Photosensitive resin composition, photosensitive resin film, photosensitive dry film, pattern forming method, and light-emitting device

Abstract

To provide a photosensitive resin composition which enables easy formation of a film having high lithography resolution and good light-emission characteristics, a photosensitive resin film and a photosensitive dry film obtained using the photosensitive resin composition and a pattern formation method using them, and a light-emitting element obtained using the photosensitive resin composition.SOLUTION: A photosensitive resin composition contains (A) a silicone resin having a glycidyl group, (B) a photo-cationic polymerization initiator, and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin film using the photosensitive resin composition, a photosensitive dry film, a pattern forming method, and a light-emitting device. [Background technology]

[0002] Various methods have been proposed to create displays with red, green, and blue subpixels. One method involves converting light from an LED array from shorter wavelength blue light to longer wavelength red and green light through a color conversion structure. Quantum dots are used to perform this color conversion.

[0003] In recent years, LED arrays have become micro-sized, and micro LED displays using these arrays have attracted attention. One method for forming a color conversion structure on an LED array is a lithography process using a photosensitive material (Patent Document 1), but in recent years, further miniaturization has been required for application to small displays. In addition, there are high demands for light-emitting characteristics in terms of display clarity. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-089347 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive resin composition that can easily form a film having high lithography resolution and good light-emitting properties, a photosensitive resin film and a photosensitive dry film obtained using the photosensitive resin composition, and a pattern formation method using these, as well as a light-emitting element obtained using the photosensitive resin composition. [Means for solving the problem]

[0006] In order to solve the above problems, the present invention provides a photosensitive resin composition, (A) a silicone resin having a glycidyl group, (B) a photocationic polymerization initiator, and (C) Quantum dots The quantum dots have a surface coating layer containing siloxane.

[0007] Such a photosensitive resin composition can easily form a film having high lithography resolution and good light-emitting properties.

[0008] In the present invention, the component (C) preferably contains a skeleton having a glycidyl group in the surface coating layer.

[0009] Such a photosensitive resin composition can prevent the quantum dots from being released during development, and can provide a pattern with high light-emitting properties.

[0010] In the present invention, the component (A) preferably contains repeating units represented by the following formulae (A1) to (A4). [ka] [In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer of 1 to 600. When m is an integer of 2 or greater, each R 3 may be the same or different, and each R 4 may be the same or different. 1 , a 2 , a 3 and a 4 is 0 1 <1, 0 2 <1, 0 <a​​3 <1, 0 4 <1, and a 1 +a 2 +a 3 +a 4 = 1. 1 is a divalent group represented by the following formula (X1): 2 is a divalent group represented by the following formula (X2). [ka] (In the formula, R 11 and R 12 are each independently a hydrogen atom or a methyl group. 1 and n 2 are each independently an integer of 0 to 7. 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain an ester bond or an ether bond between its carbon atoms. [ka] (In the formula, R 21 and R 22 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom, and k is an integer of 0 to 10.)

[0011] The photosensitive resin composition of the present invention preferably contains the repeating units described above.

[0012] In addition, in the present invention, it is preferable that the quantum dots of component (C) have ligands coordinated to their surfaces, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands have one or more of an amino group, a thiol group, a carboxy group, a phosphino group, a phosphine oxide group, and an ammonium ion.

[0013] Quantum dots having such ligands are preferred because they are easily coordinated to the surface.

[0014] ​In the present invention, the component (C) is preferably contained in an amount of 5 to 80% by mass in the photosensitive resin composition.

[0015] Such a photosensitive resin composition allows fine pattern formation while maintaining good light-emitting properties.

[0016] In the present invention, it is preferable that the composition further contains (D) a cationically polymerizable crosslinking agent.

[0017] Such a photosensitive resin composition can further increase the strength of the resin film after photocuring.

[0018] In the present invention, it is preferable that the composition further contains a solvent (E).

[0019] Such a photosensitive resin composition can improve the coating properties.

[0020] The present invention also provides a photosensitive resin film which is a dried product of the above-described photosensitive resin composition.

[0021] Such a photosensitive resin film has high lithography resolution and good light-emitting properties.

[0022] The present invention also provides a photosensitive dry film comprising a support film and the above-described photosensitive resin film on the support film.

[0023] Such a photosensitive dry film has high lithography resolution and good light-emitting properties.

[0024] Further, the present invention provides a pattern forming method, comprising the steps of: (i) applying the photosensitive resin composition described above onto a substrate to form a photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern. The present invention provides a pattern formation method comprising the steps of:

[0025] Further, the present invention provides a pattern forming method, comprising the steps of: (i') a step of attaching the photosensitive resin film of the photosensitive dry film described above onto a substrate to form the photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern. The present invention provides a pattern formation method comprising the steps of:

[0026] These patterning methods allow for the formation of patterns with high lithographic resolution, and can provide film patterns with good light-emitting properties.

[0027] The present invention also provides a light-emitting device comprising a cured film obtained by the above-described pattern formation method.

[0028] Such a light-emitting element has high lithography resolution and good light-emitting properties. [Effects of the Invention]

[0029] The photosensitive resin composition of the present invention contains a silicone resin having a glycidyl group, a photocationic polymerization initiator, and quantum dots having a specific surface coating layer, and therefore can easily form a film having high resolution and good light-emitting properties, making it suitable for light-emitting devices. DETAILED DESCRIPTION OF THE INVENTION

[0030] As described above, there has been a need for the development of a photosensitive resin composition that can easily form a film having high lithography resolution and good light-emitting properties, a photosensitive resin film and a photosensitive dry film obtained using the photosensitive resin composition, a pattern formation method using these, and a light-emitting element obtained using the photosensitive resin composition.

[0031] As a result of extensive research into the above-mentioned problems, the present inventors have discovered that a photosensitive resin composition comprising (A) a silicone resin having a glycidyl group, (B) a photocationic polymerization initiator, and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane, has high lithography resolution and can easily form a film (photosensitive resin film) having good luminescence properties, thereby completing the present invention.

[0032] That is, the present invention provides a photosensitive resin composition, (A) a silicone resin having a glycidyl group, (B) a photocationic polymerization initiator, and (C) Quantum dots wherein the quantum dots have a surface coating layer containing siloxane.

[0033] The present invention will be described in detail below, but the present invention is not limited thereto.

[0034] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a silicone resin having a glycidyl group, (B) a photocationic polymerization initiator, and (C) quantum dots having a specific surface coating layer. If necessary, the composition may further contain other components such as (D) a cationic polymerizable crosslinker and (E) a solvent. Each component constituting the photosensitive resin composition will be described below.

[0035] [(A) Silicone resin having a glycidyl group] The glycidyl group-containing silicone resin (A) used in the present invention is not particularly limited as long as it contains a glycidyl group.

[0036] Such silicone resins are preferably those containing repeating units represented by the following formulas (A1) to (A4) (hereinafter also referred to as repeating units A1 to A4, respectively). [ka]

[0037] In formulas (A2) and (A4), R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer of 1 to 600. When m is an integer of 2 or greater, each R 3 may be the same or different, and each R 4 may be the same or different. When the repeating units A2 and A4 contain two or more siloxane units, the siloxane units may all be the same, or two or more different types of siloxane units may be included. When two or more different types of siloxane units are included (i.e., when m is an integer of 2 or more), the siloxane units may be bonded randomly or alternately, or may include multiple blocks of the same type of siloxane units.

[0038] The monovalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include monovalent aliphatic hydrocarbon groups such as alkyl groups having 1 to 20 carbon atoms and alkenyl groups having 2 to 20 carbon atoms, and monovalent aromatic hydrocarbon groups such as aryl groups having 6 to 20 carbon atoms and aralkyl groups having 7 to 20 carbon atoms.

[0039] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, a norbornyl group, an adamantyl group, etc. Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, etc.

[0040] The monovalent aliphatic hydrocarbon group may contain a heteroatom, and specifically, some or all of the hydrogen atoms of the monovalent aliphatic hydrocarbon group may be substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, and the carbon atoms may be interposed by a carbonyl group, an ether bond, a thioether bond, etc. Examples of such monovalent aliphatic hydrocarbon groups containing a heteroatom include a 2-oxocyclohexyl group.

[0041] Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group, etc. Examples of the aralkyl group include a benzyl group, a phenethyl group, etc.

[0042] The monovalent aromatic hydrocarbon group may contain a heteroatom, and specifically, some or all of the hydrogen atoms of the monovalent aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, or the like.

[0043] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, a cyclopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a cyclobutyloxy group, an n-pentyloxy group, a cyclopentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, a norbornyloxy group, and an adamantyloxy group.

[0044] Examples of the alkylthio group having 1 to 10 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, a cyclopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a cyclobutylthio group, an n-pentylthio group, a cyclopentylthio group, an n-hexylthio group, a cyclohexylthio group, an n-heptylthio group, an n-octylthio group, an n-nonylthio group, an n-decylthio group, a norbornylthio group, and an adamantylthio group.

[0045] Examples of the aryloxy group having 6 to 20 carbon atoms include a phenyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, a 2-ethylphenyloxy group, a 3-ethylphenyloxy group, a 4-ethylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-butylphenyloxy group, a dimethylphenyloxy group, a naphthyloxy group, a biphenylyloxy group, and a terphenylyloxy group.

[0046] Examples of the arylthio group having 6 to 20 carbon atoms include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, a 2-ethylphenylthio group, a 3-ethylphenylthio group, a 4-ethylphenylthio group, a 4-tert-butylphenylthio group, a 4-butylphenylthio group, a dimethylphenylthio group, a naphthylthio group, a biphenylylthio group, and a terphenylylthio group.

[0047] For example, aryl groups substituted with these groups include a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group, a 3-ethoxyphenyl group, a 4-ethoxyphenyl group, a 3-tert-butoxyphenyl group, a 4-tert-butoxyphenyl group, a biphenylyloxyphenyl group, and a biphenylylthiophenyl group.

[0048] The monovalent aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8. The monovalent aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, more preferably 6 to 10.

[0049] Of these, R 1 ~R 4 As the alkyl group, a methyl group, an ethyl group, an n-propyl group or a phenyl group is preferable, and a methyl group or a phenyl group is more preferable.

[0050] In formulae (A2) and (A4), m each independently represents an integer of 1 to 600, preferably an integer of 8 to 100.

[0051] In formulas (A1) to (A4), a 1 , a 2 , a 3 and a 4 is 0 1 <1, 0 2 <1, 0 3 <1, 0 4 <1, and a 1 +a 2 +a 3 +a 4 = 1. Preferably, 0.010≦a 1 +a 2 ≦0.490, 0.010≦a 3 +a 4 ≦0.490, 0.050≦a 1 +a 3 ≦0.490, 0.010≦a 2 +a 4 ≦0.450, and a 1 +a 2 +a 3 +a​​​​4 = 1, and more preferably, 0.050≦a 1 +a 2 ≦0.450, 0.050≦a 3 +a 4 ≦0.450, 0.100≦a 1 +a 3 ≦0.475, 0.025≦a 2 +a 4 ≦0.400, and a 1 +a 2 +a 3 +a 4 =1.

[0052] In particular, the silicone content is preferably 20 to 80% by weight, and more preferably 30 to 70% by weight.

[0053] In formulas (A1) and (A2), X 1 is a divalent group represented by the following formula (X1). [ka]

[0054] In formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group. 1 and n 2 are each independently an integer of 0 to 7.

[0055] In formula (X1), R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain an ester bond or an ether bond between its carbon atoms. The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include alkanediyl groups such as methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, and butane-1,4-diyl. An ester bond or an ether bond may be present between the carbon atoms of the divalent hydrocarbon group. Of these, R 13As the alkyl group, a methylene group or an ethylene group is preferred, and a methylene group is more preferred.

[0056] In formulas (A3) and (A4), X 2 is a divalent group represented by the following formula (X2). [ka]

[0057] In formula (X2), R 21 and R 22 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom. 1 ~R 4 The same as those mentioned in the explanation of R 21 and R 22 is preferably a hydrogen atom or a methyl group.

[0058] In formula (X2), k is an integer of 0 to 10, with 0 being preferred.

[0059] The weight average molecular weight (Mw) of the component (A) according to the present invention is preferably 3,000 to 500,000, more preferably 5,000 to 200,000. When the Mw is within the above range, the polymer can be obtained as a solid, and film-forming properties can be ensured. In the present invention, the Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an elution solvent.

[0060] The component (A) according to the present invention may be one in which the repeating units A1 to A4 are bonded randomly or alternately, and may contain multiple blocks of each unit.

[0061] [(A) Method for producing silicone resin having glycidyl groups] The component (A) according to the present invention is preferably produced by addition polymerization of a compound represented by the following formula (1) (hereinafter also referred to as compound (1)), a compound represented by the following formula (2) (hereinafter also referred to as compound (2)), a compound represented by the following formula (3) (hereinafter also referred to as compound (3)), and a compound represented by the following formula (4) (hereinafter also referred to as compound (4)) in the presence of a metal catalyst.

[0062] [ka] (In the formula, R 1 ~R 4 , R 11 ~R 13 , R 21 , R 22 , m, n 1 , n 2 and k are the same as above.

[0063] Examples of the metal catalyst include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chlorides, chloroplatinic acids, and chloroplatinic salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (where x is preferably an integer of 0 to 6, particularly preferably 0 or 6); alcohol-modified chloroplatinic acid (such as that described in U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum group metals such as platinum black and palladium supported on a support such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (the so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinyl group-containing siloxanes (particularly vinyl group-containing cyclic siloxanes), and the like can be used.

[0064] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1 mass % as platinum group metal based on the total mass of the compounds (1) to (4).

[0065] A solvent may be used in the polymerization reaction, if necessary. Preferred examples of the solvent include hydrocarbon solvents such as toluene and xylene. As polymerization conditions, the polymerization temperature is preferably 40 to 150°C, particularly 60 to 120°C, from the viewpoint of not deactivating the catalyst and completing the polymerization in a short time. The polymerization time varies depending on the type and amount of the raw material compounds, but is preferably completed within approximately 0.5 to 100 hours, particularly 0.5 to 30 hours, to prevent moisture from entering the polymerization system. After completing the polymerization reaction in this manner, if a solvent was used, it can be distilled off to obtain (A) a silicone resin having glycidyl groups.

[0066] The reaction method is not particularly limited, but it is preferable to first mix and heat compound (3) and compound (4), then add a metal catalyst to the mixed solution, and then add compound (1) and compound (2) dropwise over 0.1 to 5 hours.

[0067] The raw material compounds are preferably blended so that the molar ratio of the hydrosilyl groups in compounds (1) and (2) to the total carbon-carbon double bonds in compounds (3) and (4) is preferably 0.67 to 1.67, more preferably 0.83 to 1.25. The Mw of component (A) according to the present invention can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylhydrosilane as a molecular weight modifier.

[0068] In the present invention, the (A) silicone resin having a glycidyl group may be used alone or in combination of two or more kinds.

[0069] [(B) Photocationic polymerization initiator] The cationic photopolymerization initiator (B) is not particularly limited as long as it decomposes upon irradiation with light to generate a cationic polymerization catalyst, but it is preferably one that generates the catalyst upon irradiation with light having a wavelength of 190 to 500 nm. The cationic photopolymerization initiator (B) is used as a curing catalyst. Examples of the cationic photopolymerization initiator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonate ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, and triazine derivatives.

[0070] Examples of the onium salt include sulfonium salts represented by the following formula (B1) and iodonium salts represented by the following formula (B2). [ka]

[0071] In formulas (B1) and (B2), R 101 ~R 105 are each independently an alkyl group having 1 to 12 carbon atoms which may have a substituent, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms which may have a substituent. - is a non-nucleophilic counterion.

[0072] The alkyl group may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a biphenylyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0073] Examples of the substituent include an oxo group, a linear, branched, or cyclic alkoxy group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aralkyl group having 7 to 25 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, and an arylthio group having 6 to 24 carbon atoms.

[0074] R 101 ~R 105 Preferred examples of the alkyl group include an alkyl group which may have a substituent such as a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, or a 2-oxocyclohexyl group; an aryl group which may have a substituent such as a phenyl group, a naphthyl group, a biphenylyl group, an o-, m-, or p-methoxyphenyl group, an ethoxyphenyl group, an m- or p-tert-butoxyphenyl group, a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, a dimethylphenyl group, a terphenylyl group, a biphenylyloxyphenyl group, or a biphenylylthiophenyl group; and an aralkyl group which may have a substituent such as a benzyl group or a phenethyl group. Of these, an aryl group which may have a substituent and an aralkyl group which may have a substituent are more preferred.

[0075] Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkanesulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkanesulfonate ions such as mesylate ion and butanesulfonate ion; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ion; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ion; and borate ions such as tetrakisphenylborate ion and tetrakis(pentafluorophenyl)borate ion.

[0076] The diazomethane derivatives include compounds represented by the following formula (B3). [ka]

[0077] In formula (B3), R 111 and R 112 are each independently an alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms.

[0078] The alkyl group may be linear, branched, or cyclic. Specific examples thereof include R 101 ~R 105 Examples of the halogenated alkyl group include the same groups as those exemplified in the description of 1. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, and a nonafluorobutyl group.

[0079] Examples of the aryl group which may have a substituent include a phenyl group; an alkoxyphenyl group such as a 2-, 3-, or 4-methoxyphenyl group, a 2-, 3-, or 4-ethoxyphenyl group, or a 3- or 4-tert-butoxyphenyl group; an alkylphenyl group such as a 2-, 3-, or 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, or a dimethylphenyl group; and a halogenated aryl group such as a fluorophenyl group, a chlorophenyl group, or a 1,2,3,4,5-pentafluorophenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0080] The glyoxime derivatives include compounds represented by the following formula (B4). [ka]

[0081] In formula (B4), R 121 ~R 124 are each independently an alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, or an aralkyl group having 7 to 12 carbon atoms. 123 and R 124 may be bonded to each other to form a ring together with the carbon atoms to which they are attached, and when they form a ring, R 123 and R 124 The group formed by bonding is a linear or branched alkylene group having 2 to 12 carbon atoms.

[0082] The alkyl group, the halogenated alkyl group, the aryl group which may have a substituent, and the aralkyl group include R 111 and R 112 Examples of the linear or branched alkylene group include an ethylene group, a propylene group, a butylene group, and a hexylene group.

[0083] Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenylsulfonium, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate sulfonium trifluoromethanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, p-toluenesulfone dicyclohexylphenylsulfonium acid, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate,Examples include triphenylsulfonium tetrakis(pentafluorophenyl)borate and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0084] Specific examples of the diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis( tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, and the like.

[0085] Specific examples of the glyoxime derivatives include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bis- Examples of such an oxime include o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0086] Specific examples of the β-ketosulfone derivative include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, and the like.

[0087] Specific examples of the disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

[0088] Specific examples of the nitrobenzyl sulfonate derivative include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0089] Specific examples of the sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0090] Specific examples of the imide-yl sulfonate derivatives include phthalimide-yl triflate, phthalimide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl triflate, 5-norbornene-2,3-dicarboximide-yl tosylate, 5-norbornene-2,3-dicarboximide-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0091] Specific examples of the oxime sulfonate derivatives include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile.

[0092] Specific examples of the iminosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, and the like.

[0093] Specific examples of the triazine derivatives include 2-[2-(furan-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-methoxyphenyl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine, and 2-[2-(3,4-dimethoxyphenyl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine.

[0094] Also suitable for use are 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like.

[0095] As the cationic photopolymerization initiator of the component (B), the above-mentioned onium salts and sulfonium salts are particularly preferred, and the above-mentioned sulfonium salts are more preferred.

[0096] The content of the (B) cationic photopolymerization initiator is preferably in the range of 0.05 to 20% by mass, more preferably 0.5 to 10% by mass, relative to the total amount of the photosensitive resin composition. When the cationic photopolymerization initiator is contained within the above range, a pattern with excellent resolution and no residual film can be obtained due to an excellent balance between sensitivity during exposure and developability. The cationic photopolymerization initiator may be used alone or in combination of two or more types.

[0097] [(C) Quantum dots with specific surface coating layers] Quantum dots are nano-sized semiconductor materials. Atoms form molecules, and molecules form small molecular aggregates called clusters to form nanoparticles. When such nanoparticles exhibit semiconductor properties, they are called quantum dots (quantum dot particles).

[0098] When quantum dots receive external energy and reach a floating state, they autonomously emit energy (emit light) according to the corresponding energy band gap.

[0099] The quantum dots (C) used in the present invention are not particularly limited as long as they have a surface coating layer containing siloxane, and can be used in any form. Quantum dots are mainly nanoparticles of 10 nm or less, but they can also be nanowires, nanorods, nanotubes, nanocubes, etc., and any shape can be used. In the present invention, the average particle size of the quantum dots was determined by directly observing at least 20 particles using a transmission electron microscope (TEM), calculating the diameter of a circle having the same area as the projected area of the particle, and using the average value of these.

[0100] The quantum dots (C) used in the present invention can be made of any suitable material, for example, a semiconductor material selected from the group consisting of II-VI group, III-V group, IV group, IV-VI group, I-III-VI group, II-IV-V group, mixed crystals or alloys thereof, or compounds having a perovskite structure. Specific examples include, but are not limited to, compounds containing ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, Si, Ge, Sn, Pb, PbS, PbSe, PbTe, SnS, SnSe, SnTe, AgGaS2, AgInS2, AgGaSe2, AgInSe2, CuGaS2, CuGaSe2, CuInS2, CuInSe2, ZnSiP2, ZnGeP2, CdSiP2, CdGeP2, CsPbCl3, CsPbBr3, CsPbI3, CsSnCl3, CsSnBr3, and CsSnI3.

[0101] The quantum dots (C) used in the present invention can have a core-shell structure. Shell materials capable of forming a core-shell structure are not particularly limited, but are preferably those with a large band gap and low lattice mismatch relative to the core material, and can be arbitrarily combined according to the core material. Specific shell materials include ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, BeS, BeSe, BeTe, MgS, MgSe, MgTe, PbS, PbSe, PbTe, SnS, SnSe, SnTe, CuF, CuCl, CuBr, CuI, and the like. The above materials may also be selected as single or multiple mixed crystals, but are not limited thereto.

[0102] There are various methods for producing the (C) quantum dots used in the present invention, such as a liquid phase method or a gas phase method, and there are no particular limitations in the present invention. However, from the viewpoint of exhibiting high fluorescence emission efficiency, it is preferable to use semiconductor nanoparticles obtained by a hot soap method or a hot injection method, in which precursor species are reacted at high temperature in a high-boiling-point nonpolar solvent, and it is desirable that organic ligands are coordinated to the surface in order to impart dispersibility in nonpolar solvents and reduce surface defects.

[0103] From the viewpoint of dispersibility, the organic ligand preferably contains an aliphatic hydrocarbon. Examples of such organic ligands include oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, decanoic acid, octanoic acid, oleylamine, stearyl (octadecyl)amine, dodecyl (lauryl)amine, decylamine, octylamine, octadecanethiol, hexadecanethiol, tetradecanethiol, dodecanethiol, decanethiol, octanethiol, trioctylphosphine, trioctylphosphine oxide, triphenylphosphine, triphenylphosphine oxide, tributylphosphine, and tributylphosphine oxide. These may be used alone or in combination.

[0104] In addition to the organic ligands described above, the quantum dots (C) used in the present invention are coordinated with ligands having substituents capable of forming siloxane bonds. The ligands having substituents capable of forming siloxane bonds preferably have a substituent that interacts with or adsorbs to the quantum dot surface. Examples of substituents that interact with or adsorb to the quantum dot surface include amino groups, thiol groups, carboxy groups, mercapto groups, phosphino groups, phosphine groups, phosphine oxide groups, sulfonyl groups, ammonium ions, and quaternary ammonium salts. Among these, amino groups, carboxy groups, mercapto groups, phosphine groups, and quaternary ammonium salts are preferred in terms of coordination strength.

[0105] The quantum dots (C) used in the present invention have their surfaces coated with siloxane. Therefore, the ligands having substituents that interact with or adsorb to the quantum dot surface have substituents capable of forming siloxane bonds. Substituents capable of forming siloxane bonds include compounds containing alkoxysilanes such as trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethylmethoxysilyl, and ethoxydimethylsilyl; compounds containing silazane bonds; compounds containing Si-OH bonds; compounds containing Si-X (X: halogen) bonds; and carboxylic acids. However, it is preferable to use alkoxysilanes, silazanes, or ligands containing Si-OH because the reaction can proceed under mild conditions without generating acid as a by-product. Phenyl-containing siloxanes can be formed by reacting these with diphenyldisilanol or the like.

[0106] The amount of siloxane coating is not particularly limited, but is preferably in the range of 1 to 50% by mass, and more preferably in the range of 5 to 30% by mass. If the amount of siloxane coating is too high, the quantum dot content will decrease, but if it is within the above range, it is possible to improve dispersibility in the base polymer and suppress deterioration of the quantum dots during exposure.

[0107] The quantum dots (C) used in the present invention may further include a skeleton having a glycidyl group in the surface coating layer.

[0108] The skeleton having a glycidyl group is preferably a skeleton structure derived from the following formula (c). [ka]

[0109] In formula (c), R 31 is a hydrogen atom or a methyl group. 1 is an integer between 0 and 7.

[0110] In formula (c), R 32 is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain an ester bond or an ether bond between its carbon atoms. The divalent hydrocarbon group may be linear, branched, or cyclic, and specific examples thereof include alkanediyl groups such as methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, and butane-1,4-diyl. An ester bond or an ether bond may be present between the carbon atoms of the divalent hydrocarbon group. Of these, R 32 As the alkyl group, a methylene group or an ethylene group is preferred, and a methylene group is more preferred.

[0111] In formula (c), R 33 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, which may contain an ester bond or an ether bond between its carbon atoms. Among these, the groups shown below are preferred. [ka]

[0112] By introducing the skeletal structure of formula (c) into the surface coating layer, the silicone resin (A) having a glycidyl group crosslinks with the surface coating layer after exposure, which prevents the quantum dots from escaping during development and results in a pattern with high luminescence properties.

[0113] Furthermore, by introducing the skeletal structure of formula (c) into the surface coating layer, compatibility with (A) the silicone resin having a glycidyl group is improved, and the generation of aggregates when made into a photosensitive resin composition can be suppressed.

[0114] The content of the quantum dots (C) used in the present invention is preferably 5 to 80 mass %, more preferably 10 to 70 mass %, of the total amount of the photosensitive resin composition. If the content of the quantum dot particles is within the above range, fine patterns can be formed while maintaining good light-emitting properties.

[0115] The method for introducing glycidyl groups into component (C) and the amount introduced are not particularly limited, but methods that can be used include adding a previously prepared skeleton containing glycidyl groups containing an alkoxysilane to form the phenyl group-containing siloxane and reacting it, or directly introducing a skeleton containing glycidyl groups by radical reaction, etc. The amount introduced can be adjusted appropriately taking into account compatibility with the resin.

[0116] [(D) Cationic polymerizable crosslinker] The photosensitive resin composition of the present invention may further contain a cationically polymerizable crosslinking agent as component (D), which is capable of undergoing a cationic polymerization reaction with the epoxy groups of component (A) and serves to facilitate pattern formation and further increase the strength of the resin film after photocuring.

[0117] The crosslinking agent is preferably a compound having a molecular weight of 100 to 15,000, more preferably a compound having a molecular weight of 200 to 1,000. A molecular weight of 100 or more can provide sufficient photocurability, while a molecular weight of 15,000 or less is preferred because it does not deteriorate the heat resistance of the composition after photocuring. The compound may be a resin (polymer), and in that case, the molecular weight is the weight-average molecular weight (Mw).

[0118] The cationically polymerizable crosslinking agent is preferably a compound having a functional group selected from an epoxy group, an oxetane group, and a vinyl ether group. These compounds may be used alone or in combination of two or more.

[0119] When component (D) is contained, the content is preferably 0.5 to 100 parts by mass, more preferably 0.5 to 60 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of component (A). When the content of component (D) is 0.5 parts by mass or more, sufficient curability is obtained upon light irradiation. The component (D) can be used alone or in combination of two or more types.

[0120] [(E) Solvent] The photosensitive resin composition of the present invention may further contain a solvent as component (E). The solvent is not particularly limited as long as it can dissolve the above-mentioned components. Adding a solvent can improve the coatability of the photosensitive resin composition.

[0121] As such a solvent, organic solvents are preferred because they have excellent solubility for these components. Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. These organic solvents can be used alone or in combination of two or more. Particularly preferred are ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixed solvents thereof, which have excellent solubility for the photocationic polymerization initiator.

[0122] From the viewpoint of compatibility and viscosity of the photosensitive resin composition, the content of the component (E) is preferably 25 to 85 mass %, more preferably 35 to 75 mass %, based on the total amount of the photosensitive resin composition.

[0123] [Photosensitive resin film] The photosensitive resin film of the present invention is a dried product of the photosensitive resin composition described above.

[0124] [Pattern Forming Method Using Photosensitive Resin Composition] The pattern forming method using the photosensitive resin composition of the present invention comprises the steps of: (i) applying the photosensitive resin composition described above onto a substrate to form a photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern. Includes.

[0125] Step (i) is a step of applying the photosensitive resin composition described above onto a substrate, such as a silicon wafer, a glass wafer, a quartz wafer, or a micro LED laminate substrate, to form a photosensitive resin film on the substrate.

[0126] The coating method may be a known method, such as dipping, spin coating, roll coating, etc. The amount of coating may be appropriately selected depending on the purpose, but it is preferable to coat the resulting photosensitive resin film so that the film thickness is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0127] To improve the film thickness uniformity on the substrate surface, a solvent may be dripped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be dripped can be appropriately selected depending on the purpose. Examples of the solvent include alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether. However, it is also possible to use the solvent used in the photosensitive resin composition.

[0128] Here, in order to efficiently carry out the photocuring reaction, the solvent and the like may be evaporated in advance by preheating (prebaking) as necessary. Prebaking can be carried out, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0129] Next, (ii) the photosensitive resin film is exposed to light. At this time, the exposure is preferably carried out with light having a wavelength of 10 to 600 nm, more preferably with light having a wavelength of 190 to 500 nm. Examples of light having such wavelengths include light of various wavelengths generated by a radiation generator, such as ultraviolet light such as g-line, h-line, and i-line, and far ultraviolet light (248 nm, 193 nm). Of these, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure dose is 10 to 10,000 mJ / cm. 2 is preferred.

[0130] The exposure may be performed through a photomask. The photomask may be, for example, a photomask having a desired pattern cut out therein. The material of the photomask is not particularly limited, but is preferably one that blocks light of the wavelengths described above. For example, a photomask having a chromium light-shielding film is preferably used, but is not limited thereto.

[0131] Furthermore, to enhance development sensitivity, post-exposure bake (PEB) may be performed. PEB is preferably performed at 40 to 150°C for 0.5 to 20 minutes. PEB crosslinks the exposed areas, forming an insolubilized pattern that is insoluble in the organic solvent used as the developer.

[0132] (iii) After exposure or PEB, the film is developed with a developer to dissolve and remove the unexposed areas to form a pattern. As the developer, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether are preferred, but solvents used in photosensitive resin compositions can also be used. Examples of development methods include conventional methods, such as immersing a patterned substrate in the developer. Thereafter, washing, rinsing, drying, etc. are performed as necessary to obtain a cured film having the desired pattern.

[0133] Furthermore, the film on which the pattern has been formed may be post-cured preferably at 100 to 200°C using an oven or a hot plate.

[0134] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin film obtained from a photosensitive resin composition on the support film.

[0135] The photosensitive dry film (support film and photosensitive resin film) is solid, and the photosensitive resin film does not contain a solvent, so there is no risk of bubbles due to volatilization remaining inside the photosensitive resin film or between the photosensitive resin film and the uneven substrate. The thickness of the photosensitive resin film is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 100 μm.

[0136] Furthermore, the viscosity and fluidity of the photosensitive resin film are closely related, and the photosensitive resin film can exhibit appropriate fluidity within an appropriate viscosity range, allowing it to penetrate deep into narrow gaps and strengthen adhesion to the substrate by softening the resin. Therefore, from the viewpoint of the fluidity of the photosensitive resin film, the viscosity of the photosensitive resin film is preferably 10 to 5,000 Pa·s, more preferably 30 to 2,000 Pa·s, and even more preferably 50 to 300 Pa·s at 80 to 120°C. Note that the viscosity in the present invention is measured using a rotational viscometer.

[0137] When the photosensitive dry film of the present invention is adhered to a substrate having irregularities, the photosensitive resin film conforms to the irregularities and covers the substrate, achieving high flatness. In particular, the photosensitive resin composition of the present invention is characterized by its softening performance, which allows it to achieve even higher flatness. Furthermore, when the photosensitive resin film is adhered to the substrate in a vacuum environment, the occurrence of gaps can be more effectively prevented.

[0138] The photosensitive dry film of the present invention can be produced by applying the photosensitive resin composition to a substrate and drying it to form a photosensitive resin film. A film coater typically used for producing adhesive products can be used as the photosensitive dry film production equipment. Examples of the film coater include a comma coater, a comma reverse coater, a multicoater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three-roll bottom reverse coater, and a four-roll bottom reverse coater.

[0139] A photosensitive dry film can be produced by applying the photosensitive resin composition to a predetermined thickness onto a support film as it is unwound from the unwinding shaft of the film coater and passed through the coater head of the film coater. The film is then passed through a hot air circulating oven at a predetermined temperature and time, and dried on the support film to form a photosensitive resin film. If necessary, the photosensitive dry film can be passed through a laminating roll at a predetermined pressure together with a protective film unwound from another unwinding shaft of the film coater to bond the photosensitive resin film on the support film to the protective film. The photosensitive dry film with a protective film can then be produced by winding the film onto the winding shaft of the film coater. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

[0140] The support film used in the photosensitive dry film of the present invention may be a single-layer film consisting of a single film or a multilayer film consisting of multiple laminated films. Examples of materials for the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Among these, polyethylene terephthalate is preferred, as it has moderate flexibility, mechanical strength, and heat resistance. These films may also be subjected to various treatments such as corona treatment or release agent coating. Commercially available products are available, such as Cerapeel WZ (RX) and Cerapeel BX8 (R) (manufactured by Toray Advanced Film Co., Ltd.), E7302 and E7304 (manufactured by Toyobo Co., Ltd.), Purex G31 and Purex G71T1 (manufactured by Teijin DuPont Films Co., Ltd.), PET38x1-A3, PET38x1-V8, and PET38x1-X08 (manufactured by Nippa Corporation).

[0141] The protective film may be the same as the support film described above, but polyethylene terephthalate and polyethylene, which have appropriate flexibility, are preferred. Commercially available products can be used for these, and examples of polyethylene terephthalate include those already exemplified, and examples of polyethylene include GF-8 (manufactured by Tamapoly Corporation) and PE Film 0 Type (manufactured by Nippa Corporation).

[0142] The thickness of each of the support film and the protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoints of stability in the production of the photosensitive dry film and prevention of curling around the core.

[0143] [Pattern formation method using photosensitive dry film] The pattern forming method using the photosensitive dry film of the present invention comprises the steps of: (i') a step of attaching the photosensitive resin film of the photosensitive dry film described above onto a substrate to form the photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern. Includes.

[0144] First, (i') a photosensitive dry film is used to adhere the photosensitive resin film to a substrate, thereby forming a photosensitive resin film on the substrate. That is, the photosensitive resin film of the photosensitive dry film is adhered to the substrate, thereby forming a photosensitive resin film on the substrate. Furthermore, if the photosensitive dry film has a protective film, the protective film is peeled off from the photosensitive dry film, and then the photosensitive resin film of the photosensitive dry film is adhered to the substrate. The adhering can be performed, for example, using a film adhering device.

[0145] The film laminating device is preferably a vacuum laminator. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is adhered to the substrate on a table at a predetermined temperature using a laminating roll at a predetermined pressure in a vacuum chamber at a predetermined vacuum level. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum level is preferably 50 to 500 Pa.

[0146] In order to efficiently carry out the photocuring reaction of the photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-baking may be performed as necessary, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0147] As in the case of the pattern formation method using the photosensitive resin composition, the photosensitive resin film attached to the substrate can be subjected to the following steps: (ii) exposing the photosensitive resin film to light, (iii) developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern, and, if necessary, (iv) performing a post-cure heat treatment. Note that the support film of the photosensitive dry film is peeled off before pre-baking or PEB, or removed by other methods, depending on the process.

[0148] The pattern formation method using the photosensitive resin composition or photosensitive dry film of the present invention allows for easy formation of fine patterns. For example, the photosensitive resin composition or photosensitive dry film of the present invention is formed to cover a large number of blue micro LEDs arranged on a substrate, and then fine patterns are formed to form cured films containing red and green quantum dots on the blue micro LEDs in parts, thereby enabling red and green light emission and enabling the production of full-color light-emitting devices.

[0149] [Light-emitting element] The light-emitting device of the present invention comprises a cured film obtained by the above-described pattern forming method. [Example]

[0150] The present invention will be described in more detail below with reference to synthesis examples, working examples, and comparative examples, but the present invention is not limited to the following examples. Note that InP / ZnSe / ZnS core-shell quantum dots were used as the quantum dot material, and the core synthesis method is as shown in [1-1] (red quantum dots) and [1-2] (green quantum dots) described below, and the subsequent shell synthesis method is as shown in [2].

[0151] [1-1] Red quantum dot core synthesis process Two flasks were prepared, and each was charged with 0.23 g (0.9 mmol) of palmitic acid, 0.088 g (0.3 mmol) of indium acetate, and 10 mL of 1-octadecene. The mixture was heated and stirred under reduced pressure at 100 °C for 1 hour to dissolve the raw materials and degassed. Nitrogen was then purged into the two flasks, and 0.75 mL (0.15 mmol) of a 0.2 M tristrimethylsilylphosphine / trioctylphosphine solution was added to each flask. One flask was then heated to 300 °C, and the solution was removed from the unheated flask and added to the flask heated to 300 °C, producing core particles.

[0152] [1-2] Green quantum dot core synthesis process A flask was charged with 0.23 g (0.9 mmol) of palmitic acid, 0.088 g (0.3 mmol) of indium acetate, and 10 mL of 1-octadecene, and the mixture was heated and stirred under reduced pressure at 100 °C for 1 hour to dissolve the raw materials. Nitrogen was then purged into the flask, and 0.75 mL (0.15 mmol) of a 0.2 M solution of tristrimethylsilylphosphine and trioctylphosphine was added. The mixture was then heated to 300 °C to generate core particles.

[0153] [2] Quantum dot shell layer synthesis process Next, 2.85 g (4.5 mmol) of zinc stearate and 15 mL of 1-octadecene were added to a separate flask, and the mixture was heated and stirred under reduced pressure at 100 °C for 1 hour while dissolving and degassing to prepare a 0.3 M zinc stearate octadecene solution. 3.0 mL (0.9 mmol) of this solution was added to the reaction solution after the core synthesis and cooled to 200 °C. Next, 0.474 g (6 mmol) of selenium and 4 mL of trioctylphosphine were added to a separate flask and heated to 150 °C to dissolve the solution, preparing a 1.5 M selenium trioctylphosphine solution. The reaction solution after the core synthesis step, which had been cooled to 200 °C, was heated to 320 °C over 30 minutes, and the selenium trioctylphosphine solution was added in 0.1 mL increments, totaling 0.6 mL (0.9 mmol), and the mixture was then maintained at 320 °C for 10 minutes before being cooled to room temperature. 0.44 g (2.2 mmol) of zinc acetate was added and dissolved by heating and stirring at 100°C under reduced pressure. The flask was again purged with nitrogen and heated to 230°C, after which 0.98 mL (4 mmol) of 1-dodecanethiol was added and maintained for 1 hour. The resulting solution was cooled to room temperature to produce a core-shell quantum dot-containing solution. The red core-shell quantum dot-containing solution synthesized via steps [1-1] to [2] is designated R-1, and the green core-shell quantum dot-containing solution synthesized via steps [1-2] to [2] is designated G-1.

[0154] [3] Ligand exchange process (3-mercaptopropyl)triethoxysilane was used as a ligand (ligand) having a substituent capable of forming a siloxane bond and a substituent that coordinates to the quantum dot surface. For the ligand exchange reaction, (3-mercaptopropyl)triethoxysilane (3.0 mmol) was added to the solution after the shell synthesis process, which had been cooled to room temperature, and the mixture was stirred for 24 hours. After the reaction was completed, ethanol was added to precipitate the reaction solution, which was then centrifuged and the supernatant was removed. The same purification was repeated and the solution was dispersed in toluene to produce a quantum dot solution coordinated with a ligand having a substituent capable of forming a siloxane bond. Quantum dots coordinated with a ligand having a substituent capable of forming a siloxane bond, synthesized using R-1, were designated R-2, and quantum dots coordinated with a ligand having a substituent capable of forming a siloxane bond, synthesized using G-1, were designated G-2.

[0155] [4-1] Surface coating layer formation process Triethoxysilylpropyl methacrylate (4.0 mmol), diphenylsilanediol (6 mmol), barium hydroxide monohydrate (0.15 mmol), and the quantum dot toluene solution after the ligand exchange process were added to a nitrogen-purged flask and heated and stirred at 65°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, and ethanol was added to precipitate the reaction solution. The precipitate was then centrifuged and the supernatant was removed. The mixture was dispersed in toluene and added to a flask previously purged with nitrogen. 2 parts by mass of the compound represented by formula (S-4) below and the quantum dot toluene solution were added per 100 parts by mass. Furthermore, 1 part by mass of Irgacure 1173 was added per 100 parts by mass of the compound represented by formula (S-4) below. After stirring and mixing, the mixture was irradiated with a UV LED at a wavelength of 365 nm and an output of 4000 mW / cm. 2 The solution was irradiated with light for 20 seconds. After the reaction was complete, ethanol was added to precipitate the solution, and after centrifugation, the supernatant was removed and the solution was dispersed in toluene again. PGMEA was then added, and the toluene solvent was removed by vacuum distillation to produce a quantum dot solution (solids concentration 60%) with a surface coating layer. Here, the quantum dots with a surface coating layer formed based on R-2 are designated R-S4, and the quantum dots with a surface coating layer formed based on G-2 are designated G-S4.

[0156] [4-2] Surface coating layer formation process Triethoxysilylpropyl methacrylate (4.0 mmol), diphenylsilanediol (6 mmol), barium hydroxide monohydrate (0.15 mmol), and the quantum dot toluene solution after the ligand exchange process were added to a nitrogen-purged flask and heated and stirred at 65°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, and ethanol was added to precipitate the reaction solution. The precipitate was then centrifuged and the supernatant was removed. The mixture was dispersed in toluene and added to a flask previously purged with nitrogen. 2 parts by mass of the compound represented by formula (S-5) below and the quantum dot toluene solution were added per 100 parts by mass. Furthermore, 1 part by mass of Irgacure 1173 was added per 100 parts by mass of the compound represented by formula (S-5) below. After stirring and mixing, the mixture was irradiated with a UV LED at a wavelength of 365 nm and an output of 4000 mW / cm. 2 The solution was irradiated with light for 20 seconds. After the reaction was complete, ethanol was added to precipitate the solution, and after centrifugation, the supernatant was removed and the solution was dispersed in toluene again. PGMEA was then added, and the toluene solvent was removed by vacuum distillation to produce a quantum dot solution (60% solids concentration solution) with a surface coating layer. Here, the quantum dots with a surface coating layer formed based on R-2 are designated R-S5, and the quantum dots with a surface coating layer formed based on G-2 are designated G-S5.

[0157] [5] Synthesis of silicone resin [Synthesis Example 1] Synthesis of Resin 1 A 10L flask equipped with a stirrer, thermometer, nitrogen purge device, and reflux condenser was charged with 238.5g (0.90 mol) of compound (S-4) and 16.2g (0.10 mol) of compound (S-3b), followed by 2,000g of toluene and heating to 70°C. Then, 1.0g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 184.3g (0.95 mol) of compound (S-1) and 79.3g (0.05 mol) of compound (S-2b) were added dropwise over 1 hour (total hydrosilyl groups / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After the dropwise addition, the mixture was heated to 100°C and aged for 6 hours. The toluene was then removed from the reaction solution by distillation under reduced pressure to obtain Resin 1 (siloxane content 15.3% by mass; the siloxane content is calculated from the charged amount). Resin 1 had an Mw of 10,000. 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the polymer contained repeating units A1 to A4.

[0158] [Synthesis Example 2] Synthesis of Resin 2 A 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 132.5 g (0.50 mol) of compound (S-4) and 60.5 g (0.50 mol) of compound (S-3a), followed by 2,000 g of toluene, and heated to 70°C. Subsequently, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0.10 mol) of compound (S-2a) were added dropwise over 1 hour (total hydrosilyl groups / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours. The toluene was then distilled off under reduced pressure from the reaction solution to obtain resin 2 (siloxane content 45.1% by mass). The Mw of resin 2 was 42,000. Resin 2 was obtained from 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the polymer contained repeating units A1 to A4.

[0159] [Synthesis Example 3] Synthesis of Resin 3 A 10-L flask equipped with a stirrer, thermometer, nitrogen purge system, and reflux condenser was charged with 159.0 g (0.60 mol) of compound (S-4) and 48.4 g (0.40 mol) of compound (S-3a), followed by 2,000 g of toluene, and heated to 70°C. Subsequently, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration 0.5% by mass) was added, and 155.2 g (0.80 mol) of compound (S-1) and 604.0 g (0.20 mol) of compound (S-2a) were added dropwise over 1 hour (total hydrosilyl groups / total carbon-carbon double bonds = 1 / 1 (molar ratio)). After completion of the dropwise addition, the mixture was heated to 100°C and aged for 6 hours. The toluene was then distilled off under reduced pressure from the reaction solution to obtain resin 3 (siloxane content 62.5% by mass). The Mw of resin 3 was 80,000. Resin 3 was obtained from 1 It was confirmed by 1 H-NMR (manufactured by Bruker) that the polymer contained repeating units A1 to A4.

[0160] The compounds (S-1), (S-2a), (S-2b), (S-3a), (S-3b), (S-4), and (S-5) used in the above synthesis examples are as follows. [ka]

[0161] [6] Preparation of photosensitive resin composition and its evaluation [Examples 1 to 12 and Comparative Examples 1 to 24] Each component was blended according to the blending amounts shown in Tables 1 to 4, then stirred and mixed at room temperature, and microfiltered through a 1.0 μm glass filter to obtain photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 24.

[0162] [Table 1]

[0163] [Table 2]

[0164] [Table 3]

[0165] [Table 4]

[0166] In Tables 1 to 4, the cationic photopolymerization initiators B-1 and B-2 used are as follows. [ka]

[0167] In Tables 1 to 4, the crosslinking agents D-1 and D-2 used are as follows. [ka]

[0168] In Tables 1 to 4, quantum dot R-3 is S-BE030 manufactured by Shoei Chemical Co., Ltd. (particle size 5 to 10 nm, material InP:ZnS:SeZn = 25:50:25), R-4 is 900514-1ML manufactured by Aldrich (particle size 5 to 10 nm, material CdSe (core) / CdS (shell) core-shell type), G-3 is S-BE029 manufactured by Shoei Chemical Co., Ltd. (particle size 3 to 5 nm, material InP:ZnS:SeZn = 25:50:25), and G-4 is 900511-1ML manufactured by Aldrich (particle size 3 to 5 nm, material CdSe (core) / CdS (shell) core-shell type).

[0169] [7] Preparation of photosensitive dry film Using a die coater as the film coater and a polyethylene terephthalate film (38 μm thick) as the support film, each of the photosensitive resin compositions listed in Tables 1 to 4 was applied onto the support film. The film was then dried by passing it through a hot air circulating oven (4 m long) set at 100°C for 5 minutes, forming a photosensitive resin film on the support film to a thickness of 30 μm, thereby obtaining a photosensitive dry film. A polyethylene film (50 μm thick) was attached as a protective film to the photosensitive resin film using a laminating roll at a pressure of 1 MPa, producing a photosensitive dry film with a protective film.

[0170] [8] Evaluation of photosensitive resin film (1) Confirmation of aggregates in the photosensitive resin film The protective film was peeled off from the photosensitive dry film with the protective film, and aggregates in the photosensitive dry film were confirmed using an optical microscope. The results are shown in Tables 5 to 8, with aggregates of 1 μm or more in size marked with an × and aggregates of no aggregates or less than 1 μm in size marked with an ○. (2) Pattern formation and its evaluation The protective film was peeled off from the photosensitive dry film with the protective film. Using a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation), the vacuum level in the vacuum chamber was set to 80 Pa, and the photosensitive resin film on the support film was adhered to a silicon wafer. The temperature condition was 100°C. After returning to normal pressure, the substrate was removed from the vacuum laminator and the support film was peeled off. Next, to enhance adhesion to the substrate, the substrate was prebaked on a hot plate at 110°C for 4 minutes. The resulting photosensitive resin film was exposed to light using an i-line stepper NSR-2205i11D (manufactured by Nikon Corporation) through a mask to form a square island pattern with a 1:1 pitch between adjacent patterns. After irradiation, post-exposure baking (PEB) was performed on a hot plate at 120°C for 5 minutes, followed by cooling. The substrate was then spray-developed with PGMEA for 90 seconds to form a pattern. The substrate was then post-cured in an oven at 160°C for 3 hours with a nitrogen purge. The resulting island patterns, each measuring 100 μm, 50 μm, 30 μm, 20 μm, or 15 μm on a side, were then observed using a scanning electron microscope (SEM). The smallest pattern size that was not connected to adjacent island patterns (with a 1:1 pitch) was defined as the limiting resolution. Patterns that did not reach 100 μm in resolution or that underwent development peeling were rated as ×. The results are shown in Tables 5 to 8.

[0171] (3) Evaluation of the luminescence characteristics of the formed pattern Using a LabRAM HR Evolution manufactured by Horiba Technoservice Co., Ltd., the patterned sample prepared in (2) above was irradiated with 457 nm laser light (0.03 mW), and the photoconverted island pattern area was measured to measure the luminescence intensity, emission wavelength, and half-width of the photoconverted light. The same measurements were also performed on the sample prepared in (2) above after the lamination and support film peeling steps to measure the luminescence intensity of the photoconverted light. The results are shown in Tables 5 to 8 (M: million).

[0172] (4) Reliability test evaluation A glass substrate was coated with the photosensitive resin composition listed in Tables 1 to 4 using a spin coater to a thickness of 80 μm. To remove the solvent from the composition, the substrate was placed on a hot plate and heated and dried at 110°C for 10 minutes. The resulting photosensitive resin film was exposed to light using a contact aligner exposure system at 365 nm to form a square island pattern with sides of 1 cm. After irradiation, the substrate was subjected to PEB at 120°C for 5 minutes on a hot plate and then cooled. The substrate was then spray-developed with PGMEA for 180 seconds to form a pattern. The substrate was then post-cured in an oven at 160°C for 3 hours with a nitrogen purge. The patterned sample was then treated at 85°C / 85% RH for 500 hours, after which the emission intensity was measured in the same manner as in (3) above, and the rate of decrease from the initial value was determined. The results are shown in Tables 5 to 8.

[0173] [Table 5]

[0174] [Table 6]

[0175] [Table 7]

[0176] [Table 8]

[0177] The above results demonstrate that the photosensitive resin composition of the present invention can form a good photosensitive coating or photosensitive dry film free of aggregates (or containing very little aggregates, if any), and can provide a cured coating that has high lithography resolution, high luminescence properties that do not change before and after the lithography process, and good reliability (low rate of change in luminescence intensity in a constant temperature and humidity test), and is suitable for light-emitting devices.

[0178] The present specification includes the following aspects. [1]: A photosensitive resin composition, (A) a silicone resin having a glycidyl group, (B) a photocationic polymerization initiator, and (C) Quantum dots wherein the quantum dots have a surface coating layer containing siloxane. [2]: The photosensitive resin composition according to the above [1], wherein the component (C) contains a skeleton having a glycidyl group in the surface coating layer. [3]: The photosensitive resin composition according to the above [1] or [2], wherein the component (A) contains repeating units represented by the following formulae (A1) to (A4): [ka] [In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer of 1 to 600. When m is an integer of 2 or greater, each R 3 may be the same or different, and each R 4 may be the same or different. 1 , a 2 , a 3 and a 4 is 0 1 <1, 0 2 <1, 0 3 <1, 0 4 <1, and a 1 +a 2 +a 3 +a 4 = 1. 1 is a divalent group represented by the following formula (X1): 2 is a divalent group represented by the following formula (X2). [ka] (In the formula, R 11 and R 12 ​​​​are each independently a hydrogen atom or a methyl group. 1 and n 2 are each independently an integer of 0 to 7. 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain an ester bond or an ether bond between its carbon atoms. [ka] (In the formula, R 21 and R 22 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom, and k is an integer of 0 to 10.) [4]: The photosensitive resin composition according to any one of [1], [2], or [3] above, wherein the quantum dots of component (C) have ligands coordinated to their surfaces, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands have one or more of an amino group, a thiol group, a carboxy group, a phosphino group, a phosphine oxide group, and an ammonium ion. [5]: The photosensitive resin composition according to [1], [2], [3] or [4], wherein the component (C) is contained in an amount of 5 to 80% by mass in the photosensitive resin composition. [6]: The photosensitive resin composition according to [1], [2], [3], [4] or [5], further comprising (D) a cationically polymerizable crosslinking agent. [7]: The photosensitive resin composition according to [1], [2], [3], [4], [5] or [6], further comprising (E) a solvent. [8]: A photosensitive resin film characterized by being a dried product of the photosensitive resin composition according to [1], [2], [3], [4], [5], [6] or [7]. [9]: A photosensitive dry film comprising a support film and the photosensitive resin film of [8] above on the support film.

[10] : A pattern forming method, (i) applying the photosensitive resin composition of [1], [2], [3], [4], [5], [6] or [7] above onto a substrate to form a photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern. A pattern forming method comprising the steps of:

[11] : A pattern forming method, (i') a step of attaching the photosensitive resin film of the photosensitive dry film [9] above onto a substrate to form the photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern. A pattern forming method comprising the steps of:

[12] : A light-emitting device comprising a cured coating obtained by the pattern formation method of

[10] or

[11] above.

[0179] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A photosensitive resin composition comprising: (A) a silicone resin having a glycidyl group, (B) a photocationic polymerization initiator, and (C) Quantum dots wherein the quantum dots have a surface coating layer containing siloxane.

2. 2. The photosensitive resin composition according to claim 1, wherein the component (C) contains a skeleton having a glycidyl group in the surface coating layer.

3. 2. The photosensitive resin composition according to claim 1, wherein the component (A) contains repeating units represented by the following formulas (A1) to (A4): 【Chemical 1】 [In the formula, R １ ~R ４ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Each m is independently an integer of 1 to 600. When m is an integer of 2 or greater, each R ３ may be the same or different, and each R ４ may be the same or different from each other. １ , a ２ , a ３ and a ４ is 0<a １ <1, 0<a ２ <1, 0<a ３ <1, 0<a ４ <1, and a １ +a ２ +a ３ +a ４ = 1. １ is a divalent group represented by the following formula (X1): ２ is a divalent group represented by the following formula (X2). 【Chemistry 2】 (In the formula, R １１ and R １２ are each independently a hydrogen atom or a methyl group. １ and n ２ are each independently an integer of 0 to 7. １３ is a divalent hydrocarbon group having 1 to 8 carbon atoms, which may contain an ester bond or an ether bond between its carbon atoms. 【Chemistry 3】 (In the formula, R ２１ and R ２２ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom, and k is an integer of 0 to 10.

4. 2. The photosensitive resin composition according to claim 1, wherein the quantum dots of component (C) have ligands coordinated to their surfaces, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands have one or more of an amino group, a thiol group, a carboxy group, a phosphino group, a phosphine oxide group, and an ammonium ion.

5. 2. The photosensitive resin composition according to claim 1, wherein the component (C) is contained in an amount of 5 to 80% by mass in the photosensitive resin composition.

6. 2. The photosensitive resin composition according to claim 1, further comprising (D) a cationic polymerizable crosslinking agent.

7. 2. The photosensitive resin composition according to claim 1, further comprising (E) a solvent.

8. A photosensitive resin film, which is a dried product of the photosensitive resin composition according to any one of claims 1 to 7.

9. A photosensitive dry film comprising a support film and the photosensitive resin film according to claim 8 on the support film.

10. A pattern formation method, comprising: (i) applying the photosensitive resin composition according to any one of claims 1 to 7 onto a substrate to form a photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern. A pattern forming method comprising the steps of:

11. A pattern formation method, comprising: (i') a step of attaching the photosensitive resin film of the photosensitive dry film according to claim 9 onto a substrate to form the photosensitive resin film on the substrate; (ii) exposing the photosensitive resin film to light; and (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the unexposed areas to form a pattern. A pattern forming method comprising the steps of:

12. A light-emitting device comprising a cured film obtained by the pattern formation method according to claim 10.

13. A light-emitting device comprising a cured film obtained by the pattern formation method according to claim 11.

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