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

Abstract

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

Description

Technical Field

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

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

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

[0004] Prior Art Documents

[0005] Patent Documents

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

[0007] Non-Patent Documents

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

[0009] (1) Technical Problem to be Solved

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

[0011] (2) Technical Solution

[0012] In order to solve the above technical problems, the present invention provides a photosensitive resin composition, which includes:

[0013] (A) a resin having a (meth)acryloyl group,

[0014] (B) A photoinduced radical generator, and

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

[0016] If it is such a photosensitive resin composition, a coating film having high photolithographic resolution and good light emission characteristics can be easily formed.

[0017] In addition, in the present invention, it is preferable that the component (C) has a skeleton having a functional group with radical reactivity in the surface coating layer of the quantum dot.

[0018] If it is such a photosensitive resin composition, the quantum dot is inhibited from coming out during development, and high light emission characteristics of the pattern can be obtained.

[0019] In addition, in the present invention, it is preferable that the coordination substituent of the silane coupling agent of the component (C) has any one or more of an amino group, a thiol group, a carboxyl group, a phosphine group, a phosphine oxide group, and an ammonium ion.

[0020] If it is such a photosensitive resin composition, it has higher photolithographic resolution.

[0021] In addition, in the present invention, it is preferable that the photosensitive resin composition contains 5 to 80% by mass of the component (C).

[0022] If it is such a photosensitive resin composition, fine pattern formation can be performed while maintaining good light emission characteristics.

[0023] In addition, in the present invention, it is preferable that the double bond equivalent of the component (A) is 240 to 1,000 g / mol.

[0024] If it is such a photosensitive resin composition, it has a high crosslinking density and can form a pattern with a good shape after development.

[0025] In addition, in the present invention, it is preferable that the component (A) is an acrylic resin having a weight average molecular weight Mw of 5,000 to 100,000 g / mol.

[0026] If it is such a photosensitive resin composition, the film reduction of the exposed portion is not likely to occur during development, and the solubility of the unexposed portion becomes good.

[0027] In addition, in the present invention, it is preferable to further contain (D) a surfactant.

[0028] If it is such a photosensitive resin composition, the coatability can be improved.

[0029] In addition, in the present invention, it is preferable to further contain (E) a silane coupling agent.

[0030] If it is such a photosensitive resin composition, the close adhesion to the substrate can be improved.

[0031] In addition, in the present invention, it is preferable to further contain (F) a crosslinking agent having a (meth)acryloyl group with a functionality of 2 or more.

[0032] If it is such a photosensitive resin composition, the obtained cured coating film has high reliability.

[0033] In addition, in the present invention, it is preferable to further contain (G) a solvent.

[0034] If it is such a photosensitive resin composition, the coatability can be improved.

[0035] In addition, in the present invention, there is provided a photosensitive resin coating film which is a dried product of the above-described photosensitive resin composition.

[0036] If it is such a photosensitive resin coating film, it will become a coating film having high lithographic resolution and good light-emitting characteristics.

[0037] In addition, in the present invention, there is provided a pattern forming method, which includes:

[0038] (i) A step of coating the above-described photosensitive resin composition on a substrate to form a photosensitive resin coating film on the substrate;

[0039] (ii) A step of exposing the photosensitive resin coating film; and

[0040] (iii) A step of developing the exposed photosensitive resin coating film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

[0041] If it is such a pattern forming method, a pattern can be formed with high lithographic resolution, and a pattern of a coating film having good light-emitting characteristics can be obtained.

[0042] In addition, in the present invention, there is provided a light-emitting element which includes a cured coating film having a pattern formed on the above-described photosensitive resin coating film.

[0043] If it is such a light-emitting element, it has high lithographic resolution and good light-emitting characteristics.

[0044] (III) Advantageous Effects

[0045] The photosensitive resin composition of the present invention can easily form a coating film having high resolution and good light-emitting characteristics by containing a resin having a (meth)acryloyl group, a photoinitiator, and a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof, and thus is suitable for a light-emitting element. Detailed Embodiments

[0046] As described above, it is desired to develop a photosensitive resin composition capable of easily forming a film having high lithographic resolution and good light-emitting characteristics, a photosensitive resin film obtained by using the photosensitive resin composition, a pattern forming method using the photosensitive resin composition and the photosensitive resin film, and a light-emitting element including a cured film obtained by using the photosensitive resin film.

[0047] The inventors of the present application have conducted intensive studies to achieve the above object, and as a result, have found a photosensitive resin composition capable of easily forming a film (photosensitive resin film) having high lithographic resolution and good light-emitting characteristics, and have thus completed the present invention. The photosensitive resin composition includes: (A) a resin having a (meth)acryloyl group, (B) a photo radical generator, and (C) a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof.

[0048] That is, the present invention is a photosensitive resin composition including:

[0049] (A) a resin having a (meth)acryloyl group,

[0050] (B) a photo radical generator, and

[0051] (C) a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof.

[0052] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0053] [Photosensitive Resin Composition]

[0054] The photosensitive resin composition of the present invention includes: (A) a resin having a (meth)acryloyl group, (B) a photo radical generator, and (C) a polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof. Other components such as (D) a surfactant, (E) a silane coupling agent, (F) a crosslinking agent having a (meth)acryloyl group with a functionality of 2 or more, and (G) a solvent may be further included as needed. Hereinafter, each component constituting the photosensitive resin composition will be described.

[0055] [(A) Resin Having a (Meth)acryloyl Group]

[0056] 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.

[0057] In the present invention, the resin having a (meth)acryloyl group (A) is preferably an acrylic resin having a weight average molecular weight Mw in the range of 5,000 to 100,000 g / mol, more preferably an acrylic resin having a weight average molecular weight Mw in the range of 10,000 to 50,000 g / mol. If the weight average molecular weight of the resin having a (meth)acryloyl group (A) is within the above range, film reduction in the exposed portion is less likely to occur during development, and the solubility of the unexposed portion is good. In addition, as long as it is an acrylic resin, it is transparent and has no color difference, which is suitable for display applications. The acrylic resin referred to here means a polymer of acrylate or methacrylate. The weight average molecular weight is a value obtained as the weight average molecular weight (weight average degree of polymerization) in terms of polystyrene obtained by GPC (gel permeation chromatography) using toluene as an eluent.

[0058] In the present invention, the double bond equivalent of the resin having a (meth)acryloyl group (A) is preferably in the range of 240 to 1,000 g / mol, more preferably in the range of 240 to 700 g / mol. In addition, the double bond equivalent means the weight of the resin per (meth)acryloyl group. As long as the double bond equivalent of the resin having a (meth)acryloyl group (A) is within the above range, the crosslinking density is high, and a pattern with good shape can be formed after development.

[0059] In the present invention, the acid value of the resin having a (meth)acryloyl group (A) 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 alkali developer becomes low, so development with an organic solvent is preferably used. As long as the acid value is 150 mgKOH / g or less, pattern peeling does not occur during alkali development.

[0060] In the present invention, the resin having a (meth)acryloyl group (A) can be used alone or two or more kinds can be used simultaneously. In addition, relative to the total amount of the photosensitive resin composition, the resin having a (meth)acryloyl group (A) is preferably in the range of 10 to 90% by mass. More preferably, it is 15 to 85% by mass.

[0061] [(B) Photo radical generator]

[0062] The photo radical generator used in the present invention is not particularly limited, and examples thereof include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, and the like.

[0063] Examples of 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

[0064] Examples of benzophenone compounds 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, 3,3'-dimethyl-2-methoxybenzophenone, etc.

[0065] Examples of thioxanthone compounds include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.

[0066] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, etc.

[0067] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(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-methoxystyryl)-s-triazine, etc.

[0068] As examples of the 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-carbazol-3-yl]ethanone 1-(O-acetyl oxime), O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, etc. can be used. As specific examples of the O-acyl oxime compounds, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 1-(4-phenylsulfonylphenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfonylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfonylphenyl)-octan-1-one oxime-O-acetate, 1-(4-phenylsulfonylphenyl)-butan-1-one oxime-O-acetate, etc. can be cited.

[0069] In addition to the above compounds, as the (B) photoinduced radical generator, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, fluorene compounds, etc. can also be used.

[0070] Relative to the total amount of the photosensitive resin composition, the (B) photoinduced radical generator is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.5 to 6% by mass. When the photoinduced radical generator is contained within the above range, the balance between the sensitivity and developability during exposure is excellent, and a pattern with excellent resolution can be obtained without residual film. In addition, the photoinduced radical generator can be used alone or two or more thereof can be used simultaneously.

[0071] [(C) A polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof]

[0072] Quantum dots refer to semiconductor substances of nanometer size. Atoms form molecules, molecules form small molecular aggregates called clusters, and then form nanoparticles. When such nanoparticles exhibit semiconductor characteristics, they are called quantum dots (quantum dot particles).

[0073] If a quantum dot receives energy from the outside and reaches an excited state, it will autonomously (self-regulate) release the energy corresponding to the band gap (emit light).

[0074] The quantum dots used in the present invention are not particularly limited and can be used in any form. The quantum dots are mainly nanoparticles of 10 nm or less and can be nanowires, nanorods, nanotubes, nanocubes, etc., and quantum dots of any shape can be appropriately used.

[0075] In the present invention, the (C) quantum dots used can be made of any suitable material. As the semiconductor material, for example, materials selected from the group consisting of II-VI group, III-V group, IV group, IV-VI group, I-III-VI group, II-IV-V group, and their mixed crystals or alloys, or compounds having a perovskite structure can be used. Specifically, examples include materials 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, AgGaS 2 , AgInS 2 , AgGaSe 2 , AgInSe 2 , CuGaS 2 , CuGaSe 2 , CuInS 2 , CuInSe 2 , ZnSiP 2 , ZnGeP 2 , CdSiP 2 , CdGeP 2 , CsPbCl 3 , CsPbBr 3 , CsPbI 3 , CsSnCl 3 , CsSnBr 3 , CsSnI 3 compounds, but are not limited thereto.

[0076] The quantum dots used in the present invention may have a core-shell structure. As the shell material that can form the core-shell structure, there is no particular limitation. Materials with a large band gap and low lattice mismatch relative to the core material are preferred, and can be arbitrarily combined according to the core material. Specific examples of the shell material include ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, BeS, BeSe, BeTe, MgS, MgSe, MgTe, PbS, PbSe, PbTe, SnS, SnSe, SnTe, CuF, CuCl, CuBr, CuI, etc. The above materials can be selected as a single one, or a mixed crystal of multiple ones, but are not limited thereto.

[0077] In the present invention, various methods such as liquid phase method or gas phase method can be used for preparing the quantum dots used. In the present invention, although there is no particular limitation, from the perspective of exhibiting high fluorescence emission efficiency, semiconductor nanoparticles obtained by a pyrolysis method or a thermal injection method in which precursor species are reacted at a high temperature in a high-boiling non-polar solvent are preferably used. In order to impart its dispersibility in non-polar solvents and reduce surface defects, it is preferably surface-coordinated with an organic ligand.

[0078] From the perspective of dispersibility, the organic ligand preferably contains aliphatic hydrocarbons. As such organic ligands, for example, oleic acid, stearic acid, palmitic acid, myristic acid, lauric acid, capric acid, octanoic acid, oleylamine, stearyl (octadecyl) amine, dodecyl (lauryl) amine, decylamine, octylamine, octadecanethiol, hexadecanethiol, tetradecanethiol, dodecanethiol, decanethiol, octanethiol, trioctylphosphine, trioctyloxophosphine, triphenylphosphine, triphenyloxophosphine, tributylphosphine, tributyloxophosphine, etc. can be cited. These ligands can be used alone or in combination of multiple kinds.

[0079] It is preferred that the component (C) has a skeleton with a functional group having free radical reactivity in the surface coating layer of the quantum dots.

[0080] The surface of the quantum dots is surface-treated with a silane coupling agent. As the coordination substituents of the silane coupling agent, those having any one or more of an amino group, a thiol group, a carboxyl group, a phosphino group, an oxophosphino group, and an ammonium ion are preferred. Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, aminophenyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl(dimethoxy)methylsilane, triethoxysilylpropylmaleamic acid, [(3-triethoxysilyl)propyl] succinic anhydride, X-12-1135 (manufactured by Shin-Etsu Chemical Co., Ltd.), diethylphosphonoethyltriethoxysilane, 3-trihydroxypropylmethylphosphate sodium salt, trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, etc.

[0081] In one embodiment, quantum dots surface-treated with a silane coupling agent are copolymerized with a condensate of an alkoxysilane or an alkoxysilane hydrolyzate. The copolymerization method is not particularly limited. For example, the surface-treated quantum dots are mixed with a condensate of an alkoxysilane or an alkoxysilane hydrolyzate in a mixed solvent of toluene and ethanol, and a small amount of water and a catalyst are added thereto to cause a reaction, whereby the quantum dots can be copolymerized with the condensate of the alkoxysilane or the alkoxysilane hydrolyzate. The type of the catalyst is not particularly limited, and an acid or a base can be used. Examples of the catalyst include formic acid, hydrochloric acid, nitric acid, acetic acid, ammonia water, and tetramethylammonium hydroxide.

[0082] In addition, the condensate of the alkoxysilane or the alkoxysilane hydrolyzate may have a cage structure, a ladder structure, a random structure, etc., and its structure is not particularly limited and can be appropriately selected according to the purpose. From the viewpoints of dispersibility and uniformity in the photosensitive resin, a random structure is preferred. In addition, the functional groups contained in the condensate of the alkoxysilane or the alkoxysilane hydrolyzate are not limited and can be appropriately substituted according to the purpose. From the viewpoint of improving the patterning of the resin composition, it is preferred to have an acryloyl group or a methacryloyl group capable of crosslinking reaction with the photosensitive resin as a substituent.

[0083] In one embodiment, quantum dots surface-treated with a silane coupling agent are copolymerized with an alkoxysilane or an alkoxysilane hydrolyzate. The copolymerization method is not particularly limited. As its synthesis method, methods such as Non-Patent Document 1 are known. For example, the surface-treated quantum dots are mixed with an alkoxysilane in a mixed solvent of toluene and ethanol, and a small amount of water and a catalyst are added thereto to cause a reaction, whereby the product can be obtained. The type or addition amount of the catalyst is not particularly limited, and an acid or a base can be used. Examples of the catalyst include formic acid, hydrochloric acid, nitric acid, acetic acid, ammonia water, and tetramethylammonium hydroxide.

[0084] The silane coupling agent is not particularly limited and can be appropriately selected according to the characteristics of the target resin. As the silane coupling agent, those having vinyl, allyl, glycidyl, phenyl, acryloyl, methacryloyl, or mercapto groups as functional groups are preferred. In addition, for the functional groups, alkoxysilanes having two or more functional groups rather than only one functional group can be used. Examples of the silane coupling agent include trimethoxyvinylsilane, triethoxyvinylsilane, trimethoxy(4-vinylphenyl)silane, allyltriethoxysilane, allyltrimethoxysilane, triethoxy(3-glycidoxypropyl)silane, 3-glycidoxypropyltrimethoxysilane, [8-(glycidoxy)-n-octyl]trimethoxysilane, KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.), (3-methacryloxypropyl)triethoxysilane, (3-methacryloxypropyl)trimethoxysilane, 3-(trimethoxysilyl)propyl acrylate, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

[0085] In addition, the alkoxysilane is not limited to trialkoxysilane and may include dialkoxysilane or monoalkoxysilane. The trialkoxysilane, dialkoxysilane, and monoalkoxysilane may have the same functional groups or may have different functional groups. The functional groups are not limited and can be appropriately substituted according to the purpose. From the perspective of improving the patterning property of the resin composition, it is preferred to have acryloyl or methacryloyl that can undergo a crosslinking reaction with the photosensitive resin as a substituent. By including dialkoxysilane or monoalkoxysilane, the crosslinking degree of the condensate of the alkoxysilane or alkoxysilane hydrolyzate obtained by copolymerization can be controlled, the viscosity of the resulting resin composition can be controlled, and the viscosity can be adjusted according to the manufacturing process. The types or ratios of these alkoxysilanes are not particularly limited and can be appropriately selected according to the purpose.

[0086] Relative to the total amount of the photosensitive resin composition, the polymer obtained by copolymerizing the (C) quantum dots coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof used in the present invention is preferably 5 to 80% by mass, more preferably 10 to 70% by mass. As long as the content rate of the quantum dot particles is within the above range, fine patterning can be performed while maintaining good light-emitting characteristics.

[0087] [(D) Surfactant]

[0088] In order to improve the coatability, the photosensitive resin composition of the present invention may further contain (D) a surfactant.

[0089] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl 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; nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyether silicone, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as FTOP EF301, FTOP EF303, FTOP EF352 (manufactured by Tohkem Products Co., Ltd.), MEGAFACE F171, MEGAFACE F172, MEGAFACE F173 (manufactured by DIC CORPORATION), Fluorad FC-4430, Fluorad FC-430, Fluorad 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, KH-40 (manufactured by AGC SEIMI CHEMICAL CO., LTD.); silicone oxygen polymer KP-341, X-70-092, X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic or methacrylic POLYFLOW No.75, POLYFLOW No.95 (manufactured by KYOEISHA CHEMICAL Co.,LTD.), and the like.

[0090] Relative to the total amount of the photosensitive resin composition, the (D) surfactant is preferably 0.01 to 3% by mass, more preferably 0.02 to 1% by mass. In addition, these components may be used alone or in combination of two or more.

[0091] [(E) Silane Coupling Agent]

[0092] In order to further improve the close adhesion to the substrate, the photosensitive resin composition of the present invention may further contain (E) a silane coupling agent.

[0093] As the silane coupling agent, examples thereof include an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, a (meth)acryloyl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a vinyl group-containing silane coupling agent, a ureido group-containing silane coupling agent, a styryl group-containing silane coupling agent, a silane coupling agent having a cyclic anhydride structure, etc. Among them, a (meth)acryloyl group-containing silane coupling agent is preferable.

[0094] As the amino group-containing silane coupling agent, examples thereof include KBM-602, KBM-603, KBM-903, KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. As the epoxy group-containing silane coupling agent, examples thereof include KBM-303, KBM-402, KBM-403, KBE-402 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. As the (meth)acryloyl group-containing silane coupling agent, examples thereof include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. As the mercapto group-containing silane coupling agent, examples thereof include KBM-802, KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. As the vinyl group-containing silane coupling agent, examples thereof include KBM-1003, KBE-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. As the ureido group-containing silane coupling agent, examples thereof include KBE-585A (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. As the styryl group-containing silane coupling agent, examples thereof include KBM-1403 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. As the silane coupling agent having a cyclic anhydride structure, examples thereof include X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0095] Relative to the total amount of the photosensitive resin composition, the (E) silane coupling agent is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass. In addition, these components may be used alone or in combination of two or more.

[0096] [(F) Crosslinking agent]

[0097] The photosensitive resin composition of the present invention may further contain (F) a crosslinking agent. The crosslinking agent is a component for crosslinking with the (A) resin having a (meth)acryloyl group or the surface coating layer of the quantum dots contained in the (C) component, so as to easily obtain a pattern with a good shape. Therefore, a crosslinking agent having a (meth)acryloyl group with a functionality of 2 or more is preferred.

[0098] Examples of the crosslinking agent having a (meth)acryloyl group with a functionality of 2 or more 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)acryloxy diethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxy polyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., the reaction product of toluene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene diisocyanate, etc. with 2-hydroxyethyl (meth)acrylate), methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, condensates of polyhydric alcohols and N-hydroxymethyl (meth)acrylamide, etc., polyfunctional monomers, or 1,3,5-triacryloyl hexahydro-1,3,5-triazine (triacrylformal), etc.

[0099] Relative to 100 parts by mass of the (A) component, the (F) crosslinking agent is preferably 0.5 to 100 parts by mass, more preferably 1 to 50 parts by mass. In addition, these components can be used alone or in combination of two or more.

[0100] [(G) Solvent]

[0101] The photosensitive resin composition of the present invention may contain a solvent as the (G) component. As the (G) solvent, there is no particular limitation as long as it can dissolve and disperse the above-mentioned (A) to (F) components or various other additives.

[0102] As the (G) solvent, an organic solvent is preferred, and examples thereof include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, 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 monoter-butyl ether acetate, and γ-butyrolactone. These components can be used alone or in combination of two or more.

[0103] As the (G) solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclopentanone, and their mixed solvents, which are particularly excellent in solubility for the resin having a (meth)acryloyl group (A) or the photoinitiator for free radicals (B), are preferred.

[0104] From the viewpoints of the compatibility and viscosity of the photosensitive resin composition, the content of the (G) component is preferably 25 to 85% by mass, more preferably 35 to 75% by mass, based on the total amount of the photosensitive resin composition.

[0105] [Photosensitive resin film laminate]

[0106] The photosensitive resin film laminate of the present invention is a dried product of the photosensitive resin composition described above.

[0107] [Pattern forming method using photosensitive resin composition]

[0108] The pattern forming method using the photosensitive resin composition of the present invention includes:

[0109] (i) A step of coating the above-described photosensitive resin composition on a substrate to form a photosensitive resin film laminate on the substrate;

[0110] (ii) A step of exposing the photosensitive resin film laminate; and

[0111] (iii) A step of developing the exposed photosensitive resin film laminate with a developer to dissolve and remove the unexposed portion, thereby forming a pattern.

[0112] Step (i) is a step of coating the above-described photosensitive resin composition on a substrate to form a photosensitive resin film laminate on the substrate. The photosensitive resin film laminate is a dried product of the above photosensitive resin composition. Examples of the substrate include silicon wafers, glass wafers, quartz wafers, plastic circuit boards, and ceramic circuit boards.

[0113] As the coating method, known methods can be used, such as dipping method, spin coating method, roll coating method, etc. The coating amount can be appropriately selected according to the purpose, and it is preferably coated in such a way that the film thickness of the obtained photosensitive resin coating film (dry body of the photosensitive resin composition) is 0.1 to 200 μm, more preferably 1 to 150 μm.

[0114] Here, in order to effectively carry out the photocuring reaction, the solvent etc. can be volatilized in advance by preheating (pre-baking) as needed. The pre-baking can be carried out at 40 to 140 °C for about 1 minute to 1 hour, for example.

[0115] Next, (ii) the photosensitive resin coating film is exposed. At this time, the exposure is preferably carried out with light having a wavelength of 10 to 600 nm, more preferably with light having a wavelength of 190 to 500 nm. As the light of such a wavelength, for example, various wavelengths of light generated by a radiation generating device can be cited, such as ultraviolet light such as g-line, h-line, i-line, far ultraviolet light (248 nm, 193 nm), etc. Among them, light having a wavelength of 248 to 436 nm is particularly preferred. The exposure amount is preferably 10 to 10,000 mJ / cm 2 .

[0116] The exposure can be carried out through a photomask. The photomask can be, for example, a film with the required pattern hollowed out. In addition, the material of the photomask is not particularly limited, and a material that shields the light of the above wavelength is preferred. For example, a material having chromium is preferably used as the light-shielding film, but it is not limited thereto.

[0117] (iii) After the exposure, development is carried out 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 well-known alkali developers represented by an aqueous solution of tetramethylammonium hydroxide are preferred. As the developing method, usual methods can be cited, such as dipping method of immersing the substrate on which the pattern has been formed in the developer, puddle method of dispensing the developer in a puddle, spray method of spraying the developer by spraying, etc. By carrying out development in this way, the non-exposed part is dissolved and removed to form a pattern. Then, washing, rinsing, drying, etc. are carried out as needed to obtain a cured coating film having the required pattern.

[0118] By using the pattern forming method of the photosensitive resin composition of the present invention, fine pattern formation can be easily carried out. For example, the photosensitive resin composition of the present invention is formed into a film so as to cover a large number of blue Micro-LEDs laid on a substrate, and then fine pattern formation is carried out. As a result, a cured coating film containing red quantum dots or green quantum dots can be formed on each part of the blue Micro-LED, so that red or green light emission can be generated, and thus a full-color light-emitting element can be produced.

[0119] [Light-emitting element]

[0120] The light-emitting element of the present invention includes a cured coating film obtained by the pattern formation method described above. That is, the light-emitting element of the present invention includes a cured coating film having a pattern formed on the photosensitive resin coating film described above.

[0121] Examples

[0122] Hereinafter, synthesis examples, examples, and comparative examples are shown to more specifically illustrate the present invention, but the present invention is not limited by the following examples. In addition, as the quantum dot material, a core-shell type quantum dot of InP / ZnSe / ZnS is used. The synthesis method of the core is as shown in [1-1] (red quantum dots) and [1-2] (green quantum dots) described later, and then the synthesis method of the shell is as shown in [2].

[0123] [1-1] Synthesis process of red quantum dot core

[0124] Prepare two flasks, add 0.23 g (0.9 mmol) of palmitic acid, 0.088 g (0.3 mmol) of indium acetate, and 10 mL of 1-octadecene to each of them, heat and stir under reduced pressure at 100 °C, and perform degassing for 1 hour while dissolving the raw materials. Then, purge nitrogen into the two flasks, and add 0.75 mL (0.15 mmol) of a solution of tris(trimethylsilyl)phosphine / trioctylphosphine (0.2 M) to the two flasks. Then, heat one flask to 300 °C, the solution is colored red from yellow, and it is confirmed that core particles are formed. Extract the solution from the unheated flask and add it to the flask heated to 300 °C to obtain the desired particle size.

[0125] [1-2] Synthesis process of green quantum dot core

[0126] Add 0.23 g (0.9 mmol) of palmitic acid, 0.088 g (0.3 mmol) of indium acetate, and 10 mL of 1-octadecene into the flask, heat and stir under reduced pressure at 100 °C, and perform degassing for 1 hour while dissolving the raw materials. Then, purge nitrogen into the flask, add 0.75 mL (0.15 mmol) of a solution prepared by mixing tris(trimethylsilyl)phosphine and trioctylphosphine to 0.2 M, heat to 300 °C, the solution is colored red from yellow, and it is confirmed that core particles are formed.

[0127] [2] Synthesis process of quantum dot shell

[0128] Next, add 2.85 g (4.5 mmol) of zinc stearate and 15 mL of 1-octadecene to another flask. Under reduced pressure, heat and stir at 100 °C to dissolve it while degassing for 1 hour to prepare a 0.3 M zinc stearate octadecene solution thus obtained. Add 3.0 mL (0.9 mmol) of this solution to the reaction solution after core synthesis and cool it to 200 °C. Next, add 0.474 g (6 mmol) of selenium and 4 mL of trioctylphosphine to another flask, heat to 150 °C to dissolve it, prepare a 1.5 M trioctylphosphine selenide solution, and while heating the reaction solution after the core synthesis process, which has been cooled to 200 °C, to 320 °C over 30 minutes, add a total of 0.6 mL (0.9 mmol) of the trioctylphosphine selenide solution in portions of 0.1 mL each, hold at 320 °C for 10 minutes, and then cool 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 hold for 1 hour. Cool the resulting solution to room temperature to prepare a solution containing core-shell quantum dots. The solution containing red core-shell quantum dots synthesized through the processes of [1-1] to [2] is designated as R-1, and the solution containing green core-shell quantum dots synthesized through the processes of [1-2] to [2] is designated as G-1.

[0129] [3] Surface treatment process

[0130] After the reaction is completed, cool to room temperature, add ethanol to precipitate the reaction solution, perform centrifugation, and remove the supernatant. Repeat the same purification again and disperse it in toluene. Add the toluene solution of quantum dots to a flask that has been purged with nitrogen. Add 0.24 mL (1.0 mmol) of (3-mercaptopropyl)triethoxysilane thereto and stir at room temperature for 24 hours for surface treatment. The quantum dots treated with R-1 are designated as R-2, and the quantum dots treated with G-1 are designated as G-2.

[0131] [4] Condensation process of alkoxysilane or alkoxysilane hydrolyzate

[0132] Mix 10 mL of 3-(methacryloyloxy)propyltrimethoxysilane, 20 mL of toluene, and 10 mL of methanol in a flask that has been purged with nitrogen. While stirring at room temperature, gradually add 4.0 mL of 1.0 N hydrochloric acid dropwise in small portions. After the addition, stir at room temperature for 60 minutes, then further raise the solution temperature to 60 °C and reflux to react for 60 minutes. Then, evacuate the system at 60 °C for 2 hours and distill off the solvent. A condensate of alkoxysilane or alkoxysilane hydrolyzate having a methacryloyl group is obtained in the flask.

[0133] [5] Copolymerization of quantum dots with condensates of alkoxysilanes or alkoxysilane hydrolyzates

[0134] Add the obtained condensate of alkoxysilane or alkoxysilane hydrolyzate and the surface-treated quantum dot solution obtained in [3] to a nitrogen-purged flask at a solid component concentration of 20% by mass. Then, further add and mix 20 mL of toluene and 10 mL of methanol. While stirring at room temperature, gradually add 4.0 mL of 1.0 N hydrochloric acid dropwise in small portions. After the addition, stir at room temperature for 60 minutes, then further raise the solution temperature to 60 °C and react while refluxing for 60 minutes. Then, add PGMEA and remove the toluene solvent by vacuum distillation to obtain a copolymer of quantum dots and a condensate of alkoxysilane or alkoxysilane hydrolyzate. The copolymer of R-2 and the condensate of alkoxysilane or alkoxysilane hydrolyzate is designated as R-3, and the copolymer of G-2 and the condensate of alkoxysilane or alkoxysilane hydrolyzate is designated as G-3.

[0135] [6] Copolymerization of quantum dots with alkoxysilanes or alkoxysilane hydrolyzates

[0136] Add 7 mL of 3-(methacryloyloxy)propyltrimethoxysilane, 3 mL of ethoxymethyltrimethoxysilane, and the surface-treated quantum dot solution obtained in [3] to a nitrogen-purged flask at a solid component concentration of 20% by mass. Then, further add and mix 20 mL of toluene and 10 mL of methanol. While stirring at room temperature, gradually add 4.0 mL of 1.0 N hydrochloric acid dropwise in small portions. After the addition, stir at room temperature for 60 minutes, then raise the solution temperature to 60 °C and react while refluxing for 60 minutes. Then, add PGMEA and remove the toluene solvent by vacuum distillation to obtain a copolymer of quantum dots and alkoxysilanes or alkoxysilane hydrolyzates. The copolymer of R-2 and alkoxysilanes or alkoxysilane hydrolyzates is designated as R-4, and the copolymer of G-2 and alkoxysilanes or alkoxysilane hydrolyzates is designated as G-4.

[0137] [7] Preparation and evaluation of a photosensitive resin composition

[0138] [Examples 1 to 16 and Comparative Examples 1 to 24]

[0139] Blend each component according to the blending amounts described in Tables 1 to 4, then stir and mix at room temperature, and perform precision filtration using a 1.0 μm glass filter to obtain the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 24.

[0140] [Table 1]

[0141]

[0142] [Table 2]

[0143]

[0144] [Table 3]

[0145]

[0146] [Table 4]

[0147]

[0148] In Tables 1 to 4, the resin is an acrylic resin manufactured by Negami Chemical Industrial Co., Ltd.: trade name "RA-4101" (Mw: 30,000 g / mol, acid value: 90 mgKOH / g, double bond equivalent: 350 g / mol), trade name "RA-3631P" (Mw: 18,000 g / mol, acid value: 5 mgKOH / g, double bond equivalent: 250 g / mol), and an acrylic resin manufactured by TAISEI FINE CHEMICAL CO,.LTD.: trade name "8KQ-2001" (Mw: 20,000 g / mol, acid value: 130 mgKOH / g, double bond equivalent: 540 g / mol), trade name "8KQ-7052" (Mw: 19,000 g / mol, acid value: 7 mgKOH / g, double bond equivalent: 500 g / mol).

[0149] In Tables 1 to 4, the photoinitiator is the product named "Irgacure184" (1-hydroxycyclohexyl-phenyl ketone) and the product named "IrgacureOXE01" manufactured by BASF Corporation.

[0150] [Chemical formula 1]

[0151]

[0152] In Tables 1 to 4, the surfactant is the product named "KP-341" (polyether type silicone) manufactured by Shin-Etsu Chemical Co., Ltd.

[0153] In Tables 1 to 4, the silane coupling agent is the product named "KBM-503" (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0154] In Tables 1 to 4, the crosslinking agents were "ARONIX (registered trademark) M-940" (dipentaerythritol hexaacrylate) manufactured by TOAGOSEI CO., LTD. and "DPCA-20" manufactured by Nippon Kayaku Co., Ltd.

[0155] [Chemical formula 2]

[0156]

[0157] In Tables 1 to 4, R-5 of the quantum dots was S-BE030 manufactured by SHOEI CHEMICAL INC. (particle size 5 to 10 nm, material InP:ZnS:SeZn = 25:50:25), R-6 was 900514-1ML manufactured by Aldrich (particle size 5 to 10 nm, material CdSe (core) / CdS (shell) core-shell type), G-5 was S-BE029 manufactured by SHOEI CHEMICAL INC. (particle size 3 to 5 nm, material InP:ZnS:SeZn = 25:50:25), and G-6 was 900511-1ML manufactured by Aldrich (particle size 3 to 5 nm, material CdSe (core) / CdS (shell) core-shell type).

[0158] [8] Evaluation of the photosensitive resin composition

[0159] (1) Confirmation of aggregates in the coating film

[0160] Each photosensitive resin composition was coated on a silicon wafer with a film thickness of 20 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 4 minutes. The aggregates in the obtained photosensitive resin coating film were confirmed using an optical microscope. The case where aggregates with a size of 1 μm or more were present in 10 mm × 10 mm was evaluated as ×, and the case where there were no aggregates or the size of the aggregates was less than 1 μm in 10 mm × 10 mm was evaluated as ○. The results are shown in Tables 5 to 8.

[0161] (2) Pattern formation and its evaluation

[0162] In order to form a square island pattern (island pattern) with a spacing width of 1:1 with the adjacent pattern through the mask on the obtained photosensitive resin coating, 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 90 seconds of puddle development to form a pattern, and for the embodiments and comparative examples numbered even, PGMEA was used for 90 seconds of puddle development to form a pattern. Then, a scanning electron microscope (SEM) was used to observe the island pattern with one side of 50μm, 40μm, 30μm, 20μm, and 5μm, and the minimum pattern size that was not connected to the adjacent island pattern (spacing width 1:1) was used as the limiting resolution. In addition, the situation where the resolution did not reach 50μm or the development peeling of the pattern was generated was evaluated as ×. The results are shown in Tables 5 to 8.

[0163] (3) Evaluation of light-emitting properties of formed patterns

[0164] The sample with pattern prepared in (2) was irradiated with 457 nm laser (0.03 mW) using LabRAM HR Evolution manufactured by HORIBA TECHNO SERVICE, Co., Ltd., and the island pattern area after photoconversion was measured, and the luminous intensity, luminous wavelength, and half-value width of the light after photoconversion were measured. In addition, the sample after 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).

[0165] (4) Reliability test evaluation

[0166] In addition, the patterned measurement sample of the above (2) was continuously irradiated with a 454nm, 1W laser in an oven at 85°C to perform a laser light resistance test. The luminous intensity of the light converted before and after the test was measured in the same manner as (3), and the change rate (reduction rate) relative to the initial value was confirmed (change rate = ((luminous intensity after the test / luminous intensity before the test) - 1) × 100). The results are shown in Tables 5 to 8.

[0167] (5) Tight fit test evaluation

[0168] Using a spin coater, the photosensitive resin compositions described in Tables 1 to 4 were coated on a silicon wafer with a film thickness of 50 μm. To remove the solvent from the composition, the substrate was placed on a hot plate and heated and dried at 110 °C for 10 minutes. The entire surface of the obtained photosensitive resin film was exposed and cured using a contact alignment exposure apparatus under exposure conditions of 365 nm. To evaluate the close adhesion to the substrate, a checkerboard peel test (JIS K 5400) was conducted. The number of peelings that occurred in 100 checkerboards was shown as the result in Tables 5 to 8.

[0169] [Table 5]

[0170]

[0171] [Table 6]

[0172]

[0173] [Table 7]

[0174]

[0175] [Table 8]

[0176]

[0177] The above results show that the photosensitive resin composition of the present invention can form a good photosensitive resin film without condensates (or with extremely small condensates even if they exist), and can provide a cured film (cured film) having high lithography resolution, no change in high luminescence characteristics before and after the lithography process, good reliability (low change rate of luminescence intensity in the laser light resistance test), high close adhesion to the substrate, and being suitable for light-emitting elements.

[0178] On the other hand, in Comparative Examples 1, 2, 5, 6, 9, 10, 13, 14, 17, 18, 21, and 22 using R-1, R-2, G-1, and G-2 in which alkoxysilane, alkoxysilane hydrolyzate, or their condensate was not copolymerized with quantum dots as the component (C), condensates were confirmed, so a good photosensitive resin film could not be formed. Compared with the photosensitive resin composition of the present invention, the lithography resolution, luminescence characteristics before and after the lithography process, change rate of luminescence intensity in the laser light resistance test, and close adhesion to the substrate were all poor, and it did not become a cured film (cured film) suitable for light-emitting elements.

[0179] In addition, similarly, in Comparative Examples 3, 4, 7, 8, 11, 12, 15, 16, 19, 20, 23, and 24 of R-5, R-6, G-5, and G-6 that used commercially available quantum dots as the component (C), condensates were also confirmed. Therefore, a good photosensitive resin coating film could not be formed. Compared with the photosensitive resin composition of the present invention, the lithography resolution, the light emission characteristics before and after the lithography process, the change rate of the light emission intensity in the laser light resistance test, and the close adhesion to the substrate were all poor, and it did not become a cured film (cured coating film) suitable for light-emitting elements.

[0180] This specification includes the following aspects.

[0181] [1]: A photosensitive resin composition, characterized in that it contains:

[0182] (A) A resin having a (meth)acryloyl group,

[0183] (B) A photoinitiator for free radicals, and

[0184] (C) A polymer obtained by copolymerizing a quantum dot coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate, or a condensate thereof.

[0185] [2]: The photosensitive resin composition according to the above [1], characterized in that the surface coating layer of the component (C) on the quantum dot contains a skeleton having a functional group with free radical reactivity.

[0186] [3]: The photosensitive resin composition according to the above [1] or the above [2], characterized in that as the coordination substituent of the silane coupling agent of the component (C), it has any one or more of an amino group, a thiol group, a carboxyl group, a phosphine group, a phosphine oxide group, and an ammonium ion.

[0187] [4]: The photosensitive resin composition according to any one of the above [1] to the above [3], characterized in that the photosensitive resin composition contains 5 to 80% by mass of the component (C).

[0188] [5]: The photosensitive resin composition according to any one of the above [1] to the above [4], characterized in that the double bond equivalent of the component (A) is 240 to 1,000 g / mol.

[0189] [6]: The photosensitive resin composition according to any one of the above [1] to the above [5], characterized in that the component (A) is an acrylic resin having a weight average molecular weight Mw of 5,000 to 100,000 g / mol.

[0190] [7]: The photosensitive resin composition according to any one of [1] to [6] above, characterized in that it further contains (D) a surfactant.

[0191] [8]: The photosensitive resin composition according to any one of [1] to [7] above, characterized in that it further contains (E) a silane coupling agent.

[0192] [9]: The photosensitive resin composition according to any one of [1] to [8] above, characterized in that it further contains (F) a crosslinking agent having a (meth)acryloyl group with a functionality of 2 or more.

[0193]

[10] : The photosensitive resin composition according to any one of [1] to [9] above, characterized in that it further contains (G) a solvent.

[0194]

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

[10] above.

[0195]

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

[0196] (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 film on the substrate;

[0197] (ii) A step of exposing the photosensitive resin film; and

[0198] (iii) A step of developing the exposed photosensitive resin film with a developer to dissolve and remove the non-exposed portion, thereby forming a pattern.

[0199]

[13] : A light-emitting element, characterized in that it has a cured film having a pattern formed on the photosensitive resin film of

[11] above.

[0200] In addition, the present invention is not limited by the above embodiments. The above embodiments are examples, and technical solutions having the same technical concept as that described in the claims of the present invention and exhibiting the same technical effects are all included in the technical scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, it comprises: (A) A resin having a (meth)acryloyl group, (B) A photoinitiator for free radicals, and (C) A polymer obtained by copolymerizing quantum dots coordinated with a silane coupling agent with an alkoxysilane, an alkoxysilane hydrolyzate or a condensate thereof.

2. The photosensitive resin composition according to claim 1, characterized in that, the component (C) has a skeleton having a functional group with radical reactivity in the surface coating layer of the quantum dots.

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

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

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 component (A) is an acrylic resin having a weight average molecular weight Mw of 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 comprises (F) a crosslinking agent having a (meth)acryloyl group with a functionality of 2 or more.

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

11. A photosensitive resin film, characterized in that, it is a dried product of the photosensitive resin composition 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 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 to dissolve and remove the non-exposed portion, thereby forming a pattern.

13. A light-emitting element, characterized in that, it has a cured film having a pattern formed on the photosensitive resin film according to claim 11.

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