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

Abstract

The present invention provides a photosensitive resin composition characterized by comprising (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) quantum dots having a surface coating layer containing siloxane. As a result, it is possible to provide: 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 obtained using the photosensitive resin composition; a photosensitive dry film; a pattern forming method using the photosensitive resin coating film and the photosensitive dry film;

Description

Technical Field

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

[0002] Various methods have been proposed for forming a display including red, green, and blue sub-pixels. One of the methods is to convert light from an LED array from blue, i.e., shorter wavelength light, into red and green, i.e., longer wavelength light, using a color conversion structure. Quantum dots are used as a substance for this color conversion.

[0003] In recent years, the LED array has become miniature, and micro-LED displays using the LED array have attracted attention. As a method of forming a color conversion structure on an LED array, there is a photolithography process using a photosensitive material (Patent Document 1). In recent years, further miniaturization is required to adapt to small displays. In addition, from the perspective of display clarity, there are also high requirements for luminous properties.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2021-089347 Summary of the invention

[0007] 1. Technical issues to be resolved

[0008] The present invention is implemented in view of the above situation, and its purpose is to provide a photosensitive resin composition that can easily form a coating with high lithography resolution and good light-emitting characteristics, a photosensitive resin coating obtained using the photosensitive resin composition, a photosensitive dry film and a pattern forming method using the same, and a light-emitting element obtained using the photosensitive resin composition.

[0009] (II) Technical solution

[0010] In order to solve the above technical problems, the present invention provides a photosensitive resin composition comprising:

[0011] (A) a silicone resin having a phenolic hydroxyl group,

[0012] (B) a photoacid generator, and

[0013] (C) Quantum dots,

[0014] The quantum dots have a surface coating layer containing siloxane.

[0015] Such a photosensitive resin composition can easily form a coating film having high photolithography resolution and good light-emitting properties.

[0016] Furthermore, in the present invention, it is preferred that the component (C) contains a skeleton having a phenolic hydroxyl group in the surface coating layer.

[0017] If such a photosensitive resin composition is used, the quantum dots are suppressed from coming out during development, and high light-emitting characteristics of the pattern can be obtained.

[0018] Furthermore, in the present invention, it is preferred that the component (A) contains a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1).

[0019] [Chemical formula 1]

[0020]

[0021] In formula (a1) and formula (b1), R 5 ~R 8 Each of X is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 0 to 600. 1 It is a divalent group represented by the following formula (X1).

[0022] [Chemical formula 2]

[0023]

[0024] In formula (X1), Y 1 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 9 and R 10 are each independently a hydrogen atom or a methyl group. 11 and R 12 Each of them is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and a 2 Each independently represents an integer from 0 to 7. 1 and b 2 Each independently represents an integer from 0 to 2.

[0025] According to such a photosensitive resin composition, the obtained cured film has high reliability.

[0026] In addition, in the present invention, it is preferred that a crosslinking agent is further included as component (D), wherein the crosslinking agent is at least one selected from melamine compounds, guanamine compounds, glycoluril compounds and urea compounds containing an average of two or more hydroxymethyl groups and / or alkoxymethyl groups in one molecule, amino condensates modified by formaldehyde or formaldehyde-alcohol, and phenol compounds having an average of two or more hydroxymethyl groups or alkoxymethyl groups in one molecule.

[0027] Such a photosensitive resin composition can further improve the strength of the resin film after photocuring.

[0028] In addition, in the present invention, it is preferred that: the quantum dots of the component (C) have ligands coordinated to the surface thereof, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands 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.

[0029] Quantum dots having the above-mentioned ligands are preferred because they are easily coordinated to the surface.

[0030] Furthermore, in the present invention, it is preferred that the photosensitive resin composition contains 5 to 80% by mass of the component (C).

[0031] Such a photosensitive resin composition can form a fine pattern while maintaining good light-emitting properties.

[0032] Moreover, in this invention, it is preferable to further contain (E) a solvent.

[0033] Such a photosensitive resin composition can improve coating properties.

[0034] In addition, the present invention provides a photosensitive resin coating, which is a dried product of the photosensitive resin composition.

[0035] Such a photosensitive resin coating can provide a coating having high photolithography resolution and good light-emitting properties.

[0036] In addition, the present invention provides a photosensitive dry film, which comprises a support film, and the photosensitive resin coating film is provided on the support film.

[0037] If it is such a photosensitive dry film, it has high lithography resolution and good luminescence properties.

[0038] In addition, the present invention provides a pattern forming method, which comprises the following steps:

[0039] (i) coating the above-mentioned photosensitive resin composition on a substrate to form a photosensitive resin coating on the substrate;

[0040] (ii) exposing the photosensitive resin film to light; and

[0041] (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.

[0042] In addition, the present invention provides a pattern forming method, which comprises the following steps:

[0043] (i') a step of attaching the photosensitive resin coating of the photosensitive dry film to a substrate to form the photosensitive resin coating on the substrate;

[0044] (ii) exposing the photosensitive resin film to light; and

[0045] (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.

[0046] According to the above-mentioned pattern forming method, a pattern can be formed with high photolithography resolution, and a pattern of a coating having good light emitting characteristics can be obtained.

[0047] Furthermore, the present invention provides a light-emitting element comprising a cured film obtained by the above-mentioned pattern forming method.

[0048] Such a light-emitting element has high photolithography resolution and good light-emitting properties.

[0049] (III) Beneficial effects

[0050] The photosensitive resin composition of the present invention contains a silicone resin having a phenolic hydroxyl group, a photoacid generator, and quantum dots having a specific surface coating layer, and can easily form a film having high resolution and good light-emitting properties, and is therefore suitable for a light-emitting element. DETAILED DESCRIPTION

[0051] As described above, there is a need to develop a photosensitive resin composition that can easily form a coating having high lithography resolution and good luminescent properties, a photosensitive resin coating obtained using the photosensitive resin composition, a photosensitive dry film and a pattern forming method using the same, and a light-emitting element obtained using the photosensitive resin composition.

[0052] The inventors of the present application have repeatedly conducted in-depth studies on the above-mentioned technical problems, and as a result, have found that a photosensitive resin composition can easily form a coating (photosensitive resin coating) with high lithography resolution and good luminescent properties, thereby completing the present invention. The photosensitive resin composition is characterized in that it contains (A) an organic silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) quantum dots, and is also characterized in that the quantum dots have a surface coating layer containing siloxane.

[0053] That is, the present invention is a photosensitive resin composition comprising:

[0054] (A) a silicone resin having a phenolic hydroxyl group,

[0055] (B) a photoacid generator, and

[0056] (C) Quantum dots,

[0057] The quantum dots have a surface coating layer containing siloxane.

[0058] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0059] [Photosensitive resin composition]

[0060] The photosensitive resin composition of the present invention contains (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) quantum dots having a specific surface coating layer. Other components such as (D) a crosslinking agent and (E) a solvent may be further contained as required. The components constituting the photosensitive resin composition are described below.

[0061] [(A) Silicone resin having phenolic hydroxyl group]

[0062] The (A) silicone resin having a phenolic hydroxyl group used in the present invention is not particularly limited as long as it has a phenolic hydroxyl group.

[0063] Preferred examples include silicone resins containing a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1).

[0064] [Chemical formula 3]

[0065]

[0066] In formula (a1), R 5 ~R 8Each of them is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms. As the monovalent hydrocarbon group, linear, branched or cyclic alkyl groups, aryl groups, etc. can be listed, and specific examples thereof include methyl, ethyl, propyl, hexyl and their structural isomers, cyclohexyl, phenyl, etc. Among them, methyl and phenyl are preferred because of easy availability of raw materials.

[0067] In formula (a1), m is an integer of 0 to 600, preferably an integer of 0 to 400, and more preferably an integer of 0 to 200.

[0068] X 1 It is a divalent group represented by the following formula (X1).

[0069] [Chemical formula 4]

[0070]

[0071] In formula (X1), Y 1 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 9 and R 10 are each independently a hydrogen atom or a methyl group. 11 and R 12 Each of them is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and a 2 Each independently represents an integer of 0 to 7, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. 1 and b 2 Each independently represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0072] The alkyl group having 1 to 4 carbon atoms may be any one of linear, branched, and cyclic, and specific examples thereof include methyl, ethyl, propyl, butyl, and structural isomers thereof. The alkoxy group having 1 to 4 carbon atoms may be any one of linear, branched, and cyclic, and specific examples thereof include methoxy, ethoxy, propoxy, butoxy, and structural isomers thereof.

[0073] Resin (A) contains repeating units in the form of a1+b1=1, and a1>0, preferably 0.1≤a1≤0.9, 0.1≤b1≤0.9, and more preferably the silicone content is 20-80% by weight, and can be 30-70% by weight.

[0074] (A) The silicone resin having a phenolic hydroxyl group imparts film-forming ability, and the phenolic hydroxyl group functions as a photo-crosslinking point.

[0075] The above-mentioned repeating units can be randomly bonded or bonded to form a block polymer. In addition, the siloxane units in each repeating unit can be randomly bonded or can include a block of multiple siloxane units of the same type. In addition, in the (A) organosilicon resin having a phenolic hydroxyl group, the organosilicon (siloxane unit) content is preferably 30 to 80% by mass.

[0076] The weight average molecular weight (Mw) of the silicone resin having a phenolic hydroxyl group (A) is preferably 3,000 to 500,000, more preferably 5,000 to 200,000. In the present invention, Mw is a polystyrene-equivalent measurement value obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.

[0077] The (A) silicone resin having a phenolic hydroxyl group of the present invention is preferably prepared by addition-polymerizing a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3) in the presence of a metal catalyst.

[0078] [Chemical formula 5]

[0079]

[0080] In formula (1) and formula (2), R 5 ~R 8 and m are the same as above.

[0081] [Chemical formula 6]

[0082]

[0083] In formula (3), R 9 ~R 12 , Y 1 、a 1 、a 2 、b 1 、b 2 Same as above.

[0084] As the metal catalyst, platinum (including platinum black), rhodium, palladium and other platinum group metal monomers can be used; 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.) and other platinum chlorides, chloroplatinic acid and chloroplatinates; alcohol-modified chloroplatinic acid Acid (for example, alcohol-modified chloroplatinic acid described in U.S. Pat. No. 3,220,972); complexes of chloroplatinic acid and olefins (for example, complexes of chloroplatinic acid and olefins described in U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,662 and U.S. Pat. No. 3,775,452); substances in which platinum group metals such as platinum black or palladium are supported on carriers such as alumina, silica, and carbon; rhodium-olefin complexes; tris(triphenylphosphine)rhodium chloride (the so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid or chloroplatinates and vinyl-containing siloxanes (especially vinyl-containing cyclic siloxanes), etc.

[0085] The amount of the catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1% by mass, more preferably 0.01 to 0.1% by mass, based on the total mass of the compounds other than the solvent used in the polyaddition reaction, calculated as the platinum group metal.

[0086] In the polyaddition reaction, a solvent may be used as necessary. As the solvent, for example, a hydrocarbon solvent such as toluene or xylene is preferred.

[0087] From the perspective of not deactivating the catalyst and completing the polymerization in a short time, the polymerization temperature is preferably 40 to 150° C., particularly preferably 60 to 120° C. The polymerization time varies depending on the type and amount of the obtained resin, but in order to prevent moisture from entering the polymerization system, it is preferably about 0.5 to 100 hours, more preferably 0.5 to 30 hours. After the reaction is completed, if a solvent is used, the solvent is distilled off, thereby obtaining (A) an organosilicon resin having a phenolic hydroxyl group.

[0088] In the present invention, the (A) silicone resin having a phenolic hydroxyl group may be used alone or in combination of two or more.

[0089] [(B) Photoacid generator]

[0090] The photoacid generator as component (B) is not particularly limited as long as it is a substance that decomposes and generates acid by light irradiation, but it is preferably generated by irradiating light with a wavelength of 190 to 500 nm. The photoacid generator (B) is used as a curing catalyst. As the photoacid generator, for example, onium salts, diazomethane derivatives, oxadioxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonate derivatives, imide-yl-sulfonate derivatives, oximesulfonate derivatives, iminosulfonate derivatives, triazine derivatives, etc. can be listed.

[0091] Examples of the onium salt include sulfonium salts represented by the following formula (B1) and iodonium salts represented by the following formula (B2).

[0092] [Chemical formula 7]

[0093]

[0094] In formula (B1) and (B2), R 101 ~R 105 Each of them is 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. - It is a non-nucleophilic counter ion.

[0095] The alkyl group may be any of a linear, branched, or cyclic group, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the aryl group include phenyl, naphthyl, and biphenyl. Examples of the aralkyl group include benzyl and phenethyl.

[0096] 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.

[0097] As R 101 ~R 105, preferably: alkyl groups optionally having substituents such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, 2-oxocyclohexyl, etc.; aryl groups optionally having substituents 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, biphenylthiophenyl, etc.; aralkyl groups optionally having substituents such as benzyl and phenethyl. Among them, more preferred are: aryl groups optionally having substituents and aralkyl groups optionally having substituents.

[0098] Examples of the non-nucleophilic counter ions include halide ions such as chloride ion and bromide ion; fluoroalkane sulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion, and nonafluorobutanesulfonate ion; aryl sulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion, and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkane sulfonate ions such as methanesulfonate ion and butanesulfonate ion; fluoroalkane sulfonyl imide ions such as trifluoromethanesulfonyl imide ion; fluoroalkane sulfonyl methide ions such as tris(trifluoromethanesulfonyl)methide ion; borate ions such as tetraphenylborate ion and tetrakis(pentafluorophenyl)borate ion, and the like.

[0099] Examples of the diazomethane derivative include compounds represented by the following formula (B3).

[0100] [Chemical formula 8]

[0101]

[0102] In formula (B3), R 111 and R 112 Each independently represents an alkyl group or a 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.

[0103] The alkyl group may be any of a linear, branched, or cyclic type, and specific examples thereof include the following: 101 ~R 105 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.

[0104] Examples of the aryl group which may have a substituent include 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, halogenated aryl such as fluorophenyl, chlorophenyl, 1,2,3,4,5-pentafluorophenyl, etc. Examples of the aralkyl group include benzyl, phenethyl, etc.

[0105] Examples of the glyoxime derivative include compounds represented by the following formula (B4).

[0106] [Chemical formula 9]

[0107]

[0108] In formula (B4), R 121 ~R 124 are each independently an alkyl group or a 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 are optionally bonded to each other to form a ring together with the carbon atoms to which they are bonded, in which case R 123 and R 124 The group formed by the bonding is a linear or branched alkylene group having 2 to 12 carbon atoms.

[0109] Examples of the alkyl group, halogenated alkyl group, aryl group and aralkyl group which may have a substituent include the following: 111 and R 112 The alkyl group, halogenated alkyl group, aryl group which may have a substituent, and aralkyl group are the same as those exemplified above. Examples of the linear or branched alkylene group include ethylene group, propylene group, butylene group, hexylene group, and the like.

[0110] 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)phenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tri(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, and trimethylsulfonium trifluoromethanesulfonate. methanesulfonate, 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-biphenylthio)phenyl]-4-biphenylphenylsulfonium tris(trifluoromethanesulfonyl) methylate ([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, and the like.

[0111] 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, and bis(isopropylsulfonyl)diazomethane. 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.

[0112] 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-pentanedioneglyoxime, bis-(p-toluenesulfonyl)-2-methyl-3,4-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedioneglyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedioneglyoxime. Glyoxime, bis-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, bis-o-(camphorsulfonyl)-α-dimethylglyoxime and the like.

[0113] Specific examples of the β-ketosulfone derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0114] Specific examples of the disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

[0115] Specific examples of the nitrobenzyl sulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate.

[0116] Specific examples of the sulfonic acid ester derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0117] Specific examples of the imido-sulfonate derivatives include phthalimido-trifluoromethanesulfonate, phthalimido-toluenesulfonate, 5-norbornene-2,3-dicarboximido-trifluoromethanesulfonate, 5-norbornene-2,3-dicarboximido-toluenesulfonate, 5-norbornene-2,3-dicarboximido-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthyl imide.

[0118] Specific examples of the oxime sulfonate derivatives include α-(phenylsulfonyloxyimino)-4-methylphenylacetonitrile and the like.

[0119] Specific examples of the imidosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophene-2-methylene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophene-2-methylene)-(2-methylphenyl)-acetonitrile.

[0120] 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.

[0121] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be preferably used.

[0122] As the photoacid generator of the component (B), the onium salts and the sulfonium salts are particularly preferred, and the sulfonium salts are more preferred.

[0123] (B) The photoacid generator is preferably in the range of 0.05 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, relative to the total amount of the photosensitive resin composition. When the photoacid generator is contained within the above range, a pattern having an excellent balance between sensitivity and developability during exposure, no residual film, and excellent resolution can be obtained. In addition, the photoacid generator may be used alone or in combination of two or more.

[0124] [(C) Quantum dots with specific surface coatings]

[0125] Quantum dots refer to nano-sized semiconductor materials. Atoms form molecules, molecules form small molecular aggregates such as clusters, and then form nanoparticles. When such nanoparticles show semiconductor properties, they are called quantum dots (quantum dot particles).

[0126] When a quantum dot receives energy from the outside and reaches an excited state, it will autonomously (self-regulatingly) release the energy brought by the corresponding energy band gap (produce light).

[0127] The (C) quantum dots used in the present invention are not particularly limited as long as they are substances having a surface coating layer containing siloxane, and can be used in any form. Quantum dots are mainly nanoparticles of less than 10 nm, and can also be nanowires, nanorods, nanotubes, nanocubes, etc., and quantum dots of any shape can be used appropriately. In the present invention, the average particle size of the quantum dots uses the following value: at least 20 particles are directly observed using a transmission electron microscope (TEM), and the diameter of a circle with the same area as the projected area of ​​the particles is calculated, and the average value of these diameters is used as the average particle size of the quantum dots.

[0128] The (C) quantum dots used in the present invention can use any suitable material. For example, as a semiconductor material, a 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 and their mixed crystals or alloys, or a compound having a perovskite structure can be used. Specific examples include 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, but are not limited to these.

[0129] The (C) quantum dots used in the present invention can have a core-shell structure. As a shell material capable of forming a core-shell structure, it is not particularly limited, preferably a material with a large band gap and low lattice mismatch relative to the core material, which 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., and the above materials can be selected from a single one, or a variety of mixed crystals, but are not limited thereto.

[0130] The preparation methods of the (C) quantum dots used in the present invention include various methods such as liquid phase method or gas phase method. In the present invention, although there is no special limitation, from the perspective of exhibiting high fluorescent luminescence efficiency, it is preferred to use semiconductor nanoparticles obtained by thermal decomposition or hot injection method in which precursor species are reacted at high temperature in a high-boiling point non-polar solvent. In order to give it dispersibility in non-polar solvents and reduce surface defects, it is best to have organic ligands on the surface.

[0131] From the perspective of dispersibility, the organic ligand preferably comprises an aliphatic hydrocarbon. As such organic ligand, for example, oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, caprylic acid, oleylamine, stearyl (octadecyl) amine, dodecyl (lauryl) amine, decylamine, octylamine, octadecyl mercaptan, hexadecyl mercaptan, tetradecyl mercaptan, dodecyl mercaptan, decanethiol, octyl mercaptan, trioctyl phosphine, trioctyl phosphine oxide, triphenylphosphine, triphenylphosphine oxide, tributylphosphine, tributylphosphine oxide, etc. can be listed, and these organic ligands can be used alone or in combination.

[0132] In addition to the above-mentioned organic ligands, the (C) quantum dots used in the present invention are also coordinated with ligands having substituents capable of forming siloxane bonds. As ligands having substituents capable of forming siloxane bonds, it is preferred to have substituents that interact or adsorb on the surface of the quantum dots. As substituents that interact or adsorb on the surface of the quantum dots, amino, thiol, carboxyl, mercapto, phosphino, phosphine, phosphine oxide, sulfonyl, ammonium ion, quaternary ammonium salt, etc. can be listed, wherein, from the perspective of the strength of coordination, amino, carboxyl, mercapto, phosphine, quaternary ammonium salt are preferred.

[0133] The (C) quantum dots used in the present invention are coated with the quantum dot surface by siloxane. Therefore, a substituent capable of forming a siloxane bond is present in the ligand having a substituent that interacts or adsorbs on the surface of the above-mentioned quantum dots. There are compounds containing alkoxysilanes such as trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethylmethoxysilyl, ethoxydimethylsilyl as substituents capable of forming siloxane bonds, compounds having silazane bonds, compounds having Si-OH bonds, compounds having Si-X (X: halogen) bonds, carboxylic acids, etc., and since it is possible to react under mild conditions without producing an acid as a reaction byproduct, it is preferred to use a ligand containing an alkoxysilane or silazane, Si-OH. By reacting it with diphenyldisilanol, etc., a phenyl-containing siloxane can be formed.

[0134] The amount of siloxane coating is not particularly limited, and is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass in the quantum dots. If the amount of siloxane coating is too much, the quantum dot content will decrease, but within the above range, the dispersibility in the base polymer can be improved and the degradation of the quantum dots during exposure can be suppressed.

[0135] The (C) quantum dot used in the present invention may further include a skeleton having a phenolic hydroxyl group in the surface coating layer.

[0136] As the skeleton having a phenolic hydroxyl group, a skeleton structure derived from the following formula (c) is preferred.

[0137] [Chemical formula 10]

[0138]

[0139] In formula (c), Y 2 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 1 and R 2 are each independently a hydrogen atom or a methyl group. 3 and R 4 Each of them is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 3 and a 4 Each independently represents an integer of 0 to 7, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3. 3 and b 4 Each independently represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0140] The alkyl group having 1 to 4 carbon atoms may be any one of linear, branched, and cyclic, and specific examples thereof include methyl, ethyl, propyl, butyl, and structural isomers thereof. The alkoxy group having 1 to 4 carbon atoms may be any one of linear, branched, and cyclic, and specific examples thereof include methoxy, ethoxy, propoxy, butoxy, and structural isomers thereof.

[0141] By introducing the skeleton structure of formula (c) into the surface coating layer, the silicone resin (A) having phenolic hydroxyl groups will crosslink with the surface coating layer after exposure, thereby suppressing the release of quantum dots during development and obtaining higher luminescence characteristics of the pattern.

[0142] Furthermore, by introducing the skeleton structure of the formula (c) into the surface coating layer, the compatibility with the silicone resin (A) having a phenolic hydroxyl group is improved, and the generation of aggregates when the photosensitive resin composition is prepared can be suppressed.

[0143] The quantum dots (C) used in the present invention are preferably 5 to 80% by mass, more preferably 10 to 70% by mass, relative to the total amount of the photosensitive resin composition. If the content of the quantum dot particles is within the above range, a fine pattern can be formed while maintaining good luminescent properties.

[0144] The method and amount of introducing the phenolic hydroxyl group in the component (C) are not particularly limited. When forming the above-mentioned phenyl-containing siloxane, the following methods can be adopted: a method of adding a pre-made skeleton having a phenolic hydroxyl group containing an alkoxysilane and reacting, a method of directly introducing the skeleton having a phenolic hydroxyl group by a free radical reaction, etc. The amount of introduction can be appropriately adjusted in consideration of the compatibility in the resin.

[0145] [(D) Cross-linking agent]

[0146] The photosensitive resin composition of the present invention may further include a crosslinking agent as component (D). The crosslinking agent is a component for condensing with the phenolic hydroxyl groups in the silicone resin (A) having phenolic hydroxyl groups to facilitate pattern formation, and is also a component for further improving the strength of the resin film after photocuring.

[0147] As the crosslinking agent, nitrogen-containing compounds such as melamine compounds, guanamine compounds, glycoluril compounds, and urea compounds containing an average of two or more hydroxymethyl and / or alkoxymethyl groups in one molecule, amino condensates modified by formaldehyde or formaldehyde-alcohol, phenol compounds having an average of two or more hydroxymethyl or alkoxymethyl groups in one molecule, and epoxy compounds having an average of two or more epoxy groups in one molecule are preferred. These crosslinking agent compounds may be used alone or in combination of two or more.

[0148] As the melamine compound, a compound represented by the following formula (D1) may be mentioned.

[0149] [Chemical formula 11]

[0150]

[0151] In formula (D1), R 201 ~R 206 Each of the hydroxymethyl groups is independently a hydroxymethyl group, an alkoxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, but an average of 2 or more hydroxymethyl groups and / or alkoxymethyl groups are contained in one molecule. Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

[0152] Examples of the melamine compound represented by the formula (D1) include trimethoxymethylmonomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, and hexaethoxymethylmelamine.

[0153] The melamine compound represented by formula (D1) can be obtained, for example, by first modifying the melamine monomer by methylolation with formaldehyde according to a known method, or by further modifying it by alkoxylation with an alcohol. In addition, the alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0154] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0155] Examples of the glycoluril compound include tetrakishydroxymethyl glycoluril and tetrakis(methoxymethyl) glycoluril, and examples of the urea compound include tetrakishydroxymethyl urea, tetrakismethoxymethyl urea, tetrakismethoxyethyl urea, tetrakisethoxymethyl urea and tetrakispropoxymethyl urea.

[0156] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include melamine condensate modified with formaldehyde or formaldehyde-alcohol, and urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0157] As the modified melamine condensate, there can be mentioned a substance obtained by adding and polycondensing a compound represented by formula (D1) or a polymer thereof (e.g., an oligomer such as a dimer or a trimer) with formaldehyde to a desired molecular weight. In addition, as the method for the addition and polycondensation, a conventionally known method can be adopted. In addition, the modified melamine represented by formula (D1) can be used alone or in combination of two or more.

[0158] Examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, propoxymethylated urea condensate, and the like.

[0159] The modified urea condensate can be obtained, for example, by subjecting urea of ​​a desired molecular weight to hydroxymethylation with formaldehyde according to a known method, or can be obtained by further subjecting the urea to alkoxylation with an alcohol.

[0160] Examples of the phenol compound having an average of two or more hydroxymethyl groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2′,6,6′-tetramethoxymethylbisphenol A.

[0161] Examples of the epoxy compound having two or more epoxy groups include bisphenol-type epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins and other novolac-type epoxy resins, trisphenol alkane-type epoxy resins, biphenyl-type epoxy resins, dicyclopentadiene-modified phenol novolac-type epoxy resins, phenol aralkyl-type epoxy resins, biphenyl aralkyl-type epoxy resins, naphthalene-ring-containing epoxy resins, glycidyl ester-type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and the like.

[0162] When the component (D) is contained, the content of the component (D) is preferably 0.5 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, and further preferably 1 to 30 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 when irradiated with light. The component (D) can be used alone or in combination of two or more.

[0163] [(E) Solvent]

[0164] 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 adding the solvent, the coating property of the photosensitive resin composition can be improved.

[0165] As such a solvent, an organic solvent is preferred because of its excellent solubility in the above-mentioned components. As the organic solvent, 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 monotert-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 photoacid generator.

[0166] The content of the component (E) is preferably 25 to 85% by mass, more preferably 35 to 75% by mass, based on the total amount of the photosensitive resin composition, from the viewpoint of compatibility and viscosity of the photosensitive resin composition.

[0167] [Photosensitive resin coating]

[0168] The photosensitive resin coating of the present invention is a dried product of the photosensitive resin composition.

[0169] [Pattern forming method using photosensitive resin composition]

[0170] The pattern forming method using the photosensitive resin composition of the present invention comprises the following steps:

[0171] (i) coating the above-mentioned photosensitive resin composition on a substrate to form a photosensitive resin coating on the substrate,

[0172] (ii) exposing the photosensitive resin film to light, and

[0173] (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.

[0174] Step (i) is a step of coating the above-mentioned photosensitive resin composition on a substrate to form a photosensitive resin coating on the substrate. Examples of the substrate include silicon wafers, glass wafers, quartz wafers, and micro-LED stacked substrates.

[0175] The coating method may be a known method, such as dip coating, spin coating, roll coating, etc. The coating amount can be appropriately selected according to the purpose, but the coating is preferably performed so that the thickness of the obtained photosensitive resin coating is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0176] For the purpose of improving the uniformity of the film thickness on the substrate surface, a solvent may be added to the substrate before applying the photosensitive resin composition (pre-wetting method). The added solvent may be appropriately selected according to the purpose. As the solvent, for example, alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, glycols such as propylene glycol monomethyl ether, etc. are preferred, and the solvent used in the photosensitive resin composition may also be used.

[0177] The solvent or the like may be volatilized in advance by preheating (prebaking) as needed to efficiently perform the photocuring reaction. The prebaking may be performed at 40 to 140° C. for about 1 minute to 1 hour, for example.

[0178] Next, (ii) the photosensitive resin coating is exposed. At this time, the exposure is preferably carried out using light with a wavelength of 10 to 600 nm, and more preferably using light with a wavelength of 190 to 500 nm. Examples of such light of such wavelength include light of various wavelengths generated by a radiation generating device, such as ultraviolet light such as g-line, h-line, i-line, and far ultraviolet light (248 nm, 193 nm). 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.

[0179] The exposure can be performed through a photomask. The photomask can be, for example, a film in which a desired pattern is hollowed out. In addition, the material of the photomask is not particularly limited, and is preferably a material that shields the light of the above wavelength, for example, a material having chromium is suitable for use as a light-shielding film, but is not limited thereto.

[0180] Furthermore, in order to improve the developing sensitivity, a post-exposure heating (PEB) treatment may be performed. PEB is preferably set to 40 to 150° C. and 0.5 to 20 minutes. Through PEB, the exposed part is cross-linked to form an insoluble pattern that is insoluble in an organic solvent as a developer. The state in which the solvent is removed through this pre-baking is set as a dry body.

[0181] After exposure or PEB, (iii) the non-exposed part is dissolved and removed by developing with a developer to form a pattern. As the developer, for example, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, glycols such as propylene glycol monomethyl ether, etc. are preferred, and the solvent used in the photosensitive resin composition can also be used. As the developing method, it can be a conventional method, for example, a method of immersing the substrate formed with the pattern in the developer, etc. Then, washing, rinsing, drying, etc. are performed as required to obtain a cured film having the desired pattern.

[0182] Furthermore, the patterned coating may be post-cured preferably at 100 to 200° C. using an oven or a hot plate.

[0183] [Photosensitive dry film]

[0184] The photosensitive dry film of the present invention comprises a supporting film, and a photosensitive resin coating film obtained from a photosensitive resin composition is disposed on the supporting film.

[0185] The photosensitive dry film (support film and photosensitive resin coating) is solid. Since the photosensitive resin coating does not contain solvent, there is no need to worry about bubbles generated by its volatilization remaining inside the photosensitive resin coating and between the substrate with uneven surfaces. The film thickness of the photosensitive resin coating is not particularly limited, preferably 1 to 200 μm, more preferably 3 to 100 μm.

[0186] In addition, the viscosity of the photosensitive resin coating is closely related to fluidity. The photosensitive resin coating can exhibit appropriate fluidity within an appropriate viscosity range, can enter deep into narrow gaps, and can enhance adhesion to the substrate by softening the resin. Therefore, from the perspective of fluidity of the photosensitive resin coating, the viscosity of the photosensitive resin coating 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 a measured value measured by a rotational viscometer.

[0187] When the photosensitive dry film of the present invention is closely attached to a substrate having uneven surfaces, the photosensitive resin coating will follow and cover the uneven surfaces, thereby achieving high flatness. In particular, since the photosensitive resin composition of the present invention is characterized by softening properties, higher flatness can be achieved. Furthermore, if the photosensitive resin coating is closely attached to the substrate in a vacuum environment, a gap between them can be more effectively prevented.

[0188] The photosensitive dry film of the present invention can be manufactured in the following manner: the photosensitive resin composition is coated on a substrate and dried to form a photosensitive resin coating. As a manufacturing device 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 multi-coater, 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.

[0189] The photosensitive dry film can be manufactured in the following manner: when the support film is unwound from the unwinding shaft of the coating machine and passed through the coating head of the coating machine, the photosensitive resin composition is coated on the support film with a specified thickness, and then passed through a hot air circulation oven at a specified temperature and time, and dried on the support film to form a photosensitive resin coating. In addition, the photosensitive dry film with a protective film can be manufactured in the following manner: as needed, the photosensitive dry film and the protective film unwound from the other unwinding shaft of the coating machine are passed through a laminating roller under a specified pressure, and the photosensitive resin coating on the support film is laminated with the protective film, and then wound on the winding shaft of the coating machine. At this time, the temperature is preferably 25~150°C, the time is preferably 1~100 minutes, and the pressure is preferably 0.01~5MPa.

[0190] The support film used in the photosensitive dry film of the present invention can be a single-layer film composed of a single film, or a multilayer film composed of a plurality of films. As the material of the film, synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate can be listed. Among them, polyethylene terephthalate having appropriate flexibility, mechanical strength, and heat resistance is preferred. These films can be films subjected to various treatments such as corona treatment or stripping agent coating. These films can use commercially available products, for example, Cerapeel WZ (RX), Cerapeel BX8 (R) (the above, manufactured by TORAY ADVANCED FILM CO., LTD.), E7302, E7304 (the above, manufactured by TOYOBO Co., Ltd.), Purex G31, Purex G71T1 (the above, manufactured by Teijin DuPont Films Japan Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (the above, manufactured by NIPPA Co., Ltd.), etc.

[0191] As the protective film, the same film as the aforementioned support film can be used, but polyethylene terephthalate and polyethylene having appropriate flexibility are preferred. These films can use commercial products, and as polyethylene terephthalate, commercially available polyethylene terephthalate that has been exemplified can be listed, and as polyethylene, for example, GF-8 (manufactured by Tamapoly CO., LTD.), PE Film 0-Type (manufactured by NIPPA Co., Ltd.) and the like can be listed.

[0192] From the perspective of stability in the manufacture of the photosensitive dry film and preventing curling of the core, the thickness of the support film and the protective film is preferably 10-100 μm, more preferably 25-50 μm.

[0193] [Pattern forming method using photosensitive dry film]

[0194] The pattern forming method using the photosensitive dry film of the present invention comprises the following steps:

[0195] (i') attaching the photosensitive resin coating of the photosensitive dry film onto a substrate to form the photosensitive resin coating on the substrate;

[0196] (ii) exposing the photosensitive resin film to light; and

[0197] (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.

[0198] First, (i') a photosensitive dry film is used, and the photosensitive resin coating is attached to a substrate to form a photosensitive resin coating on the substrate. That is, the photosensitive resin coating of the photosensitive dry film is attached to the substrate to form a photosensitive resin coating on the substrate. In addition, when the photosensitive dry film has a protective film, after the protective film is peeled off from the photosensitive dry film, the photosensitive resin coating of the photosensitive dry film is attached to the substrate. The attachment can be implemented using a film attaching device, for example.

[0199] As the film laminating device, a vacuum laminator is preferred. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is closely attached to the substrate on a workbench at a specified temperature using a laminating roller at a specified pressure in a vacuum chamber at a specified vacuum degree. In addition, the temperature is preferably 60-120°C, the pressure is preferably 0-5.0MPa, and the vacuum degree is preferably 50-500Pa.

[0200] In order to efficiently perform 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 needed. The pre-baking may be performed at 40 to 140° C. for about 1 minute to 1 hour, for example.

[0201] The photosensitive resin film attached to the substrate can be patterned by (ii) exposing the photosensitive resin film, (iii) developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed portion, and (iv) performing a post-curing heat treatment as required. In addition, the support film of the photosensitive dry film is peeled off before pre-baking or PEB according to the process, or removed by other methods.

[0202] The pattern forming method using the photosensitive resin composition or photosensitive dry film of the present invention can easily form a fine pattern. For example, the photosensitive resin composition or photosensitive dry film of the present invention is formed into a film in a manner of covering a plurality of blue micro-LEDs on a substrate, and then a fine pattern is formed, thereby partially forming a cured film containing red or green quantum dots on the blue micro-LEDs, so that red or green light can also be generated, and thus a full-color light-emitting element can be manufactured.

[0203] [Light-emitting element]

[0204] The light emitting element of the present invention includes a cured film obtained by the above-mentioned pattern forming method.

[0205] Example

[0206] The following are synthesis examples, embodiments and comparative examples to explain the present invention in more detail, but the present invention is not limited to the following embodiments. In addition, as quantum dot materials, core-shell quantum dots of InP / ZnSe / ZnS are used, and the synthesis method of the core is shown in [1-1] (red quantum dots) and [1-2] (green quantum dots) described later, and the synthesis method of the shell is shown in [2].

[0207] [1-1] Synthesis process of red quantum dot core

[0208] Prepare two flasks, add 0.23g (0.9mmol) of palmitic acid, 0.088g (0.3mmol) of indium acetate, and 10mL of 1-octadecene, respectively, and heat and stir at 100°C under reduced pressure to dissolve the raw materials, and degas for 1 hour at the same time. Then, purge the inside of the two flasks with nitrogen, and add 0.75mL (0.15mmol) of tri(trimethylsilyl)phosphine / trioctylphosphine solution (0.2M) to the two flasks. Then, heat one of the flasks to 300°C, extract the solution from the unheated flask, and add it to the flask heated to 300°C to generate core particles.

[0209] [1-2] Synthesis process of green quantum dot core

[0210] 0.23 g (0.9 mmol) of palmitic acid, 0.088 g (0.3 mmol) of indium acetate, and 10 mL of 1-octadecene were added to the flask, and heated and stirred at 100° C. under reduced pressure to dissolve the raw materials, and degassing was performed for 1 hour. Then, the inside of the flask was purged with nitrogen, 0.75 mL (0.15 mmol) of a 0.2 M solution of a mixed tri(trimethylsilyl)phosphine and trioctylphosphine was added, and the temperature was raised to 300° C. to generate core particles.

[0211] [2] Synthesis process of quantum dot shell

[0212] Next, 2.85 g (4.5 mmol) of zinc stearate and 15 mL of 1-octadecene were added to another flask, and the mixture was heated and stirred at 100° C. under reduced pressure to dissolve the mixture, while degassing for 1 hour to prepare a 0.3 M degassed zinc stearate octadecene solution, which was added to the reaction solution after the core synthesis at 3.0 mL (0.9 mmol) 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. and dissolved to prepare a 1.5 M trioctylphosphine selenide solution, and the reaction solution after the core synthesis step, which had been previously cooled to 200° C., was heated to 320° C. over 30 minutes, while a total of 0.6 mL (0.9 mmol) of the trioctylphosphine selenide solution was added every 0.1 mL, and the mixture was kept at 320° C. for 10 minutes and then cooled to room temperature. Add 0.44 g (2.2 mmol) of zinc acetate, heat and stir at 100°C under reduced pressure to dissolve it. Purge the inside of the flask with nitrogen again and raise the temperature to 230°C, add 0.98 mL (4 mmol) of 1-dodecanethiol, and keep it for 1 hour. The obtained solution is cooled to room temperature to prepare a solution containing core-shell quantum dots. The red core-shell quantum dots synthesized by steps [1-1] to [2] are referred to as R-1, and the solution containing green core-shell quantum dots synthesized by steps [1-2] to [2] is referred to as G-1.

[0213] [3] Ligand exchange process

[0214] As a ligand having a substituent capable of forming a siloxane bond and a substituent coordinated to the surface of the quantum dot, (3-mercaptopropyl) triethoxysilane is used. As a ligand exchange reaction, (3-mercaptopropyl) triethoxysilane (3.0mmol) is added to the solution after the shell synthesis step cooled to room temperature and stirred for 24 hours. After the reaction is completed, ethanol is added to precipitate the reaction solution, centrifuged, and the supernatant is removed. The same purification is performed again, and it is dispersed in toluene to prepare a quantum dot solution coordinated with a ligand having a substituent capable of forming a siloxane bond. The quantum dots synthesized using R-1 coordinated with a ligand having a substituent capable of forming a siloxane bond are used as R-2, and the quantum dots synthesized using G-1 coordinated with a ligand having a substituent capable of forming a siloxane bond are used as G-2.

[0215] [4-1] Surface coating layer formation process

[0216] 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 flask previously purged with nitrogen, and heated and stirred at 65°C for 24 hours. After the reaction was completed, it was cooled to room temperature, ethanol was added to precipitate the reaction solution, centrifuged, and the supernatant was removed. It was dispersed in toluene and added to a flask previously purged with nitrogen. 2 parts by mass of the compound represented by the following formula (1) were added to 100 parts by mass of the quantum dot toluene solution. Furthermore, 1 part by mass of Irgacure 1173 was added to 100 parts by mass of the compound represented by the following formula (1), and the mixture was stirred and mixed, and then irradiated for 20 seconds by a UVLED irradiation device with a wavelength of 365 nm and an output of 4000 mW / cm 2 After the reaction, ethanol was added to precipitate it, and the supernatant was removed by centrifugation and redispersed in toluene. Then, PGMEA was added, and the toluene solvent was removed by vacuum distillation to prepare a quantum dot solution with a surface coating layer (solid content concentration of 60%). Among them, the quantum dots with a surface coating layer formed on the basis of R-2 were referred to as R-(1), and the quantum dots with a surface coating layer formed on the basis of G-2 were referred to as G-(1).

[0217] [4-2] Surface coating layer formation process

[0218] 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 flask previously purged with nitrogen, and heated and stirred at 65°C for 24 hours. After the reaction was completed, it was cooled to room temperature, ethanol was added to precipitate the reaction solution, and centrifuged to remove the supernatant. It was dispersed in toluene and added to a flask previously purged with nitrogen. With respect to 100 parts by mass of the quantum dot toluene solution, 2 parts by mass of the compound represented by the following formula (1') were added. Furthermore, 1 part by mass of Irgacure 1173 was added to 100 parts by mass of the compound represented by the following formula (1'), and the mixture was stirred and mixed, and then irradiated with a UVLED irradiation device for 20 seconds with a wavelength of 365 nm and an output of 4000 mW / cm 2After the reaction, ethanol was added to precipitate it, and the supernatant was removed after centrifugation and redispersed in toluene. Then, PGMEA was added, and the toluene solvent was removed by vacuum distillation to prepare a quantum dot solution with a surface coating layer (solid content concentration of 60%). Among them, the quantum dots with a surface coating layer formed on the basis of R-2 were referred to as R-(1'), and the quantum dots with a surface coating layer formed on the basis of G-2 were referred to as G-(1').

[0219] [5] Synthesis of silicone resin

[0220] [Synthesis Example 1] Synthesis of Resin 1

[0221] After adding 215.0 g (0.50 mol) of compound (1) to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 mass %) was added, and 58.2 g (0.30 mol) of compound (2) and 604.0 g (0.20 mol) of compound (4) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was removed from the reaction solution under reduced pressure to obtain resin 1. GPC confirmed the disappearance of the peaks of each raw material and the Mw of resin 1 was 80,000 (organic silicon content: 68.9 mass %; the organic silicon content is a calculated value obtained from the added amount).

[0222] [Synthesis Example 2] Synthesis of Resin 2

[0223] After adding 215.0 g (0.50 mol) of compound (1) to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 mass %) was added, and 67.9 g (0.35 mol) of compound (2), 6.7 g (0.05 mol) of compound (3) and 302.0 g (0.10 mol) of compound (4) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was removed from the reaction solution under reduced pressure to obtain resin 2. GPC confirmed the disappearance of the peaks of each raw material and the Mw of resin 2 was 40,000 (organic silicon content: 52.2 mass %).

[0224] [Synthesis Example 3] Synthesis of Resin 3

[0225] After adding 215.0 g (0.50 mol) of compound (1) to a 3 L flask equipped with a stirrer, a thermometer, a nitrogen replacement device and a reflux condenser, 2,000 g of toluene was added and heated to 70°C. Then, 1.0 g of a chloroplatinic acid toluene solution (platinum concentration: 0.5 mass %) was added, and 87.3 g (0.45 mol) of compound (2), 6.7 g (0.05 mol) of compound (3) and 151.0 g (0.05 mol) of compound (4) (total of hydrosilyl groups / total of alkenyl groups = 1 / 1 (molar ratio)) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 100°C and aged for 6 hours, and then toluene was removed from the reaction solution under reduced pressure to obtain resin 2. GPC confirmed the disappearance of the peaks of each raw material and the Mw of resin 3 was 13,000 (organic silicon content: 34.3 mass %).

[0226] The compounds (1) to (4) used in the above synthesis examples are shown below.

[0227] [Chemical formula 12]

[0228]

[0229] [6] Preparation and evaluation of photosensitive resin compositions

[0230] [Examples 1 to 12 and Comparative Examples 1 to 24]

[0231] The components were blended in the amounts listed in Tables 1 to 4, stirred and mixed at room temperature, and microfiltered using a 1.0 μm glass filter to obtain photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 24.

[0232] [Table 1]

[0233]

[0234] [Table 2]

[0235]

[0236] [Table 3]

[0237]

[0238] [Table 4]

[0239]

[0240] The photoacid generators B-1 and B-2 used in Tables 1 to 4 are shown below.

[0241] [Chemical formula 13]

[0242]

[0243] The crosslinking agents D-1 and D-2 used in Tables 1 to 4 are shown below.

[0244] [Chemical formula 14]

[0245]

[0246] In Tables 1 to 4, quantum dot R-3 is S-BE030 manufactured by Shoei Chemical (Co., Ltd.) (particle size is 5 to 10 nm, material is InP:ZnS:SeZn=25:50:25), R-4 is 900514-1ML manufactured by Aldrich (particle size is 5 to 10 nm, material is CdSe (core) / CdS (shell) core-shell type), G-3 is S-BE029 manufactured by Shoei Chemical (Co., Ltd.) (particle size is 3 to 5 nm, material is InP:ZnS:SeZn=25:50:25), and G-4 is 900511-1ML manufactured by Aldrich (particle size is 3 to 5 nm, material is CdSe (core) / CdS (shell) core-shell type).

[0247] [7]Manufacturing of photosensitive dry film

[0248] A die coater was used as a coating machine, a polyethylene terephthalate film (thickness 38 μm) was used as a support film, and the photosensitive resin compositions described in Tables 1 to 4 were coated on the support film, respectively. Then, the film was passed through a hot air circulation oven (length 4 m) set at 100° C. for 5 minutes for drying, thereby forming a photosensitive resin coating with a thickness of 20 μm on the support film to obtain a photosensitive dry film. A polyethylene film (thickness 50 μm) was laminated as a protective film from above the photosensitive resin coating at a pressure of 1 MPa and attached to produce a photosensitive dry film with a protective film.

[0249] [8] Evaluation of photosensitive resin coating

[0250] (1) Confirmation of aggregates in the photosensitive resin film

[0251] The protective film of the photosensitive dry film with a protective film was peeled off, and the agglomerates in the photosensitive dry film were confirmed using an optical microscope. The presence of agglomerates larger than 1 μm was evaluated as ×, and the absence of agglomerates or the presence of agglomerates smaller than 1 μm was evaluated as ○. The results are shown in Tables 5 to 8.

[0252] (2) Pattern formation and evaluation

[0253] 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 tightly attached to the silicon wafer. The temperature condition is set to 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 adhesion with the substrate, pre-bake at 110°C for 3 minutes on a hot plate. In order to form a square island pattern with a pitch width of 1:1 with the adjacent pattern through a mask for the obtained photosensitive resin coating, an i-line photolithography machine NSR-2205i11D (manufactured by Nikon) is used for exposure. After irradiation, PEB is performed at 120°C for 3 minutes on a hot plate and then cooled, and the substrate is spray-developed for 60 seconds using PGMEA to form a pattern. Then, nitrogen was purged in an oven at 150°C for 2 hours and post-cured at the same time. Then, the island patterns with a side of 100 μm, 50 μm, 30 μm, 20 μm, and 10 μm were observed by scanning electron microscopy (SEM), and the smallest pattern size that was not connected to the adjacent island pattern (pitch width was 1:1) was taken as the limiting resolution. In addition, the evaluation of the resolution not reaching 100 μm or the development peeling of the pattern occurred was ×. The results are shown in Tables 5 to 8.

[0254] (3) Evaluation of light-emitting properties of formed patterns

[0255] The patterned sample manufactured in (2) was irradiated with a 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 laminate manufactured in (2) and the sample after the support film peeling process were subjected to the same measurement, and the luminous intensity of the light after photoconversion was measured. The results are shown in Tables 5 to 8 (M: 1 million).

[0256] (4) Reliability test evaluation

[0257] The photosensitive resin compositions described in Tables 1 to 4 were coated on a glass substrate with a film thickness of 100 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 20 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 aligner type exposure device was used for exposure under an exposure condition of 365 nm. After irradiation, PEB was performed at 140°C for 5 minutes using a hot plate and then cooled, and the substrate was sprayed with PGMEA for 300 seconds to form a pattern. Then, an oven was used to purge nitrogen at 150°C for 2 hours and cure at the same time. The patterned sample was subjected to a thermal cycle test (the following cycle was repeated 1,000 times: kept at -55°C for 10 minutes and kept at 125°C for 10 minutes), and the state of peeling of the cured coating from the substrate after the thermal cycle test and the presence or absence of cracks were confirmed. The case where no peeling or cracking occurred was marked as ○, and the case where peeling or cracking occurred at least once was marked as ×. The results are shown in Tables 5 to 8.

[0258] [Table 5]

[0259]

[0260] [Table 6]

[0261]

[0262] [Table 7]

[0263]

[0264] [Table 8]

[0265]

[0266] The above results show that the photosensitive resin composition of the present invention can form a good photosensitive coating and photosensitive dry film without agglomerates (or even if agglomerates are present, they are extremely small), which can provide a cured coating with high lithography resolution, high luminescence properties that do not change before and after the lithography process, good reliability (close adhesion, crack resistance) and suitable for light-emitting elements.

[0267] The following protocols are included in this manual.

[0268] [1]: A photosensitive resin composition, characterized in that it contains:

[0269] (A) a silicone resin having a phenolic hydroxyl group,

[0270] (B) a photoacid generator, and

[0271] (C) Quantum dots,

[0272] The quantum dots have a surface coating layer containing siloxane.

[0273] [2]: The photosensitive resin composition according to [1] above, wherein the component (C) contains a skeleton having a phenolic hydroxyl group in the surface coating layer.

[0274] [3]: The photosensitive resin composition according to [1] or [2], wherein the component (A) comprises a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1).

[0275] [Chemical formula 15]

[0276]

[0277] In formula (a1) and formula (b1), R 5 ~R 8 Each of X is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer of 0 to 600. 1 It is a divalent group represented by the following formula (X1).

[0278] [Chemical formula 16]

[0279]

[0280] In formula (X1), Y 1 R is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl. 9 and R 10 are each independently a hydrogen atom or a methyl group. 11 and R 12 Each of them is independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 1 and a 2 Each independently represents an integer from 0 to 7. 1 and b 2 Each independently represents an integer from 0 to 2.

[0281] [4]: The photosensitive resin composition according to [1], [2] or [3], further comprising a crosslinking agent as component (D), wherein the crosslinking agent is selected from at least one of melamine compounds, guanamine compounds, glycoluril compounds and urea compounds containing an average of two or more hydroxymethyl groups and / or alkoxymethyl groups in one molecule, amino condensates modified by formaldehyde or formaldehyde-alcohol, and phenol compounds having an average of two or more hydroxymethyl groups or alkoxymethyl groups in one molecule.

[0282] [5]: The photosensitive resin composition according to [1], [2], [3] or [4], characterized in that the quantum dots of the component (C) have ligands coordinated to the surface thereof, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands 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.

[0283] [6]: The photosensitive resin composition according to [1], [2], [3], [4] or [5], wherein the photosensitive resin composition contains 5 to 80% by mass of the component (C).

[0284] [7]: The photosensitive resin composition according to [1], [2], [3], [4], [5] or [6], further comprising (E) a solvent.

[0285] [8]: A photosensitive resin coating, characterized in that it is a dried product of the photosensitive resin composition of [1], [2], [3], [4], [5], [6] or [7].

[0286] [9]: A photosensitive dry film, characterized in that it comprises a support film and the photosensitive resin coating of [8] is provided on the support film.

[0287]

[10] : A pattern forming method, characterized in that it comprises the following steps:

[0288] (i) a step of coating the photosensitive resin composition of [1], [2], [3], [4], [5], [6] or [7] on a substrate to form a photosensitive resin film on the substrate;

[0289] (ii) exposing the photosensitive resin film to light; and

[0290] (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.

[0291]

[11] : A pattern forming method, characterized in that it comprises the following steps:

[0292] (i') a step of attaching the photosensitive resin coating of the photosensitive dry film of [9] to a substrate to form the photosensitive resin coating on the substrate;

[0293] (ii) exposing the photosensitive resin film to light; and

[0294] (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.

[0295]

[12] : A light-emitting element, characterized in that it comprises a cured film obtained by the pattern forming method of

[10] or

[11] above.

[0296] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are examples, and all technical solutions having substantially the same structure and achieving the same technical effects as the technical concept described in the claims of the present invention are included in the technical scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that: contain: (A) a silicone resin having a phenolic hydroxyl group, (B) a photoacid generator, and (C) Quantum dots, The quantum dots have a surface coating layer containing siloxane.

2. The photosensitive resin composition according to claim 1, characterized in that: The component (C) includes a skeleton having a phenolic hydroxyl group in the surface coating layer.

3. The photosensitive resin composition according to claim 1 or 2, characterized in that: The component (A) comprises a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1), [Chemical formula 1] In formula (a1) and formula (b1), R 5 ~R 8 are independently monovalent hydrocarbon groups having 1 to 8 carbon atoms; m is an integer of 0 to 600; X 1 is a divalent group represented by the following formula (X1), [Chemical formula 2] In formula (X1), Y 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl; R 9 and R 10 are independently a hydrogen atom or a methyl group; R 11 and R 12 are independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; a 1 and a 2 are independently integers from 0 to 7; 1 and b 2 Each independently represents an integer from 0 to 2.

4. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that The invention further comprises a crosslinking agent as the component (D), wherein the crosslinking agent is at least one selected from melamine compounds containing an average of two or more hydroxymethyl groups, alkoxymethyl groups or both in one molecule, guanamine compounds, glycoluril compounds and urea compounds, amino condensates modified by formaldehyde or formaldehyde-alcohol, and phenol compounds having an average of two or more hydroxymethyl groups or alkoxymethyl groups in one molecule.

5. The photosensitive resin composition according to any one of claims 1 to 4, characterized in that The quantum dots of the component (C) have ligands coordinated on their surfaces, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands have any one or more of amino, thiol, carboxyl, phosphine, phosphine oxide and ammonium ions.

6. The photosensitive resin composition according to any one of claims 1 to 5, characterized in that: The photosensitive resin composition contains 5 to 80 mass % of the component (C).

7. The photosensitive resin composition according to any one of claims 1 to 6, characterized in that: It further contains (E) a solvent.

8. A photosensitive resin coating, characterized in that: The photosensitive resin composition is a dried product according to any one of claims 1 to 7.

9. A photosensitive dry film, characterized in that: A supporting film is provided, and the photosensitive resin coating according to claim 8 is provided on the supporting film.

10. A pattern forming method, characterized in that: Including the following processes: (i) 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; (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 non-exposed portion, thereby forming a pattern.

11. A pattern forming method, characterized in that: Including the following processes: (i') a step of attaching the photosensitive resin coating of the photosensitive dry film according to claim 9 to a substrate to form the photosensitive resin coating 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 non-exposed portion, thereby forming a pattern.

12. A light emitting element, characterized in that: A cured film obtained by the pattern forming method according to claim 10 or 11.

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