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

Abstract

The present invention is a photosensitive resin composition characterized by containing (A) a silicone resin having a glycidyl group, (B) a cationic photopolymerization initiator, and (C) a polymer obtained by copolymerizing quantum dots coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolysate, or a condensate thereof. As a result, provided are: a photosensitive resin composition capable of easily forming a coating film having high lithography resolution and good light-emitting characteristics; a photosensitive resin coating film and a photosensitive dry film obtained using the photosensitive resin composition; a pattern forming method using the photosensitive resin coating film and the photosensitive dry film; and a light-emitting element provided with a cured coating film obtained using the photosensitive resin coating film.

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 element. Background Art

[0002] In order to form a display including sub-pixels of red, green, and blue, various methods have been proposed. As one of these methods, there is a method of converting light from an LED array from blue, that is, light of a shorter wavelength, to red and green, that is, light of a longer wavelength, by a color conversion structure. As the substance responsible for this color conversion, quantum dots are used.

[0003] In recent years, the LED array has been miniaturized, and Micro-LED displays using the LED array have received attention. As a method of forming a color conversion structure on the LED array, there is a photolithography process using a photosensitive material (Patent Document 1), but in recent years, further miniaturization has been required to adapt to small displays. In addition, from the perspective of the clarity of the display, high requirements are also placed on the light emission characteristics.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2021-089347

[0007] Non-Patent Documents

[0008] Non-Patent Document 1: Journal of Photopolymer Science and Technology, Vol 23, 2010, p115-119 Summary of the Invention

[0009] (1) Technical Problem to be Solved

[0010] In view of the above circumstances, the present invention aims to provide a photosensitive resin composition capable of easily forming a film having high lithographic resolution and good light emission characteristics, a photosensitive resin film obtained using the photosensitive resin composition, a photosensitive dry film, a pattern forming method using the photosensitive resin composition and the photosensitive resin film, and a light emitting element including a cured film obtained using the photosensitive resin film.

[0011] (2) Technical Solution

[0012] In order to solve the above technical problem, the present invention provides a photosensitive resin composition comprising:

[0013] (A) an organosilicon resin having a glycidyl group,

[0014] (B) A cationic photopolymerization initiator, and

[0015] (C) A polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof.

[0016] When such a photosensitive resin composition is used, a film having high lithographic resolution and good light-emitting characteristics can be easily formed.

[0017] In addition, in the present invention, it is preferable that the component (C) contains a skeleton having a glycidyl group.

[0018] When such a photosensitive resin composition is used, the quantum dots are inhibited from coming out during development, and high light-emitting characteristics of the pattern can be obtained.

[0019] In addition, in the present invention, it is preferable that the component (A) contains repeating units represented by the following formulas (A1) to (A4).

[0020] [Chemical formula 1]

[0021]

[0022] [In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may optionally contain a heteroatom. m is each independently an integer of 1 to 600. When m is an integer of 2 or more, each R 3 may be the same or different from each other, and each R 4 may be the same or different from each other. a 1 , a 2 , a 3 and a 4 are numbers satisfying 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. X 1 is a divalent group represented by the following formula (X1). X 2 is a divalent group represented by the following formula (X2).

[0023] [Chemical formula 2]

[0024]

[0025] (In the formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group. n1 and n 2 are each independently an integer of 0 to 7. R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms, optionally containing an ester bond or an ether bond between its carbon atoms.)

[0026] [Chemical Formula 3]

[0027]

[0028] (In formula (X2), R 21 and R 22 are each independently an alkyl group having 1 to 20 carbon atoms optionally containing a hydrogen atom or a heteroatom. k is an integer of 0 to 10.)]

[0029] If such a photosensitive resin composition is used, the obtained cured film has high reliability.

[0030] In addition, in the present invention, the coordination substituents of the silane coupling agent, which is particularly preferably the component (C), preferably have any one or more of an amino group, a thiol group, a carboxyl group, a phosphino group, a phosphine oxide group, and an ammonium ion.

[0031] If such a photosensitive resin composition is used, the quantum dots are inhibited from coming out during development, and high luminescence characteristics of the pattern can be obtained.

[0032] In addition, in the present invention, it is preferred that the photosensitive resin composition contains 5 to 80% by mass of the component (C).

[0033] If such a photosensitive resin composition is used, fine pattern formation can be carried out while maintaining good luminescence characteristics.

[0034] In addition, in the present invention, it is preferred to further contain (D) a cationic polymerization crosslinking agent.

[0035] If such a photosensitive resin composition is used, the strength of the resin film after photocuring can be further improved.

[0036] In addition, in the present invention, it is preferred to further contain (E) a solvent.

[0037] If such a photosensitive resin composition is used, the coatability can be improved.

[0038] In addition, the present invention provides a photosensitive resin film, which is a dried product of the above-described photosensitive resin composition.

[0039] If such a photosensitive resin composition is used, a film having high lithographic resolution and good luminescence characteristics will be obtained.

[0040] In addition, the present invention provides a photosensitive dry film, which includes a support film and the above-described photosensitive resin coating film on the support film.

[0041] If such a photosensitive dry film is used, it has high lithographic resolution and good light-emitting characteristics.

[0042] In addition, the present invention provides a method for forming a pattern, which includes:

[0043] (i) A step of coating the above-described photosensitive resin composition on a substrate to form a photosensitive resin coating film on the substrate;

[0044] (ii) A step of exposing the photosensitive resin coating film; and

[0045] (iii) A step of developing the exposed photosensitive resin coating film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

[0046] In addition, the present invention provides a method for forming a pattern, which includes:

[0047] (i’) A step of attaching the photosensitive resin coating film of the above-described photosensitive dry film to a substrate to form the photosensitive resin coating film on the substrate;

[0048] (ii) A step of exposing the photosensitive resin coating film; and

[0049] (iii) A step of developing the exposed photosensitive resin coating film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

[0050] If such methods for forming a pattern are used, a pattern can be formed with high lithographic resolution, and a pattern of a coating film having good light-emitting characteristics can be obtained.

[0051] In addition, the present invention provides a light-emitting element, which includes a cured coating film having a pattern formed on the above-described photosensitive resin coating film.

[0052] In addition, the present invention provides a light-emitting element, which includes a cured coating film having a pattern formed on the photosensitive resin coating film of the above-described photosensitive dry film.

[0053] If such a light-emitting element is used, it has high lithographic resolution and good light-emitting characteristics.

[0054] (III) Advantageous Effects

[0055] The photosensitive resin composition of the present invention can easily form a film having high resolution and good light-emitting characteristics by containing an organosilicon resin having a glycidyl group, a cationic photopolymerization initiator, and a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof, and is thus suitable for light-emitting elements. Detailed Description of the Invention

[0056] As described above, there is a need to develop a photosensitive resin composition capable of easily forming a film having high photolithographic resolution and good light-emitting characteristics, a photosensitive resin film obtained by using the photosensitive resin composition, a photosensitive dry film, a method for forming a pattern using the photosensitive resin composition and the photosensitive dry film, and a light-emitting element including a cured film obtained by using the photosensitive resin film.

[0057] The inventors of the present application have conducted in-depth research on the above technical problems and found that a photosensitive resin composition can easily form a film (photosensitive resin film) having high photolithographic resolution and good light-emitting characteristics, and thus completed the present invention. The photosensitive resin composition is characterized in that it contains: (A) an organosilicon resin having a glycidyl group, (B) a cationic photopolymerization initiator, and (C) a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof.

[0058] That is, the present invention is a photosensitive resin composition, which contains:

[0059] (A) an organosilicon resin having a glycidyl group,

[0060] (B) a cationic photopolymerization initiator, and

[0061] (C) a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof.

[0062] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0063] [Photosensitive Resin Composition]

[0064] The photosensitive resin composition of the present invention contains: (A) an organosilicon resin having a glycidyl group, (B) a cationic photopolymerization initiator, and (C) a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof. It may further contain other components such as (D) a cationic polymerization crosslinking agent, (E) a solvent, etc. as needed. Hereinafter, each component constituting the photosensitive resin composition will be described.

[0065] [(A) Organosilicon resin having glycidyl group]

[0066] The (A) organosilicon resin having glycidyl group used in the present invention is not particularly limited as long as it has a glycidyl group.

[0067] As such an organosilicon resin, it preferably contains repeating units represented by the following formulas (A1) to (A4) (hereinafter, also referred to as repeating units A1 to A4, respectively).

[0068] [Chemical formula 4]

[0069]

[0070] In formulas (A2) and (A4), R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may optionally contain a heteroatom. m is each independently an integer of 1 to 600. When m is an integer of 2 or more, each R 3 may be the same or different from each other, and each R 4 may be the same or different from each other. In repeating units A2 and A4, when there are two or more siloxane units, all the siloxane units may be the same, or may contain two or more different siloxane units. When containing two or more different siloxane units (i.e., when m is an integer of 2 or more), the siloxane units may be randomly bonded, may be alternately bonded, or may contain blocks of multiple same siloxane units.

[0071] The monovalent hydrocarbon group may be any of linear, branched, and cyclic types. As specific examples thereof, monovalent aliphatic hydrocarbon groups such as alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms can be cited.

[0072] As the alkyl group, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, norbornyl, adamantyl, etc. can be cited. As the alkenyl group, vinyl, propenyl, butenyl, pentenyl, etc. can be cited.

[0073] In addition, the monovalent aliphatic hydrocarbon group may contain a heteroatom. Specifically, a part or all of the hydrogen atoms of the monovalent aliphatic hydrocarbon group may be substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc., and a carbonyl group, an ether bond, a thioether bond, etc. may be interposed between its carbon atoms. As such a monovalent aliphatic hydrocarbon group containing a heteroatom, 2-oxocyclohexyl, etc. can be cited.

[0074] Examples of the aryl group include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, naphthyl, biphenyl, terphenyl, etc. Examples of the aralkyl group include benzyl, phenethyl, etc.

[0075] In addition, the monovalent aromatic hydrocarbon group may contain a heteroatom. Specifically, part 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, etc.

[0076] Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy, n-pentyloxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, norbornyloxy, adamantyloxy, etc.

[0077] Examples of the alkylthio group having 1 to 10 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, cyclopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, cyclobutylthio, n-pentylthio, cyclopentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, norbornylthio, adamantylthio, etc.

[0078] Examples of the aryloxy group having 6 to 20 carbon atoms include phenyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 2-ethylphenyloxy, 3-ethylphenyloxy, 4-ethylphenyloxy, 4-tert-butylphenyloxy, 4-butylphenyloxy, dimethylphenyloxy, naphthyloxy, biphenyloxy, terphenyloxy, etc.

[0079] Examples of the arylthio group having 6 to 20 carbon atoms include phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-ethylphenylthio, 3-ethylphenylthio, 4-ethylphenylthio, 4-tert-butylphenylthio, 4-butylphenylthio, dimethylphenylthio, naphthylthio, biphenylthio, terphenylthio, etc.

[0080] For example, as the aryl group substituted by the above groups, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 3-tert-butoxyphenyl, 4-tert-butoxyphenyl, biphenyloxyphenyl, biphenylthiophenyl, etc. can be cited.

[0081] The number of carbon atoms of the monovalent aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 8. In addition, the number of carbon atoms of the monovalent aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10.

[0082] Among them, as R 1 ~R 4 , methyl, ethyl, n-propyl or phenyl is preferred, and methyl or phenyl is more preferred.

[0083] In formulas (A2) and (A4), m are each independently an integer of 1 to 600, preferably an integer of 8 to 100.

[0084] In formulas (A1) to (A4), a 1 , a 2 , a 3 and a 4 are numbers satisfying 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. Preferably, they are numbers satisfying 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 they are numbers satisfying 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 a1 +a 2 +a 3 +a 4 a number equal to 1.

[0085] In formulas (A1) and (A2), X 1 is a divalent group represented by the following formula (X1).

[0086] [Chemical formula 5]

[0087]

[0088] In formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group. n 1 and n 2 are each independently an integer from 0 to 7.

[0089] 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 any of linear, branched, and cyclic, and specific examples thereof include 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, butane-1,4-diyl, and other alkanediyls. In addition, an ester bond or an ether bond may be contained between the carbon atoms of the divalent hydrocarbon group. Among them, as R 13 , methylene or ethylene is preferred, and methylene is more preferred.

[0090] In formulas (A3) and (A4), X 2 is a divalent group represented by the following formula (X2).

[0091] [Chemical formula 6]

[0092]

[0093] In formula (X2), R 21 and R 22 are each independently an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a heteroatom. As the alkyl group, the same groups as those described in the description of R 1 ~R 4 can be cited. As R 21 and R 22 , a hydrogen atom or a methyl group is preferred.

[0094] In formula (X2), k is an integer from 0 to 10, preferably 0.

[0095] The weight-average molecular weight (Mw) of the component (A) of the present invention is preferably from 3,000 to 500,000, more preferably from 5,000 to 200,000. When Mw is within the above range, the polymer can be obtained in solid form, and film-forming properties can also be ensured. In addition, in the present invention, Mw is a polystyrene conversion measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.

[0096] The component (A) of the present invention may be formed by randomly bonding the repeating units A1 to A4, may be formed by alternately bonding the repeating units A1 to A4, or may contain blocks of multiple units of each.

[0097] In the present invention, relative to the total amount of the photosensitive resin composition, the (A) organosilicon resin having a glycidyl group is preferably in the range of 10 to 90% by mass. More preferably, it is 15 to 85% by mass.

[0098] [Preparation method of the (A) organosilicon resin having a glycidyl group]

[0099] The component (A) of the present invention can be prepared by subjecting the compound represented by the following formula (1) (hereinafter also referred to as compound (1)), the compound represented by the following formula (2) (hereinafter also referred to as compound (2)), the compound represented by the following formula (3) (hereinafter also referred to as compound (3)), and the compound represented by the following formula (4) (hereinafter also referred to as compound (4)) to addition polymerization in the presence of a metal catalyst.

[0100] [Chemical formula 7]

[0101]

[0102] (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.)

[0103] As the metal catalyst, a single platinum group metal such as platinum (including platinum black), rhodium, palladium, etc. can be used; platinum chlorides such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, Na2HPtCl4·xH2O (wherein x is preferably an integer of 0 to 6, particularly preferably 0 or 6), chloroplatinic acid and chloroplatinate salts; alcohol-modified chloroplatinic acid (such as the substance described in U.S. Patent No. 3,220,972); a complex of chloroplatinic acid and an olefin (such as the substances described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, U.S. Patent No. 3,775,452); a substance obtained by supporting platinum black or a platinum group metal such as palladium on a carrier such as alumina, silica, carbon, etc.; a rhodium-olefin complex; tris(triphenylphosphine)rhodium chloride (so-called Wilkinson's catalyst); a complex of platinum chloride, chloroplatinic acid or chloroplatinate salt and a vinyl-containing siloxane (especially a vinyl-containing cyclic siloxane), etc.

[0104] The amount of the catalyst used is a catalytic amount, and generally in the total mass of compounds (1) to (4), it is preferably 0.001 to 0.1% by mass in terms of platinum group metal.

[0105] In the polymerization reaction, a solvent can be used as needed. As the solvent, for example, hydrocarbon solvents such as toluene and xylene are preferably used. As the polymerization conditions, from the viewpoint of not deactivating the catalyst and being able to complete the polymerization in a short time, the polymerization temperature is, for example, 40 to 150 °C, particularly preferably 60 to 120 °C. The polymerization time varies depending on the type and amount of the raw material compounds, but in order to prevent moisture from entering the polymerization system, it is preferably completed in approximately 0.5 to 100 hours, more preferably in 0.5 to 30 hours. After the polymerization reaction is completed in the above manner, when a solvent is used, the solvent is distilled off, whereby an organosilicon resin (A) having a glycidyl group can be obtained.

[0106] The reaction method is not particularly limited. Compounds (3) and (4) can be first mixed and heated, then a metal catalyst is added to the mixed solution, and then compounds (1) and (2) are added dropwise over 0.1 to 5 hours.

[0107] Each raw material compound may be blended in the following manner: relative to the total number of carbon-carbon double bonds in compound (3) and compound (4), in terms of molar ratio, the hydrosilyl groups in compound (1) and compound (2) are preferably blended in a manner such that the ratio is 0.67 to 1.67, more preferably 0.83 to 1.25. The Mw of component (A) of the present invention can be controlled by using a monoallyl compound such as o-allylphenol, or a monohydrosilane or monohydrosiloxane such as triethylsilane as a molecular weight regulator.

[0108] In the present invention, the organosilicon resin (A) having a glycidyl group may be used alone or two or more thereof may be used simultaneously.

[0109] [(B) Cationic photoinitiator]

[0110] As the cationic photoinitiator of component (B), any substance that decomposes upon light irradiation to generate a catalyst for cationic polymerization is not particularly limited, but a substance that generates a catalyst for cationic polymerization upon irradiation with light having a wavelength of 190 to 500 nm is preferred. The (B) cationic photoinitiator is used as a curing catalyst. Examples of the cationic photoinitiator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate derivatives, imide-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, and the like.

[0111] Examples of the onium salt include sulfonium salts represented by the following formula (B1) or iodonium salts represented by the following formula (B2).

[0112] [Chemical formula 8]

[0113]

[0114] In formulas (B1) and (B2), R 101 ~R 105 are each independently an alkyl group having 1 to 12 carbon atoms that may have a substituent, an aryl group having 6 to 12 carbon atoms that may have a substituent, or an aralkyl group having 7 to 12 carbon atoms that may have a substituent. A - is a non-nucleophilic counterion.

[0115] The alkyl group can be any one of linear, branched, or cyclic. Specific examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc. Examples of the aryl group include phenyl, naphthyl, biphenyl, etc. Examples of the aralkyl group include benzyl, phenethyl, etc.

[0116] Examples of the substituent include an oxo group, linear, branched, or cyclic alkoxy groups having 1 to 12 carbon atoms, linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 24 carbon atoms, aralkyl groups having 7 to 25 carbon atoms, aryloxy groups having 6 to 24 carbon atoms, arylthio groups having 6 to 24 carbon atoms, etc.

[0117] As for R 101 ~R 105 , preferably alkyl groups such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, 2-oxocyclohexyl, etc., which may have substituents; aryl groups such as phenyl, naphthyl, biphenyl, o-methoxyphenyl, m-methoxyphenyl, or p-methoxyphenyl, ethoxyphenyl, m-tert-butoxyphenyl or p-tert-butoxyphenyl, 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenyloxyphenyl, biphenylthiophhenyl, etc., which may have substituents; aralkyl groups such as benzyl, phenethyl, etc., which may have substituents. Among them, aryl groups and aralkyl groups that may have substituents are more preferred.

[0118] Examples of the non-nucleophilic counterion include halide ions such as chloride ion, bromide ion, etc.; fluoroalkane sulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion, nonafluorobutanesulfonate ion, etc.; aryl sulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, 1,2,3,4,5-pentafluorobenzenesulfonate ion, etc.; alkane sulfonate ions such as methanesulfonate ion, butanesulfonate ion, etc.; fluoroalkane sulfimide ions such as trifluoromethanesulfonimide ion, etc.; fluoroalkane sulfonylmethylated ions such as tris(trifluoromethanesulfonyl)methylated ion, etc.; borate ions such as tetraphenylborate ion, tetrakis(pentafluorophenyl)borate ion, etc.

[0119] Examples of the diazomethane derivative include the compound represented by the following formula (B3).

[0120] [Chemical formula 9]

[0121]

[0122] In formula (B3), R 111 and R112 Each independently is an alkyl or haloalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have substituents, or an aralkyl group having 7 to 12 carbon atoms.

[0123] The alkyl group may be any of linear, branched, or cyclic, and as specific examples thereof, groups the same as those exemplified in the description of R 101 ~R 105 can be cited. As the haloalkyl group, trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, nonafluorobutyl, etc. can be cited.

[0124] As the aryl group which may have substituents, phenyl; alkoxyphenyl such as 2-methoxyphenyl, 3-methoxyphenyl or 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl or 4-ethoxyphenyl, 3-tert-butoxyphenyl or 4-tert-butoxyphenyl; alkylphenyl such as 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl; haloaryl such as fluorophenyl, chlorophenyl, 1,2,3,4,5-pentafluorophenyl, etc. can be cited. As the aralkyl group, benzyl, phenethyl, etc. can be cited.

[0125] As the glyoxime derivative, a compound represented by the following formula (B4) can be cited.

[0126] [Chemical formula 10]

[0127]

[0128] In formula (B4), R 121 ~R 124 Each independently is an alkyl or haloalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have substituents, or an aralkyl group having 7 to 12 carbon atoms. Further, R 123 and R 124 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, and when forming a ring, the group formed by the bonding of R 123 and R 124 is a linear or branched alkylene group having 2 to 12 carbon atoms.

[0129] As the alkyl group, haloalkyl group, aryl group which may have substituents, and aralkyl group, groups the same as those exemplified as R 111 and R 112 can be cited. As the linear or branched alkylene group, ethylene, propylene, butylene, hexylene, etc. can be cited.

[0130] As the onium salt, specific examples include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyl iodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, 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, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, 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, triphenylsulfonium tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate, etc.

[0131] As the diazomethane derivative, specific examples include bis(phenylsulfonyl)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, etc.

[0132] As the glyoxime derivative, specifically, bis-o-(p-toluenesulfonyl)-α-dimethyglyoxime, 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-dimethyglyoxime, 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-o-(methanesulfonyl)-α-dimethyglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethyglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethyglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethyglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethyglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethyglyoxime, bis-o-(benzenesulfonyl)-α-dimethyglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethyglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethyglyoxime, bis-o-(xylenesulfonyl)-α-dimethyglyoxime, bis-o-(camphorsulfonyl)-α-dimethyglyoxime, etc. can be cited.

[0133] As the β-ketosulfone derivative, specifically, 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane, 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane, etc. can be cited.

[0134] As the disulfone derivative, specifically, diphenyl disulfone, dicyclohexyl disulfone, etc. can be cited.

[0135] As the nitrobenzyl sulfonate derivative, specifically, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate, etc. can be cited.

[0136] As the sulfonate derivative, specifically, 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1,2,3-tris(p-toluenesulfonyloxy)benzene, etc. can be cited.

[0137] As the imido-sulfonate derivative, specifically, phthalimido-trifluoromethanesulfonate, phthalimido-toluenesulfonate, 5-norbornene-2,3-dicarboximido-trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximido-toluenesulfonate, 5-norbornene-2,3-dicarboximido-n-butanesulfonate, norbornene-2,3-dicarboximido-trifluoromethanesulfonate, etc. can be cited.

[0138] As the oxime sulfonate derivative, specifically, α-(phenylsulfonyloxyimino)-4-methylphenylacetonitrile and the like can be mentioned.

[0139] As the iminosulfonate derivative, specifically, (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile and the like can be mentioned.

[0140] As the triazine derivative, specifically, 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, 2-[2-(3,4-dimethoxyphenyl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine and the like can be mentioned.

[0141] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can be appropriately used.

[0142] As the cationic photopolymerization initiator of component (B), the onium salt and the sulfonium salt are particularly preferably used, and the sulfonium salt is more preferably used.

[0143] Relative to the total amount of the photosensitive resin composition, the (B) cationic photopolymerization initiator is preferably in the range of 0.05 to 20% by mass, more preferably in the range of 0.5 to 10% by mass. When the cationic photopolymerization initiator is included within the above range, a pattern having excellent balance between sensitivity and developability during exposure, no residual film, and excellent resolution can be obtained. In addition, the cationic photopolymerization initiator can be used alone or two or more kinds can be used simultaneously.

[0144] [(C) A polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate or a condensate thereof]

[0145] A quantum dot refers to a semiconductor substance having a nanoscale size. Atoms form molecules, molecules form small molecular aggregates called clusters, and further form nanoparticles. When such nanoparticles exhibit semiconductor characteristics, they are called quantum dots (quantum dot particles).

[0146] When quantum dots receive energy from the outside and reach an excited state, they will autonomously (self-regulate) release the energy corresponding to the energy band gap (luminescence).

[0147] The quantum dots used in the present invention are not particularly limited, and any form can be used. The quantum dots are mainly nanoparticles with a size of 10 nm or less, and can also be nanowires, nanorods, nanotubes, nanocubes, etc. Quantum dots of any shape can be used.

[0148] The (C) quantum dots used in the present invention can be made of any suitable material. For example, materials 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 and their mixed crystals or alloys, or compounds having a perovskite structure can be used as semiconductor materials. Specifically, compounds including 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, CsSnI3 can be cited, but are not limited thereto.

[0149] The quantum dots used in the present invention may have a core-shell structure. The shell material that can form the core-shell structure is not particularly limited. Materials with a large band gap and low lattice mismatch relative to the core material are preferred, and can be arbitrarily combined according to the core material. Specific shell materials can 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, etc. The above materials can be selected as a single one or a mixed crystal of multiple ones, but are not limited thereto.

[0150] In the present invention, various methods such as liquid phase method or gas phase method can be used for preparing the quantum dots used in the present invention. In the present invention, although there is no particular limitation, from the perspective of exhibiting high fluorescence emission efficiency, it is preferable to use semiconductor nanoparticles obtained by a pyrolysis method or a thermal injection method in which a precursor species reacts at a high temperature in a high-boiling non-polar solvent. In order to impart its dispersibility in a non-polar solvent and reduce surface defects, it is preferably surface coordinated with an organic ligand.

[0151] From the perspective of dispersibility, the organic ligand preferably contains an aliphatic hydrocarbon. As such an organic ligand, for example, oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, octanoic acid, oleylamine, stearoyl (octadecyl) amine, dodecyl (lauryl) amine, decylamine, octylamine, octadecanethiol, hexadecanethiol, tetradecanethiol, dodecanethiol, decanethiol, octanethiol, trioctylphosphine, trioctyloxide phosphine, triphenylphosphine, triphenylphosphine oxide, tributylphosphine, tributylphosphine oxide, etc. can be cited. These ligands can be used alone or in combination of multiple kinds.

[0152] The surface of the quantum dots is surface-treated with a silane coupling agent. As the coordination substituents of the silane coupling agent, it is preferable to have one or more of an amino group, a thiol group, a carboxyl group, a phosphine group, a phosphine oxide group, and an ammonium ion. As the silane coupling agent, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminophenyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl(dimethoxy)methylsilane, triethoxysilylpropylmaleamic acid, [(3-triethoxysilyl)propyl] succinic anhydride, X-12-1135 (manufactured by Shin-Etsu Chemical Co., Ltd.), diethylphosphonoethyltriethoxysilane, 3-trihydroxypropylmethyl phosphate sodium salt, trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, etc. can be exemplified.

[0153] In a certain embodiment, the quantum dots surface-treated with a silane coupling agent are copolymerized with a condensate of an alkoxysilane or an alkoxysilane hydrolyzate. The method of copolymerization is not particularly limited. For example, the surface-treated quantum dots are mixed with a condensate of an alkoxysilane or an alkoxysilane hydrolyzate in a mixed solvent of toluene and ethanol, and a small amount of water and a catalyst are added to make them react, whereby the quantum dots can be copolymerized with the condensate of an alkoxysilane or an alkoxysilane hydrolyzate. The type of the catalyst is not particularly limited, and an acid or a base can be used. As the catalyst, formic acid, hydrochloric acid, nitric acid, acetic acid, ammonia water, tetramethylammonium hydroxide, etc. can be exemplified.

[0154] In addition, the condensate of an alkoxysilane or an alkoxysilane hydrolyzate can have a cage structure, a ladder structure, a random structure, etc., and its structure is not particularly limited and can be appropriately selected according to the purpose. From the perspectives of dispersibility and uniformity in the photosensitive resin, a random structure is preferred. In addition, the functional groups contained in the condensate of an alkoxysilane or an alkoxysilane hydrolyzate are not limited and can be appropriately substituted according to the purpose. From the perspective of improving the patterning of the resin composition, a glycidyl group capable of crosslinking reaction with the photosensitive resin is particularly preferably used as a substituent.

[0155] In a certain embodiment, the quantum dots surface-treated with a silane coupling agent are copolymerized with an alkoxysilane or an alkoxysilane hydrolyzate. The copolymerization method is not particularly limited. As its synthesis method, the methods in Non-Patent Document 1 etc. are known. For example, the surface-treated quantum dots and an alkoxysilane can be mixed in a mixed solvent of toluene and ethanol, and a small amount of water and a catalyst are added and reacted to obtain the product. The type or addition amount of the catalyst is not particularly limited, and an acid or a base can be used. Examples of the catalyst include formic acid, hydrochloric acid, nitric acid, acetic acid, ammonia water, tetramethylammonium hydroxide, etc.

[0156] The silane coupling agent is not particularly limited and can be appropriately selected according to the target resin characteristics. As the silane coupling agent, those having vinyl, allyl, glycidyl, phenyl, acryloyl, methacryloyl, mercapto groups as functional groups are preferred. In addition, for the functional groups, an alkoxysilane having two or more functional groups rather than only one functional group can be used. Examples of the silane coupling agent include trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxy(4-vinylphenyl)silane, allyltriethoxysilane, allyltrimethoxysilane, triethoxy(3-glycidylethoxypropyl)silane, 3-glycidylethoxypropyltrimethoxysilane, [8-(glycidylethoxy)-n-octyl]trimethoxysilane, KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.), (3-methacryloxypropyl)triethoxysilane, (3-methacryloxypropyl)trimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

[0157] In addition, the alkoxysilane is not only a trialkoxysilane, but may also include a dialkoxysilane or a monoalkoxysilane. The trialkoxysilane, dialkoxysilane, and monoalkoxysilane may have the same functional groups, and in addition, may also have different functional groups. There is no limitation on the functional groups, and they can be appropriately substituted according to the purpose. From the perspective of improving the patterning of the resin composition, it is preferable to have a glycidyl group capable of crosslinking reaction with the photosensitive resin as a substituent. By including a dialkoxysilane or a monoalkoxysilane, the crosslinking degree of the condensate of the alkoxysilane or alkoxysilane hydrolyzate obtained by copolymerization can be controlled, the viscosity of the resulting resin composition can be controlled, and the viscosity can be adjusted according to the manufacturing process. The types or ratios of these alkoxysilanes are not particularly limited and can be appropriately selected according to the purpose.

[0158] In addition, in the present invention, from the perspective of improving the patterning of the resin composition, it is particularly preferable that the polymer (C) obtained by copolymerizing the quantum dots coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof has a glycidyl group capable of crosslinking reaction with the photosensitive resin as a substituent.

[0159] Relative to the total amount of the photosensitive resin composition, the polymer (C) obtained by copolymerizing the quantum dots coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof used in the present invention is preferably 5 to 80% by mass, more preferably 10 to 70% by mass. As long as the content rate of the quantum dot particles is within the above range, fine patterning can be performed while maintaining good light emission characteristics.

[0160] [(D) Cationic polymerization crosslinking agent]

[0161] The photosensitive resin composition of the present invention may further contain a cationic polymerization crosslinking agent as the component (D). The cationic polymerization crosslinking agent can undergo a cationic polymerization reaction with the epoxy group of the component (A), and it is a component that makes the formation of the pattern easier and further improves the strength of the resin film after photocuring.

[0162] As the crosslinking agent, a compound having a molecular weight of 100 to 15,000 is preferred, and a compound having a molecular weight of 200 to 1,000 is more preferred. If the molecular weight is 100 or more, sufficient photocurability can be obtained, and if it is 15,000 or less, the heat resistance of the composition after photocuring will not deteriorate, so it is preferred. In addition, the compound may be a resin (polymer), and in this case, the molecular weight is the weight average molecular weight (Mw).

[0163] As the cationic polymerization crosslinking agent, a compound having a functional group selected from an epoxy group, an oxetanyl group, and a vinyl ether group is preferred. These compounds may be used alone or in combination of two or more.

[0164] When the component (D) is contained, the content of the component (D) is preferably 0.5 to 100 parts by mass, preferably 0.5 to 60 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the component (A). If the content of the component (D) is 0.5 parts by mass or more, sufficient curability can be obtained upon light irradiation. If it is 100 parts by mass or less, sufficient film formability can be ensured. The component (D) may be used alone or in combination of two or more.

[0165] [(E) Solvent]

[0166] The photosensitive resin composition of the present invention may further contain a solvent as the component (E). The solvent is not particularly limited as long as it can dissolve the above-mentioned components. By blending the solvent, the coatability of the photosensitive resin composition can be improved.

[0167] As such a solvent, an organic solvent is preferred because of its excellent solubility in the above components. Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentanone; 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; 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 monoterbutyl ether acetate, and γ-butyrolactone. These organic solvents can be used alone or in combination of two or more. Ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and a mixed solvent of these solvents, which have excellent solubility for the cationic photopolymerization initiator, are particularly preferred.

[0168] From the viewpoints of the compatibility and viscosity of the photosensitive resin composition, the content of the component (E) is preferably 25 to 85% by mass, more preferably 35 to 75% by mass, relative to the total amount of the photosensitive resin composition.

[0169] [Photosensitive resin film]

[0170] The photosensitive resin film of the present invention is a dried product of the above-described photosensitive resin composition.

[0171] [Pattern forming method using the photosensitive resin composition]

[0172] The method for forming a pattern using the photosensitive resin composition of the present invention includes:

[0173] (i) A step of coating the above-described photosensitive resin composition on a substrate to form a photosensitive resin coating film on the substrate;

[0174] (ii) A step of exposing the photosensitive resin coating film; and

[0175] (iii) A step of developing the exposed photosensitive resin coating film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

[0176] Step (i) is a step of coating the above-described photosensitive resin composition on a substrate to form a photosensitive resin coating film on the substrate. As the substrate, for example, a silicon wafer, a glass wafer, a quartz wafer, a Micro-LED stacked substrate, etc. can be cited.

[0177] As the coating method, a known method can be used, and examples thereof include an immersion method, a spin coating method, a roll coating method, etc. The coating amount can be appropriately selected according to the purpose, and it is preferably coated in such a manner that the film thickness of the obtained photosensitive resin coating film is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0178] In order to improve the film thickness uniformity on the substrate surface, a solvent can be dropped onto the substrate before coating the photosensitive resin composition (pre-wetting method). The dropped solvent can be appropriately selected according to the purpose. As the solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and alcohols such as propylene glycol monomethyl ether are preferred, and the solvent used in the photosensitive resin composition can also be used.

[0179] Here, in order to effectively carry out the photocuring reaction, the solvent, etc. can be volatilized in advance by preheating (pre-baking) as needed. The pre-baking can be carried out at 40 to 140 °C for about 1 minute to 1 hour, for example.

[0180] Next, (ii) the photosensitive resin coating film is exposed. At this time, the exposure is preferably carried out using light with a wavelength of 10 to 600 nm, more preferably using light with a wavelength of 190 to 500 nm. As the light of this wavelength, for example, various wavelengths of light generated by a radiation generating device can be cited, such as ultraviolet light such as g-line, h-line, i-line, far ultraviolet light (248 nm, 193 nm), etc. Among them, light with a wavelength of 248 to 436 nm is particularly preferred. The exposure amount is preferably 10 to 10,000 mJ / cm 2 .

[0181] Exposure can be carried out through a photomask. The photomask can be, for example, a film with the required pattern cut out. In addition, the material of the photomask is not particularly limited, and a material that shields light of the above wavelength is preferred. For example, a material containing chromium is preferably used as the light-shielding film, but it is not limited thereto.

[0182] In addition, in order to improve the development sensitivity, a post-exposure baking (PEB) treatment can be carried out. The PEB is preferably carried out at 40 to 150 °C for 0.5 to 20 minutes. Through the PEB, the exposed part is crosslinked to form an insolubilized pattern that is insoluble in the organic solvent used as the developer.

[0183] (iii) After exposure or PEB, development is carried out using a developer to dissolve and remove the non-exposed part, thereby forming a pattern. As the developer, for example, organic solvents such as alcohols like IPA, ketones like cyclohexanone, and alcohols like propylene glycol monomethyl ether are preferred, but the solvents used in the photosensitive resin composition can also be used. As the development method, a conventional method can be used, for example, a method of immersing the substrate with the formed pattern in the developer can be cited. Then, washing, rinsing, drying, etc. are carried out as required, and a cured coating film with the required pattern can be obtained.

[0184] Furthermore, an oven or a hot plate can be used to post-cure the formed coating film preferably at 100 to 200 °C.

[0185] [Photosensitive dry film]

[0186] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin coating film obtained from a photosensitive resin composition on the support film.

[0187] The photosensitive dry film (support film and photosensitive resin coating film) is solid, and the photosensitive resin coating film does not contain a solvent. Therefore, there is no need to worry about bubbles generated by its volatilization remaining inside the photosensitive resin coating film and between the photosensitive resin coating film and the substrate with unevenness. The film thickness of the photosensitive resin coating film is not particularly limited, and is preferably 1 to 200 μm, more preferably 3 to 100 μm.

[0188] In addition, the viscosity of the photosensitive resin coating film is closely related to its fluidity. The photosensitive resin coating film can exhibit appropriate fluidity within an appropriate viscosity range, can enter the deep part of a narrow gap, and can enhance the adhesion to the substrate by resin softening. Therefore, from the perspective of the fluidity of the photosensitive resin coating film, the viscosity of the photosensitive resin coating film is preferably 10 to 5,000 Pa·s at 80 to 120 °C, more preferably 30 to 2,000 Pa·s, and further preferably 50 to 300 Pa·s. In addition, in the present invention, the viscosity is the measured value obtained by a rotational viscometer.

[0189] When the photosensitive dry film of the present invention is closely attached to a substrate with unevenness, the photosensitive resin coating film will follow and cover the unevenness, enabling high flatness. In particular, due to the softening property of the photosensitive resin composition of the present invention, higher flatness can be achieved. Further, if the photosensitive resin coating film is closely attached to the substrate in a vacuum environment, the generation of gaps between them can be more effectively prevented.

[0190] The photosensitive dry film of the present invention can be manufactured by the following method: coating the photosensitive resin composition on a substrate and drying it to form a photosensitive resin coating film. As the manufacturing apparatus for the photosensitive dry film, a film coater commonly used for manufacturing adhesive products can be used. As the film coater, for example, 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 3-roll bottom reverse coater, a 4-roll bottom reverse coater, etc. can be cited.

[0191] The photosensitive dry film can be manufactured by the following method: when unwinding a support film from the unwind reel of the film coater and passing it through the coating head of the film coater, coating the photosensitive resin composition on the support film with a specified thickness, and then passing it through a hot air circulation oven at a specified temperature and time to dry it on the support film to form a photosensitive resin coating film. In addition, a photosensitive dry film with a protective film can be manufactured by the following method: if necessary, passing the photosensitive dry film and a protective film unwound from another unwind reel of the film coater through a laminating roll under a specified pressure, laminating the photosensitive resin coating film on the support film and the protective film, and then winding it on the take-up reel of the film coater. At this time, 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.

[0192] The support film used in the photosensitive dry film of the present invention may be a single-layer film composed of a single film or a multi-layer film in which a plurality of films are laminated. As the material of the film, synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate can be cited. Among them, polyethylene terephthalate having appropriate flexibility, mechanical strength, and heat resistance is preferred. These films may be films that have been subjected to various treatments such as corona treatment or release agent coating. These films can use commercially available products. For example, Cerapeel WZ(RX), Cerapeel BX8(R) (above, manufactured by TORAY ADVANCED FILM CO., LTD.), E7302, E7304 (above, manufactured by TOYOBO Co., Ltd.), PurexG31, Purex G71T1 (above, manufactured by Teijin DuPont Films Japan Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (above, manufactured by NIPPA Co., Ltd.) etc. can be cited.

[0193] As the protective film, the same film as the above-mentioned support film can be used, but polyethylene terephthalate and polyethylene having appropriate flexibility are preferred. These films can use commercially available products. As polyethylene terephthalate, the commercially available polyethylene terephthalates exemplified above can be cited. As polyethylene, for example, GF-8 (manufactured by Tamapoly CO., LTD.), PE Film 0-Type (manufactured by NIPPA Co., Ltd.) etc. can be cited.

[0194] From the viewpoints of the stability of manufacturing the photosensitive dry film and preventing curling of the core, that is, so-called curl, the thicknesses of both the support film and the protective film are preferably 10 to 100 μm, and more preferably 25 to 50 μm.

[0195] [Pattern formation method using a photosensitive dry film]

[0196] The pattern formation method using the photosensitive dry film of the present invention is characterized in that it includes:

[0197] (i’) A step of attaching the photosensitive resin coating film of the above-described photosensitive dry film to a substrate and forming the photosensitive resin coating film on the substrate;

[0198] (ii) A step of exposing the photosensitive resin coating film; and

[0199] (iii) A step of developing the exposed photosensitive resin coating film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

[0200] First, (i) a photosensitive dry film is used to laminate the photosensitive resin film on a substrate, thereby forming a photosensitive resin film on the substrate. That is, the photosensitive resin film of the photosensitive dry film is laminated on the substrate, whereby a photosensitive resin film is formed on the substrate. In addition, when the photosensitive dry film has a protective film, after peeling off the protective film from the photosensitive dry film, the photosensitive resin film of the photosensitive dry film is laminated on the substrate. For example, a laminating device can be used for lamination.

[0201] As the laminating device, a vacuum laminator is preferably used. For example, the protective film of the photosensitive dry film is peeled off, and in a vacuum chamber with a specified vacuum degree, using an attaching roller with a specified pressure, the exposed photosensitive resin film is closely attached to the substrate on a workbench at a specified temperature. Additionally, the temperature is preferably 60 to 120 °C, the pressure is preferably 0 to 5.0 MPa, and the vacuum degree is preferably 50 to 500 Pa.

[0202] In order to effectively carry out the photocuring reaction of the photosensitive resin film and to improve the close adhesion between the photosensitive resin film and the substrate, pre-baking can be performed as needed. Pre-baking can be carried out, for example, at 40 to 140 °C for about 1 minute to 1 hour.

[0203] The photosensitive resin film laminated on the substrate, similar to the case of the pattern formation method using the photosensitive resin composition, can form a pattern through the steps of (ii) exposing the photosensitive resin film, (iii) developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed part, and (iv) post-curing heat treatment as needed. Additionally, the support film of the photosensitive dry film is peeled off before pre-baking or before PEB according to the process, or removed by other methods.

[0204] Through the pattern formation method of the present invention using a photosensitive resin composition or a photosensitive dry film, a fine pattern can be easily formed. For example, the photosensitive resin composition or the photosensitive dry film of the present invention is formed in a manner that covers multiple blue micro-LEDs laid on a substrate, and then a fine pattern is formed. Thus, a cured film containing red or green quantum dots is formed on the blue micro-LED in parts, and red or green light emission can also be generated, so that a full-color light-emitting element can be manufactured.

[0205] [Light-emitting element]

[0206] The light-emitting element of the present invention includes a cured film obtained by the pattern formation method described above. That is, it is a light-emitting element including a cured film with a pattern formed on the photosensitive resin film described above, or a light-emitting element including a cured film with a pattern formed on the photosensitive resin film of the photosensitive dry film described above.

[0207] Example

[0208] Hereinafter, synthesis examples, examples and comparative examples are shown to illustrate the present invention more specifically, but the present invention is not limited to the following examples. In addition, as the quantum dot material, a core-shell type quantum dot of InP / ZnSe / ZnS is used. The synthesis method of the core is as shown in [1-1] (red quantum dot) and [1-2] (green quantum dot) described later, and the subsequent synthesis method of the shell is as shown in [2].

[0209] [1-1] Synthesis process of red quantum dot core

[0210] Prepare two flasks, add 0.23 g (0.9 mmol) of palmitic acid, 0.088 g (0.3 mmol) of indium acetate, and 10 mL of 1-octadecene to each flask, heat and stir under reduced pressure at 100 °C to dissolve the raw materials, and at the same time perform degassing for 1 hour. Then, purge the interiors of the two flasks with nitrogen, and add 0.75 mL (0.15 mmol) of a solution of tris(trimethylsilyl)phosphine / trioctylphosphine (0.2 M) to the two flasks. Then, heat one of the flasks to 300 °C, and the solution turns from yellow to red, generating core particles. Extract the solution from the unheated flask and add it to the flask heated to 300 °C to prepare the desired particle size.

[0211] [1-2] Synthesis process of green quantum dot core

[0212] Add 0.23 g (0.9 mmol) of palmitic acid, 0.088 g (0.3 mmol) of indium acetate, and 10 mL of 1-octadecene to the flask, heat and stir under reduced pressure at 100 °C to dissolve the raw materials, and at the same time perform degassing for 1 hour. Then, purge the interior of the flask with nitrogen, add 0.75 mL (0.15 mmol) of a solution prepared by mixing tris(trimethylsilyl)phosphine and trioctylphosphine and adjusting to 0.2 M, heat to 300 °C, and the solution turns from yellow to red, confirming the formation of core particles.

[0213] [2] Synthesis process of quantum dot shell

[0214] Next, 2.85 g (4.5 mmol) of zinc stearate and 15 mL of 1-octadecene were added to another flask, and heated and stirred at 100 °C under reduced pressure. While dissolving it, degassing was carried out for 1 hour to prepare a 0.3 M zinc stearate octadecene solution thus obtained. 3.0 mL (0.9 mmol) of this solution was added to the reaction solution after core synthesis and cooled to 200 °C. Next, 0.474 g (6 mmol) of selenium and 4 mL of trioctylphosphine were added to another flask, heated to 150 °C to dissolve it, and a 1.5 M trioctylphosphine selenide solution was prepared. While heating the reaction solution after the core synthesis process, which had been cooled to 200 °C, to 320 °C over 30 minutes, a total of 0.6 mL (0.9 mmol) of the trioctylphosphine selenide solution was added in portions of 0.1 mL each, and maintained at 320 °C for 10 minutes, and then cooled to room temperature. 0.44 g (2.2 mmol) of zinc acetate was added, and heated and stirred at 100 °C under reduced pressure to dissolve it. The inside of the flask was purged with nitrogen again and heated to 230 °C, and 0.98 mL (4 mmol) of 1-dodecanethiol was added and maintained for 1 hour. The resulting solution was cooled to room temperature to prepare a solution containing core-shell quantum dots. The solution containing red core-shell quantum dots synthesized through the processes of [1-1] to [2] was designated as R-1, and the solution containing green core-shell quantum dots synthesized through the processes of [1-2] to [2] was designated as G-1.

[0215] [3] Surface treatment process

[0216] After the reaction was completed and cooled to room temperature, ethanol was added to precipitate the reaction solution, and centrifuged to remove the supernatant. The same purification was carried out again and dispersed in toluene. A toluene solution of quantum dots was added to a flask purged with nitrogen. 0.24 mL (1.0 mmol) of (3-mercaptopropyl)triethoxysilane was added thereto, and stirred at room temperature for 24 hours for surface treatment. The quantum dots surface-treated with R-1 were designated as R-2, and the quantum dots surface-treated with G-1 were designated as G-2.

[0217] [4] Condensation process of alkoxysilane or alkoxysilane hydrolyzate

[0218] 10 mL of 3-glycidoxypropyltrimethoxysilane, 20 mL of toluene, and 10 mL of methanol were mixed in a flask purged with nitrogen, and 4.0 mL of 1.0 N hydrochloric acid was added dropwise little by little while stirring at room temperature. After the dropwise addition, it was stirred at room temperature for 60 minutes, then the solution temperature was raised to 60 °C, and the reaction was carried out while refluxing for 60 minutes. Then, the system was evacuated at 60 °C for 2 hours, and the solvent was distilled off. A condensate of alkoxysilane or alkoxysilane hydrolyzate having a glycidyl group was obtained in the flask.

[0219] [5] Copolymerization of quantum dots with condensates of alkoxysilanes or hydrolyzates of alkoxysilanes

[0220] Add the obtained condensate of alkoxysilane or hydrolyzate of alkoxysilane and the surface-treated quantum dot solution obtained in [3] to a flask purged with nitrogen so that the solid component concentration is 20% by mass. Further add and mix 20 mL of toluene and 10 mL of methanol. While stirring at room temperature, gradually add dropwise 4.0 mL of 1.0 N hydrochloric acid in small portions. After the addition, stir at room temperature for 60 minutes, then raise the solution temperature to 60 °C and react with reflux for 60 minutes. Then, add PGMEA and remove the toluene solvent by distillation under reduced pressure to obtain a copolymer of quantum dots and a condensate of alkoxysilane or hydrolyzate of alkoxysilane. The copolymer of R-2 and the condensate of alkoxysilane or hydrolyzate of alkoxysilane is designated as R-3, and the copolymer of G-2 and the condensate of alkoxysilane or hydrolyzate of alkoxysilane is designated as G-3.

[0221] [6] Copolymerization of quantum dots with alkoxysilanes or hydrolyzates of alkoxysilanes

[0222] Add 7 mL of 3-glycidoxypropyltrimethoxysilane, 3 mL of ethoxymethyltrimethoxysilane, and the surface-treated quantum dot solution obtained in [3] to a flask purged with nitrogen so that the solid component concentration is 20% by mass. Then add and mix 20 mL of toluene and 10 mL of methanol. While stirring at room temperature, gradually add dropwise 4.0 mL of 1.0 N hydrochloric acid in small portions. After the addition, stir at room temperature for 60 minutes, then raise the solution temperature to 60 °C and react with reflux for 60 minutes. Then, add PGMEA and remove the toluene solvent by distillation under reduced pressure to obtain a copolymer of quantum dots and alkoxysilane or hydrolyzate of alkoxysilane. The copolymer of R-2 and alkoxysilane or hydrolyzate of alkoxysilane is designated as R-4, and the copolymer of G-2 and alkoxysilane or hydrolyzate of alkoxysilane is designated as G-4.

[0223] [7] Synthesis of organosilicon resin

[0224] [Synthesis Example 1] Synthesis of Resin 1

[0225] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 238.5 g (0.90 mol) of compound (S-4) and 16.2 g (0.10 mol) of compound (S-3b) were added, and then 2,000 g of toluene was added, and the mixture was heated to 70 °C. Then, 1.0 g of a toluene solution of chloroplatinic acid (platinum concentration: 0.5% by mass) was added, and 184.3 g (0.95 mol) of compound (S-1) and 79.3 g (0.05 mol) of compound (S-2b) (total of hydrosilyl groups / total of carbon-carbon double bonds = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After completion of the dropwise addition, the mixture was heated to 100 °C and aged for 6 hours, and then toluene was removed by distillation under reduced pressure from the reaction solution to obtain Resin 1 (siloxane content: 15.3% by mass). The Mw of Resin 1 was 10,000. In addition, it was confirmed by 1 1H-NMR (manufactured by Bruker K.K.) that Resin 1 was a polymer containing repeating units A1 to A4.

[0226] [Synthesis Example 2] Synthesis of Resin 2

[0227] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device, and a reflux condenser, 132.5 g (0.50 mol) of compound (S-4) and 60.5 g (0.50 mol) of compound (S-3a) were added, and then 2,000 g of toluene was added, and the mixture was heated to 70 °C. Then, 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) (total of hydrosilyl groups / total of carbon-carbon double bonds = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After completion of the dropwise addition, the mixture was heated to 100 °C and aged for 6 hours, and then toluene was removed by distillation 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. In addition, it was confirmed by 1 1H-NMR (manufactured by Bruker K.K.) that Resin 2 was a polymer containing repeating units A1 to A4.

[0228] [Synthesis Example 3] Synthesis of Resin 3

[0229] To a 10 L flask equipped with a stirrer, a thermometer, a nitrogen displacement device, and a reflux condenser, 159.0 g (0.60 mol) of compound (S-4) and 48.4 g (0.40 mol) of compound (S-3a) were added, and then 2,000 g of toluene was added and heated to 70 °C. Then, 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) (total of hydrosilyl groups / total of carbon-carbon double bonds = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After completion of the dropwise addition, the mixture was heated to 100 °C and aged for 6 hours, and then toluene was removed by distillation 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. In addition, 1 1H-NMR (manufactured by Bruker K.K.) confirmed that Resin 3 was a polymer containing repeating units A1 to A4.

[0230] Compounds (S-1), (S-2a), (S-2b), (S-3a), (S-3b), and (S-4) used in the above synthesis example are as follows.

[0231] [Chemical Formula 11]

[0232]

[0233] [8] Preparation and Evaluation of Photosensitive Resin Composition

[0234] [Examples 1 to 12 and Comparative Examples 1 to 24]

[0235] Each component was blended in the blending amounts described in Tables 1 to 4, and then stirred and mixed at room temperature, and precisely filtered through a 1.0 μm glass filter to obtain the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 24.

[0236] [Table 1]

[0237]

[0238] [Table 2]

[0239]

[0240] [Table 3]

[0241]

[0242] [Table 4]

[0243]

[0244] In Tables 1 to 4, the cationic photopolymerization initiators B-1 and B-2 used are as follows.

[0245] [Chemical formula 12]

[0246]

[0247] In Tables 1 to 4, the crosslinking agents D-1 and D-2 used are as follows.

[0248] [Chemical formula 13]

[0249]

[0250] In Tables 1 to 4, R-5 of the quantum dots is S-BE030 manufactured by SHOEI CHEMICAL INC. (particle size 5 to 10 nm, material InP:ZnS:SeZn = 25:50:25), R-6 is 900514-1ML manufactured by Aldrich (particle size 5 to 10 nm, material CdSe(core) / CdS(shell) core-shell type), G-5 is S-BE029 manufactured by SHOEI CHEMICAL INC. (particle size 3 to 5 nm, material InP:ZnS:SeZn = 25:50:25), and G-6 is 900511-1ML manufactured by Aldrich (particle size 3 to 5 nm, material CdSe(core) / CdS(shell) core-shell type).

[0251] [9] Production of photosensitive dry film

[0252] Using a die coater as the film coating machine and using a polyethylene terephthalate film (thickness 38 μm) as the support film, the photosensitive resin compositions described in Tables 1 to 4 were respectively coated on the support film. Then, it was dried by passing through a hot air circulation oven (length 4 m) set at 100 °C for 5 minutes, and a photosensitive resin coating film with a thickness of 30 μm was formed on the support film to obtain a photosensitive dry film (B). From above the photosensitive resin coating film, a polyethylene film (thickness 50 μm) as a protective film was laminated with a pressure of 1 MPa using a laminating roller, thereby producing a photosensitive dry film with a protective film.

[0253]

[10] Evaluation of photosensitive resin coating film

[0254] (1) Confirmation of aggregates in photosensitive resin coating film

[0255] Peel off the protective film of the photosensitive dry film with a protective film, and confirm the aggregates in the photosensitive dry film using an optical microscope. The case where aggregates with a size of 1 μm or more exist is evaluated as ×, and the case where there are no aggregates or the size of the aggregates is less than 1 μm is evaluated as ○. The results are shown in Tables 5 to 8.

[0256] (2) Pattern formation and evaluation

[0257] For the photosensitive dry film with a protective film, the protective film is peeled off, and a vacuum laminator TEAM-100RF (manufactured by Takatori Corporation) is used to set the vacuum degree in the vacuum chamber to 80 Pa so that the photosensitive resin coating on the support film is closely attached to the silicon wafer. The temperature condition is 100°C. After returning to normal pressure, the substrate is taken out of the vacuum laminator and the support film is peeled off. Then, in order to improve the close fit with the substrate, a heating plate is used to pre-bake at 110°C for 4 minutes. In order to form a square island pattern (island pattern) with a spacing width of 1:1 with the adjacent pattern through the mask for the obtained photosensitive resin coating, an i-line photolithography machine NSR-2205i11D (manufactured by Nikon Corporation) is used for exposure. After irradiation, PEB is performed at 120°C for 5 minutes using a heating plate, and then cooled, and the substrate is sprayed and developed for 90 seconds using PGMEA to form a pattern. Then, an oven was used to perform post-curing at 160°C for 3 hours while purging nitrogen. Then, a scanning electron microscope (SEM) was used to observe the island patterns with one side of 100 μm, 50 μm, 30 μm, 20 μm, and 15 μm, and the minimum pattern size that was not connected to the adjacent island pattern (pitch width 1:1) was taken as the limiting resolution. In addition, the situation where the resolution did not reach 100 μm or the development peeling of the pattern occurred was evaluated as ×. The results are shown in Tables 5 to 8.

[0258] (3) Evaluation of light-emitting properties of formed patterns

[0259] The sample with pattern prepared in (2) was irradiated with 457 nm laser (0.03 mW) using LabRAM HR Evolution manufactured by HORIBA TECHNO SERVICE, Co., Ltd., and the island pattern area after photoconversion was measured, and the luminous intensity, luminous wavelength, and half-value width of the light after photoconversion were measured. In addition, the sample after lamination and support film peeling process prepared in (2) was measured in the same manner, and the luminous intensity of the light after photoconversion was measured. The results are shown in Tables 5 to 8 (M: 1 million).

[0260] (4) Reliability test evaluation

[0261] The photosensitive resin composition described in Tables 1 to 4 was coated on a glass substrate with a film thickness of 80 μm using a spin coater. In order 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. In order to form a square island pattern with a side of 1 cm on the obtained photosensitive resin coating through a mask, a contact alignment exposure device was used to expose it under an exposure condition of 365 nm. After irradiation, PEB was performed at 120°C for 5 minutes using a hot plate, and then cooled, and the substrate was spray-developed for 180 seconds using PGMEA to form a pattern. Then, an oven was used to perform post-curing at 160°C for 3 hours while purging nitrogen. The patterned sample was treated at 120°C for 500 hours, and then the luminescence intensity was measured in the same manner as above (3) to confirm the reduction rate relative to the initial. In addition, the peeling state of the cured coating from the substrate after the test and the presence or absence of cracks were confirmed. The case where no peeling or cracking occurred was evaluated as ○, and the case where peeling or cracking occurred at least once was evaluated as ×. The results are shown in Tables 5 to 8.

[0262] [Table 5]

[0263]

[0264] [Table 6]

[0265]

[0266] [Table 7]

[0267]

[0268] [Table 8]

[0269]

[0270] The above results show that the photosensitive resin composition of the present invention can form a good photosensitive coating or photosensitive dry film without agglomerates (or even if agglomerates are present, they are extremely small), and can provide a cured coating with high lithography resolution, no change in high luminescence characteristics before and after the lithography process, good reliability (low rate of change of luminescence intensity in heat resistance test, crack resistance, and tight adhesion) and suitable for light-emitting elements.

[0271] On the other hand, in Comparative Examples 1 to 6 and 13 to 18 using R-1, R-2, G-1, and G-2 in which an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof not copolymerized with quantum dots is used as the component (C), since condensates were confirmed, a good photosensitive resin coating film could not be formed. Compared with the photosensitive resin composition of the present invention, the lithographic resolution, the light-emitting characteristics before and after the lithography process, the change rate of the light-emitting intensity in the laser light resistance test, and the close adhesion to the substrate are all poor, and it does not become a cured film (cured coating film) suitable for light-emitting elements.

[0272] Furthermore, similarly, in Comparative Examples 7 to 12 and 19 to 24 using commercially available quantum dots as the component (C) of R-5, R-6, G-5, and G-6, since condensates were confirmed, a good photosensitive resin coating film could not be formed. Compared with the photosensitive resin composition of the present invention, the lithographic resolution, the light-emitting characteristics before and after the lithography process, the change rate of the light-emitting intensity in the laser light resistance test, and the close adhesion to the substrate are all poor, and it does not become a cured film (cured coating film) suitable for light-emitting elements.

[0273] This specification includes the following aspects.

[0274] [1]: A photosensitive resin composition, characterized in that it comprises:

[0275] (A) An organosilicon resin having a glycidyl group,

[0276] (B) A cationic photopolymerization initiator, and

[0277] (C) A polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof.

[0278] [2]: The photosensitive resin composition according to the above [1], characterized in that the component (C) comprises a skeleton having a glycidyl group.

[0279] [3]: The photosensitive resin composition according to the above [1] or the above [2], characterized in that the component (A) comprises repeating units represented by the following formulas (A1) to (A4),

[0280] [Chemical formula 14]

[0281]

[0282] [In the formula, R 1 ~R 4 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms optionally containing a heteroatom. m is each independently an integer of 1 to 600. When m is an integer of 2 or more, each R 3 is optionally the same as or different from each other, and each R4 are each independently the same as or different from each other. a 1 、a 2 、a 3 and a 4 are numbers satisfying 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; X 1 is a divalent group represented by the following formula (X1); X 2 is a divalent group represented by the following formula (X2),

[0283] [Chemical formula 15]

[0284]

[0285] (In formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group; n 1 and n 2 are each independently an integer from 0 to 7; R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms, optionally containing an ester bond or an ether bond between its carbon atoms.)

[0286] [Chemical formula 16]

[0287]

[0288] (In formula (X2), R 21 and R 22 are each independently an alkyl group having 1 to 20 carbon atoms optionally containing a hydrogen atom or a heteroatom. k is an integer from 0 to 10.)]

[0289] [4]: The photosensitive resin composition according to any one of the above [1] to the above [3], characterized in that, as the coordination substituent of the silane coupling agent of the component (C), it has any one or more of an amino group, a thiol group, a carboxyl group, a phosphino group, a phosphine oxide group, and an ammonium ion.

[0290] [5]: The photosensitive resin composition according to any one of the above [1] to the above [4], characterized in that the photosensitive resin composition contains 5 to 80% by mass of the component (C).

[0291] [6]: The photosensitive resin composition according to any one of the above [1] to the above [5], characterized in that it further contains a (D) cationic polymerization crosslinking agent.

[0292] [7]: The photosensitive resin composition according to any one of the above [1] to the above [6], characterized in that it further comprises (E) a solvent.

[0293] [8]: A photosensitive resin film, characterized in that it is a dried body of the photosensitive resin composition according to any one of the above [1] to the above [7].

[0294] [9]: A photosensitive dry film, characterized in that it comprises a support film and the photosensitive resin film according to the above [8] on the support film.

[0295]

[10] : A pattern forming method, characterized in that it includes:

[0296] (i) A step of coating the photosensitive resin composition according to any one of claims 1 to 7 on a substrate to form a photosensitive resin film on the substrate;

[0297] (ii) A step of exposing the photosensitive resin film; and

[0298] (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

[0299]

[11] : A pattern forming method, characterized in that it includes:

[0300] (i) A step of attaching the photosensitive resin film of the photosensitive dry film according to the above [9] to a substrate to form the photosensitive resin film on the substrate;

[0301] (ii) A step of exposing the photosensitive resin film; and

[0302] (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

[0303]

[12] : A light-emitting element, characterized in that it comprises a cured film having a pattern formed on the photosensitive resin film of the above [8].

[0304]

[13] : A light-emitting element, characterized in that it comprises a cured film having a pattern formed on the photosensitive resin film of the photosensitive dry film according to the above [9].

[0305] In addition, the present invention is not limited by the above embodiments. The above embodiments are examples, and technical solutions having the same composition as the technical concept described in the claims of the present invention and achieving the same technical effects are all included in the technical scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, It includes: (A) an organosilicon resin having a glycidyl group, (B) a cationic photopolymerization initiator, and (C) a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof.

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

3. The photosensitive resin composition according to claim 1, wherein The component (A) contains repeating units represented by the following formulas (A1) to (A4), [Chemical formula 1] In the formula, R 1 ~R 4 each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms which may optionally contain a heteroatom; m each independently represents an integer of 1 to 600; when m is an integer of 2 or more, each R 3 may optionally be the same as or different from each other, and each R 4 may optionally be the same as or different from each other; a 1 、a 2 、a 3 and a 4 are numbers satisfying 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; X 1 is a divalent group represented by the following formula (X1); X 2 is a divalent group represented by the following formula (X2); [Chemical formula 2] In formula (X1), R 11 and R 12 are each independently a hydrogen atom or a methyl group; n 1 and n 2 are each independently an integer from 0 to 7; R 13 is a divalent hydrocarbon group having 1 to 8 carbon atoms, optionally containing an ester bond or an ether bond between its carbon atoms; [Chemical formula 3] In formula (X2), R 21 and R 22 each independently represents an alkyl group having 1 to 20 carbon atoms which optionally contains a hydrogen atom or a heteroatom; k is an integer from 0 to 10.

4. The photosensitive resin composition according to claim 1, characterized in that, As the coordination substituents of the silane coupling agent as the component (C), it has any one or more of an amino group, a thiol group, a carboxyl group, a phosphine group, a phosphine oxide group, and an ammonium ion.

5. The photosensitive resin composition according to claim 1, characterized in that, The photosensitive resin composition contains 5 to 80% by mass of the component (C).

6. The photosensitive resin composition according to claim 1, wherein It further contains (D) a cationic polymerization crosslinking agent.

7. The photosensitive resin composition according to claim 1, wherein It further contains (E) a solvent.

8. A photosensitive resin coating film, characterized in that, It is a dried body of the photosensitive resin composition according to any one of claims 1 to 7.

9. A photosensitive dry film, characterized in that, It includes a support film and the photosensitive resin coating film according to claim 8 on the support film.

10. A pattern forming method, characterized in that, It includes: (i) a step of coating the photosensitive resin composition according to any one of claims 1 to 7 on a substrate to form a photosensitive resin coating film on the substrate; (ii) a step of exposing the photosensitive resin coating film; and (iii) a step of developing the exposed photosensitive resin coating film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

11. A pattern forming method, characterized in that, It includes: (i’) a step of attaching the photosensitive resin coating film of the photosensitive dry film according to claim 9 to a substrate to form the photosensitive resin coating film on the substrate; (ii) a step of exposing the photosensitive resin coating film; and (iii) a step of developing the exposed photosensitive resin coating film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

12. A light-emitting element, characterized in that, It includes a cured coating film having a pattern formed on the photosensitive resin coating film according to claim 8.

13. A light-emitting element, characterized in that, It includes a cured coating film having a pattern formed on the photosensitive resin coating film of the photosensitive dry film according to claim 9.

Images