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

Abstract

The present invention provides a photosensitive resin composition characterized by comprising (A) a resin having a (meth) acryloyl group, (B) a light radical generator, and (C) quantum dots having a surface coating layer containing a siloxane. Consequently, provided are: a photosensitive resin composition capable of easily forming a coating film having high lithography resolution and good light-emitting characteristics; a photosensitive resin coating film obtained using the photosensitive resin composition; a pattern forming method using the photosensitive resin coating film and the photosensitive resin coating film; and a light-emitting element obtained using the photosensitive resin composition.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a photosensitive resin coating using the photosensitive resin composition, a pattern forming 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. One of the methods is to convert light from an LED array from blue, i.e., shorter wavelength light, to 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 miniaturized, 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 completed 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 pattern forming method using them, 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, which comprises (A) a resin having a (meth)acryloyl group, (B) a photo radical generator and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane.

[0011] Such a photosensitive resin composition can easily form a coating film having high photolithography resolution and good light-emitting properties.

[0012] Furthermore, in the present invention, it is preferred that the component (C) contains a skeleton having a (meth)acryloyl group in the surface coating layer.

[0013] 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.

[0014] In addition, in the present invention, it is preferred that: the quantum dots of the component (C) have ligands coordinated on 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.

[0015] Quantum dots having such ligands are preferred because they are easily coordinated to the surface.

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

[0017] Such a photosensitive resin composition can form a fine pattern while maintaining good light-emitting properties.

[0018] Furthermore, in the present invention, it is preferred that the double bond equivalent of the component (A) is 240 to 1,000 g / mol.

[0019] Such a photosensitive resin composition has a high crosslinking density and can form a pattern with a good shape after development.

[0020] In the present invention, it is preferred that the weight average molecular weight Mw of the component (A) is 5,000 to 100,000 g / mol.

[0021] According to such a photosensitive resin composition, film reduction in the exposed portion is less likely to occur during development, and the solubility of the non-exposed portion becomes good.

[0022] Furthermore, in the present invention, it is preferred that (D) a surfactant is further contained.

[0023] Such a photosensitive resin composition can improve coating properties.

[0024] Moreover, in the present invention, it is preferred that (E) a silane coupling agent is further contained.

[0025] Such a photosensitive resin composition can improve the adhesion with the substrate.

[0026] Moreover, in this invention, it is preferable to further contain (F) a crosslinking agent which has a bifunctional or more (meth)acryloyl group.

[0027] According to such a photosensitive resin composition, the obtained cured film has high reliability.

[0028] Furthermore, in the present invention, it is preferred that (G) a solvent is further contained.

[0029] Such a photosensitive resin composition can improve coating properties.

[0030] Furthermore, the present invention provides a photosensitive resin film, which is a dried product of the photosensitive resin composition described above.

[0031] Such a photosensitive resin coating can provide a coating having high photolithography resolution and good light-emitting properties.

[0032] In addition, the present invention provides a pattern forming method, which comprises:

[0033] (i) coating the above-described photosensitive resin composition on a substrate to form a photosensitive resin coating on the substrate;

[0034] (ii) exposing the photosensitive resin film to light; and

[0035] (iii) a step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed portions to form a pattern.

[0036] According to such a 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.

[0037] Furthermore, the present invention provides a light-emitting element comprising a cured film obtained by the above-described pattern forming method.

[0038] Such a light-emitting element has high photolithography resolution and good light-emitting properties.

[0039] (III) Beneficial effects

[0040] The photosensitive resin composition of the present invention contains a resin having a (meth)acryloyl group, a photoradical generator, and quantum dots having a specific surface coating layer, and can easily form a coating having high resolution and good light-emitting properties, and is therefore suitable for light-emitting devices. DETAILED DESCRIPTION

[0041] As described above, a photosensitive resin composition capable of easily forming a coating having high photolithography resolution and good light-emitting characteristics, a photosensitive resin coating obtained using the photosensitive resin composition, a pattern forming method using the same, and a light-emitting element obtained using the photosensitive resin composition are sought to be developed.

[0042] The inventors of the present application have conducted in-depth research to achieve the above-mentioned purpose, 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) a resin having a (meth) acryloyl group, (B) a photo radical generator and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane.

[0043] That is, the present invention is a photosensitive resin composition comprising (A) a resin having a (meth)acryloyl group, (B) a photoradical generator, and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane.

[0044] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0045] [Photosensitive resin composition]

[0046] The photosensitive resin composition of the present invention comprises (A) a resin having a (meth)acryloyl group, (B) a photoradical generator, and (C) quantum dots having a specific surface coating layer. Other components such as (D) a surfactant, (E) a silane coupling agent, (F) a crosslinking agent having a (meth)acryloyl group with two or more functional groups, and (G) a solvent may be further included as needed. The components constituting the photosensitive resin composition are described below.

[0047] [(A) Resin having a (meth)acryloyl group]

[0048] The (A) resin having a (meth)acryloyl group used in the present invention is not particularly limited as long as it has a (meth)acryloyl group.

[0049] In the present invention, the weight average molecular weight Mw of the resin (A) having a (meth)acryloyl group is preferably in the range of 5,000 to 100,000 g / mol, and more preferably in the range of 10,000 to 50,000 g / mol. As long as the weight average molecular weight of the resin (A) having a (meth)acryloyl group is within the above range, the film reduction of the exposed part is less likely to occur during development, and the solubility of the non-exposed part is good. The weight average molecular weight is a value obtained as a weight average molecular weight (weight average degree of polymerization) in terms of polystyrene obtained by GPC (gel permeation chromatography) analysis using toluene as an elution solvent.

[0050] In the present invention, the double bond equivalent of the resin (A) having a (meth)acryloyl group is preferably in the range of 240 to 1,000 g / mol, and more preferably in the range of 240 to 700 g / mol. In addition, the double bond equivalent is the weight of the resin per acryloyl group. When the double bond equivalent of the resin (A) having a (meth)acryloyl group is within the above range, the crosslinking density is high, and a pattern with a good shape can be formed after development.

[0051] In the present invention, the acid value of the resin (A) having a (meth)acryloyl group is preferably in the range of 0 to 150 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility in the alkaline developer becomes low, so it is preferred to develop using an organic solvent. As long as the acid value is 150 mgKOH / g or less, the pattern will not be peeled off during alkaline development.

[0052] In the present invention, (A) the resin having a (meth)acryloyl group may be used alone or in combination of two or more. In addition, (A) the resin having a (meth)acryloyl group is preferably in the range of 10 to 90% by mass relative to the total amount of the photosensitive resin composition. More preferably, it is 15 to 85% by mass.

[0053] [(B) Photoradical generator]

[0054] The photoradical generator used in the present invention is not particularly limited, and examples thereof include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, and oxime compounds.

[0055] Examples of the acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one.

[0056] Examples of the benzophenone compound include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0057] Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

[0058] Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzil dimethyl ketal.

[0059] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine. 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(trichloromethyl)-6-piperonyl-s-triazine, 2-(trichloromethyl)-6-(4-methoxyphenyl)-s-triazine, 2-(1-naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-s-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-s-triazine, etc.

[0060] As examples of oxime compounds, 1,2-octanedione, O-acyl oxime compounds, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime), O-ethoxycarbonyl-α-oxyamino-1-phenylpropane-1-one, etc. can be used. Specific examples of O-acyl oxime compounds include 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butane-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylthiophenyl)-butane-1-one oxime-O-acetate.

[0061] In addition to the above compounds, the photoradical generator (B) may include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, fluorene compounds, and the like.

[0062] The amount of the photoradical generator (B) is preferably in the range of 0.1 to 10% by mass, and more preferably in the range of 0.5 to 6% by mass, relative to the total amount of the photosensitive resin composition. When the photoradical generator is contained within the above range, the sensitivity during exposure and the developability are well balanced, and a pattern with excellent resolution can be obtained without residual film. In addition, the photoradical generator may be used alone or in combination of two or more.

[0063] [(C) Quantum dots with specific surface coatings]

[0064] Quantum dots refer to nano-sized semiconductor materials. Atoms form molecules, molecules form clusters, and small molecular aggregates form nanoparticles. When such nanoparticles show semiconductor properties, they are called quantum dots (quantum dot particles).

[0065] If 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 (to emit light).

[0066] The (C) quantum dots used in the present invention are not particularly limited as long as they have a surface coating layer containing siloxane, and can be used in any state. Quantum dots are mainly nanoparticles below 10 nm, and can be nanowires, nanorods, nanotubes, nanocubes, etc., and can be used in any shape. In the present invention, the average particle size of 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.

[0067] The (C) quantum dots used in the present invention can use any suitable material, for example, a semiconductor material selected from the group consisting of II-VI, III-V, IV, IV-VI, I-III-VI, II-IV-V and their mixed crystals or alloys, or a compound having a perovskite structure. Specifically, 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 can be listed, but the present invention is not limited to these.

[0068] 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, and preferably a material with a larger band gap than the core material and a lower lattice mismatch can be arbitrarily combined according to the core material. Specific shell materials include ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, BeS, BeSe, BeTe, MgS, MgSe, MgTe, PbS, PbSe, PbTe, SnS, SnSe, SnTe, CuF, CuCl, CuBr, CuI, etc., and the above materials can be selected singly or multiple mixed crystals can be selected, but are not limited thereto.

[0069] The method for producing the (C) quantum dots used in the present invention includes various methods such as liquid phase method or gas phase method, and there is no particular limitation in the present invention. However, from the perspective of showing high fluorescent luminescence efficiency, it is preferred to use semiconductor nanoparticles obtained by a hot soap method or a hot injection method in which precursor species are reacted at high temperature in a non-polar solvent with a high boiling point. In order to impart dispersibility in a non-polar solvent and reduce surface defects, it is best to have organic ligands coordinated on the surface.

[0070] 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, dodecanethiol, 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.

[0071] In addition to the organic ligand, the (C) quantum dot used in the present invention is also coordinated with a ligand having a substituent capable of forming a siloxane bond. As a ligand having a substituent capable of forming a siloxane bond, it is best to have a substituent that interacts with the surface of the quantum dot or a substituent that is adsorbed on the surface of the quantum dot. As a substituent that interacts with the surface of the quantum dot or a substituent that is adsorbed on the surface of the quantum dot, amino, thiol, carboxyl, mercapto, phosphino, phosphine, phosphine oxide, sulfonyl, ammonium ion, quaternary ammonium salt, etc. can be listed, among which, from the perspective of the strength of coordination, amino, carboxyl, mercapto, phosphine, quaternary ammonium salt are preferred.

[0072] The (C) quantum dots used in the present invention are coated with siloxane to coat the surface of the quantum dots. Therefore, in the above-mentioned ligand having a substituent that interacts with the surface of the quantum dots or a substituent that is adsorbed on the surface of the quantum dots, there is a substituent that can form a siloxane bond. As a substituent that can form a siloxane bond, there are trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, dimethylmethoxysilyl, ethoxydimethylsilyl and other alkoxysilane-containing compounds, compounds with silazane bonds, compounds with Si-OH bonds, compounds with Si-X (X: halogen) bonds, carboxylic acids, etc., but it is preferred to use alkoxysilane or silazane, Si-OH-containing ligands, the reason being that it can react under mild conditions without producing acids as reaction byproducts. By reacting it with diphenyldisilanol and the like, phenyl-containing siloxane can be formed.

[0073] The coating amount of siloxane is not particularly limited, but is preferably in the range of 1 to 50% by mass, and more preferably in the range of 5 to 30% by mass. If the coating amount of siloxane is too much, the quantum dot content will decrease, but when it is contained 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.

[0074] The (C) quantum dot used in the present invention may further include a skeleton having a (meth)acryloyl group in the surface coating layer.

[0075] By introducing a (meth)acryloyl group into the surface coating layer, the resin (A) having a (meth)acryloyl group and the surface coating layer are cross-linked after exposure, thereby suppressing the detachment of quantum dots during development and obtaining high luminescence characteristics of the pattern. In addition, the compatibility with the resin (A) having a (meth)acryloyl group is improved, and the generation of agglomerates when the photosensitive resin composition is prepared can be suppressed.

[0076] 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. As long as the content of the quantum dot particles is within the above range, fine pattern formation can be performed while maintaining good luminescent properties.

[0077] The method and amount of introduction of the (meth)acryloyl group in the component (C) are not particularly limited. When the phenyl-containing siloxane is formed, a method of adding a pre-made skeleton having a (meth)acryloyl group containing an alkoxysilane and reacting the skeleton, or a method of directly introducing the skeleton having a (meth)acryloyl group by free radical reaction, etc. can be used. The amount of introduction can be appropriately adjusted in consideration of the compatibility with the resin.

[0078] [(D) Surfactant]

[0079] In order to improve coating properties, the photosensitive resin composition of the present invention may further include (D) a surfactant.

[0080] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyether silicone, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters such as nonionic surfactants, EFTOP EF301, EF303, and EF352 (manufactured by Tohkem Products Corporation), and Megaface Fluorine-based surfactants such as F171, F172, and F173 (manufactured by DIC CORPORATION), Fluorad FC-4430, FC-430, and FC-431 (manufactured by Sumitomo 3M Limited), Surfynol E1004 (manufactured by Nissin Chemical Co., Ltd.), AsahiGuard AG710, Surflon S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, KH-10, KH-20, KH-30, and KH-40 (manufactured by AGC SEIMICHEMICAL CO., LTD.), organosiloxane polymers KP-341, X-70-092, and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic or methacrylic POLYFLOW No.75, No.95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), etc.

[0081] The (D) surfactant is preferably 0.01 to 3% by mass, more preferably 0.02 to 1% by mass, based on the total amount of the photosensitive resin composition. These components may be used alone or in combination of two or more.

[0082] [(E) Silane coupling agent]

[0083] In order to improve the adhesion with the substrate, the photosensitive resin composition of the present invention may further contain (E) a silane coupling agent.

[0084] Examples of the silane coupling agent include amino-containing silane coupling agents, epoxy-containing silane coupling agents, (meth)acryl-containing silane coupling agents, mercapto-containing silane coupling agents, vinyl-containing silane coupling agents, urea-containing silane coupling agents, sulfide-containing silane coupling agents, and silane coupling agents having a cyclic anhydride structure. Among them, (meth)acryl-containing silane coupling agents are suitable.

[0085] Examples of the (meth)acryloyl group-containing silane coupling agent include KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0086] The (E) silane coupling agent is preferably present in an amount of 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, relative to the total amount of the photosensitive resin composition. These components may be used alone or in combination of two or more.

[0087] [(F) Cross-linking agent]

[0088] The photosensitive resin composition of the present invention may further include (F) a crosslinking agent. The crosslinking agent is a component that causes a crosslinking reaction with (A) a resin having a (meth)acryloyl group or (C) a surface coating layer of quantum dots and can easily form a pattern with a good shape, and therefore, a crosslinking agent having a (meth)acryloyl group with two or more functional groups is preferred.

[0089] Examples of the crosslinking agent having a bifunctional or higher (meth)acryloyl group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxy) Polyfunctional monomers such as 2-hydroxy-3-(meth)acryloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., a reaction product of toluene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate), methylenebis(acrylamide), (meth)acrylamide methylene ether, a condensate of a polyol and N-hydroxymethyl (meth)acrylamide, or 1,3,5-triacryloylhexahydro-1,3,5-triazine (triacrylformal) and the like.

[0090] The amount of the crosslinking agent (F) is preferably 0.5 to 100 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the component (A). These components may be used alone or in combination of two or more.

[0091] [(G) Solvent]

[0092] The photosensitive resin composition of the present invention may contain a solvent as the component (G). The solvent (G) is not particularly limited as long as it can dissolve and disperse the components (A) to (F) and other various additives.

[0093] As the (G) solvent, an organic solvent is preferred, for example, 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; esters such as propylene glycol monomethyl ether acetate, 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, etc. These components may be used alone or in combination of two or more.

[0094] As the (G) solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, and a mixed solvent thereof, which have excellent solubility in (A) the resin having a (meth)acryloyl group and (B) the photoradical generator, are particularly preferred.

[0095] From the viewpoint of compatibility and viscosity of the photosensitive resin composition, the content of the component (G) is preferably 25 to 85% by mass, more preferably 35 to 75% by mass, based on the total amount of the photosensitive resin composition.

[0096] [Photosensitive resin coating]

[0097] The photosensitive resin film of the present invention is a dried product of the photosensitive resin composition described above.

[0098] [Pattern forming method using photosensitive resin composition]

[0099] The pattern forming method using the photosensitive resin composition of the present invention comprises:

[0100] (i) coating the above-described photosensitive resin composition on a substrate to form a photosensitive resin coating on the substrate;

[0101] (ii) exposing the photosensitive resin film to light; and

[0102] (iii) a step of developing the exposed photosensitive resin film using a developer.

[0103] Step (i) is a step of applying the above-described photosensitive resin composition onto a substrate to form a photosensitive resin coating on the substrate. The photosensitive resin coating is a dried product of the above-described photosensitive resin composition. Examples of the substrate include silicon wafers, glass wafers, quartz wafers, plastic circuit boards, ceramic circuit boards, and the like.

[0104] The coating method may be a known method, and examples thereof include dipping, spin coating, roll coating, etc. The coating amount may be appropriately selected according to the purpose, and the coating is preferably performed so that the film thickness of the obtained photosensitive resin film (dried product of the photosensitive resin composition) is preferably 0.1 to 200 μm, more preferably 1 to 150 μm.

[0105] Here, in order to effectively perform the photocuring reaction, the solvent and the like may be volatilized in advance by preheating (prebaking) as necessary. The prebaking may be performed at 40 to 140° C. for about 1 minute to 1 hour, for example.

[0106] Next, (ii) the photosensitive resin coating is exposed. At this time, the exposure is preferably performed with light having a wavelength of 10 to 600 nm, and more preferably with light having a wavelength of 190 to 500 nm. Examples of light of this 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 having a wavelength of 248 to 436 nm is particularly preferred. The exposure amount is preferably 10 to 10,000 mJ / cm 2 .

[0107] The exposure can be performed through a photomask. The photomask can be, for example, a photomask in which a desired pattern is hollowed out. In addition, the material of the photomask is not particularly limited, and a photomask that shields light of the wavelength is preferred, for example, a photomask having chrome as a light-shielding film is suitable, but is not limited thereto.

[0108] (iii) After exposure, development is performed using 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, and aqueous solutions of tetramethylammonium hydroxide are preferably used, such as well-known alkaline developers. As a developing method, common methods can be listed, such as an immersion method in which the substrate formed with the pattern is immersed in the developer, a puddle method in which the developer is distributed in a puddle, and a spray method in which the developer is sprayed by a spray. By performing development in this way, the non-exposed part is dissolved and removed to form a pattern. Then, cleaning, rinsing, drying, etc. are performed as needed to obtain a cured film having the desired pattern.

[0109] The pattern forming method using the photosensitive resin composition of the present invention can easily form a fine pattern. For example, the photosensitive resin composition of the present invention is formed into a film in a manner of covering a large number of blue Micro-LEDs laid on a substrate, and then fine patterning is performed, thereby forming a cured film containing red quantum dots or green quantum dots on each part of the blue Micro-LED, thereby also being able to generate red or green light, so that a full-color light-emitting element can be produced.

[0110] [Light-emitting element]

[0111] The light-emitting element of the present invention comprises a cured film obtained by the above-described pattern forming method.

[0112] Example

[0113] The following is a more specific description of the present invention by showing synthesis examples, embodiments and comparative examples, 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 thereafter is shown in [2].

[0114] [1-1] Red quantum dot nucleosynthesis process

[0115] 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 thereto respectively. The mixture was heated and stirred at 100 ° C under reduced pressure, and degassed for 1 hour while the raw materials were dissolved. Then, nitrogen was blown into the two flasks, and 0.75 mL (0.15 mmol) of tris(trimethylsilyl)phosphine / trioctylphosphine solution (0.2 M) was added to the two flasks. Then, one flask was heated to 300 ° C, and the solution was extracted from the unheated flask and added to the flask heated to 300 ° C, thereby generating core particles.

[0116] [1-2] Green quantum dot nucleation process

[0117] 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, and degassed for 1 hour while dissolving the raw materials. Then, nitrogen was blown into the flask, and 0.75 mL (0.15 mmol) of a solution obtained by mixing tris(trimethylsilyl)phosphine and trioctylphosphine and adjusting to 0.2 M was added, and the temperature was raised to 300° C. to generate core particles.

[0118] [2] Quantum dot shell synthesis process

[0119] Next, 2.85 g (4.5 mmol) of zinc stearate and 15 mL of 1-octadecene were added to another flask, and heated and stirred at 100° C. under reduced pressure, and degassed for 1 hour while dissolving to prepare a 0.3 M zinc stearate octadecene solution. 3.0 mL (0.9 mmol) of the solution was added to the reaction solution after the nucleus synthesis, and the solution was 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 the solution, and a 1.5 M selenium trioctylphosphine solution was prepared. The reaction solution after the nucleus synthesis step, which had been cooled to 200° C., was heated to 320° C. over 30 minutes, and the selenium trioctylphosphine solution was added in an amount of 0.1 mL each time, with a total of 0.6 mL (0.9 mmol) being added. The temperature was maintained at 320° C. for 10 minutes, and the solution was 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 flask with nitrogen again and heat to 230 ° C, add 0.98 mL (4 mmol) of 1-dodecanethiol and maintain for 1 hour. The obtained solution is cooled to room temperature to prepare a solution containing core-shell quantum dots. The solution containing red core-shell quantum dots synthesized by the steps [1-1] to [2] is designated as R-1, and the solution containing green core-shell quantum dots synthesized by the steps [1-2] to [2] is designated as G-1.

[0120] [3] Ligand exchange process

[0121] 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 that has been 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, dispersed in toluene, and a quantum dot solution coordinated with a ligand having a substituent capable of forming a siloxane bond is prepared. The quantum dots synthesized using R-1 and coordinated with a ligand having a substituent capable of forming a siloxane bond are set to R-2, and the quantum dots synthesized using G-1 and coordinated with a ligand having a substituent capable of forming a siloxane bond are set to G-2.

[0122] [4-1] Surface coating layer forming process

[0123] Add 3-(trimethoxysilyl)propyl methacrylate (4.0mmol), diphenylsilanediol (6mmol), barium hydroxide monohydrate (0.15mmol) and the quantum dot toluene solution after the ligand exchange process to a flask purged with nitrogen, and heat and stir at 65°C for 24 hours. After the reaction is completed, cool to room temperature, add ethanol to precipitate the reaction solution, centrifuge and remove the supernatant. Disperse it in toluene, then add PGMEA, remove the toluene solvent by vacuum distillation, and prepare a quantum dot solution with a surface coating layer (solid content concentration of 60%). The quantum dots synthesized using R-2 with a surface coating layer are set to RS, and the quantum dots synthesized using G-2 with a surface coating layer are set to GS.

[0124] [4-2] Surface coating layer forming process

[0125] To a flask purged with nitrogen, add 3-(trimethoxysilyl)propyl methacrylate (4.0 mmol), diphenylsilanediol (6 mmol), barium hydroxide monohydrate (0.15 mmol) and the quantum dot toluene solution after the ligand exchange process, and heat and stir at 65°C for 24 hours. After the reaction is completed, cool to room temperature, add ethanol to precipitate the reaction solution, centrifuge and remove the supernatant. Disperse it in toluene and add it to a flask that has been purged with nitrogen in advance. Add 2 parts by mass of (A) a resin with a (meth) acryloyl group to 100 parts by mass of the quantum dot toluene solution. Then, add 1 part by mass of Irgacure 1173 to 100 parts by mass of the resin with a (meth) acryloyl group, stir and mix, and irradiate with a UVLED irradiation device for 20 seconds with a wavelength of 365nm and an output of 4000mW / cm 2of light. After the reaction is completed, ethanol is added to precipitate it, and the supernatant is removed after centrifugation, and it is dispersed in toluene again. Then PGMEA is added, and the toluene solvent is removed by vacuum distillation to prepare a quantum dot solution having a surface coating layer (a solution with a solid content concentration of 60%). At this time, as (A) a resin having a (meth)acryloyl group, the product name "RA-4101" (Mw: 30,000, acid value: 90 mgKOH / g, double bond equivalent: 350) manufactured by Negami Chemical Industrial Co., Ltd., the product name "8KQ-2001" (Mw: 20,000, acid value: 130 mgKOH / g, double bond equivalent: 540) manufactured by TAISEI FINE CHEMICAL CO,.LTD., and the product name "8KQ-7052" (Mw: 19,000, acid value: 7 mgKOH / g, double bond equivalent: 500) are used. Here, the quantum dots forming the surface coating layer of the combination of R-2 and RA-4101 are set to R4101, the quantum dots forming the surface coating layer of the combination of G-2 and RA-4101 are set to G4101, the quantum dots forming the surface coating layer of the combination of R-2 and 8KQ-2001 are set to R2001, the quantum dots forming the surface coating layer of the combination of G-2 and 8KQ-2001 are set to G2001, the quantum dots forming the surface coating layer of the combination of R-2 and 8KQ-7052 are set to R7052, and the quantum dots forming the surface coating layer of the combination of G-2 and 8KQ-7052 are set to G7052.

[0126] [5] Preparation and evaluation of photosensitive resin compositions

[0127] [Examples 1 to 24 and Comparative Examples 1 to 24]

[0128] The components were blended in the amounts listed in Tables 1 to 4, stirred and mixed at room temperature, and finely filtered using a 1.0 μm glass filter to obtain photosensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 24.

[0129] [Table 1]

[0130]

[0131] [Table 2]

[0132]

[0133] [Table 3]

[0134]

[0135] [Table 4]

[0136]

[0137] In Tables 1 to 4, the resins are trade names “RA-4101” (Mw: 30,000 g / mоl, acid value: 90 mgKOH / g, double bond equivalent: 350 g / mоl) manufactured by Negami Chemical Industrial Co., Ltd., trade name “RA-3631P” (Mw: 18,000 g / mоl, acid value: 5 mgKOH / g, double bond equivalent: 250 g / mоl), trade name “8KQ-2001” (Mw: 20,000 g / mоl, acid value: 130 mgKOH / g, double bond equivalent: 540 g / mоl) manufactured by TAISEI FINE CHEMICAL CO,.LTD., and trade name “8KQ-7052” (Mw: 19,000 g / mоl, acid value: 7 mgKOH / g, double bond equivalent: 500 g / mоl).

[0138] In Tables 1 to 4, the photoradical generators are trade names "Irgacure 184" (1-hydroxycyclohexyl phenyl ketone) and "Irgacure OXE01" manufactured by BASF.

[0139] [Chemical formula 1]

[0140]

[0141] In Tables 1 to 4, the surfactant is a product name "KP-341" (polyether silicone) manufactured by Shin-Etsu Chemical Co., Ltd.

[0142] In Tables 1 to 4, the silane coupling agent is a trade name “KBM-503” (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0143] In Tables 1 to 4, the crosslinking agent is a trade name "ARONIX (registered trademark) M-940" (dipentaerythritol hexaacrylate) manufactured by TOAGOSEI CO., LTD. and a trade name "DPCA-20" manufactured by Nippon Kayaku Co., Ltd.

[0144] [Chemical formula 2]

[0145]

[0146] In Tables 1 to 4, quantum dot R-3 is S-BE030 manufactured by SHOEI CHEMICAL INC. (particle size 5 to 10 nm, material InP: ZnS: SeZn = 25: 50: 25), R-4 is 900514-1ML manufactured by Aldrich (particle size 5 to 10 nm, material CdSe (core) / CdS (shell) core-shell type), G-3 is S-BE029 manufactured by SHOEI CHEMICAL INC. (particle size 3 to 5 nm, material InP: ZnS: SeZn = 25: 50: 25), and G-4 is 900511-1ML manufactured by Aldrich (particle size 3 to 5 nm, material CdSe (core) / CdS (shell) core-shell type).

[0147] [6] Evaluation of photosensitive resin composition

[0148] (1) Confirmation of aggregates in the coating

[0149] Each photosensitive resin composition was coated on a silicon wafer with a film thickness of 10 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 2 minutes. The agglomerates in the obtained photosensitive resin film were confirmed using an optical microscope, and the range of 10 mm × 10 mm was observed. The presence of agglomerates larger than 1 μm was marked as ×, and the absence of agglomerates or the size of agglomerates smaller than 1 μm was marked as ○. The results are shown in Tables 5 to 8.

[0150] (2) Pattern formation and evaluation

[0151] In order to form a square island pattern (island pattern) with a pitch width of 1:1 with the adjacent pattern on the obtained photosensitive resin coating through a mask, an i-line photolithography machine NSR-2205i11D (manufactured by Nikon Corporation) was used for exposure. After light irradiation, for the embodiments and comparative examples numbered odd, a 2.38% aqueous solution of tetramethylammonium hydroxide was used for 60 seconds of puddle development to form a pattern, and for the embodiments and comparative examples numbered even, PGMEA was used for 60 seconds of puddle development to form a pattern. Then, using a scanning electron microscope (SEM), the island patterns with a side of 50μm, 30μm, 20μm, 10μm, and 5μm were observed, and the minimum pattern size that was not connected to the adjacent island pattern (pitch width 1:1) was taken as the limiting resolution. In addition, the case where the resolution did not reach 50μm or the development peeling of the pattern occurred was recorded as ×. The results are shown in Tables 5 to 8.

[0152] (3) Evaluation of light-emitting properties of formed patterns

[0153] The patterned sample prepared in (2) was irradiated with a 457 nm laser (0.03 mW) using a LabRAM HR Evolution manufactured by HORIBA TECHNO SERVICE, Co., Ltd., and the island pattern area after photoconversion was measured, and the luminous intensity, luminous wavelength, and half-value width of the light after photoconversion were measured. In addition, the sample after the heating and drying process prepared in (1) was measured in the same manner, and the luminous intensity of the light after photoconversion was measured. The results are shown in Tables 5 to 8 (M: 1 million).

[0154] (4) Reliability test evaluation

[0155] In addition, the Atlas SUNTEST XLS+ manufactured by Toyo Seiki Seisaku-sho, Ltd. was used with an illuminance of 65W / m 2 The patterned sample of (3) was subjected to a sunlight light resistance test for 300 hours at an ambient temperature of 100°C. The luminous intensity of the light converted before and after the test was measured in the same manner as (3), and the rate of change (reduction rate) relative to the initial value was confirmed. The results are shown in Tables 5 to 8.

[0156] Change rate = ((luminous intensity after the test / luminous intensity before the test) - 1) × 100

[0157] [Table 5]

[0158]

[0159] [Table 6]

[0160]

[0161] [Table 7]

[0162]

[0163] [Table 8]

[0164]

[0165] The above results show that the photosensitive resin composition of the present invention can form a good photosensitive resin coating without agglomerates (or even if there are agglomerates, they are extremely small), and can provide a cured film (cured coating) having high lithography resolution, high luminescence properties that do not change before and after the lithography process, good reliability (low rate of change of luminescence intensity in the sunlight photostability test) and suitable for light-emitting elements.

[0166] This specification includes the following protocols.

[0167] [1] A photosensitive resin composition, characterized in that it comprises (A) a resin having a (meth)acryloyl group, (B) a photoradical generator and (C) quantum dots, wherein the quantum dots have a surface coating layer containing siloxane.

[0168] [2]: The photosensitive resin composition according to [1] above, wherein the component (C) contains a skeleton having a (meth)acryloyl group in the surface coating layer.

[0169] [3]: The photosensitive resin composition according to the above [1] or [2] is 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.

[0170] [4]: The photosensitive resin composition according to [1], [2] or [3], wherein the photosensitive resin composition contains 5 to 80% by mass of the component (C).

[0171] [5]: The photosensitive resin composition according to [1], [2], [3] or [4], characterized in that the double bond equivalent of the component (A) is 240 to 1,000 g / mol.

[0172] [6]: The photosensitive resin composition according to [1], [2], [3], [4] or [5], characterized in that the weight average molecular weight Mw of the component (A) is 5,000 to 100,000 g / mol.

[0173] [7]: The photosensitive resin composition according to [1], [2], [3], [4], [5] or [6], further comprising (D) a surfactant.

[0174] [8]: The photosensitive resin composition according to [1], [2], [3], [4], [5], [6] or [7], further comprising (E) a silane coupling agent.

[0175] [9]: The photosensitive resin composition according to [1], [2], [3], [4], [5], [6], [7] or [8], further comprising (F) a crosslinking agent having two or more functional (meth)acryloyl groups.

[0176]

[10] : The photosensitive resin composition according to [1], [2], [3], [4], [5], [6], [7], [8] or [9], further comprising (G) a solvent.

[0177]

[11] : A photosensitive resin coating, characterized in that it is a dried product of the photosensitive resin composition of [1], [2], [3], [4], [5], [6], [7], [8], [9] or

[10] .

[0178]

[12] : A pattern forming method, characterized in that it comprises:

[0179] (i) a step of applying the photosensitive resin composition of [1], [2], [3], [4], [5], [6], [7], [8], [9] or

[10] above onto a substrate to form a photosensitive resin film on the substrate;

[0180] (ii) exposing the photosensitive resin film to light; and

[0181] (iii) a step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed portions to form a pattern.

[0182]

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

[12] above.

[0183] The present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any technical solution having substantially the same structure and exerting the same function and effect as the technical concept described in the claims of the present invention is included in the protection scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that: The invention comprises (A) a resin having a (meth)acryloyl group, (B) a photoradical generator and (C) quantum dots, wherein 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 (meth)acryloyl group in the surface coating layer.

3. The photosensitive resin composition according to claim 1, 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.

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

5. The photosensitive resin composition according to claim 1, characterized in that: The double bond equivalent of the component (A) is 240 to 1,000 g / mol.

6. The photosensitive resin composition according to claim 1, characterized in that: The weight average molecular weight Mw of the component (A) is 5,000 to 100,000 g / mol.

7. The photosensitive resin composition according to claim 1, characterized in that: It further comprises (D) a surfactant.

8. The photosensitive resin composition according to claim 1, characterized in that: It further comprises (E) a silane coupling agent.

9. The photosensitive resin composition according to claim 1, characterized in that: It further contains (F) a crosslinking agent having a bifunctional or higher-functional (meth)acryloyl group.

10. The photosensitive resin composition according to claim 1, characterized in that: It further comprises (G) a solvent.

11. A photosensitive resin coating, characterized in that: The photosensitive resin composition is a dried product according to any one of claims 1 to 10.

12. A pattern forming method, characterized in that: It includes: (i) a step of coating the photosensitive resin composition according to any one of claims 1 to 10 on a substrate to form a 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 portions to form a pattern.

13. A light emitting element, characterized in that: The present invention comprises a cured film obtained by the pattern forming method according to claim 12.

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