Photosensitive resin composition, cured film, substrate with cured film, method for manufacturing the same, and display device.

Abstract

To provide a photosensitive resin composition that has high wavelength conversion efficiency and is less prone to particle sedimentation during storage. [Solution] A photosensitive resin composition comprising (A) a photocurable compound, (B) particles made of a metal oxide with a refractive index of 1.9 to 2.7, having an average particle size of 100 nm to 600 nm and a hollowness of 10% to 90%, (C) a photopolymerization initiator, and (F) quantum dots. The content of component (B) is 5% to 70% by mass relative to the total mass of solids.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a cured film, a substrate with a cured film, a method for manufacturing the same, and a display device. [Background technology]

[0002] Display devices that show images and videos sometimes use cured films to convert the wavelength of light from a light source. These cured films often contain particles such as metal oxides to scatter light within the film (for example, Patent Document 1).

[0003] Regarding the above-mentioned particles, Patent Document 2 states that the wavelength conversion efficiency of the wavelength conversion layer can be increased by using particles that have an average particle diameter of 8% or less of the thickness of the cured film and a refractive index of 0.10 or more relative to the refractive index of the binder resin. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-129034 [Patent Document 2] Japanese Patent Publication No. 2016-159445 [Overview of the project] [Problems that the invention aims to solve]

[0005] The cured films having the wavelength conversion function described above require a higher wavelength conversion efficiency. Furthermore, the photosensitive resin compositions used to produce these cured films have a high specific gravity due to the light scattering of the particles they contain, which makes them prone to sedimentation during storage. This necessitates frequent stirring or shaking to suppress particle sedimentation.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive resin composition that has high wavelength conversion efficiency and is less prone to particle sedimentation during storage, a cured film made from the photosensitive resin composition, a substrate with the cured film having the cured film, a method for manufacturing the substrate with the cured film, and a display device having the substrate with the cured film. [Means for solving the problem]

[0007] A photosensitive resin composition according to one aspect of the present invention for solving the above problems comprises (A) a photocurable compound, (B) particles made of a metal oxide with a refractive index of 1.9 to 2.7, having an average particle size of 100 nm to 600 nm and a hollowness of 10% to 90%, (C) a photopolymerization initiator, and (F) quantum dots. The content of component (B) is 5% to 70% by mass relative to the total mass of solids.

[0008] Another aspect of the present invention relates to a cured film obtained by curing the photosensitive resin composition.

[0009] A substrate with a cured film according to another aspect of the present invention includes the cured film.

[0010] A method for manufacturing a substrate with a cured film according to another aspect of the present invention comprises the steps of applying the photosensitive resin composition onto a substrate and exposing the applied photosensitive resin composition to light. [Effects of the Invention]

[0011] The present invention provides a photosensitive resin composition that has high wavelength conversion efficiency and is less prone to particle sedimentation during storage, a cured film made from the photosensitive resin composition, a substrate with the cured film having the cured film, a method for manufacturing the substrate with the cured film, and a display device having the substrate with the cured film. [Modes for carrying out the invention]

[0012] 1. Photosensitive resin composition The following photosensitive resin composition according to one embodiment of the present invention comprises (A) a photocurable compound, (B) particles made of a metal oxide having an average particle size of 100 nm to 600 nm and a hollowness of 10% to 90%, and a refractive index of 1.9 to 2.7, (C) a photopolymerization initiator, and (F) quantum dots.

[0013] 1-1. (A) Component Component (A) is a photocurable compound that polymerizes and hardens upon irradiation with light. Component (A) imparts a predetermined photosensitivity to the photosensitive resin composition.

[0014] Component (A) can be appropriately selected and used depending on the application of the photosensitive resin composition. For example, when patterning a cured film by photolithography, component (A) preferably contains (A1) an alkali-soluble resin containing unsaturated groups to impart alkali developability to the coating film of the photosensitive resin composition, and further preferably contains (A2) a photopolymerizable compound having at least two ethylenically unsaturated bonds to increase exposure sensitivity. Also, when curing a photosensitive resin composition in a fine pattern by an inkjet method, component (A) should contain at least (A2) a photopolymerizable compound having at least two ethylenically unsaturated bonds.

[0015] 1-1-1. (A1) Component Component (A1) is an alkali-soluble resin containing an unsaturated group. Component (A1) can impart solubility for alkali development to the coating film of the photosensitive resin composition.

[0016] (Component (A1) preferably has a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility in one molecule, and more preferably has a polymerizable unsaturated group and a carboxy group. Component (A1) is not particularly limited as long as it is the above resin and can be various types of resins. Since component (A1) has a polymerizable unsaturated group, it imparts excellent photocurability to the photosensitive resin composition, and the molecular weight increases during curing to exhibit the function as a binder. Further, since component (A1) has an acidic group, it improves the physical properties of the cured film such as developability and patterning properties (pattern line width, pattern linearity).

[0017] (Component (A1) is preferably an unsaturated group-containing alkali-soluble resin obtained by reacting a reaction product of an epoxy compound having two or more epoxy groups and (meth)acrylic acid with a polybasic carboxylic acid or its anhydride. During the production of the above unsaturated group-containing alkali-soluble resin, polyester is formed by the reaction of a hydroxy group and a polybasic carboxylic acid. Component (A1) is preferably a low molecular weight resin with an average degree of polymerization of the above polyester of about 2 to 500. Note that "(meth)acrylic acid"" is a general term for acrylic acid and methacrylic acid, "(meth)acryloyl group"" is a general term for acryloyl group and methacryloyl group, and "(meth)acrylate"" is a general term for acrylate and methacrylate, all of which mean one or both of these.

[0018] Examples of epoxy compounds having two or more of the above 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, phenol novolac type epoxy compounds, (o,m,p-)cresol novolac 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), phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: Manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds (e.g., EPPN-501H: Manufactured by Nippon Kayaku Co., Ltd.), epoxy compounds having aromatic structures such as tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polyhydric carboxylic acids, and (meth)acrylics containing glycidyl (meth)acrylate as a unit, represented by copolymers of methacrylic acid and glycidyl methacrylate. Copolymers of monomers having a royl group, epoxy compounds having a glycidyl group such as hydrogenated bisphenol A diglycidyl ether (e.g., Recarezin HBE-100: manufactured by Shin Nippon Rika Co., Ltd., "Recarezin" is a registered trademark of the company), 1,4-cyclohexanedimethanol-bis-3,4-epoxycyclohexanecarboxylate, 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: manufactured by Dow Chemical Company), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (e.g., Celoxide 2021P: manufactured by Daicel Corporation, "Celoxide" is a registered trademark of the company), butanetetracarboxylic acid tetra(3,4-Epoxycyclohexylmethyl)-modified ε-caprolactone (e.g., Epolide GT401: manufactured by Daicel Corporation, "Epolide" is a registered trademark of the company), an epoxy compound having an epoxycyclohexyl group (e.g., HiREM-1: manufactured by Shikoku Kasei Kogyo Co., Ltd.), a polyfunctional epoxy compound having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), an alicyclic epoxy compound such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxy polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the company), an epoxy compound having a silicone skeleton, etc. are included.,

[0019] Examples of other preferred resins for the component (A1) include an alkali-soluble resin which is an acrylic copolymer.

[0020] Examples of the above acrylic copolymers include copolymers of (meth)acrylic acid, (meth)acrylic acid esters, etc., which have (meth)acryloyl groups and carboxyl groups. Examples of the above resins include polymerizable unsaturated group-containing alkali-soluble resins obtained by copolymerizing (meth)acrylic acid esters containing glycidyl (meth)acrylate in a solvent, reacting the copolymer with (meth)acrylic acid, and finally reacting it with an anhydride of a dicarboxylic acid or tricarboxylic acid. The above copolymer can be referenced from the copolymer described in Japanese Patent Publication No. 2014-111722, which consists of 20-90 mol% repeating units derived from diester glycerol with hydroxyl groups at both ends esterified with (meth)acrylic acid, and 10-80 mol% repeating units derived from one or more polymerizable unsaturated compounds copolymerizable thereto, with a number average molecular weight (Mn) of 2000-20000 and an acid value of 35-120 mgKOH / g, and the polymerizable unsaturated group-containing alkali-soluble resin described in Japanese Patent Publication No. 2018-141968, which contains units derived from (meth)acrylic acid ester compounds and units having (meth)acryloyl groups and di or tricarboxylic acid residues, with a weight average molecular weight (Mw) of 3000-50000 and an acid value of 30-200 mg / KOH.

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

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

[0023] [ka] (In formula (2), W is a divalent or trivalent carboxylic acid residue, m is 1 or 2, and * is a binding site.)

[0024] Next, a method for producing the alkali-soluble resin represented by the above 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 "epoxy compound (a-1)") is reacted with an unsaturated group-containing monocarboxylic acid (e.g., (meth)acrylic acid) to obtain epoxy (meth)acrylate. Note that "(meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, meaning one or both of these.

[0026] [ka] (In formula (3), R1, R2, R3, and R4 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and X is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond.)

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

[0028] Examples of the bisphenols listed above include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, bis(4-hydroxy-3,5-dichlorophenyl)sulfone, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxy- 3,5-Dichlorophenyl)Hexafluoropropane, Bis(4-Hydroxyphenyl)dimethylsilane, Bis(4-Hydroxy-3,5-Dichlorophenyl)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-Dichlorophenyl)propane , 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(4-hydroxy- This includes 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 may be used individually or in combination of two or more.

[0029] Examples of the above-mentioned unsaturated group-containing monocarboxylic acid compounds include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid or methacrylic acid with acid monoanhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride.

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

[0031] [ka] (In formula (4), R1, R2, R3, and R4 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; 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-, a fluorene-9,9-diyl group, or a direct bond.)

[0032] In the synthesis of diol (d) represented by general formula (4), followed by the addition reaction of a polycarboxylic acid or its anhydride, and further reacting with a monofunctional epoxy compound having a polymerizable unsaturated group that reacts with a carboxyl group, the reaction is usually carried out in a solvent with a catalyst as needed.

[0033] Examples of solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling-point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone solvents such as cyclohexanone and diisobutyl ketone. There are no particular restrictions on the reaction conditions, such as the solvent and catalyst used, but it is preferable to use a solvent that does not contain hydroxyl groups and has a boiling point higher than the reaction temperature as the reaction solvent.

[0034] Furthermore, it is preferable to use a catalyst in the reaction between a carboxyl group and an epoxy group. For example, Japanese Patent Publication No. 9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0035] Next, a diol (d) represented by general formula (4), obtained by the reaction of epoxy compound (a-1) with (meth)acrylic acid, is reacted with a dicarboxylic acid or tricarboxylic acid or its acid anhydride (b), and a tetracarboxylic acid or its acid dianhydride (c) to obtain an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule, represented by general formula (1).

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

[0037] [ka] (In formula (2), W is a divalent or trivalent carboxylic acid residue, m is 1 or 2, and * is a binding site.)

[0038] The acid component used to synthesize the alkali-soluble resin represented by general formula (1) is a polyvalent acid component that can react with the hydroxyl group in the diol (d) molecule represented by general formula (4), and it is necessary to use a combination of a dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) and a tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the above acid component may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, these carboxylic acid residues may contain bonds containing heteroatoms such as -O-, -S-, and carbonyl groups.

[0039] The above-mentioned dicarboxylic acid or tricarboxylic acid or its acid monoanhydride (b) can be a chain-type hydrocarbon dicarboxylic acid or tricarboxylic acid, an alicyclic hydrocarbon dicarboxylic acid or tricarboxylic acid, an aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid, or its acid monoanhydride.

[0040] Examples of the above-mentioned chain-like hydrocarbon dicarboxylic acid or tricarboxylic acid acid monoanhydrides include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and other acid monoanhydrides of dicarboxylic acid or tricarboxylic acid to which any substituent has been introduced.

[0041] Examples of acid monoanhydrides of alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methyl-3,6-endomethylenetetrahydrophthalic acid, norbornanedicarboxylic acid, chloridenic acid, and hexahydrotrimellitic acid, as well as acid monoanhydrides of dicarboxylic acids or tricarboxylic acids to which any substituent has been introduced.

[0042] Examples of acid monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as phthalic acid, isophthalic acid, trimellitic acid, 1,8-naphthalenedicarboxylic acid, and 2,3-naphthalenedicarboxylic acid, as well as acid monoanhydrides of dicarboxylic acids or tricarboxylic acids to which any substituents have been introduced.

[0043] Among the acid monoanhydrides of dicarboxylic acids or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, with succinic acid, itaconic acid, and tetrahydrophthalic acid being more preferred. Furthermore, in the case of dicarboxylic acids or tricarboxylic acids, it is preferable to use their acid monoanhydrides. The above-mentioned acid monoanhydrides of dicarboxylic acids or tricarboxylic acids may be used individually or in combination of two or more.

[0044] Furthermore, as the tetracarboxylic acid or its acid dianhydride (c), chain-type hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid, or their acid dianhydrides can be used.

[0045] Examples of chain-type hydrocarbon tetracarboxylic acids include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain-type hydrocarbon tetracarboxylic acids to which substituents such as alicyclic hydrocarbon groups and unsaturated hydrocarbon groups have been introduced.

[0046] Examples of the above-mentioned alicyclic tetracarboxylic acids include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and alicyclic tetracarboxylic acids into which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups have been introduced.

[0047] Examples of aromatic tetracarboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ethertetracarboxylic acid, diphenyl sulfonetetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

[0048] Among tetracarboxylic acids or their acid dianhydrides, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenyl ethertetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenyl ethertetracarboxylic acid are more preferred. Furthermore, in the case of tetracarboxylic acids or their acid dianhydrides, it is preferable to use the acid dianhydride. The above-mentioned tetracarboxylic acids or their acid dianhydrides may be used individually or in combination of two or more.

[0049] The reaction method between the diol (d) and the acid components (b) and (c) is not particularly limited, and known methods can be employed. For example, Japanese Patent Publication No. 9-325494 describes a method of reacting epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0050] In this case, it is preferable to react the epoxy (meth)acrylate (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b), and tetracarboxylic dianhydride (c) in such a way that the terminal end of the compound becomes a carboxyl group that the molar ratio of (d):(b):(c) = 1.0:0.01 to 1.0:0.2 to 1.0.

[0051] For example, when using acid monoanhydride (b) and acid dianhydride (c), it is preferable to react them such that the molar ratio of the amount of acid component [(b) / 2+(c)] to the diol (d) [[(b) / 2+(c)] / (d)] is greater than 0.5 and 1.0 or less. If the above molar ratio is greater than 0.5, the end of the unsaturated group-containing curable resin represented by general formula (1) will not become an acid anhydride, thereby suppressing an increase in the content of unreacted acid dianhydride and improving the long-term stability of the curable composition. Also, if the above molar ratio is 1.0 or less, it is possible to suppress an increase in the remaining amount of unreacted components among the polymerizable unsaturated group-containing diol (d) and improve the long-term stability of the curable composition. Note that the molar ratios of each component (b), (c), and (d) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the unsaturated group-containing curable resin represented by general formula (1).

[0052] The synthesis of diol (d), and the subsequent reaction of the polycarboxylic acid or its anhydride, are usually carried out in a solvent with a catalyst as needed.

[0053] Examples of the solvents mentioned above include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling-point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone solvents such as cyclohexanone and diisobutyl ketone. There are no particular restrictions on the reaction conditions such as the solvent and catalyst used, but it is preferable to use a solvent as the reaction solvent that does not have hydroxyl groups and has a boiling point higher than the reaction temperature.

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

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

[0056] (A1) From a similar viewpoint, it is preferable that the acid value of component (A1) is 30 mg KOH / g or more and 200 mg KOH / g or less.

[0057] In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of each component may be expressed as styrene-converted values ​​obtained by gel permuration chromatography (GPC) (for example, "HLC-8220GPC" (manufactured by Tosoh Corporation)). The acid value may be expressed as a value obtained using a potentiometric titrator (for example, "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.)). However, for compounds whose molecular weight can be calculated from their structure, such as monomers, the value obtained from the structure may be used as the molecular weight of that compound.

[0058] Furthermore, component (A1) may be used alone or in combination of two or more types.

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

[0060] (A2)Specific examples of components 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 This includes (meth)acrylic acid esters such as (meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa(meth)acrylate, (meth)acrylic acid esters having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, and dendritic polymers having a (meth)acryloyl group as a compound having an ethylenic double bond.

[0061] From the viewpoint of further increasing the exposure sensitivity of the photosensitive resin composition and increasing the crosslinking density of the cured film to improve adhesion, component (A2) preferably has three or more ethylenically unsaturated bonds, and more preferably has five or more ethylenically unsaturated bonds.

[0062] From a similar viewpoint, the acrylic equivalent of component (A2) is preferably 50 to 300, and more preferably 80 to 200. Note that component (A2) does not contain free carboxyl groups.

[0063] Furthermore, when applying a photosensitive resin composition by an inkjet method to form a pattern, it is preferable that component (A2) has two ethylenically unsaturated bonds from the viewpoint of suppressing an increase in the viscosity of the photosensitive resin composition. From a similar viewpoint, preferred components for (A2) are 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.

[0064] Furthermore, when the photosensitive resin composition contains a compound having two ethylenically unsaturated bonds as component (A2), a macromer with a high molecular weight, such as a dendritic polymer, may be used in combination from the viewpoint of suppressing changes in the shape and shrinkage of the cured film. Examples of the above-mentioned dendritic polymers include dendrimer acrylates, hyperbranched acrylic polymers, and hyperbranched acrylic oligomers, which are spherical macromolecules formed by radially assembling branch molecules having acrylic groups.

[0065] When forming patterns using photolithography or the like, it is preferable to use components (A1) and (A2) in combination to impart alkali developability to the coating film of the photosensitive resin composition while improving the adhesion, linearity, fineness, and hardness of the cured film. In this case, it is preferable that the content of component (A1) is 5% to 70% by mass relative to the total mass of solids, and the content of component (A2) is 1% to 20% by mass relative to the total mass of solids. Photosensitive resin compositions tend to have reduced alkali developability due to component (B). Therefore, it is preferable to use a larger amount of component (A1) to impart alkali developability to the cured film. On the other hand, by increasing the amount of component (A2), the exposure sensitivity of the photosensitive resin composition, as well as the adhesion, linearity, fineness, and hardness of the cured film, can be further improved. The content of components (A1) and (A2) should be adjusted while considering the balance of these properties, while adding component (B) to ensure light scattering.

[0066] For example, the content of component (A1) is preferably 5% to 70% by mass, more preferably 5% to 60% by mass, even more preferably 10% to 50% by mass, and particularly preferably 10% to 40% by mass, based on the total mass of solids. Also, the content of component (A2) is preferably 1% to 20% by mass, more preferably 2% to 15% by mass, and even more preferably 2% to 10% by mass, based on the total mass of solids.

[0067] Furthermore, component (A2) may be used alone or in combination of two or more types.

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

[0069] 1-2.(B) Component Component (B) consists of particles made of a metal oxide with an average particle size of 100 nm to 600 nm, a hollowness of 10% to 90%, and a refractive index of 1.9 to 2.7. Component (B) scatters light transmitted through the cured film, allowing more light to be irradiated onto component (F) to increase the wavelength conversion efficiency of the cured film.

[0070] If the average particle size of component (B) is 100 nm or more, the light scattering properties of the cured film can be further enhanced. If the average particle size of component (B) is 600 nm or less, the adhesion, linearity, fineness, and flatness of the cured film are less likely to deteriorate. In addition, if the average particle size of component (B) is 600 nm or less, the ejection properties by the inkjet method are easier to improve. From the above viewpoint, the average particle size of component (B) is preferably 100 nm or more and 450 nm or less, and more preferably 150 nm or more and 400 nm or less.

[0071] If component (B) consists of particles made of a metal oxide with a refractive index of 1.9 to 2.7, the light transmitted through the cured film can be appropriately refracted, thereby further enhancing the light scattering properties of the cured film. From the above viewpoint, the refractive index of the metal oxide material of component (B) is preferably 2.1 to 2.7, and more preferably 2.3 to 2.7.

[0072] The average particle size of component (B) can be determined by the cumulant method using a dynamic light scattering particle size analyzer, "Particle Size Analyzer FPAR-1000". The refractive index of the metal oxide can be measured with an Abbe refractometer using light at a wavelength of 589 nm.

[0073] Examples of metal oxides with a refractive index of 1.9 to 2.7 as the material for component (B) include titanium oxide (titania: TiO2), zirconium oxide (zirconia: ZrO2), zinc oxide (ZnO), tin oxide (SnO2), antimond-doped tin oxide (ATO), indium tin oxide (ITO), barium titanate (BaTiO3), and niobium pentoxide (Sb2O5). Of these, titanium oxide and zirconium oxide are preferred, with titanium oxide being more preferred, because they have excellent refractive and transmittance properties and easily scatter light isotropically.

[0074] Component (B) consists of hollow particles with a hollowness of 10% to 90%. According to the inventors' findings, hollow particles scatter light more isotropically and can easily achieve a scattering state closer to Lambertian scattering. In particular, the effect of isotropically scattering light by making the particles hollow is significant in particles made of materials with a high refractive index, such as component (B). Furthermore, because hollow particles have a higher particle transmittance than solid particles, they can easily transmit light inside the cured film and distribute light to the quantum dots dispersed in the cured film.

[0075] In this specification, the hollow ratio refers to the ratio of the volume of the void inside the particle, calculated from the hollow diameter of the particle, to the volume of the particle, calculated from the outer diameter of the particle. The outer diameter and hollow diameter of the particle can be measured by observation using an electron microscope.

[0076] Furthermore, particles made of materials with a high refractive index, such as component (B), often have a high specific gravity and tend to settle during storage of the photosensitive resin composition. Therefore, in order to ensure a uniform concentration in the photosensitive resin composition, it is necessary to shake or stir the composition periodically during storage. In contrast, hollow particles have a lower specific gravity and are therefore less likely to settle, thus reducing the effort required for shaking and stirring during storage.

[0077] The content of component (B) is 5% by mass or more and 70% by mass or less relative to the total mass of solids, 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 more preferably 5% by mass or more and 35% by mass or less. By increasing the amount of component (B), the light transmittance of the cured film can be increased and light can be scattered more isotropically. However, in order to suppress the decrease in various properties such as adhesion, linearity, fineness and flatness of the cured film due to the relative amount of other components, the above content of component (B) is 70% by mass or less.

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

[0079] Component (C) is not particularly limited as long as it is a compound that has polymerizable unsaturated bonds and can initiate the polymerization of addition polymerizable compounds. Examples of component (C) include photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, and acyloxime compounds. In this specification, the term "photopolymerization initiator" is used to include sensitizers.

[0080] Examples of acetophenone compounds include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

[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, and 2-(4-methoxynaphthyl Examples include 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, and 2-(pipronil)-4,6-bis(trichloromethyl)-1,3,5-triazine.

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

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

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

[0085] Examples of imidazole compounds include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,4,5-triarylimidazole dimer.

[0086] Examples of acyloxime compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-bicycloheptyl-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantilmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-adamantilmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- 3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-tetrahydrofuranylmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-thiophenylmethane-1-oneoxime-O-acetate, 1-[9-E [9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-oneoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-molofonylmethane-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-oneoxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-oneoxime-O- Xime-O-tricyclodecane carbosichlate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-adamantane carbosichlate, 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione,2-O-benzoyl oxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-yl]ethanone-O-acetyl oxime, (2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-acetyl oxime, ethanone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H-fluoren-2-yl]-1-(O-acetyloxime), etanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-1-O-acetyloxime, etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime), 1,2-octanedien, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], etanone, 1-[9-ethyl-6-(2-methylbenzoyl]- This includes tylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 1-(4-phenylsulfanylphenyl)butan-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butan-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazol-3-yl-O-acetyloxime, etc. The above photopolymerization initiators may be used individually or in combination of two or more.

[0087] Of these, component (C) is preferably an acyloxime-based (including ketoxime) photopolymerization initiator. Because acyloxime-based photopolymerization initiators have high sensitivity, sufficient photosensitivity can be ensured even in photosensitive resin compositions containing component (A2) with a relatively large acrylic equivalent, and the developability (resolution) of the cured film can be sufficiently improved.

[0088] Examples of acyloxime photopolymerization initiators include O-acyloxime photopolymerization initiators represented by general formula (5) or general formula (6), 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione-,2-o-benzoyloxime (IrgacureOXE-01, manufactured by BASF, "Irgacure" is a registered trademark of the company), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (IrgacureOXE-02, manufactured by BASF), and others.

[0089] [ka]

[0090] In formula (5), R6 and R7 are each independently a C1-C15 alkyl group, a C6-C18 aryl group, a C7-C20 arylalkyl group, or a C4-C12 heterocyclic group, and R8 is a C1-C15 alkyl group, a C6-C18 aryl group, or a C7-C20 arylalkyl group. Here, the alkyl groups and aryl groups may be substituted with C1-C10 alkyl groups, C1-C10 alkoxy groups, C1-C10 alkanoyl groups, or halogens, and the alkylene portion may contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. Furthermore, the alkyl group may be linear, branched, or cyclic alkyl groups.

[0091] [ka]

[0092] In equation (6), R9 and R 10 Each of these is independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 11 These are independently linear or branched alkyl or alkenyl groups having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl or alkenyl group may be substituted with -O- groups. Furthermore, these R9~R 11 Some of the hydrogen atoms in the base may be substituted with halogen atoms.

[0093] Furthermore, from the viewpoint of preventing damage to quantum dots (component (F)) during curing, it is preferable to cure the photosensitive resin composition with long-wavelength ultraviolet light, and from the viewpoint of increasing the effectiveness of long-wavelength ultraviolet light, it is also preferable to use 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO, IGM resins) or Omnirad 380 (IGM resins).

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

[0095] Examples of active 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, benzyl, 9,10-phenancelenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds.

[0096] Examples of acid generators include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylates and benzoin tosylates.

[0097] Furthermore, compounds that do not act as photoinitiators or sensitizers on their own but can increase the photoinitiator or sensitizer capabilities when used in combination with the above-mentioned compounds may be added. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Examples of the above-mentioned amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone.

[0098] The content of component (C) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.2 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total of component (A). When the content of component (C) is 0.1 parts by mass or more, a suitable photopolymerization rate is obtained, so sufficient sensitivity can be ensured. Furthermore, when the content of component (C) is 30 parts by mass or less, the line width can be faithfully reproduced for the mask and the pattern edges can be made sharp. The content of component (C) can be set to a suitable range depending on the type of component (C) used.

[0099] Furthermore, component (C) may be used alone or in combination of two or more types.

[0100] 1-4.(D) component, (E) component The photosensitive resin composition may contain (D) an epoxy compound, and (E) an optional component, a curing agent and a curing accelerator for the epoxy compound. The photosensitive resin composition may contain both a curing agent and a curing accelerator as component (E), or contain only one of them.

[0101] Component (D) can improve the solvent resistance of the cured film. Furthermore, when patterning the cured film by photolithography, component (D) allows the photosensitive resin composition to be cured by post-bake at low temperatures (e.g., below 150°C), thereby improving the efficiency of cured film production. Additionally, component (E) enhances the curability of component (D), making it easier to cure even at low temperatures during post-bake. In particular, component (F) has low heat resistance and may degrade when post-baked at high temperatures. In contrast, components (D) and (E) make it easier to cure the photosensitive resin composition at low temperatures such as below 150°C, and help suppress the decrease in light conversion efficiency due to the degradation of component (F).

[0102] Examples of component (D) include epoxy compounds having two or more epoxy groups as described above for component (A). These compounds may be used individually or in combination of two or more.

[0103] Component (D) is preferably a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol fluorene type epoxy compound, a bisnaphthol fluorene type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, or a biphenyl type epoxy compound, with biphenyl type epoxy compounds being more preferred. Biphenyl type epoxy compounds can achieve both the mechanical strength and solvent resistance of the cured product tailored to the required properties, as well as the patternability of the microlens formation composition during photocuring, and also allow for greater freedom in designing the photosensitive resin composition.

[0104] The epoxy equivalent of component (D) is preferably 100 g / eq to 500 g / eq, more preferably 100 g / eq to 400 g / eq, and even more preferably 100 g / eq to 250 g / eq. Furthermore, the number-average molecular weight (Mn) of component (D) is preferably 100 to 5000. When the epoxy equivalent of component (D) is 100 g / eq or more, the solvent resistance of the cured film is enhanced. When the epoxy equivalent of component (D) is 500 g / eq or less, sufficient alkali resistance can be maintained even when alkaline chemicals are used in subsequent processes. Furthermore, when the Mn of component (D) is 5000 or less, sufficient alkali resistance can be maintained even when alkaline chemicals are used in subsequent processes.

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

[0106] Furthermore, component (D) may be used alone or in combination of two or more types.

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

[0108] Examples of polycarboxylic acid compounds include polycarboxylic acids, polycarboxylic acid anhydrides, and pyrolytic esters of polycarboxylic acids. A polycarboxylic acid is a compound having two or more carboxyl groups in one molecule, and examples include 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, and butane-1,2,3,4-tetracarboxylic acid. Examples of polycarboxylic acid anhydrides include acid anhydrides of the above compounds. These may be intermolecular acid anhydrides, but generally intramolecularly cyclized acid anhydrides are used. Examples of pyrolytic esters of polycarboxylic acids include t-butyl esters, 1-(alkyloxy)ethyl esters, and 1-(alkylsulfanyl)ethyl esters of the above compounds (wherein alkyl 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 substituent). In addition, polymers or copolymers having two or more carboxyl groups can be used as polycarboxylic acid compounds, and the carboxyl groups may be anhydrides or pyrolytic esters.

[0109] Furthermore, examples of the polymers or copolymers mentioned above include polymers or copolymers containing (meth)acrylic acid as a component (excluding component (A1)), copolymers containing maleic anhydride as a component, and compounds obtained by reacting tetracarboxylic dianhydride with diamine or diol to open the ring of an acid anhydride. Of these, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and benzene-1,2,4-tricarboxylic acid anhydrides are preferred. When using polycarboxylic acid compounds as curing agents for epoxy compounds, it is preferable to blend them so that the carboxyl groups of the polycarboxylic acid compound are 0.5 to 1.5 moles, more preferably 0.6 to 1.2 moles, per mole of epoxy groups of the epoxy compound.

[0110] Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, and imidazoles, which contribute to accelerating the curing of epoxy resins. Of these, 1,8-diazabicyclo[5.4.0]undeca-7-ene or 1,5-diazabicyclo[4.3.0]nona-5-ene or salts thereof are preferred.

[0111] The content of components (D) and (E) is preferably 5% by mass or more and 35% by mass or less, and more preferably 10% by mass or more and 30% by mass or less, relative to the total mass of solids. If the above content of components (D) and (E) is 5% by mass or more, the solvent resistance of the cured film can be further improved, and in particular, a cured film with high solvent resistance can be obtained even if post-baking is performed at a low temperature. If the above content of components (D) and (E) is 35% by mass or less, the adhesion of the cured film to the substrate can be further improved.

[0112] The amount of curing accelerator is preferably between 0.01 parts by mass and 2 parts by mass when the content of component (D) is 100 parts by mass. If the amount of curing accelerator added is 0.01 parts by mass or more, the amount can be adjusted depending on the solvent resistance of the resin film pattern after heat curing. If the amount of curing accelerator added is 2 parts by mass or less, the curing rate of the epoxy compound can be kept within an appropriate range.

[0113] Furthermore, component (E) may be used alone or in combination of two or more types.

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

[0115] A quantum dot is a nanoparticle (for example, with a particle diameter of 2 nm to 20 nm) that emits light of a different wavelength (for example, red or green light) when irradiated with light of a predetermined wavelength (for example, blue light). The wavelength of light emitted by a quantum dot changes depending on the size of the particle. Therefore, it is sufficient to have a size that matches the wavelength of the light to be emitted.

[0116] For example, component (F) can 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. However, the quantum dot is not limited to these, and can emit red light, green light, blue light, etc., when irradiated with light of a predetermined wavelength.

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

[0118] The type of quantum dot is not particularly limited, and semiconductors containing combinations of atoms such as Group II-VI, Group III-V, and Group IV-VI that have the above properties can be used. Examples of the above semiconductors include CdSe, CdTe, CdS, CdTe, ZnO, ZnS, ZnSe, InP, PbSe, and PbS.

[0119] Component (F) may be core-shell type particles with these materials as the core and shell, and may further have their surface coated with a resin, or be modified with a ligand having a functional group. Component (F) preferably has an average particle diameter of 1 nm or more and 40 nm or less.

[0120] The content of component (F) is preferably 10% to 60% by mass, more preferably 15% to 50% by mass, and even more preferably 15% to 40% by mass, relative to the total mass of solids. Increasing the amount of component (F) can improve the photoconversion efficiency of the cured film. However, in order to suppress the decrease in various properties such as adhesion, linearity, fineness, and flatness of the cured film due to the relative amount of other components, the above content of component (F) should be 60% by mass or less.

[0121] 1-6.(G) Component The photosensitive resin composition may contain (G) a solvent.

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

[0123] The content of component (G) varies depending on the target viscosity, but it is preferably 30% by mass or more and 90% by mass or less of the total mass of the photosensitive resin composition. If the content of component (G) is 30% by mass or more, the viscosity can be made suitable for coating the photosensitive resin composition onto the substrate, and 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 ingredients The photosensitive resin composition may optionally contain additives such as (H) coupling agents, (I) surfactants, (J) thermal polymerization inhibitors and antioxidants, other resin components, plasticizers, fillers, leveling agents, defoamers, ultraviolet absorbers, and viscosity modifiers.

[0125] Examples of coupling agents include silane coupling agents. Silane coupling agents are preferably those having amino groups, isocyanate groups, ureido groups, epoxy groups, vinyl groups, (meth)acrylic groups, mercapto groups, etc., as reactive groups, and more preferably those having epoxy groups, isocyanate groups, or methacrylic groups. Specific examples of the above coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

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

[0127] Other resin components include vinyl resin, polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, and melamine resin.

[0128] Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina.

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

[0130] Examples of UV absorbers include benzotriazole compounds, benzophenone compounds, and triazine compounds.

[0131] 1-8. Manufacturing method A photosensitive resin composition can be obtained by mixing the above-mentioned components.

[0132] 2.Applications The above-described photosensitive resin composition makes it possible to produce a cured film with good light transmittance and high light conversion efficiency. Therefore, the above-described photosensitive resin composition can be suitably used to produce wavelength conversion layers for image display devices and the like.

[0133] The cured film can be produced by the steps of applying the above-mentioned photosensitive resin composition onto a substrate and curing the applied photosensitive resin composition by exposure.

[0134] The photosensitive resin composition can be applied by methods such as immersion, spraying, spin coating, roll coating, curtain coating, and screen printing. After applying the composition to the desired thickness using these methods, the solvent is removed (pre-baking) to form a coating film. Pre-baking is performed by heating using an oven, hot plate, etc. The heating temperature and time during pre-baking should be appropriately selected depending on the solvent used; for example, heating at a temperature of 60-110°C (set so as not to exceed the heat resistance temperature of the substrate) for 1-3 minutes may be sufficient.

[0135] In exposure, the coating film is exposed to radiation through a photomask, thereby photo-curing only the resist in the areas corresponding to the pattern. Examples of radiation include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Of these, ultraviolet light with a wavelength of 250 nm to 450 nm 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 25 mJ / cm². 2 More than 3000mJ / cm 2 The following is preferable:

[0136] Alkaline development removes the paint film from areas that were not exposed. Alkaline development can be performed using an aqueous solution containing sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. A surfactant may be added to the developer as needed. The paint film that was not exposed and did not harden is removed by bringing the developer into contact with the paint film using methods such as shower development, spray development, dip development, or paddle development. The development temperature is preferably 20 to 35°C.

[0137] After alkaline development, post-baking is performed to fully cure the patterned cured film and improve its adhesion to the substrate. Post-baking can be performed by known methods, such as at a temperature of 180-250°C for 20-60 minutes. However, when a light-scattering cured 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 80-140°C (set so as not to exceed the heat resistance temperature of the substrate) for 20-90 minutes, and more preferably at a temperature of 90-120°C for 30-60 minutes. When components (D) and (E) are included, the photosensitive resin composition can be sufficiently cured and adhered even at such low temperatures.

[0138] Alternatively, the photosensitive resin composition may be applied by an inkjet method to form a patterned coating film. The coating film can then be cured by exposure with the aforementioned radiation to produce a cured film on the substrate. Alternatively, the coating film may be exposed by irradiating it with radiation through a photomask, and the unexposed portions of the coating film may then be removed by the aforementioned alkaline development. [Examples]

[0139] The embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited thereto.

[0140] First, we will explain the synthesis examples of the alkali-soluble resin of component A. Unless otherwise noted, the evaluation of the resin in these synthesis examples was performed as follows. For various measuring instruments, the manufacturer's name is omitted from the second time onward if the same model was used. Also, in [Experiment 1] and [Experiment 2], the glass substrates used to prepare the cured film substrates for measurement were all glass substrates that had undergone the same treatment.

[0141] [Solid content concentration] The weight of 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W0 (g)] and weighed [W1 (g)], and the weight after heating at 160°C for 2 hours [W2 (g)] was calculated using the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0142] [Epoxy equivalent] The resin solution was dissolved in dioxane, then an acetic acid solution of tetraethylammonium bromide was added, and the result was obtained by titrating with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0143] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" to determine the result.

[0144] [Molecular weight] The molecular weight was measured using gel permulation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2) + TSKgelSuper H-3000 (1) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (manufactured by Tosoh Corporation), temperature: 40℃, rate: 0.6 ml / min), and the weight-average molecular weight (Mw) was determined as a value converted to standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0145] Furthermore, the abbreviations used in the following synthesis examples are as follows: AA: Acrylic acid BPFE: Bisphenol fluorene type epoxy compound (reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane) 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 the mixture was stirred at 100-105°C for 20 hours to allow it to react. Next, BPDA (35.3 g, 0.12 mol) and THPA (18.3 g, 0.12 mol) were charged into the flask, and the mixture was stirred at 120-125°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin (A1-1). The solid content concentration of the obtained resin solution was 56.5% by mass, the acid value (based on solid content) was 103 mg KOH / g, and the Mw value determined by GPC analysis was 3600.

[0147] [Synthesis Example 2] A polymerizable unsaturated group-containing alkali-soluble resin (A1-2) was obtained using the same input quantities and synthesis method as in Synthesis Example 1, except that the BPFE in Synthesis Example 1 was replaced with BPFE in which the degree of polymerization of the bisphenol fluorene skeleton was increased. The solid content concentration of the obtained resin solution was 50.0% by mass, the acid value (based on solid content) was 92 mgKOH / g, and the Mw determined by GPC analysis was 6000.

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

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

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

[0151] (Metal oxide particle dispersion) (B-1): Hollow titania particle dispersion (average particle size 306 nm), hollowness approximately 30%, concentration 30% by mass, dispersant 3% by mass, PGMEA 67% by mass. (B-2): Solid titania particles (average particle size 200 nm), 0% hollowness, 30% by mass concentration, 3% by mass dispersant, 67% by mass PGMEA, titania particle dispersion.

[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 (Celoxide 2021P (epoxy equivalent 135), manufactured by Daicel Corporation)

[0154] (Hardening agent and curing accelerator) (E-1): Benzene 1,2,4-tricarboxylic acid-1,2-anhydride (E-2): A PGMEA solution containing 2% by mass of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU(R)), manufactured by Sunapro Co., Ltd.)

[0155] (Quantum dot dispersion) (F-1): CdSe / ZnS core-shell type, ligand-modified, emission wavelength 540 nm (MERCK), concentration 50% by mass, PGMEA 50% by mass, green quantum dot dispersion. (F-2): CdSe / ZnS core-shell type, ligand-modified, emission wavelength 630nm (MERCK), concentration 50% by mass, PGMEA 50% by mass, red quantum dot dispersion.

[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 (Surfactants) (I): Megafac F-560 (20% by mass PGMEA solution) (manufactured by DIC Corporation)

[0158] [Experiment 1] The above-mentioned components were blended in the proportions shown in Table 1 to prepare the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-2. All values ​​in Table 1 represent parts by mass.

[0159] [Table 1]

[0160] [evaluation] The following evaluations were performed using the photosensitive resin compositions of Examples 1-8 and Comparative Examples 1-2. The evaluation results are shown in Table 2.

[0161] [Settlement Assessment] (Evaluation method) Approximately 50 ml of the composition was placed in a 110 ml screw-cap bottle and the cap was closed. The screw-cap bottle containing the composition was left undisturbed in an environment of 5°C. After one month, the screw-cap bottle was laid on its side, and the bottom of the bottle was visually inspected. The sedimentation was evaluated according to the evaluation criteria below. (Evaluation Criteria) ○: No precipitation of white solid is observed at the bottom of the bottle. △: A slight precipitation of white solid is observed at the bottom of the bottle. ×: Precipitation of white solid is observed at the bottom of the bottle.

[0162] [Development Property Evaluation] (Preparation of Cured Film for Development Property Evaluation) The photosensitive resin composition shown in Table 1 was irradiated with ultraviolet light having an illuminance of 1000 mJ / cm at a wavelength of 254 nm using a low-pressure mercury lamp in advance to clean the surface. Then, it was applied onto a 125 mm × 125 mm glass substrate "#1737" (manufactured by Corning Co., Ltd.) (hereinafter referred to as "glass substrate") using a spin coater so that the film thickness after heat curing treatment would be 4.0 μm, and pre-baked at 90°C for 2 minutes using a hot plate to form a hard film (coating film). Next, the exposure gap was adjusted to 100 μm, a negative photomask of 10 - 50 μm (in 5-μm increments) was placed on the above cured film (coating film), and ultraviolet light of 2000 mJ / cm was irradiated from an LED light source having a wavelength of 395 nm in a nitrogen atmosphere to carry out a photocuring reaction. 2 2

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

[0164] The evaluation results of the cured films obtained by curing the photosensitive resin compositions of Examples 1 - 8 and Comparative Examples 1 - 2 obtained above for the following items are shown in Table 2.

[0165] (Pattern Adhesion) (Evaluation Method) The 20 μm mask pattern after final curing (post-bake) was observed using an optical microscope. A result of △ or higher was considered acceptable. (Evaluation Criteria) ○: Not peeling off at all △: Partially peeled off ×: Mostly peeled off

[0166] (Pattern linearity) (Evaluation method) The 20 μm mask pattern after final curing (post-bake) was observed using an optical microscope. A result of △ or higher was considered acceptable. (Evaluation Criteria) ○: No jaggedness is observed in the pattern edges. △: Some jaggedness is observed in the pattern edges. ×: Jagged edges are visible in most of the pattern.

[0167] (Pattern resolution) (Evaluation method) The 10-50 μm mask patterns after final curing (post-bake) were observed under an optical microscope. A result of △ or higher was considered acceptable. (Evaluation Criteria) ○: A pattern is formed that is between 15 μm and 25 μm in size. △: A pattern is formed that is between 25 μm and 50 μm in size. ×: No pattern has been formed.

[0168] [Chemical resistance evaluation] (Preparation of cured films for solvent resistance evaluation) The photosensitive resin compositions shown in Table 1 were applied to a glass substrate using a spin coater to achieve a film thickness of 4.0 μm after heat curing. A hard film (coating) was then prepared by pre-baking at 90°C for 2 minutes using a hot plate. Next, a negative photomask with a line / space of 20 μm / 20 μm was placed over the hardened film (coating), and 2000 mJ / cm² was applied from a 395 nm wavelength LED light source under a nitrogen atmosphere. 2 The photocuring reaction was carried out by irradiating it with ultraviolet light.

[0169] Next, the exposed cured film (coating) was subjected to a 1 kgf / cm² treatment with a 0.05% potassium hydroxide solution at 25°C. 2 After developing with a shower pressure of 5 kgf / cm² for 60 seconds, the treatment is performed. 2 The cured film (coating) was then sprayed with water to remove the unexposed portion and form a cured film pattern on the glass substrate. The substrate was then fully cured (post-bake) using a hot air dryer at 120°C for 60 minutes to obtain the cured film substrates according to Examples 1-8 and Comparative Examples 1-2. (Evaluation method) The surface of the cured film fabricated on the glass substrate was rubbed back and forth 20 times in a row with a cloth soaked in PGMEA. A result of △ or higher was considered acceptable. (Evaluation Criteria) ○: No dissolution was observed on the surface of the hardened film, and there were no scratches. △: Dissolution is observed on a very small part of the surface of the hardened film, and there are also scratches on a very small part. ×: The surface of the hardened film has softened and is scratched in most areas.

[0170] [Optical properties evaluation] (Evaluation of light conversion efficiency) (Evaluation method) Using a cured film similar to the one prepared for solvent resistance evaluation, the photoconversion efficiency was measured using the following method.

[0171] A blue LED (peak wavelength 450 nm) was used as a surface light source, and the substrate with the cured film of this embodiment was placed on it. The spectral distribution was measured using a spectroradiometer with an integrating sphere. First, the integral value from 400 nm to 480 nm was taken as the blue light intensity from the spectrum obtained with a glass substrate without the cured film. Then, the integral value from 480 nm to 590 nm was taken as the green emission intensity from the spectrum obtained with a cured film substrate containing green quantum dots. Furthermore, the integral value from 590 nm to 750 nm was taken as the red emission intensity from the spectrum obtained with a cured film substrate containing red quantum dots. Using these 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

[0172] Furthermore, a score of △ or higher was considered a passing grade based on the following evaluation criteria. (Evaluation criteria: Quantum dot dispersion (F-1) (green)) ○: Light conversion efficiency of 40% or more △: Light conversion efficiency is between 35% and 40% ×: Light conversion efficiency is less than 35% (Evaluation criteria: Quantum dot dispersion (F-2) (red)) ○: Light conversion efficiency of 45% or higher △: Light conversion efficiency is between 40% and 45%

[0173] [Table 2]

[0174] As is clear from the results of Examples 1-8 and Comparative Examples 1-2 above, it was found that by using a photosensitive resin composition containing hollow particles having a specific average particle size and metal oxide particles having a specific refractive index, it is possible to produce a cured film that has high photoconversion efficiency and forms a fine wavelength conversion layer. These cured films are ideal as wavelength conversion layers in displays.

[0175] [Example 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 Kyoeisha Chemical Co., Ltd.)

[0177] (Metal oxide particle dispersion) (B-3): Hollow titania particle dispersion (average particle size 306 nm), hollowness approximately 30%, concentration 60% by mass, dispersant 6% by mass, 1.6HX-A 34% by mass. (B-4): Solid titania particle dispersion (average particle size 200 nm), 0% hollowness, 60% by mass concentration, 6% by mass dispersant, 34% by mass of 1.6HX-A.

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

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

[0180] (Other additives) (Surfactants) (I): Megafuck F-563 (manufactured by DIC Corporation) (Antioxidant) (J): ADEKA Stab C (manufactured by ADEKA Corporation)

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

[0182] [Table 3]

[0183] [evaluation] The following evaluations were performed using the photosensitive resin compositions of Examples 9-16 and Comparative Examples 3-4. The evaluation results are shown in Table 4.

[0184] [Settlement Assessment] (Evaluation method) Approximately 50 ml of the composition was placed in a 110 ml screw-cap bottle and the cap was closed. The screw-cap bottle containing the composition was left undisturbed in an environment of 5°C. After one month, the screw-cap bottle was laid on its side, and the bottom of the bottle was visually inspected. The sedimentation was evaluated according to the evaluation criteria below. (Evaluation Criteria) ○: No white solid precipitate is observed at the bottom of the bottle. △: A small amount of white solid precipitate is visible at the bottom of the bottle. ×: A white solid precipitate is visible at the bottom of the bottle.

[0185] [Chemical resistance evaluation] (Preparation of cured films for solvent resistance evaluation) The photosensitive resin compositions shown in Table 3 were applied to a glass substrate using a spin coater to produce a film with a cured thickness of 4.0 μm. Next, the film was exposed to a 2000 mJ / cm² light from a 395 nm LED light source under a nitrogen atmosphere. 2 By irradiating with ultraviolet light, a photocuring reaction was carried out to obtain substrates with cured films according to Examples 9-16 and Comparative Examples 3-4.

[0186] (Evaluation method) The surface of the cured film fabricated on the glass substrate was rubbed back and forth 20 times in a row with a cloth soaked in PGMEA. A result of △ or higher was considered acceptable. (Evaluation Criteria) ○: No dissolution was observed on the surface of the hardened film, and there were no scratches. △: Dissolution is observed on a very small part of the surface of the hardened film, and there are also scratches on a very small part. ×: The surface of the hardened film has softened and is scratched in most areas.

[0187] [Optical properties evaluation] (Evaluation of light conversion efficiency) (Evaluation method) Using a cured film similar to the one prepared for solvent resistance evaluation, the photoconversion efficiency was measured using the following method.

[0188] A blue LED (peak wavelength 450 nm) was used as a surface light source, and the substrate with the cured film of this embodiment was placed on it. The spectral distribution was measured using a spectroradiometer with an integrating sphere. First, the integral value from 400 nm to 480 nm was taken as the blue light intensity from the spectrum obtained with a glass substrate without the cured film. Then, the integral value from 480 nm to 590 nm was taken as the green emission intensity from the spectrum obtained with a cured film substrate containing green quantum dots. Furthermore, the integral value from 590 nm to 750 nm was taken as the red emission intensity from the spectrum obtained with a cured film substrate containing red quantum dots. Using these 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] Furthermore, a score of △ or higher was considered a passing grade based on the following evaluation criteria. (Evaluation criteria: Quantum dot dispersion (F-1) (green)) ○: Light conversion efficiency of 40% or more △: Light conversion efficiency is between 35% and 40% ×: Light conversion efficiency is less than 35% (Evaluation criteria: Quantum dot dispersion (F-2) (red)) ○: Light conversion efficiency of 45% or higher △: Light conversion efficiency is between 40% and 45%

[0190] [Table 4]

[0191] As is clear from the results of Examples 9-16 and Comparative Examples 3-4, it was found that by using a photosensitive resin composition containing hollow particles with a specific average particle size and metal oxide particles with a specific refractive index, it is possible to produce a cured film with high light conversion efficiency and a fine wavelength conversion layer. These cured films are ideal as wavelength conversion layers in displays. Furthermore, when the processable resin compositions of Examples 9-16 and Comparative Examples 3-4 were ejected from a commercially available inkjet print head, patterns could be formed without any problems. [Industrial applicability]

[0192] The photosensitive resin composition of the present invention exhibits its effect in the wavelength conversion layer of a wavelength conversion display. Furthermore, since this photosensitive resin composition can obtain solvent resistance even when cured at low temperatures, it does not adversely affect quantum dots or organic EL displays, which have low heat resistance, and is therefore suitable for the manufacture of displays such as these.

Claims

[Claim 1] (A) Photocurable compound and (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 made of a metal oxide with a refractive index of 1.9 or more and 2.7 or less, (C) Photopolymerization initiator and (F) Quantum dots and Includes, (B) The content of component is 5% by mass or more and 70% by mass or less, relative to the total mass of solids. Photosensitive resin composition.

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