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

Abstract

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

Description

Technical Field

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

Background Art

[0002] Various methods have been proposed to form a display including red, green, and blue sub-pixels. As one of these methods, there is a method of converting light from an LED array through a color conversion structure from a shorter wavelength of blue light to longer wavelength light of red and green. Quantum dots are used to perform this color conversion.

[0003] In recent years, this LED array has become micro-sized, and micro-LED displays using it have attracted attention. As a method of forming a color conversion structure on an LED array, there is a lithography process using a photosensitive material (Patent Document 1), but in recent years, further miniaturization has been required for application to small displays. Also, from the viewpoint of the sharpness of the display, high requirements are also placed on the light-emitting characteristics.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition capable of easily forming a film having high lithography resolution and good light-emitting characteristics, a photosensitive resin film obtained using the photosensitive resin composition, a photosensitive dry film, a patterning method using these, and a light-emitting element obtained using the photosensitive resin composition. [Means for solving the problem]

[0006] To solve the above problems, the present invention provides a photosensitive resin composition, (A) Silicone resin having phenolic hydroxyl groups, (B) Photoacid generator, and (C) Quantum Dot The present invention provides a photosensitive resin composition comprising a quantum dot having a surface coating layer containing siloxane.

[0007] Such a photosensitive resin composition allows for the easy formation of a film with high lithographic resolution and excellent luminescence properties.

[0008] Furthermore, in the present invention, it is preferable that component (C) contains a skeleton having phenolic hydroxyl groups in the surface coating layer.

[0009] Such a photosensitive resin composition suppresses the loss of quantum dots during development, resulting in a highly luminescent pattern.

[0010] Furthermore, in the present invention, it is preferable that component (A) includes a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1). [ka] [In the formula, R 5 ~R 8 Each of these is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer from 0 to 600. 1 This is a divalent group represented by the following formula (X1). [ka] (In the formula, Y 1is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or a fluorene-9,9-diyl group. R 9 and R 10 are each independently a hydrogen atom or a methyl group. R 11 and R 12 are each 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 each independently an integer from 0 to 7. b 1 and b 2 are each independently an integer from 0 to 2. )]

[0011] For such a photosensitive resin composition, the obtained cured film has high reliability.

[0012] In addition, in the present invention, as the component (D), a crosslinking agent which is at least one selected from a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, formaldehyde or an amino condensate modified with formaldehyde-alcohol, which contains an average of 2 or more methylol groups and / or alkoxymethyl groups in one molecule, and a phenol compound having an average of 2 or more methylol groups or alkoxymethyl groups in one molecule is preferably further contained.

[0013] For such a photosensitive resin composition, the strength of the resin film after photocuring can be further increased.

[0014] In addition, in the present invention, the quantum dots of the component (C) have a ligand coordinated on the surface thereof, the surface coating layer contains a siloxane bond bonded to the ligand, and the substituent of the ligand preferably has any one or more of an amino group, a thiol group, a carboxy group, a phosphino group, a phosphine oxide group, and an ammonium ion.

[0015] Quantum dots having such a ligand are preferable because they are easily coordinated on the surface.

[0016] Furthermore, in the present invention, it is preferable that the photosensitive resin composition contains 5 to 80% by mass of component (C).

[0017] Such a photosensitive resin composition allows for the formation of fine patterns while maintaining good luminescence properties.

[0018] Furthermore, in the present invention, it is preferable that (E) the solvent is further included.

[0019] Such a photosensitive resin composition can improve the coatability of the surface.

[0020] Furthermore, the present invention provides a photosensitive resin film which is a dried body of the photosensitive resin composition described above.

[0021] Such a photosensitive resin coating would result in a coating with high lithographic resolution and excellent luminescence properties.

[0022] Furthermore, the present invention provides a photosensitive dry film comprising a support film and a photosensitive resin coating described above on the support film.

[0023] Such a photosensitive dry film would offer high lithographic resolution and excellent luminescence characteristics.

[0024] Furthermore, the present invention provides a pattern forming method, (i) A step of applying the photosensitive resin composition described above onto a substrate to form a photosensitive resin film on the substrate. (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film with a developer solution to dissolve and remove the unexposed areas and form a pattern. The present invention provides a pattern formation method that includes [specific details].

[0025] Furthermore, the present invention provides a pattern forming method, (i') A step of attaching the photosensitive resin coating of the photosensitive dry film described above onto a substrate to form the photosensitive resin coating on the substrate, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film with a developer solution to dissolve and remove the unexposed areas and form a pattern. The present invention provides a pattern formation method that includes [specific details].

[0026] These pattern formation methods allow for the formation of patterns with high lithographic resolution, resulting in film patterns with excellent luminescence properties.

[0027] Furthermore, the present invention provides a light-emitting element comprising a cured film obtained by the pattern formation method described above.

[0028] Such a light-emitting element would have high lithographic resolution and excellent luminescence characteristics. [Effects of the Invention]

[0029] The photosensitive resin composition of the present invention, by comprising a silicone resin having phenolic hydroxyl groups, a photoacid generator, and quantum dots having a specific surface coating layer, can easily form a film with high resolution and good luminescence properties, making it suitable for light-emitting devices. [Modes for carrying out the invention]

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

[0031] As a result of diligent research into the above-mentioned problems, the present inventors have found that a photosensitive resin composition comprising (A) a silicone resin having phenolic hydroxyl groups, (B) a photoacid generator, and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane, can easily form a film (photosensitive resin film) with high lithographic resolution and good luminescence properties, thus completing the present invention.

[0032] That is, the present invention relates to a photosensitive resin composition, (A) Silicone resin having phenolic hydroxyl groups, (B) Photoacid generator, and (C) Quantum Dot The photosensitive resin composition includes a quantum dot having a surface coating layer containing siloxane.

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

[0034] [Photosensitive resin composition] The photosensitive resin composition of the present invention comprises (A) a silicone resin having phenolic hydroxyl groups, (B) a photoacid generator, and (C) quantum dots having a specific surface coating layer. Optionally, it may further contain other components such as (D) a crosslinking agent and (E) a solvent. The individual components constituting the photosensitive resin composition are described below.

[0035] [(A) Silicone resin having phenolic hydroxyl groups] The silicone resin having a phenolic hydroxyl group (A) used in the present invention is not particularly limited as long as it has a phenolic hydroxyl group.

[0036] A preferred example is a silicone resin containing repeating units represented by the following formula (a1) and repeating units represented by the following formula (b1). [ka]

[0037] In formula (a1), R 5 ~R 8 Each of these is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms, with those having 1 to 6 carbon atoms being preferred. Examples of the monovalent hydrocarbon group include linear, branched, or cyclic alkyl groups and aryl groups. Specific examples include methyl groups, ethyl groups, propyl groups, hexyl groups and their structural isomers, cyclohexyl groups, and phenyl groups. Of these, methyl and phenyl groups are preferred due to the ease of obtaining the raw materials.

[0038] In formula (a1), m is an integer between 0 and 600, preferably between 0 and 400, and more preferably between 0 and 200.

[0039] X 1 This is a divalent group represented by the following formula (X1). [ka]

[0040] In formula (X1), Y 1 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 9 and R 10 Each of these is independently either a hydrogen atom or a methyl group. 11 and R 12 Each of these 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 of these is an integer between 0 and 7, but integers between 1 and 5 are preferred, and integers between 1 and 3 are more preferred. 1 and b 2 Each of these is an integer between 0 and 2, but 0 or 1 is preferred, and 0 is more preferred.

[0041] The C1-C4 alkyl group may be linear, branched, or cyclic, and specific examples include methyl, ethyl, propyl, and butyl groups, as well as their structural isomers. The C1-C4 alkoxy group may be linear, branched, or cyclic, and specific examples include methoxy, ethoxy, propoxy, and butoxy groups, as well as their structural isomers.

[0042] In resin (A), repeating units are included such that a1 + b1 = 1, and a1 > 0, preferably 0.1 ≤ a1 ≤ 0.9 and 0.1 ≤ b1 ≤ 0.9. Furthermore, the silicone content is preferably 20 to 80% by weight, and preferably 30 to 70% by weight.

[0043] (A) Silicone resins having phenolic hydroxyl groups provide film-forming ability, and the phenolic hydroxyl groups function as photocrosslinking sites.

[0044] The repeating units described above may be bonded randomly or as a block polymer. Furthermore, the siloxane units within each repeating unit may be bonded randomly or may contain multiple blocks of the same type of siloxane unit. In addition, (A) in the silicone resin having phenolic hydroxyl groups, the silicone (siloxane unit) content is preferably 30 to 80% by mass.

[0045] (A) The weight-average molecular weight (Mw) of the silicone resin having phenolic hydroxyl groups is preferably 3,000 to 500,000, and more preferably 5,000 to 200,000. In this invention, Mw is a polystyrene-converted value measured by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent.

[0046] (A) Silicone resins having phenolic hydroxyl groups are preferably produced by addition polymerization of a compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3) in the presence of a metal catalyst.

[0047] [ka] (In the formula, R 5 ~R 8 (And m are the same as above.) [ka] (In the formula, R 9 ~R 12 , Y 1 a 1 a 2 , b 1 , b 2 (This is the same as above.)

[0048] The aforementioned metal catalysts include elemental platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chloride, chloroplatinic acid, and chloroplatinate salts such as H2PtCl4·xH2O, H2PtCl6·xH2O, NaHPtCl6·xH2O, KHPtCl6·xH2O, Na2PtCl6·xH2O, K2PtCl4·xH2O, PtCl4·xH2O, PtCl2, and Na2HPtCl4·xH2O (where x is preferably an integer from 0 to 6, and particularly preferably 0 or 6); and alcohol-modified chloroplatinic acid (for example, as described in U.S. Patent No. 3,220,972). ); complexes of chloroplatinic acid and olefins (for example, those described in U.S. Patent No. 3,159,601, U.S. Patent No. 3,159,662, and U.S. Patent No. 3,775,452); platinum group metals such as platinum black and palladium supported on a carrier such as alumina, silica, or carbon; rhodium-olefin complexes; chlorotris(triphenylphosphine)rhodium (so-called Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate salts with vinyl group-containing siloxanes (especially vinyl group-containing cyclic siloxanes), etc. can be used.

[0049] The amount of catalyst used is a catalytic amount, and is usually preferably 0.001 to 0.1% by mass, and more preferably 0.01 to 0.1% by mass, as platinum group metals, in the total mass of compounds other than the solvent used in the addition polymerization reaction.

[0050] In the addition polymerization reaction described above, a solvent may be used as needed. Hydrocarbon solvents such as toluene and xylene are preferred as solvents.

[0051] The reaction temperature is preferably 40 to 150°C, and more preferably 60 to 120°C, from the viewpoint of preventing catalyst deactivation and enabling polymerization to be completed in a short time. The polymerization time depends on the type and amount of resin obtained, but to prevent moisture from entering the polymerization system, it is preferably about 0.5 to 100 hours, and more preferably 0.5 to 30 hours. After the reaction is complete, if a solvent was used, it can be removed by distillation to obtain (A) a silicone resin having phenolic hydroxyl groups.

[0052] In the present invention, (A) the silicone resin having a phenolic hydroxyl group may be used alone or in combination of two or more types.

[0053] [(B) Photoacid Generator] The photoacid generator of component (B) is not particularly limited as long as it decomposes upon light irradiation and generates acid, but it is preferable that it generates acid when irradiated with light of a wavelength of 190 to 500 nm. The photoacid generator (B) is used as a curing catalyst. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonic acid ester derivatives, imido-yl-sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, and the like.

[0054] Examples of the onium salt include sulfonium salts represented by the following formula (B1) or iodonium salts represented by the following formula (B2). [ka]

[0055] In formulas (B1) and (B2), R 101 ~R 105 Each of these is independently an alkyl group having 1 to 12 carbon atoms that may have substituents, an aryl group having 6 to 12 carbon atoms that may have substituents, or an aralkyl group having 7 to 12 carbon atoms that may have substituents. - It is a non-nucleophilic counterion.

[0056] The alkyl group may be 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, and adamantyl groups. Examples of the aryl group include phenyl, naphthyl, and biphenylyl groups. Examples of the aralkyl group include benzyl and phenethyl groups.

[0057] Examples of the substituents include oxo groups, 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, and arylthio groups having 6 to 24 carbon atoms.

[0058] R 101 ~R 105Preferred alkyl groups include alkyl groups which may have substituents such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, and 2-oxocyclohexyl groups; aryl groups which may have substituents such as phenyl, naphthyl, biphenylyl, o-, m-, or p-methoxyphenyl, ethoxyphenyl, m-, or p-tert-butoxyphenyl, 2-, 3-, or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenylyl, biphenylyloxyphenyl, and biphenylylthiophenyl groups; and aralkyl groups which may have substituents such as benzyl and phenethyl groups. Of these, aryl groups which may have substituents and aralkyl groups which may have substituents are more preferred.

[0059] Examples of the aforementioned non-nucleophilic counterions include halide ions such as chloride ions and bromide ions; fluoroalkanesulfonate ions such as triflate ions, 1,1,1-trifluoroethanesulfonate ions, and nonafluorobutanesulfonate ions; arylsulfonate ions such as tosylate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, and 1,2,3,4,5-pentafluorobenzenesulfonate ions; alkanesulfonate ions such as mesylate ions and butanesulfonate ions; fluoroalkanesulfonimide ions such as trifluoromethanesulfonimide ions; fluoroalkanesulfonylmethide ions such as tris(trifluoromethanesulfonyl)methide ions; and borate ions such as tetrakisphenylborate ions and tetrakis(pentafluorophenyl)borate ions.

[0060] Examples of the aforementioned diazomethane derivatives include compounds represented by the following formula (B3). [ka]

[0061] In formula (B3), R 111 and R112 Each of these is independently an alkyl group or alkyl halogenated 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.

[0062] The alkyl group may be linear, branched, or cyclic, and a specific example is R 101 ~R 105 Examples similar to those exemplified in the explanation can be given. Examples of the halogenated alkyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, nonafluorobutyl group, etc.

[0063] Examples of aryl groups that may have the substituent include phenyl groups; alkoxyphenyl groups such as 2-,3- or 4-methoxyphenyl groups, 2-,3- or 4-ethoxyphenyl groups, and 3- or 4-tert-butoxyphenyl groups; alkylphenyl groups such as 2-,3- or 4-methylphenyl groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, and dimethylphenyl groups; and aryl halogen groups such as fluorophenyl groups, chlorophenyl groups, and 1,2,3,4,5-pentafluorophenyl groups. Examples of aralkyl groups include benzyl groups and phenethyl groups.

[0064] Examples of the glyoxime derivative include compounds represented by the following formula (B4). [ka]

[0065] In formula (B4), R 121 ~R 124 Each of these is independently an alkyl group or alkyl halogenated 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. Also, R 123 and R 124 These may be bonded to each other and form a ring with the carbon atoms to which they are bonded, and when a ring is formed, R123 and R 124 The group formed by the bonding of these atoms is a linear or branched alkylene group having 2 to 12 carbon atoms.

[0066] The alkyl group, halogenated alkyl group, optionally substituted aryl group, and aralkyl group are R 111 and R 112 Examples similar to those exemplified above include ethylene groups, propylene groups, butylene groups, hexylene groups, and the like.

[0067] Specifically, the onium salts mentioned above include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and bis(p-tert-butoxyphenyl) trifluoromethanesulfonate. Phenyl(xyphenyl)phenylsulfonium, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate Trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, p-toluenesulfon Dicyclohexylphenylsulfonium acid, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, diphenyl(4-thiophenoxyphenyl)sulfonium hexafluoroantimonate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium tris(trifluoromethanesulfonyl)methide, triphenylsulfonium tetrakis(fluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(fluorophenyl)borate,Examples include triphenylsulfonium tetrakis(pentafluorophenyl)borate and tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0068] Specifically, the aforementioned diazomethane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, bis(isopropylsulfonyl)diazomethane, bis( Examples include 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, and 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane.

[0069] Specifically, the aforementioned 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- Examples include o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0070] Specific examples of the β-ketosulfone derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0071] Examples of the aforementioned disulfone derivatives include diphenyldisulfone and dicyclohexyldisulfone.

[0072] Specific examples of the nitrobenzyl sulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonic acid and 2,4-dinitrobenzyl p-toluenesulfonic acid.

[0073] 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.

[0074] Specific examples of the aforementioned imido-yl-sulfonate derivatives include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate, and n-trifluoromethylsulfonyloxynaphthylimide.

[0075] Specific examples of the oxime sulfonate derivative include α-(benzenesulfonium oxyimino)-4-methylphenylacetonitrile.

[0076] Specific examples of the iminosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile.

[0077] Specific examples of the aforementioned 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.

[0078] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane and the like can also be suitably used.

[0079] As the photoacid generator for component (B), the onium salt and the sulfonium salt are particularly preferred, and the sulfonium salt is more preferred.

[0080] (B) The amount of the photoacid generator is preferably in the range of 0.05 to 20% by mass, and 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 included within the above range, a pattern with excellent resolution can be obtained with an excellent balance of sensitivity and developability during exposure and no residual film. Furthermore, the photoacid generator may be used alone or in combination of two or more types.

[0081] [(C) Quantum dots having a specific surface coating layer] Quantum dots are nanoscale semiconductor materials. Atoms form molecules, and these molecules form clusters of smaller molecules to create nanoparticles. When such nanoparticles exhibit semiconductor properties, they are called quantum dots (quantum dot particles).

[0082] When a quantum dot receives energy from an external source and becomes levitated, it autonomously emits energy through its corresponding energy band gap (it emits light).

[0083] The (C) quantum dots used in this invention are not particularly limited as long as they have a surface coating layer containing siloxane, and can be used in any form. The quantum dots are mainly nanoparticles of 10 nm or less, but they can also be nanowires, nanorods, nanotubes, nanocubes, etc., and can be applied in any shape. In this invention, the average particle size of the quantum dots was determined by directly observing at least 20 particles using a transmission electron microscope (TEM), calculating the diameter of a circle having the same area as the projected area of ​​the particles, and using the average of these values.

[0084] The (C) quantum dot used in the present invention can be any suitable material, for example, as a semiconductor material, one selected from the group consisting of Group II-VI, Group III-V, Group IV, Group IV-VI, Group I-III-VI, Group II-IV-V and mixed crystals or alloys thereof, or compounds having a perovskite structure. Specifically, examples include, but are not limited to, compounds containing ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, Si, Ge, Sn, Pb, PbS, PbSe, PbTe, SnS, SnSe, SnTe, AgGaS2, AgInS2, AgGaSe2, AgInSe2, CuGaS2, CuGaSe2, CuInS2, CuInSe2, ZnSiP2, ZnGeP2, CdSiP2, CdGeP2, CsPbCl3, CsPbBr3, CsPbI3, CsSnCl3, CsSnBr3, and CsSnI3.

[0085] The (C) quantum dots used in the present invention can have a core-shell structure. The shell material capable of forming a core-shell structure is not particularly limited, but it is preferable to have a large band gap and low lattice mismatch with respect to the core material, and can be arbitrarily combined with the core material. Specific shell materials include ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, BeS, BeSe, BeTe, MgS, MgSe, MgTe, PbS, PbSe, PbTe, SnS, SnSe, SnTe, CuF, CuCl, CuBr, CuI, etc., and these materials may be selected as a single or multiple mixed crystal, but are not limited thereto.

[0086] While there are various methods for producing the (C) quantum dots used in the present invention, such as liquid-phase and gas-phase methods, the present invention is not particularly limited. However, from the viewpoint of exhibiting high fluorescence emission efficiency, it is preferable to use semiconductor nanoparticles obtained by the hot soap method or hot injection method, which involves reacting precursor species at high temperatures in a high-boiling-point nonpolar solvent. It is desirable that organic ligands are coordinated to the surface in order to impart dispersibility in nonpolar solvents and reduce surface defects.

[0087] From the viewpoint of dispersibility, the organic ligand preferably contains an aliphatic hydrocarbon. Examples of such organic ligands include oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, decanoic acid, octanoic acid, oleylamine, stearyl(octadecyl)amine, dodecyl(lauryl)amine, decylamine, octylamine, octadecanethiol, hexadecanethiol, tetradecanethiol, dodecanethiol, decanethiol, octanthiol, trioctylphosphine, trioctylphosphine oxide, triphenylphosphine, triphenylphosphine oxide, tributylphosphine, tributylphosphine oxide, etc., and these may be used individually or in combination.

[0088] In the (C) quantum dots used in the present invention, a ligand having a substituent capable of forming a siloxane bond is coordinated in addition to the organic ligand described above. It is desirable that the ligand having a substituent capable of forming a siloxane bond interacts with or adsorbs to the quantum dot surface. Examples of substituents that interact with or adsorb to the quantum dot surface include amino groups, thiol groups, carboxyl groups, mercapto groups, phosphino groups, phosphine groups, phosphine oxide groups, sulfonyl groups, ammonium ions, and quaternary ammonium salts. Among these, amino groups, carboxyl groups, mercapto groups, phosphine groups, and quaternary ammonium salts are preferred from the viewpoint of strong coordination.

[0089] The (C) quantum dots used in the present invention have their quantum dot surfaces coated with siloxane. Therefore, ligands having substituents that interact with or adsorb to the quantum dot surface have substituents capable of forming siloxane bonds. Substituents capable of forming siloxane bonds include compounds containing alkoxysilanes such as trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethylmethoxysilyl group, and ethoxydimethylsilyl group, compounds having silazane bonds, compounds having Si-OH bonds, compounds having Si-X (X: halogen) bonds, and carboxylic acids. However, it is preferable to use ligands containing alkoxysilanes, silazanes, or Si-OH, as this allows the reaction to proceed under mild conditions without the generation of acid as a byproduct. Phenyl group-containing siloxanes can be formed by reacting these with diphenyldisilanol or the like.

[0090] The amount of siloxane coating is not particularly limited, but it is preferably in the range of 1 to 50% by mass of the quantum dots, and more preferably in the range of 5 to 30% by mass. If the amount of siloxane coating is too high, the quantum dot content will decrease, but if it is within the above range, it is possible to improve dispersibility in the base polymer and suppress the degradation of quantum dots during exposure.

[0091] The (C) quantum dots used in the present invention may further include a skeleton having phenolic hydroxyl groups in the surface coating layer.

[0092] As a skeleton having a phenolic hydroxyl group, a skeleton structure derived from the following formula (c) is preferred. [ka]

[0093] In formula (c), Y 2 R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 1 and R 2 Each of these is independently either a hydrogen atom or a methyl group. 3 and R 4 Each of these 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 of these is an integer between 0 and 7, but integers between 1 and 5 are preferred, and integers between 1 and 3 are more preferred. 3 and b 4 Each of these is an integer between 0 and 2, but 0 or 1 is preferred, and 0 is more preferred.

[0094] The C1-C4 alkyl group may be linear, branched, or cyclic, and specific examples include methyl, ethyl, propyl, and butyl groups, as well as their structural isomers. The C1-C4 alkoxy group may be linear, branched, or cyclic, and specific examples include methoxy, ethoxy, propoxy, and butoxy groups, as well as their structural isomers.

[0095] By introducing the skeletal structure of formula (c) into the surface coating layer, the silicone resin having phenolic hydroxyl groups (A) and the surface coating layer crosslink after exposure, suppressing the loss of quantum dots during development and resulting in high luminescence characteristics for the pattern.

[0096] Furthermore, by introducing the skeletal structure of formula (c) into the surface coating layer, compatibility with silicone resin having phenolic hydroxyl groups (A) is improved, and the generation of aggregates when it is made into a photosensitive resin composition can be suppressed.

[0097] The (C) quantum dots used in the present invention are preferably in an amount of 5 to 80% by mass, and more preferably 10 to 70% by mass, relative to the total amount of the photosensitive resin composition. If the content of quantum dot particles is within the above range, fine patterns can be formed while maintaining good luminescence characteristics.

[0098] The method and amount of phenolic hydroxyl groups introduced into component (C) are not particularly limited, but when forming the phenyl group-containing siloxane, a previously prepared skeleton containing alkoxysilane phenolic hydroxyl groups can be added and reacted, or a skeleton containing phenolic hydroxyl groups can be directly introduced by radical reaction or the like. The amount introduced should be adjusted as appropriate considering compatibility with the resin.

[0099] [(D) Crosslinking agent] The photosensitive resin composition of the present invention may further contain a crosslinking agent as component (D). The crosslinking agent undergoes a condensation reaction with the phenolic hydroxyl groups in the silicone resin having (A) phenolic hydroxyl groups, facilitating the formation of patterns, and further increasing the strength of the resin film after photocuring.

[0100] Preferred crosslinking agents include nitrogen-containing compounds such as melamine compounds, guanamine compounds, glycoluryl compounds, and urea compounds, which contain an average of two or more methylol groups and / or alkoxymethyl groups per molecule; amino condensates modified with formaldehyde or formaldehyde-alcohol; phenol compounds having an average of two or more methylol groups or alkoxymethyl groups per molecule; and epoxy compounds having an average of two or more epoxy groups per molecule. These compounds can be used individually or in combination of two or more.

[0101] Examples of the melamine compound mentioned above include those represented by the following formula (D1). [ka]

[0102] In formula (D1), R 201 ~R 206 Each of these is independently a methylol group, an alkoxymethyl group having 2 to 5 carbon atoms, or a hydrogen atom, but each molecule contains an average of two or more methylol groups and / or alkoxymethyl groups. Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

[0103] Examples of melamine compounds represented by formula (D1) include trimethoxymethylmonomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, and hexaethoxymethylmelamine.

[0104] The melamine compound represented by formula (D1) can be obtained, for example, by first methylolating and modifying a melamine monomer with formaldehyde according to a known method, or by further modifying it by alkoxylation with an alcohol. A lower alcohol, such as an alcohol having 1 to 4 carbon atoms, is preferred as the alcohol.

[0105] Examples of the guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, and tetramethoxyethylguanamine.

[0106] Examples of the glycoluryl compounds include tetramethylol glycoluryl and tetrakis(methoxymethyl) glycoluryl. Examples of the urea compounds include tetramethylol urea, tetramethoxymethyl urea, tetramethoxyethyl urea, tetraethoxymethyl urea, and tetrapropoxymethyl urea.

[0107] Examples of amino condensates modified with formaldehyde or formaldehyde-alcohol include melamine condensates modified with formaldehyde or formaldehyde-alcohol, and urea condensates modified with formaldehyde or formaldehyde-alcohol.

[0108] Examples of the modified melamine condensate include those obtained by addition-condensation polymerization of a compound represented by formula (D1) or a polymer thereof (e.g., an oligomer such as a dimer or trimer) with formaldehyde until a desired molecular weight is reached. Conventional known methods can be used as the addition-condensation polymerization method. Furthermore, the modified melamine represented by formula (D1) can be used alone or in combination of two or more types.

[0109] Examples of urea condensates modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, and propoxymethylated urea condensates.

[0110] The modified urea condensate can be obtained, for example, by methylolating a urea condensate of a desired molecular weight with formaldehyde according to a known method, or by further modifying it by alkoxylation with an alcohol.

[0111] Examples of phenol compounds having an average of two or more methylol groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol and 2,2',6,6'-tetramethoxymethylbisphenol A.

[0112] Examples of epoxy compounds having two or more epoxy groups include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin and bisphenol F-type epoxy resin, novolac-type epoxy resins such as phenol novolac-type epoxy resin and cresol novolac-type epoxy resin, triphenol alkane-type epoxy resin, biphenyl-type epoxy resin, dicyclopentadiene-modified phenol novolac-type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, naphthalene ring-containing epoxy resin, glycidyl ester-type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, and the like.

[0113] The content of component (D) is preferably 0.5 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of component (A). If the content of component (D) is 0.5 parts by mass or more, sufficient curability can be obtained when irradiated with light. Component (D) can be used alone or in combination of two or more types.

[0114] [(E) Solvent] The photosensitive resin composition of the present invention may further contain a solvent as component (E). The solvent is not particularly limited as long as it can dissolve each of the components described above. By incorporating a solvent, the coatability of the photosensitive resin composition can be improved.

[0115] Organic solvents are preferred as such solvents because they exhibit excellent solubility of these components. Examples of such organic solvents include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and γ-butyrolactone. These organic solvents can be used individually or in combination of two or more. Ethyl lactate, cyclohexanone, cyclopentanone, PGMEA, γ-butyrolactone, and mixtures thereof are particularly preferred due to their excellent solubility of photoacid generators.

[0116] (E) The content of component (E) is preferably 25 to 85% by mass, and more preferably 35 to 75% by mass, relative to the total amount of the photosensitive resin composition, from the viewpoint of compatibility and viscosity of the photosensitive resin composition.

[0117] [Photosensitive resin coating] The photosensitive resin coating of the present invention is a dried body of the photosensitive resin composition described above.

[0118] [Pattern formation method using photosensitive resin composition] The pattern forming method using the photosensitive resin composition of the present invention is: (i) A step of applying the photosensitive resin composition described above onto a substrate to form a photosensitive resin film on the substrate. (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film with a developer solution to dissolve and remove the unexposed areas and form a pattern. Includes.

[0119] Step (i) is a step of applying the photosensitive resin composition onto a substrate to form a photosensitive resin film on the substrate. Examples of the substrate include silicon wafers, glass wafers, quartz wafers, and micro-LED laminated substrates.

[0120] The coating method can be any known method, such as the dip method, spin coating method, or roll coating method. The amount of coating can be appropriately selected depending on the purpose, but it is preferable to coat the film so that the thickness of the resulting photosensitive resin film is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0121] To improve film thickness uniformity on the substrate surface, a solvent may be dropped onto the substrate before applying the photosensitive resin composition (pre-wetting method). The solvent to be dropped can be appropriately selected depending on the purpose. Preferred solvents include alcohols such as isopropyl alcohol (IPA), ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether, but it is also possible to use a solvent used in the photosensitive resin composition.

[0122] To ensure efficient photocuring, preheating (pre-baking) may be performed to evaporate solvents and other substances beforehand, if necessary. Pre-baking can be carried out, for example, at 40-140°C for 1 minute to 1 hour.

[0123] Next, (ii) the photosensitive resin film is exposed to light. At this time, exposure is preferably carried out with light of a wavelength of 10 to 600 nm, and more preferably with light of 190 to 500 nm. Examples of such wavelengths of light include various wavelengths of light generated by a radiation generator, such as ultraviolet light (g-rays, h-rays, i-rays, etc.) and far-ultraviolet light (248 nm, 193 nm). Of these, light with a wavelength of 248 to 436 nm is particularly preferred. The exposure amount is 10 to 10,000 mJ / cm². 2 It is preferable.

[0124] Exposure may be performed via a photomask. The photomask may, for example, have a desired pattern cut out of it. The material of the photomask is not particularly limited, but it is preferably one that blocks light of the aforementioned wavelength. For example, one containing chromium as a light-shielding film is preferably used, but is not limited to this.

[0125] Furthermore, to increase development sensitivity, post-exposure heat treatment (PEB) may be performed. PEB is preferably performed at 40-150°C for 0.5-20 minutes. PEB causes the exposed areas to crosslink, forming an insolubilized pattern that is insoluble in the organic solvent used as the developer. The material is then dried after removing the solvent following this pre-baking process.

[0126] (iii) After exposure or PEB, the substrate is developed with a developer to dissolve and remove the unexposed areas and form a pattern. As the developer, organic solvents such as alcohols such as IPA, ketones such as cyclohexanone, and glycols such as propylene glycol monomethyl ether are preferred, but solvents used in photosensitive resin compositions can also be used. As for the development method, a conventional method is used, for example, by immersing the patterned substrate in the developer. After that, washing, rinsing, drying, etc. are performed as necessary to obtain a cured film having the desired pattern.

[0127] Furthermore, the patterned film may be post-cured using an oven or hot plate, preferably at 100-200°C.

[0128] [Photosensitive dry film] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin coating obtained from a photosensitive resin composition on the support film.

[0129] The photosensitive dry film (support film and photosensitive resin coating) is solid, and since the photosensitive resin coating does not contain solvents, there is no risk of bubbles remaining between the photosensitive resin coating and the uneven substrate due to its volatilization. The thickness of the photosensitive resin coating is not particularly limited, but is preferably 1 to 200 μm, and more preferably 3 to 100 μm.

[0130] Furthermore, the viscosity and fluidity of the photosensitive resin film are closely related. The photosensitive resin film can exhibit appropriate fluidity within an appropriate viscosity range, allowing it to penetrate deep into narrow gaps and strengthen adhesion to the substrate as the resin softens. Therefore, from the viewpoint of fluidity, the viscosity of the photosensitive resin film is preferably 10 to 5,000 Pa·s, more preferably 30 to 2,000 Pa·s, and even more preferably 50 to 300 Pa·s at 80 to 120°C. In this invention, viscosity is measured using a rotational viscometer.

[0131] When the photosensitive dry film of the present invention is adhered to an uneven substrate, the photosensitive resin coating conforms to the unevenness, achieving high flatness. In particular, the photosensitive resin composition of the present invention is characterized by its softening properties, which enables even higher flatness to be achieved. Furthermore, when the photosensitive resin coating is adhered to the substrate in a vacuum environment, the occurrence of gaps can be prevented more effectively.

[0132] The photosensitive dry film of the present invention can be manufactured by applying the photosensitive resin composition onto a substrate and drying it to form a photosensitive resin film. A film coater for manufacturing adhesive products can generally be used as the manufacturing apparatus for the photosensitive dry film. Examples of film coaters include comma coaters, comma reverse coaters, multi coaters, die coaters, lip coaters, lip reverse coaters, direct gravure coaters, offset gravure coaters, three-bottom reverse coaters, four-bottom reverse coaters, and the like.

[0133] A photosensitive dry film can be manufactured by unwinding a support film from the unwinding shaft of the film coater and passing it through the coater head of the film coater, applying the photosensitive resin composition to the support film to a predetermined thickness, then passing it through a hot air circulation oven at a predetermined temperature and time to dry it on the support film and form a photosensitive resin coating. Alternatively, if necessary, a photosensitive dry film with a protective film can be manufactured by passing the photosensitive dry film together with a protective film unwinding from another unwinding shaft of the film coater through a laminating roll at a predetermined pressure to bond the photosensitive resin coating on the support film with the protective film, and then winding it onto the winding shaft of the film coater. In this case, the temperature is preferably 25 to 150°C, the time is preferably 1 to 100 minutes, and the pressure is preferably 0.01 to 5 MPa.

[0134] The support film used in the photosensitive dry film of the present invention may be a single-layer film consisting of a single film, or a multilayer film formed by laminating multiple films. Examples of materials for the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Of these, polyethylene terephthalate, which has appropriate flexibility, mechanical strength, and heat resistance, is preferred. These films may have undergone various treatments such as corona treatment or coating with a release agent. Commercially available products can be used, such as Therapiel WZ(RX), Therapiel BX8(R) (both manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (both manufactured by Toyobo Co., Ltd.), Purex G31, Purex G71T1 (both manufactured by Teijin DuPont Films Ltd.), PET38×1-A3, PET38×1-V8, and PET38×1-X08 (all manufactured by Nippa Co., Ltd.).

[0135] The protective film can be the same as the support film described above, but polyethylene terephthalate and polyethylene, which have appropriate flexibility, are preferred. Commercially available products can be used, and examples of polyethylene terephthalate include those already exemplified, while examples of polyethylene include GF-8 (manufactured by Tamapoly Co., Ltd.) and PE film type 0 (manufactured by Nipper Co., Ltd.).

[0136] The thickness of the support film and protective film is preferably 10 to 100 μm, more preferably 25 to 50 μm, from the viewpoint of stability in the production of the photosensitive dry film and prevention of curling on the core.

[0137] [Pattern formation method using photosensitive dry film] The pattern formation method using the photosensitive dry film of the present invention is: (i') A step of attaching the photosensitive resin film of the photosensitive dry film described above to a substrate to form the photosensitive resin film on the substrate, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film with a developer solution to dissolve and remove the unexposed areas and form a pattern. Includes.

[0138] First, (i') the photosensitive resin coating is attached to the substrate using a photosensitive dry film to form a photosensitive resin coating on the substrate. In other words, a photosensitive resin coating is formed on the substrate by attaching the photosensitive resin coating of the photosensitive dry film to the substrate. If the photosensitive dry film has a protective film, the protective film is peeled off from the photosensitive dry film before attaching the photosensitive resin coating of the photosensitive dry film to the substrate. The attachment can be performed, for example, using a film attachment device.

[0139] A vacuum laminator is preferred as the film application apparatus. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is pressed onto the substrate on a table at a predetermined temperature using an application roll at a predetermined pressure in a vacuum chamber with a predetermined vacuum level. The temperature is preferably 60 to 120°C, the pressure is preferably 0 to 5.0 MPa, and the vacuum level is preferably 50 to 500 Pa.

[0140] To efficiently carry out the photocuring reaction of the photosensitive resin film and to improve the adhesion between the photosensitive resin film and the substrate, pre-baking may be performed as needed. Pre-baking can be performed, for example, at 40 to 140°C for about 1 minute to 1 hour.

[0141] 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 solution to dissolve and remove the unexposed areas and form a pattern, and (iv) performing a post-curing heat treatment as necessary, similar to the pattern formation method using the photosensitive resin composition. The support film of the photosensitive dry film is peeled off before pre-baking or before PEB, or removed by other means, depending on the process.

[0142] The pattern formation method using the photosensitive resin composition and photosensitive dry film of the present invention makes it easy to form fine patterns. For example, by forming the photosensitive resin composition or photosensitive dry film of the present invention to cover a large number of blue microLEDs arranged on a substrate, and then performing fine pattern formation, a cured film containing red and green quantum dots in different parts is formed on the blue microLEDs, thereby generating red and green light emission, making it possible to create a full-color light-emitting element.

[0143] [Light-emitting element] The light-emitting element of the present invention comprises a cured film obtained by the pattern formation method described above. [Examples]

[0144] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In this invention, an InP / ZnSe / ZnS core-shell type quantum dot is used as the quantum dot material, and the method of synthesizing the core is as shown in [1-1] (red quantum dots) and [1-2] (green quantum dots) below, and the method of synthesizing the shell thereafter is as shown in [2].

[0145] [1-1] Red quantum dot core synthesis process Two flasks were prepared, and 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 each. The mixtures were heated and stirred under reduced pressure at 100°C for 1 hour while dissolving the starting materials and degassing. Then, nitrogen was purged into both flasks, and 0.75 mL (0.15 mmol) of tritrimethylsilylphosphine / trioctylphosphine solution (0.2 M) was added to both flasks. Subsequently, one of the flasks was heated to 300°C, the solution was withdrawn from the flask that was not heated, and added to the flask that was heated to 300°C, and core particles were generated.

[0146] [1-2] Green quantum dot core synthesis process 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 a flask. The mixture was heated and stirred under reduced pressure at 100°C for 1 hour while dissolving the raw materials. Then, nitrogen was purged into the flask, and 0.75 mL (0.15 mmol) of a 0.2 M solution prepared by mixing tritrimethylsilylphosphine with trioctylphosphine was added. The temperature was raised to 300°C, and core particles were formed.

[0147] [2] Quantum dot shell layer synthesis process Next, 2.85 g (4.5 mmol) of zinc stearate and 15 mL of 1-octadecene were added to another flask, and the mixture was heated and stirred under reduced pressure at 100°C for 1 hour while dissolving to prepare a 0.3 M zinc stearate octadecene solution. 3.0 mL (0.9 mmol) of this solution was added to the reaction solution after 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 and heated to 150°C to dissolve to prepare a 1.5 M selentrioctylphosphine solution. The reaction solution after the core synthesis step, which had been cooled to 200°C, was heated to 320°C over 30 minutes, and the selentrioctylphosphine solution was added in 0.1 mL increments for a total of 0.6 mL (0.9 mmol). The mixture was held at 320°C for 10 minutes and then cooled to room temperature. 0.44 g (2.2 mmol) of zinc acetate was added and dissolved by heating and stirring under reduced pressure at 100°C. The flask was again purged with nitrogen and the temperature was raised to 230°C, and 0.98 mL (4 mmol) of 1-dodecanethiol was added and held for 1 hour. The resulting solution was cooled to room temperature to prepare a core-shell type quantum dot-containing solution. The red core-shell type quantum dots synthesized through steps [1-1] to [2] were designated as R-1, and the green core-shell type quantum dot-containing solution synthesized through steps [1-2] to [2] were designated as G-1.

[0148] [3] Ligand exchange process (3-mercaptopropyl)triethoxysilane was used as the ligand (ligand) having substituents capable of forming siloxane bonds and substituents that coordinate to the quantum dot surface. For the ligand exchange reaction, (3-mercaptopropyl)triethoxysilane (3.0 mmol) was added to the solution after the shell synthesis step, which had been cooled to room temperature, and the mixture was stirred for 24 hours. After the reaction was complete, ethanol was added to precipitate the reaction solution, and the supernatant was removed by centrifugation. The same purification was performed again, and the quantum dot solution with ligands capable of forming siloxane bonds was dispersed in toluene to prepare a quantum dot solution coordinated with ligands capable of forming siloxane bonds. The quantum dots with ligands capable of forming siloxane bonds, synthesized using R-1, were designated as R-2, and the quantum dots with ligands capable of forming siloxane bonds, synthesized using G-1, were designated as G-2.

[0149] [4-1] Surface coating layer formation process In a flask purged with nitrogen, triethoxysilylpropyl methacrylate (4.0 mmol), diphenylsilanediol (6 mmol), barium hydroxide monohydrate (0.15 mmol), and the quantum dot toluene solution after ligand exchange were added and heated and stirred at 65°C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, ethanol was added to precipitate the reaction solution, and the supernatant was removed by centrifugation. The supernatant was dispersed in toluene and added to a flask that had been pre-purged with nitrogen. Then, 2 parts by mass of the compound shown in formula (1) below were added per 100 parts by mass of the quantum dot toluene solution. Furthermore, 1 part by mass of Irgacure1173 was added per 100 parts by mass of the compound shown in formula (1) below, and after stirring and mixing, irradiation was performed using a UV LED irradiation device at a wavelength of 365 nm and an output of 4000 mW / cm². 2 The mixture was irradiated with light for 20 seconds. After the reaction was complete, ethanol was added to precipitate the mixture, and after centrifugation, the supernatant was removed and dispersed again in toluene. Then, PGMEA was added, and the toluene solvent was removed by vacuum distillation to prepare a quantum dot solution (solid content 60%) with a surface coating layer formed. Here, quantum dots with a surface coating layer formed on R-2 are designated as R-(1), and quantum dots with a surface coating layer formed on G-2 are designated as G-(1).

[0150] [4-2] Surface coating layer formation process In a flask purged with nitrogen, triethoxysilylpropyl methacrylate (4.0 mmol), diphenylsilanediol (6 mmol), barium hydroxide monohydrate (0.15 mmol), and the quantum dot toluene solution after ligand exchange were added and heated and stirred at 65°C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, ethanol was added to precipitate the reaction solution, and the supernatant was removed by centrifugation. The supernatant was dispersed in toluene and added to a flask that had been pre-purged with nitrogen. Then, 2 parts by mass of the compound shown in formula (1') below were added per 100 parts by mass of the quantum dot toluene solution. Furthermore, 1 part by mass of Irgacure1173 was added per 100 parts by mass of the compound shown in formula (1') below, and after stirring and mixing, irradiation was performed using a UV LED irradiation device at a wavelength of 365 nm and an output of 4000 mW / cm². 2 The mixture was irradiated with light for 20 seconds. After the reaction was complete, ethanol was added to precipitate the mixture, and after centrifugation, the supernatant was removed and dispersed again in toluene. Then, PGMEA was added, and the toluene solvent was removed by vacuum distillation to prepare a quantum dot solution (solid content 60%) with a surface coating layer formed. Here, quantum dots with a surface coating layer formed on R-2 are designated as R-(1'), and quantum dots with a surface coating layer formed on G-2 are designated as G-(1').

[0151] [5] Synthesis of silicone resin [Synthesis Example 1] Synthesis of Resin 1 In a 3L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 215.0 g (0.50 mol) of compound (1) was added, followed by 2,000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by mass) was added, and 58.2 g (0.30 mol) of compound (2) and 604.0 g (0.20 mol) of compound (4) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then 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 confirmed to be 80,000 (silicone content was 68.9% by mass: silicone content was calculated from the amount charged).

[0152] [Synthesis Example 2] Synthesis of Resin 2 In a 3L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 215.0 g (0.50 mol) of compound (1) was added, followed by 2,000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by 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) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Toluene was then removed from the reaction solution under reduced pressure to obtain resin 2. GPC confirmed the disappearance of the peaks for each raw material and the Mw of resin 2 was confirmed to be 40,000 (silicone content 52.2% by mass).

[0153] [Synthesis Example 3] Synthesis of Resin 3 In a 3 L flask equipped with a stirrer, thermometer, nitrogen purging device, and reflux condenser, 215.0 g (0.50 mol) of compound (1) was added, followed by 2,000 g of toluene, and the mixture was heated to 70°C. Then, 1.0 g of toluene chloroplatinate solution (platinum concentration 0.5% by 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) were added dropwise over 1 hour (total hydrosilyl groups / total alkenyl groups = 1 / 1 (molar ratio)). After the dropwise addition was complete, the mixture was heated to 100°C and aged for 6 hours. Then, toluene was removed from the reaction solution under reduced pressure, and the resin was collected. 3 The following was obtained. In GPC, the peaks of each raw material disappeared and the Mw of resin 3 was confirmed to be 13,000 (silicone content was 34.3% by mass).

[0154] The compounds (1) to (4) used in the above synthesis example are as follows: [ka]

[0155] [6] Preparation of photosensitive resin composition and evaluation thereof [Examples 1-12 and Comparative Examples 1-24] Each component was blended according to the proportions listed in Tables 1-4, then stirred and mixed at room temperature, and microfiltration was performed using a 1.0 μm glass filter to obtain the photosensitive resin compositions of Examples 1-12 and Comparative Examples 1-24.

[0156] [Table 1]

[0157] [Table 2]

[0158] [Table 3]

[0159] [Table 4]

[0160] In Tables 1-4, the photoacid generators B-1 and B-2 used are as follows: [ka]

[0161] In Tables 1-4, the crosslinking agents D-1 and D-2 used are as follows: [ka]

[0162] In Tables 1-4, quantum dots R-3 are S-BE030 manufactured by Shoei Chemical Co., Ltd. (particle size 5-10 nm, material InP:ZnS:SeZn=25:50:25), R-4 is 900514-1ML manufactured by Aldrich (particle size 5-10 nm, material CdSe (core) / CdS (shell) core-shell type), G-3 is S-BE029 manufactured by Shoei Chemical Co., Ltd. (particle size 3-5 nm, material InP:ZnS:SeZn=25:50:25), and G-4 is 900511-1ML manufactured by Aldrich (particle size 3-5 nm, material CdSe (core) / CdS (shell) core-shell type).

[0163] [7] Preparation of photosensitive dry film A die coater was used as the film coater, and a polyethylene terephthalate film (38 μm thick) was used as the support film. The photosensitive resin compositions described in Tables 1 to 4 were applied to the support film. The films were then dried by passing them through a hot air circulation oven (4 m long) set to 100°C for 5 minutes, forming a photosensitive resin film on the support film to a thickness of 20 μm, thereby obtaining a photosensitive dry film. A polyethylene film (50 μm thick) was then laminated onto the photosensitive resin film as a protective film using a laminating roll at a pressure of 1 MPa to produce a photosensitive dry film with a protective film.

[0164] [8] Evaluation of photosensitive resin coating (1) Confirmation of aggregates in the photosensitive resin coating The protective film was removed from the aforementioned photosensitive dry film with protective film, and aggregates in the photosensitive dry film were examined using an optical microscope. Aggregates larger than 1 μm were marked with ×, and those without aggregates or smaller than 1 μm were marked with ○. The results are shown in Tables 5 to 8.

[0165] (2) Pattern formation and evaluation thereof The photosensitive dry film with protective film was prepared by removing the protective film and using a vacuum laminator TEAM-100RF (manufactured by Takatori Co., Ltd.) to set the vacuum level in the vacuum chamber to 80 Pa, and pressing the photosensitive resin film on the support film against the silicon wafer. The temperature was set to 100°C. After returning to atmospheric pressure, the substrate was removed from the vacuum laminator and the support film was removed. Next, to improve adhesion to the substrate, pre-bake was performed on a hot plate at 110°C for 3 minutes. To form a square island pattern with a pitch width of 1:1 between adjacent patterns on the obtained photosensitive resin film via a mask, exposure was performed using an i-line stepper NSR-2205i11D (manufactured by Nikon Corporation). After irradiation, PEB was performed on a hot plate at 120°C for 3 minutes, followed by cooling, and the substrate was spray-developed with PGMEA for 60 seconds to form the pattern. After that, post-curing was performed in an oven at 150°C for 2 hours while purging with nitrogen. Subsequently, island patterns with side lengths of 100 μm, 50 μm, 30 μm, 20 μm, and 10 μm were observed using a scanning electron microscope (SEM). The smallest pattern size that was not connected to an adjacent island pattern (with a pitch width of 1:1) was defined as the critical resolution. Patterns that did not reach a resolution of 100 μm or where development peeling of the pattern occurred were marked with an "X". The results are shown in Tables 5-8.

[0166] (3) Evaluation of the luminescence characteristics of the formed pattern Using a LabRAM HR Evolution manufactured by Horiba Techno Service Co., Ltd., the patterned sample prepared in (2) above was irradiated with 457 nm laser light (0.03 mW), and the light-converted island pattern region was measured. The emission intensity, emission wavelength, and full width at half maximum of the light-converted light were then measured. Similarly, the sample prepared in (2) above after the lamination and support film peeling process was also measured to determine the emission intensity of the light-converted light. The results are shown in Tables 5 to 8 (M: 1 million).

[0167] (4) Reliability testing and evaluation A photosensitive resin composition described in Tables 1-4 was coated onto a glass substrate to a thickness of 100 μm using a spin coater. 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. To form a 1 cm square island pattern on the obtained photosensitive resin film through a mask, the substrate was exposed using a contact aligner exposure apparatus at an exposure condition of 365 nm. After irradiation, PEB was performed on a hot plate at 140°C for 5 minutes, followed by cooling. The substrate was then spray-developed with PGMEA for 300 seconds to form the pattern. Subsequently, it was post-cured in an oven at 150°C for 2 hours while purging with nitrogen. This patterned sample was subjected to a heat cycle test (held at -55°C for 10 minutes, held at 125°C for 10 minutes, repeated 1,000 times) to check the peeling state of the cured film from the substrate and the presence or absence of cracks after the heat cycle test. Samples that showed no delamination or cracking were marked with ○, and those that showed even one instance of delamination or cracking were marked with ×. The results are shown in Tables 5-8.

[0168] [Table 5]

[0169] [Table 6]

[0170] [Table 7]

[0171] [Table 8]

[0172] The results above demonstrate that the photosensitive resin composition of the present invention can form a good photosensitive film or photosensitive dry film without (or with very small) aggregates, and can provide a cured film suitable for light-emitting devices, possessing high lithography resolution, high luminescence characteristics that do not change before and after the lithography process, and good reliability (adhesion, crack resistance).

[0173] This specification includes the following embodiments: [1]: A photosensitive resin composition, (A) Silicone resin having phenolic hydroxyl groups, (B) Photoacid generator, and (C) Quantum Dot A photosensitive resin composition comprising, wherein the quantum dots have a surface coating layer containing siloxane. [2]: The photosensitive resin composition according to [1], characterized in that the component (C) contains a skeleton having phenolic hydroxyl groups in the surface coating layer. [3]: The photosensitive resin composition according to [1] or [2] above, characterized in that the component (A) includes a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1). [ka] [In the formula, R 5 ~R 8 Each of these is independently a monovalent hydrocarbon group having 1 to 8 carbon atoms. m is an integer from 0 to 600. 1 This is a divalent group represented by the following formula (X1). [ka] (In the formula, Y 1R is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. 9 and R 10 Each of these is independently either a hydrogen atom or a methyl group. 11 and R 12 Each of these 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 These are each an integer between 0 and 7, independently of each other. 1 and b 2 Each of these is an integer between 0 and 2, independently of the others. [4]: The photosensitive resin composition according to [1], [2], or [3] above, characterized in that component (D) further comprises at least one crosslinking agent selected from melamine compounds, guanamine compounds, glycoluryl compounds and urea compounds, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenol compounds having an average of two or more methylol groups or alkoxymethyl groups per molecule. [5]: The photosensitive resin composition according to [1], [2], [3], or [4] above, characterized in that the quantum dots of component (C) have ligands that coordinate to their surface, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands are one or more of the following: amino groups, thiol groups, carboxyl groups, phosphino groups, phosphine oxide groups, and ammonium ions. [6]: The photosensitive resin composition according to [1], [2], [3], [4], or [5], characterized in that it contains 5 to 80% by mass of component (C) in the photosensitive resin composition. [7]: The photosensitive resin composition according to [1], [2], [3], [4], [5], or [6], further characterized by containing (E) a solvent. [8]: A photosensitive resin film characterized by being a dried body of the photosensitive resin composition described in [1], [2], [3], [4], [5], [6], or [7] above. [9]: A photosensitive dry film comprising a support film and the photosensitive resin coating described in [8] above on the support film.

[10] A method for forming a pattern, (i) A step of applying the photosensitive resin composition described in [1], [2], [3], [4], [5], [6] or [7] above onto a substrate to form a photosensitive resin film on the substrate. (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film with a developer solution to dissolve and remove the unexposed areas and form a pattern. A pattern forming method characterized by including the following.

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

[12] : A light-emitting element characterized by comprising a cured film obtained by the pattern forming method of

[10] or

[11] above.

[0174] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention.

Claims

1. A photosensitive resin composition, (A) Silicone resin having phenolic hydroxyl groups, (B) Photoacid generator, and (C) Quantum Dot A photosensitive resin composition comprising, wherein component (A) comprises a repeating unit represented by the following formula (a1) and a repeating unit represented by the following formula (b1), the quantum dot has a surface coating layer containing siloxane, and component (C) comprises a skeleton having phenolic hydroxyl groups in the surface coating layer. 【Chemistry 1】 [In the formula, R5 to R8 are each independently monovalent hydrocarbon groups having 1 to 8 carbon atoms. m is an integer from 0 to 600. X1 is a divalent group represented by the following formula (X1). 【Chemistry 2】 (In the formula, Y1 is a single bond, a methylene group, a propane-2,2-diyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, or a fluorene-9,9-diyl group. R9 and R10 are each independently a hydrogen atom or a methyl group. R11 and R12 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. a1 and a2 are each independently integers from 0 to 7. b1 and b2 are each independently integers from 0 to 2.)

2. The photosensitive resin composition according to claim 1, further comprising as component (D), a crosslinking agent selected from melamine compounds, guanamine compounds, glycoluryl compounds and urea compounds, amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenol compounds having an average of two or more methylol groups and / or alkoxymethyl groups per molecule.

3. The photosensitive resin composition according to claim 1, characterized in that the quantum dots of component (C) have ligands that coordinate to their surface, the surface coating layer contains siloxane bonds bonded to the ligands, and the substituents of the ligands are one or more of the following: amino groups, thiol groups, carboxyl groups, phosphino groups, phosphine oxide groups, and ammonium ions.

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

5. Furthermore, the photosensitive resin composition according to claim 1, characterized in that it further contains (E) a solvent.

6. A photosensitive resin film characterized by being a dried body of the photosensitive resin composition described in any one of claims 1 to 5.

7. A photosensitive dry film characterized by comprising a support film and a photosensitive resin coating according to claim 6 on the support film.

8. A pattern formation method, (i) A step of applying the photosensitive resin composition according to any one of claims 1 to 5 onto a substrate to form a photosensitive resin film on the substrate. (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film with a developer solution to dissolve and remove the unexposed areas and form a pattern. A pattern forming method characterized by including the following.

9. A pattern formation method, (i') A step of forming the photosensitive resin film on the substrate by attaching the photosensitive resin film of the photosensitive dry film according to claim 7 to a substrate, (ii) A step of exposing the photosensitive resin film, and (iii) A step of developing the exposed photosensitive resin film with a developer solution to dissolve and remove the unexposed areas and form a pattern. A pattern forming method characterized by including the following.

10. A light-emitting element characterized by comprising a cured film obtained by the pattern forming method described in claim 8.

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