFE having an increased degree of polymerization of the bisphenol fluorene backbone. All other than this, the same loading amount and synthesis method as in Synthesis Example 1 were used to obtain an alkali-soluble resin (A1-2) containing polymerizable unsaturated groups. The obtained resin solution had a solids content of 50.0% by mass, an acid value (converted from solids content) of 92 mgKOH / g, and a Mw of 6000 obtained by GPC analysis.

[0148] [Experiment 1] A photosensitive resin composition for photolithography was prepared using the following components.

[0149] (Base-soluble resin containing polymerizable unsaturated groups) (A1-1): Resin solution obtained in Synthesis Example 1 (solids concentration 56.5% by mass) (A1-2): Resin solution obtained in Synthesis Example 2 (solids concentration 50.0% by mass)

[0150] (Photopolymerizable compound) (A2-1): A mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA (acrylate equivalent 96-115), manufactured by Nippon Kayaku Co., Ltd.)

[0151] (Metal Oxide Particle Dispersion) (B-1): Hollow titanium dioxide particle dispersion with an average particle size of 306 nm, a hollowness of approximately 30%, a concentration of 30% by mass, a dispersant concentration of 3% by mass, and PGMEA concentration of 67% by mass. (B-2): Solid titanium dioxide particle dispersion with an average particle size of 200 nm, a hollowness of 0%, a concentration of 30% by mass, a dispersant concentration of 3% by mass, and PGMEA concentration of 67% by mass.

[0152] (Photopolymerization initiator) (C): 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO, manufactured by IGM Resins)

[0153] (Epoxy Compound) (D): 3,4-Epoxycyclohexanecarboxylic acid (3',4'-Epoxycyclohexyl) methyl ester (Celloxide 2021P (epoxy equivalent 135), manufactured by Daicel Inc.)

[0154] (Curing agent and curing accelerator) (E-1): Benzene-1,2,4-tricarboxylic acid-1,2-anhydride (E-2): PGMEA solution containing 2% by mass of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU(R)) (manufactured by San-Apro Corporation)

[0155] (Quantum dot dispersions) (F-1): Green quantum dot dispersion of CdSe / ZnS core-shell type, with complete ligand modification, emission wavelength of 540 nm (manufactured by Merck), concentration of 50% by mass and 50% by mass of PGMEA. (F-2): Red quantum dot dispersion of CdSe / ZnS core-shell type, with complete ligand modification, emission wavelength of 630 nm (manufactured by Merck), concentration of 50% by mass and 50% by mass of PGMEA.

[0156] (Solvent) (G-1): Propylene glycol monomethyl ether acetate (PGMEA) (G-2): 1-Methoxy-2-propanol (MMPG)

[0157] (Other Additives) (Coupling Agent) (H): 3-Glycidoxypropyltrimethoxysilane (Surfactant) (I): Megafac F-560 (containing 20% ​​by mass of PGMEA solution) (manufactured by DIC Corporation)

[0158] The formulation components were prepared according to the proportions shown in Table 1 to prepare the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 2. All values ​​in Table 1 represent parts by mass.

[0159] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Alkali-soluble resins (A1-1) 3.5 5.6 9.3 10.2 3.5 5.6 9.3 10.2 10.4 9.3 (A1-2) 4.3 6.9 11.6 12.7 4.3 6.9 11.6 12.7 12.9 11.6 Photopolymer compounds (A2-1) 1.0 1.5 2.5 2.8 1.0 1.5 2.5 2.8 2.8 2.5 metal oxide particle dispersion (B-1) 47.1 35.2 11.6 5.7 47.1 35.2 11.6 5.7 5.0 (B-2) 11.4 Photopolymerization initiator (C) 0.9 0.9 1.0 1.0 0.9 0.9 1.0 1.0 1.1 1.0 Epoxy compounds (D) 1.5 2.4 3.9 4.3 1.5 2.4 3.9 4.3 4.4 3.9 hardener (E-1) 1.5 1.5 1.8 1.8 1.5 1.5 1.8 1.8 1.9 1.8 hardening accelerator (E-2) 0.3 0.2 0.3 0.3 0.3 0.2 0.3 0.3 0.3 0.3 Quantum dot dispersion (F-1) 21.2 21.1 20.9 20.8 20.8 20.9 (F-2) 21.2 21.1 20.9 20.8 solvent (G-1) 9.6 15.7 26.2 29.2 9.6 15.7 26.2 29.2 29.0 26.4 (G-2) 8.7 8.6 10.4 10.7 8.7 8.6 10.4 10.7 10.9 10.4 Coupling agent (H) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 surfactants (I) 0.3 0.3 0.4 0.4 0.3 0.3 0.4 0.4 0.4 0.4

[0160] [Evaluation] The photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 2 were evaluated as follows. The evaluation results are shown in Table 2.

[0161] [Sedimentation Evaluation] (Evaluation Method) Place approximately 50 ml of the composition into a 110 ml spiral tube and cap it. Incubate the spiral tube containing the composition at 5°C. After one month, lay the spiral tube horizontally and visually observe the bottom of the tube. Evaluate the sedimentation according to the following evaluation criteria: (Evaluation Criteria) ○: No white solid precipitation observed at the bottom of the tube △: Slight white solid precipitation observed at the bottom of the tube ×: White solid precipitation observed at the bottom of the tube

[0162] [Developability Evaluation] (Preparation of the Hardened Film for Developability Evaluation) Using a spin coater, the photosensitive resin composition shown in Table 1 was coated onto a 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiation with ultraviolet light at a wavelength of 254 nm and an illuminance of 1000 mJ / cm² using a low-pressure mercury lamp. The substrate was then pre-baked at 90°C for 2 minutes using a hot plate to prepare the hardened film (coating). Subsequently, the exposure gap was adjusted to 100 μm, and a negative photomask of 10 μm to 50 μm (in 5 μm increments) was applied to the hardened film (coating). The substrate was then irradiated with ultraviolet light at a wavelength of 395 nm from a light-emitting diode (LED) source at a wavelength of 2000 mJ / cm² under a nitrogen atmosphere to induce a photocuring reaction.

[0163] Subsequently, the exposed hardened film (coating) was subjected to a development treatment at 25°C using a 0.04% potassium hydroxide solution at a spray pressure of 1 kgf / cm² for 20 seconds from the time the pattern began to appear (break time = BT). Then, it was sprayed with water at 5 kgf / cm² to remove the unexposed portion of the hardened film (coating) and form a hardened film pattern on the glass substrate. The hardened film was then formally cured (post-baked) at 120°C for 60 minutes using a hot air dryer to obtain the substrates with hardened films of Examples 1 to 8 and Comparative Examples 1 to 2.

[0164] Regarding the hardened films obtained by curing the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 2, the results of the evaluation of the following items are shown in Table 2.

[0165] (Pattern Adhesion) (Evaluation Method) The 20 μm mask pattern after formal curing (post-baking) is observed using an optical microscope. Furthermore, △ and above are considered acceptable. (Evaluation Criteria) ○: Completely unpeeled △: Partially peeled ×: Mostly peeled

[0166] (Pattern Straightness) (Evaluation Method) The 20 μm mask pattern after formal curing (post-baking) is observed using an optical microscope. Furthermore, a result of △ or higher is considered acceptable. (Evaluation Criteria) ○: No jagged edges observed at the pattern edges △: Jagged edges observed in a portion of the pattern edges ×: Jagged edges observed in most portions of the pattern edges

[0167] (Pattern Refinement) (Evaluation Method) The 10 μm to 50 μm mask pattern after formal curing (post-baking) is observed under an optical microscope. Furthermore, △ or higher is considered acceptable. (Evaluation Criteria) ○: Pattern formed with a diameter of 15 μm or more but less than 25 μm △: Pattern formed with a diameter of 25 μm or more but less than 50 μm ×: No pattern formed

[0168] [Chemical Resistance Evaluation] (Preparation of the Hardened Film for Solvent Resistance Evaluation) Using a spin coater, the photosensitive resin composition shown in Table 1 was coated onto a glass substrate to a thickness of 4.0 μm after heat curing. The substrate was then pre-baked at 90°C for 2 minutes using a hot plate to prepare the hardened film (coating). Subsequently, a negative photomask with a line / space ratio of 20 μm / 20 μm was applied to the hardened film (coating), and photocuring was performed by irradiating it with 2000 mJ / cm² ultraviolet light from a 395 nm LED light source under nitrogen atmosphere.

[0169] Subsequently, the exposed hardened film (coating) was developed at 25°C using a 0.05% potassium hydroxide solution at a spray pressure of 1 kgf / cm² for 60 seconds, followed by a water spray wash at 5 kgf / cm² to remove the unexposed portions of the hardened film (coating) and form a hardened film pattern on the glass substrate. The substrate was then formally hardened (post-baked) at 120°C using a hot air dryer for 60 minutes, thereby obtaining the substrates with hardened films of Examples 1 to 8 and Comparative Examples 1 to 2. (Evaluation Method) The surface of the hardened film formed on the glass substrate was continuously rubbed 20 times back and forth using cotton fibers impregnated in PGMEA. Furthermore, △ or higher was considered acceptable. (Evaluation Criteria) ○: No dissolution or damage was observed on the surface of the hardened film. △: Dissolution was observed on only a portion of the surface of the hardened film, and only a portion was damaged. ×: The surface of the hardened film softened, and most of it was damaged.

[0170] [Optical property evaluation] (Evaluation of light conversion efficiency) (Evaluation method) The same hardened film as the one used for solvent resistance evaluation was used, and the light conversion efficiency was determined using the following method.

[0171] As a blue light source, a blue LED (peak wavelength: 450 nm) is used as a surface-emitting light source, and the substrate with a hardening film of this embodiment is placed thereon. A spectro-radiometer with an integrating sphere is used to measure the spectral distribution. First, based on the spectrum obtained in the state where a glass substrate without a hardening film is placed, the integrated value in the range of 400 nm to 480 nm is defined as the blue light intensity. Additionally, based on the spectrum obtained in the state where a substrate with a hardening film containing green quantum dots is placed, the integrated value in the range of 480 nm to 590 nm is defined as the green emission intensity. Further, based on the spectrum obtained in the state where a substrate with a hardening film containing red quantum dots is placed, the integrated value in the range of 590 nm to 750 nm is defined as the red emission intensity. Using the above light intensities, the light conversion efficiency is calculated according to the following formula. Green light conversion efficiency (%) = (green emission intensity) / (blue light intensity) × 100 Red light conversion efficiency (%) = (red emission intensity) / (blue light intensity) × 100

[0172] In addition, according to the following evaluation criteria, those with Δ or above are considered qualified. (Evaluation criteria: Quantum dot dispersion (F-1) (green)) ○: Light conversion efficiency is 40% or more. Δ: Light conversion efficiency is 35% or more and less than 40%. ×: Light conversion efficiency is less than 35%. (Evaluation criteria: Quantum dot dispersion (F-2) (red)) ○: Light conversion efficiency is 45% or more. Δ: Light conversion efficiency is 40% or more and less than 45%.

[0173] [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Stability Settling property ○ ○ ○ ○ ○ ○ ○ ○ ○ × Developability Pattern adhesion ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ linearity of the pattern ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pattern fineness ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Chemical resistance Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Optical properties Light conversion efficiency ○ ○ ○ △ ○ ○ ○ △ × ×

[0174] Based on the results of Examples 1 to 8 and Comparative Examples 1 to 2, it is clear that by using a photosensitive resin composition containing metal oxide particles with a specific refractive index that are hollow particles with a specific average particle size, a hardened film with high light conversion efficiency and forming a fine wavelength conversion layer can be produced. These hardened films are most suitable as wavelength conversion layers in displays.

[0175] [Experiment 2] A photosensitive resin composition for inkjet coating was prepared using the following components.

[0176] (Photopolymerizable compound) (A2-2): 1,6-Hexanediol diacrylate (1,6HX-A) (Light Acrylate 1,6HX-A, manufactured by Kyoei Chemical Co., Ltd.)

[0177] (Metal Oxide Particle Dispersion) (B-3): Hollow titanium dioxide particles (average particle size 306 nm), hollowness approximately 30%, concentration 60% by mass, dispersant 6% by mass, 1.6HX-A 34% by mass of hollow titanium dioxide particle dispersion. (B-4): Solid titanium dioxide particles (average particle size 200 nm), hollowness 0%, concentration 60% by mass, dispersant 6% by mass, 1.6HX-A 34% by mass of solid titanium dioxide particle dispersion.

[0178] (Photopolymerization initiator) (C): 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO, manufactured by IGM Resins)

[0179] (Quantum dot dispersions) (F-3): Green quantum dot dispersion of CdSe / ZnS core-shell type, ligand modified, emission wavelength 540 nm (manufactured by Merck), concentration 50% by mass, 1.6HX-A 50% by mass. (F-4): Red quantum dot dispersion of CdSe / ZnS core-shell type, ligand modified, emission wavelength 630 nm (manufactured by Merck), concentration 50% by mass, 1.6HX-A 50% by mass.

[0180] (Other Additives) (Surfactants) (I): Megafac F-563 (manufactured by DIC Corporation) (Antioxidants) (J): Adekastab C (manufactured by ADEKA Corporation)

[0181] The formulation components were prepared according to the proportions shown in Table 3 to prepare the photosensitive resin compositions of Examples 9 to 16 and Comparative Examples 3 to 4. All values ​​in Table 3 represent parts by mass.

[0182] [Table 3] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 3 Comparative Example 4 Photopolymer compounds (A2-2) 7.2 23.5 40.0 48.9 7.2 23.5 40.0 48.9 49.6 40.1 metal oxide particle dispersion (B-3) 50.0 33.4 16.6 8.3 50.0 33.4 16.6 8.3 7.1 - (B-4) - - - - - - - - - 16.5 Photopolymerization initiator (C) 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 Quantum dot dispersion (F-3) 39.5 39.7 40.0 39.4 - - - - 39.9 40.0 (F-4) - - - - 39.5 39.7 40.0 39.4 - - surfactants (I) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 antioxidants (J) 0.2 0.3 0.3 0.3 0.2 0.3 0.3 0.3 0.3 0.3

[0183] [Evaluation] The photosensitive resin compositions of Examples 9 to 16 and Comparative Examples 3 to 4 were evaluated as follows. The evaluation results are shown in Table 4.

[0184] [Sedimentation Evaluation] (Evaluation Method) Place approximately 50 ml of the composition into a 110 ml spiral tube bottle and cap it. Incubate the spiral tube bottle containing the composition at 5°C. After one month, lay the spiral tube bottle horizontally and visually observe the bottom of the bottle. Evaluate the sedimentation according to the following evaluation criteria. (Evaluation Criteria) ○: No white solid precipitation observed at the bottom of the bottle △: Slight white solid precipitation observed at the bottom of the bottle ×: White solid precipitation observed at the bottom of the bottle

[0185] [Chemical Resistance Evaluation] (Production of Hardened Film for Solvent Resistance Evaluation) Using a spin coater, the photosensitive resin composition shown in Table 3 was coated on a glass substrate so that the film thickness after the hardening treatment became 4.0 μm, thereby producing a coating film. Subsequently, for the said coating film, ultraviolet rays of 2000 mJ / cm 2 were irradiated from an LED light source with a wavelength of 395 nm in a nitrogen atmosphere to perform a photocuring reaction, thereby obtaining substrates with hardened films of Examples 9 to 16 and Comparative Examples 3 to 4.

[0186] (Evaluation Method) The surface of the hardened film produced on the glass substrate was continuously rubbed 20 times back and forth with a cotton thread immersed in PGMEA. In addition, those with △ or more were regarded as qualified. (Evaluation Criteria) ○: No dissolution was observed on the surface of the hardened film, and it was not damaged. △: Dissolution was observed only on a part of the surface of the hardened film, and only a part was damaged. ×: The surface of the hardened film softened and most of it was damaged.

[0187] [Optical Property Evaluation] (Evaluation of Light Conversion Efficiency) (Evaluation Method) The same hardened film as that used for the solvent resistance evaluation was used, and the light conversion efficiency was measured by the following method.

[0188] As a blue light source, a blue LED (peak wavelength 450 nm) was used as a surface-emitting light source, and the substrate with the hardened film of this example was placed thereon, and a spectro-radiometer with an integrating sphere was used to measure the spectral distribution. First, based on the spectrum obtained in the state where a glass substrate without a hardened film was placed, the integrated value from 400 nm to 480 nm was set as the blue light intensity. In addition, based on the spectrum obtained in the state where a substrate with a hardened film containing green quantum dots was placed, the integrated value in the range from 480 nm to 590 nm was set as the green light emission intensity. Furthermore, based on the spectrum obtained in the state where a substrate with a hardened film containing red quantum dots was placed, the integrated value in the range from 590 nm to 750 nm was set as the red light emission intensity. Using the above light intensities, the light conversion efficiency was calculated according to the following formula. Green light conversion efficiency (%) = (green light emission intensity) / (blue light intensity) × 100 Red light conversion efficiency (%) = (red light emission intensity) / (blue light intensity) × 100

[0189] In addition, according to the following evaluation criteria, those with △ or more were regarded as qualified. (Evaluation Criteria: Quantum Dot Dispersion (F-1) (Green)) ○: The light conversion efficiency is 40% or more. △: The light conversion efficiency is 35% or more and less than 40%. ×: The light conversion efficiency is less than 35%. (Evaluation Criteria: Quantum Dot Dispersion (F-2) (Red)) ○: The light conversion efficiency is 45% or more. △: The light conversion efficiency is 40% or more and less than 45%.

[0190] [Table 4] Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 3 Comparative Example 4 stability Settling ○ ○ ○ ○ ○ ○ ○ ○ ○ × Chemical resistance Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Optical properties Light conversion efficiency ○ ○ ○ △ ○ ○ ○ △ × ×

[0191] Based on the results of Examples 9 to 16 and Comparative Examples 3 to 4, it is evident that by using a photosensitive resin composition containing metal oxide particles with a specific refractive index that are hollow particles with a specific average particle size, a hardened film with high light conversion efficiency and forming a fine wavelength conversion layer can be produced. These hardened films are most suitable as wavelength conversion layers in displays. Furthermore, when the processable resin compositions of Examples 9 to 16 and Comparative Examples 3 to 4 are ejected from a commercially available inkjet head, patterns can be formed without problems. [Industrial Applicability]

[0192] The photosensitive resin composition of the present invention exerts its effect in the wavelength conversion layer of a wavelength conversion display. Furthermore, the photosensitive resin composition can obtain solvent resistance even when cured at low temperatures, so it will not have an adverse effect even when used with quantum dot or organic electroluminescence (EL) displays with low heat resistance, making it suitable for manufacturing displays represented by these.

Claims

1. A photosensitive resin composition comprising: (A) a photocurable compound; (B) particles having an average particle size of 100 nm or more and 600 nm or less, a hollowness of 10% or more and 90% or less, and including a metal oxide with a refractive index of 1.9 or more and 2.7 or less; (C) a photopolymerization initiator; and (F) quantum dots, wherein the content of component (B) is 5% by mass or more and 70% by mass or less relative to the total mass of the solid components, and component (A) comprises (A1) an alkali-soluble resin containing an unsaturated group and (A2) a photopolymerizable compound having at least two ethylene unsaturated bonds, wherein the content of component (A1) is 5% by mass or more and 70% by mass or less relative to the total mass of the solid components, and the content of component (A2) is 1% by mass or more and 20% by mass or less relative to the total mass of the solid components.

2. The photosensitive resin composition as claimed in claim 1, wherein component (A1) is an alkali-soluble resin containing an unsaturated group as represented by general formula (1), (in formula (1), R1, R2, R3 and R4 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, halogen atoms or phenyl groups, R5 is a hydrogen atom or a methyl group, X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or a direct bond, Y is a tetravalent carboxylic acid residue, and Z are independently hydrogen atoms or substituents represented by general formula (2); wherein, One or more of Z are substituents represented by general formula (2), and the average value of n is 1 to 20. (In formula (2), W is a divalent or trivalent carboxylic acid residue, m is 1 or 2, and * is the bonding site).

3. The photosensitive resin composition as claimed in claim 1 or claim 2, comprising (D) an epoxy compound and (E) a curing agent and / or curing accelerator of the epoxy compound as an optional component, wherein the total content of component (D) and component (E) is 5% by mass or more and 35% by mass or less relative to the total mass of the solid components.

4. A curing film formed by curing a photosensitive resin composition as described in any one of claims 1 to 3.

5. A substrate with a hardening film, having the hardening film as described in claim 4.

6. A display device having a substrate with a hardened film as described in claim 5.

7. A method for manufacturing a substrate with a hardening film, comprising: a step of coating a photosensitive resin composition as described in any one of claims 1 to 3 onto a substrate; and a step of exposing the coated photosensitive resin composition to light.

8. The method for manufacturing a substrate with a hardened film as claimed in claim 7, wherein the exposure step is a step of exposing the coated photosensitive resin composition to a photomask.

9. A method for manufacturing a substrate with a hardened film as described in claim 7 or claim 8, wherein the coating step is a step of coating the photosensitive resin composition by inkjet printing.