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

Abstract

The present application is a photosensitive resin composition characterized by comprising: (A) a silicone resin containing an acid crosslinking group, (B) a photoacid generator, and (C) quantum dot particles. The present application provides a photosensitive resin composition capable of easily forming a coating film having good heat resistance, photolithography resolution, and light emission properties, a photosensitive resin coating film obtained using the photosensitive resin composition, a photosensitive dry film, and a pattern forming method using the same, and a light emitting element obtained using the photosensitive resin composition.

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, photosensitive resin films using the photosensitive resin compositions, photosensitive dry films, patterning methods, and light-emitting elements. Background Technology

[0002] Various methods have been proposed to create displays containing red, green, and blue subpixels. One such method involves using a color conversion structure to convert light from an LED array, which has a shorter wavelength of blue, into longer wavelengths of red and green light. In this method, quantum dots are used to perform the color conversion.

[0003] In recent years, such LED arrays have reached the micrometer scale, and micro-LED displays using such arrays have attracted attention. One method for forming color conversion structures on LED arrays is photolithography using photosensitive materials (see Patent Document 1), but recent efforts have focused on further miniaturization and improving heat resistance. Furthermore, from the perspective of display resolution, there are also higher requirements for luminous properties.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2016-53716 Summary of the Invention

[0007] The technical problem to be solved by the present invention

[0008] The present invention was made in view of the above circumstances, and its object is to provide a photosensitive resin composition capable of easily forming a coating with good heat resistance, photolithographic resolution and light emission characteristics, a photosensitive resin coating obtained using the photosensitive resin composition, a photosensitive dry film and a patterning method using the thereof, and a light-emitting element obtained using the photosensitive resin composition.

[0009] Technical means to solve technical problems

[0010] To solve the above-mentioned technical problems, the present invention provides a photosensitive resin composition, characterized in that it comprises:

[0011] (A) Organosilicon resins containing acid crosslinking groups,

[0012] (B) Photoacid generators, and

[0013] (C) Quantum dot particles.

[0014] If it is such a photosensitive resin composition, it is easy to form a coating (photosensitive resin coating) with good heat resistance (heat resistance reliability), photolithographic resolution and luminescence properties.

[0015] In this case, component (A) preferably comprises an organosilicon resin containing repeating units represented by the following formulas (A1) to (A6).

[0016] [Chemical Formula 1]

[0017]

[0018] In the formula, R 1 ~R 4 Each R is independently a monovalent hydrocarbon group containing 1 to 20 carbon atoms, which can be chosen independently. m is independently an integer from 1 to 600. When m is an integer greater than 2, each R... 3 Choose any two that are the same or different from each other, each R 4 Choose any numbers that are the same or different from each other. a, b, c, d, e, and f are numbers that satisfy 0 ≤ a ≤ 1, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, 0 ≤ d ≤ 1, 0 ≤ e ≤ 1, 0 ≤ f ≤ 1, 0 < c + d + e + f ≤ 1, and a + b + c + d + e + f = 1. X 1 X is the divalent group represented by the following formula (X1). 2 X represents the divalent group indicated by the following formula (X2). 3 It is a divalent group represented by the following formula (X3).

[0019] [Chemical Formula 2]

[0020]

[0021] In the formula, R 11 ~R 14 Each is independently a monovalent hydrocarbon group containing 1 to 20 carbon atoms, which can be arbitrarily selected. p is an integer from 1 to 600. When p is an integer greater than 2, each R 13 Choose any two that are the same or different from each other, each R 14 Choose either the same as or different from each other. R 15 and R 16 Each of the following is an independent hydrogen atom or a methyl group. Each of the following is an independent integer from 0 to 7.

[0022] [Chemical Formula 3]

[0023]

[0024] In the formula, Y 1 It is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R21 and R 22 Each is independently an alkyl or alkoxy group having 1 to 4 carbon atoms, and g and h are independently 0, 1, or 2. When g is 2, each R 21 Choose any two numbers that are the same or different from each other. When h is 2, each R... 22 Choose either the same or different from each other, R 23 and R 24 Each is independently a hydrogen atom or a methyl group. Each y is an independent integer from 0 to 7.

[0025] [Chemical Formula 4]

[0026]

[0027] In the formula, R 31 and R 32 Each can be independently a hydrogen atom or a methyl group. Each z can be an independent integer from 0 to 7. R 33 It can be a monovalent hydrocarbon group with 1 to 8 carbon atoms that contains an ester bond or an ether bond, or a monovalent group represented by the following formula (X3-1).

[0028] [Chemical Formula 5]

[0029]

[0030] In the formula, R 34 It is a divalent hydrocarbon group with 1 to 8 carbon atoms that may contain ester or ether bonds.

[0031] If such a photosensitive resin composition is used, it is easy to form a coating (photosensitive resin coating) with better heat resistance (heat resistance reliability), photolithographic resolution and luminescence properties.

[0032] Furthermore, the quantum dot particles (C) can be red quantum dot particles or green quantum dot particles, or they can be composed of group II-VI semiconductor compounds, group III-V semiconductor compounds, group IV-VI semiconductor compounds, group IV elements or compounds containing such elements, or combinations thereof.

[0033] The photosensitive resin composition of the present invention can appropriately use such quantum dot particles.

[0034] Furthermore, the photosensitive resin composition of the present invention preferably contains 3 to 80% by mass of the (C) quantum dot particles in all solid components.

[0035] If the quantum dot content is within the above range, fine patterns can be formed while maintaining good luminescence intensity.

[0036] Furthermore, the photosensitive resin composition of the present invention can further include (D) a crosslinking agent.

[0037] If a crosslinking agent is included, it can easily form patterns by reacting with epoxy groups of component (A), and can further improve the strength of the resin coating after photocuring.

[0038] Furthermore, the photosensitive resin composition of the present invention can further include (E) an antioxidant.

[0039] By including antioxidants, heat resistance can be improved.

[0040] Furthermore, the photosensitive resin composition of the present invention can further contain (F) solvent.

[0041] The photosensitive resin composition of the present invention can improve its coatability by including a solvent.

[0042] Furthermore, the present invention provides a photosensitive resin coating as a dry body of the above-mentioned photosensitive resin composition, and provides a photosensitive dry film having a support film and the photosensitive resin coating on the support film.

[0043] The photosensitive resin coating of the present invention can be easily formed using the above-described photosensitive resin composition. The photosensitive dry film can be manufactured by coating the photosensitive resin composition onto a substrate and drying it to form the photosensitive resin coating. In particular, the photosensitive dry film is a solid, and the photosensitive resin coating does not contain solvents, therefore no air bubbles caused by solvent evaporation remain inside the photosensitive resin coating or between it and the uneven substrate.

[0044] Furthermore, the present invention provides a pattern forming method, comprising:

[0045] (i) The step of coating the above-mentioned photosensitive resin composition onto a substrate to form a photosensitive resin coating on the substrate;

[0046] (ii) The process of exposing the photosensitive resin coating, and

[0047] (iii) A process of developing the exposed photosensitive resin coating with a developing solution to dissolve and remove the unexposed areas, thereby forming a pattern.

[0048] Furthermore, the present invention provides a pattern forming method, comprising:

[0049] (i') The process of forming a photosensitive resin coating on a substrate using the above-mentioned photosensitive dry film,

[0050] (ii) The process of exposing the photosensitive resin coating, and

[0051] (iii) A process of developing the exposed photosensitive resin coating with a developing solution to dissolve and remove the unexposed areas, thereby forming a pattern.

[0052] By using the patterning method of the photosensitive resin composition or photosensitive dry film of the present invention, it is possible to easily form fine patterns in a thick film.

[0053] In this case, it can be further included (iv) a step of post-curing the resin coating with a pattern formed by development at a temperature of 100 to 250°C.

[0054] By including such a post-curing process, the crosslinking density of the photosensitive resin composition can be increased and residual volatile components can be removed. Therefore, it is preferred from the perspective of adhesion to the substrate, heat resistance, strength, electrical properties and bonding strength.

[0055] Furthermore, the present invention provides a light-emitting element as a material having the above-mentioned photosensitive resin coating.

[0056] The photosensitive resin coating of the present invention has good dry film properties, resolution, luminescence characteristics, and heat resistance (adhesion, crack resistance, and maintenance of luminescence intensity), and is suitable for light-emitting elements.

[0057] Invention Effects

[0058] The photosensitive resin composition of the present invention can be easily coated by comprising an organosilicon resin containing acid crosslinking groups, a photoacid generator, and quantum dot particles. The coating exhibits good dry film properties, resolution, luminescence characteristics, and heat resistance (adhesion, crack resistance, and maintenance of luminescence intensity), making it suitable for light-emitting elements. Detailed Implementation

[0059] As mentioned above, in photolithography processes using photosensitive materials, when seeking further miniaturization and having high requirements for heat resistance and luminescence properties, it is also necessary to develop a photosensitive material that can meet these requirements.

[0060] In order to achieve the above objectives, the inventors of this application have conducted repeated and in-depth research and found that a photosensitive resin composition containing an organosilicon resin with acid crosslinking groups, a photoacid generator, and quantum dots can easily form a coating, thereby providing a cured film with good dry film properties, resolution, luminescence characteristics, heat resistance (adhesion, crack resistance, and maintenance of luminescence intensity) and suitable for light-emitting elements, thus completing the present invention.

[0061] That is, the present invention is a photosensitive resin composition, characterized in that it comprises (A) an organosilicon resin containing acid crosslinking groups, (B) a photoacid generator, and (C) quantum dot particles.

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

[0063] [Photosensitive Resin Composition]

[0064] The photosensitive resin composition of the present invention comprises (A) an organosilicon resin containing acid crosslinking groups, (B) a photoacid generator, and (C) quantum dot particles. Depending on the need, it may further comprise other components such as (D) a crosslinking agent, (E) an antioxidant, and (F) a solvent. The components constituting the photosensitive resin composition will be described below.

[0065] [(A) Organosilicon resin containing acid crosslinking groups]

[0066] (A) The organosilicon resin containing acid crosslinking groups is a resin having a siloxane structure and acid crosslinking groups. Here, acid crosslinking groups refer to groups that can be chemically linked by the action of an acid. The siloxane structure and acid crosslinking groups are not particularly limited, but as the acid crosslinking groups in this invention, epoxy groups, oxetane groups, vinyl ether groups, etc., are preferred, with epoxy groups being particularly preferred.

[0067] The organosilicon resin containing acid crosslinking groups as component (A) is preferably an organosilicon resin containing repeating units (hereinafter also referred to as repeating units A1 to A6) represented by the following formulas (A1) to (A6), and more preferably contains epoxy groups.

[0068] [Chemical Formula 6]

[0069]

[0070] In equations (A2), (A4) and (A6), R 1 ~R 4 Each R is independently a monovalent hydrocarbon group containing 1 to 20 carbon atoms, which can be chosen independently. m is independently an integer from 1 to 600. When m is an integer greater than 2, each R... 3 Choose any two that are the same or different from each other, each R 4 The units can be chosen to be the same or different from each other. In repeating units A2, A4, and A6, when there are two or more siloxane units, each siloxane unit can be completely identical or contain two or more different siloxane units. When there are two or more different siloxane units (i.e., when m is an integer greater than 2), the siloxane units can be bonded randomly or alternately, and can also contain blocks of multiple identical siloxane units.

[0071] The monovalent hydrocarbon group can be straight-chain, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, and other monovalent aromatic hydrocarbon groups.

[0072] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, norbornyl, and adamantylyl. Examples of alkenyl groups include vinyl, propenyl, butenyl, and pentenyl.

[0073] Furthermore, the monovalent aliphatic hydrocarbon group may also contain heteroatoms. Specifically, some or all of the hydrogen atoms in the monovalent aliphatic hydrocarbon group may be replaced by halogen atoms such as fluorine, chlorine, bromine, and iodine, and carbonyl groups, ether bonds, thioether bonds, etc., may also be intercalated between its carbon atoms. Examples of such monovalent aliphatic hydrocarbon groups containing heteroatoms include 2-oxocyclohexyl groups.

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

[0075] Furthermore, the monovalent aromatic hydrocarbon group may contain heteroatoms. Specifically, some or all of the hydrogen atoms of the monovalent aromatic hydrocarbon group may be replaced by alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, aryloxy groups with 6 to 20 carbon atoms, arylthio groups with 6 to 20 carbon atoms, etc.

[0076] Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy, n-pentoxy, cyclopentoxy, n-hexyloxy, cyclohexyloxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, norbornoxy, and adamantoxy.

[0077] Examples of alkylthio groups with 1 to 10 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, cyclopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, cyclobutylthio, n-pentylthio, cyclopentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, norbornylthio, and adamantanethio.

[0078] Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2-ethylphenoxy, 3-ethylphenoxy, 4-ethylphenoxy, 4-tert-butylphenoxy, 4-butylphenoxy, dimethylphenoxy, naphthyloxy, biphenyloxy, terphenyloxy and the like.

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

[0080] For example, examples of the aryl group substituted with these groups include 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 3-tert-butoxyphenyl, 4-tert-butoxyphenyl, biphenyloxyphenyl, biphenylthiophenyl and the like.

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

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

[0083] In the formulas (A2), (A4) and (A6), m is each independently an integer of 1 to 600, preferably 1 to 300, more preferably 1 to 100.

[0084] In the formulas (A1) to (A6), a, b, c, d, e and f are numbers satisfying 0 ≤ a ≤ 1, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, 0 ≤ d ≤ 1, 0 ≤ e ≤ 1, 0 ≤ f ≤ 1, 0 < c + d + e + f ≤ 1, and a + b + c + d + e + f = 1. Numbers satisfying 0.2 ≤ a + c + e ≤ 0.95, 0.05 ≤ b + d + f ≤ 0.8, 0 ≤ a + b ≤ 0.9, 0 ≤ c + d ≤ 0.7 and 0 < e + f ≤ 1 are preferred, and numbers satisfying 0.3 ≤ a + c + e ≤ 0.9, 0.1 ≤ b + d + f ≤ 0.7, 0 ≤ a + b ≤ 0.6, 0 ≤ c + d ≤ 0.4 and 0.4 ≤ e + f ≤ 1 are more preferred.

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

[0086] [Chemical formula 7]

[0087]

[0088] In equation (X1), R 11 ~R 14 Each is independently a monovalent hydrocarbon group containing 1 to 20 carbon atoms, which can be arbitrarily selected. p is an integer from 1 to 600. When p is an integer greater than 2, each R 13 Choose any two that are the same or different from each other, each R 14 Choose either the same as or different from each other. R 15 and R 16 Each is independently a hydrogen atom or a methyl group. x is independently an integer from 0 to 7. In the group represented by formula (X1), when there are two or more siloxane units, all siloxane units can be identical, or they can contain two or more different siloxane units. When there are two or more different siloxane units (i.e., when p is an integer greater than 2), the siloxane units can be bonded randomly or alternately, and can also contain blocks of multiple identical siloxane units.

[0089] The optional monovalent hydrocarbon group containing heteroatoms can be straight-chain, branched, or cyclic. Specific examples include those related to R... 1 ~R 4 The same substance as described above. Among them, R... 11 ~R 14 Preferably, methyl, ethyl, n-propyl, phenyl, etc., more preferably methyl or phenyl.

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

[0091] [Chemical Formula 8]

[0092]

[0093] In equation (X2), Y 1 It is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl, or fluorene-9,9-diyl. R 21 and R 22 Each is independently an alkyl or alkoxy group having 1 to 4 carbon atoms, and g and h are independently 0, 1, or 2. When g is 2, each R 21 Choose any two numbers that are the same or different from each other. When h is 2, each R... 22 Choose either the same as or different from each other. R 23 and R 24 Each is independently a hydrogen atom or a methyl group. Each y is an independent integer from 0 to 7.

[0094] In equations (A5) and (A6), X 3 It is a divalent group represented by the following formula (X3).

[0095] [Chemical Formula 9]

[0096]

[0097] In equation (X3), R 31 and R 32 Each can be a hydrogen atom or a methyl group. Each z can be an integer from 0 to 7.

[0098] In equation (X3), R 33 It can be a monovalent hydrocarbon group with 1 to 8 carbon atoms that may contain ester or ether bonds, or a monovalent group represented by the following formula (X3-1). Preferably, it is a glycidyl group of formula (X3-1).

[0099] [Chemical Formula 10]

[0100]

[0101] In the formula, R 34 It is a divalent hydrocarbon group with 1 to 8 carbon atoms that may contain ester or ether bonds.

[0102] The monovalent hydrocarbon group can be straight-chain, branched, or cyclic. Specific examples include alkyl groups such as methyl, ethyl, and n-propyl; and aryl groups such as phenyl. Methyl or phenyl is preferred, and methyl is more preferred. Furthermore, ester or ether bonds may be intercalated between the carbon atoms of the monovalent hydrocarbon group.

[0103] In equation (X3-1), R 34 The divalent hydrocarbon group, optionally containing an ester or ether bond, has 1 to 8 carbon atoms. The divalent hydrocarbon group can be linear, branched, or cyclic; specific examples include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, and butane-1,4-diyl alkane dimethyl groups. Methylene or ethylene is preferred, and methylene is more preferred. Furthermore, ester or ether bonds may be intercalated between the carbon atoms of the divalent hydrocarbon group.

[0104] As R 33 Preferably methyl, phenyl or glycidyl, more preferably methyl or glycidyl.

[0105] The repeating units A1 to A6 can be bonded randomly or as block polymers.

[0106] Furthermore, in the organosilicon resin containing acid crosslinking groups, the organosilicon (siloxane unit) content is preferably 30 to 80% by mass.

[0107] The weight-average molecular weight (Mw) of the organosilicon resin containing acid crosslinking groups is preferably 3,000 to 500,000, more preferably 5,000 to 200,000. Furthermore, in this invention, Mw is a polystyrene equivalent value obtained using tetrahydrofuran as the elution solvent and by gel permeation chromatography (GPC).

[0108] Component (A) can be prepared, for example, by mixing a vinyl compound corresponding to each part of component (A) with a hydrosilyl alkyl organosilicon compound in the required amounts and performing a hydrosilylation reaction according to conventional methods.

[0109] (A) The organosilicon resin containing acid crosslinking groups can be used alone or in combination of two or more. Furthermore, the organosilicon content of component (A) (which can be determined by...) 29 (Determined by Si-NMR), preferably using component (A) containing 30-80% by mass of organosilicon.

[0110] [(B) Photoacid generator]

[0111] (B) The photoacid generator is not particularly limited to any substance that can decompose and produce acid by light irradiation, but is preferably a substance that produces acid by irradiation with light of wavelength 190-500 nm. (B) The photoacid generator can be used as a curing catalyst. Examples of such photoacid generators include onium salts, diazomethane derivatives, dioxime derivatives, β-ketosulfonate derivatives, disulfonate derivatives, nitrobenzylsulfonate derivatives, sulfonate derivatives, imide sulfonate derivatives, oxime sulfonate derivatives, iminosulfonate derivatives, triazine derivatives, etc.

[0112] Examples of such onium salts include thioonium salts represented by formula (B1) or ioonium salts represented by formula (B2).

[0113] [Chemical Formula 11]

[0114]

[0115] In equations (B1) and (B2), R 101 ~R 105 Each is independently an alkyl group having 1 to 12 carbon atoms with a substituent, an aryl group having 6 to 12 carbon atoms with a substituent, or an aralkyl group having 7 to 12 carbon atoms with a substituent. A - It is a non-nucleophilic counterion.

[0116] The alkyl group can be linear, branched, or cyclic, and examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl. The aryl group can be phenyl, naphthyl, or biphenyl. The aralkyl group can be benzyl or phenethyl.

[0117] Examples of substituents include oxy groups; alkoxy groups with 1 to 12 carbon atoms in a straight-chain, branched, or cyclic form; alkyl groups with 1 to 12 carbon atoms in a straight-chain, branched, or cyclic form; aryl groups with 6 to 24 carbon atoms; aralkyl groups with 7 to 25 carbon atoms; aryloxy groups with 6 to 24 carbon atoms; and arylthio groups with 6 to 24 carbon atoms.

[0118] As R 101 ~R 105 Preferably, the alkyl group has substituents such as methyl, ethyl, propyl, butyl, cyclohexyl, norbornyl, adamantyl, 2-oxocyclohexyl, etc.; aryl group has substituents such as phenyl, naphthyl, biphenyl, o-methoxyphenyl, m-methoxyphenyl or p-methoxyphenyl, ethoxyphenyl, m-tert-butoxyphenyl or p-tert-butoxyphenyl, 2-methylphenyl, 3-methylphenyl or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, terphenyl, biphenyloxyphenyl, biphenylthiophenyl, etc.; and aralkyl group has substituents such as benzyl, phenethyl, etc. More preferably, aryl group with substituents and aralkyl group with substituents are preferred.

[0119] Examples of non-nucleophilic counterions include halide ions such as chloride ions and bromide ions; fluoroalkane sulfonate ions such as trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, and nonafluorobutanesulfonate ions; aryl sulfonate ions such as toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, and 1,2,3,4,5-pentafluorobenzenesulfonate ions; alkane sulfonate ions such as methanesulfonate ions and butanesulfonate ions; fluoroalkane sulfonate imide ions such as trifluoromethanesulfonylimide ions; fluoroalkane sulfonylmethyl ions such as tri(trifluoromethanesulfonyl)methyl ions; and borate ions such as tetraphenylborate ions and tetra(pentafluorophenyl)borate ions.

[0120] As diazomethane derivatives, compounds represented by the following formula (B3) can be listed.

[0121] [Chemical Formula 12]

[0122]

[0123] In equation (B3), R 111and R 112 Each of them is independently an alkyl or haloalkyl group having 1 to 12 carbon atoms, optionally an aryl group having 6 to 12 carbon atoms with substituents, or an aralkyl group having 7 to 12 carbon atoms.

[0124] The alkyl group can be straight-chain, branched, or cyclic. Specific examples include those related to R. 101 ~R 105 The same substances as those exemplified in the description. Examples of the haloalkyl groups include trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, and nonafluorobutyl.

[0125] Examples of aryl groups optionally having the aforementioned substituents include phenyl groups; alkoxyphenyl groups such as 2-methoxyphenyl, 3-methoxyphenyl, or 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, or 4-ethoxyphenyl, 3-tert-butoxyphenyl, or 4-tert-butoxyphenyl; alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, or 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl; and halogenated aryl groups such as fluorophenyl, chlorophenyl, and 1,2,3,4,5-pentafluorophenyl. Examples of arylalkyl groups include benzyl and phenethyl.

[0126] Compounds represented by the formula (B4) can be listed as dioxime derivatives.

[0127] [Chemical Formula 13]

[0128]

[0129] In equation (B4), R 121 ~R 124 Each is independently an alkyl or haloalkyl group having 1 to 12 carbon atoms, optionally an aryl group having 6 to 12 carbon atoms with substituents, or an aralkyl group having 7 to 12 carbon atoms. Furthermore, R 123 and R 124 They can bond to each other and form rings together with the carbon atoms they are bonded to. When a ring is formed, R 123 and R 124 The bonded groups are straight-chain or branched alkylene groups with 1 to 12 carbon atoms.

[0130] As the alkyl, haloalkyl, optional aryl and aralkyl groups having substituents, examples can be listed that are related to R. 111 and R 112 The substances illustrated are the same as those listed. Examples of linear or branched alkylene groups include methylene, ethylene, propylene, butylene, and hexylene.

[0131] Specifically, examples of the onyx salts include diphenyliodonium trifluoromethane sulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethane sulfonate, diphenyliodonium p-toluene sulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluene sulfonate, triphenylthionium trifluoromethane sulfonate, (p-tert-butoxyphenyl)diphenylthionium trifluoromethane sulfonate, bis(p-tert-butoxyphenyl)phenylthionium trifluoromethane sulfonate, tri(p-tert-butoxyphenyl)thionium trifluoromethane sulfonate, triphenylthionium p-toluene sulfonate, (p-tert-butoxyphenyl)diphenylthionium p-toluene sulfonate, and bis(p-tert-butoxyphenyl)phenylthionium. p-Toluenesulfonate, Tris(p-tert-butoxyphenyl)thionium p-toluenesulfonate, Triphenylthionium nonafluorobutanesulfonate, Triphenylthionium butanesulfonate, Trimethylthionium trifluoromethanesulfonate, Trimethylthionium p-toluenesulfonate, Cyclohexylmethyl(2-oxocyclohexyl)thionium trifluoromethanesulfonate, Cyclohexylmethyl(2-oxocyclohexyl)thionium p-toluenesulfonate, Dimethylphenylthionium trifluoromethanesulfonate, Dimethylphenylthionium p-toluenesulfonate, Dicyclohexylphenylthionium trifluoromethanesulfonate, Dicyclohexylphenylthionium p-toluenesulfonate, Bis(4-tert-butylphenyl)iodothionium hexafluorophosphate, Diphenyl(4- thiophenoxy Phenyl)thionium hexafluoroantimonate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylthionium tri(trifluoromethanesulfonyl)methyl salt, triphenylthionium tetra(fluorophenyl)borate, tri[4-(4-acetylphenyl)thionium tetra(fluorophenyl)borate, triphenylthionium tetra(pentafluorophenyl)borate, tri[4-(4-acetylphenyl)thionium tetra(pentafluorophenyl)borate, etc.

[0132] Specifically, examples of the diazonium methane derivatives include bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(xylbenzenesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonyl)diazomethane, bis(isobutylsulfonyl)diazomethane, bis(sec-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, and bis(isopropylsulfonyl)diazomethane. Acyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, bis(sec-pentylsulfonyl)diazomethane, bis(tert-pentylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-pentylsulfonyl)diazomethane, 1-tert-pentylsulfonyl-1-(tert-butylsulfonyl)diazomethane, etc.

[0133] Specifically, examples of the oxime derivatives include bis(p-toluenesulfonyl)-α-dimethyloxime, bis(p-toluenesulfonyl)-α-diphenyloxime, bis(p-toluenesulfonyl)-α-dicyclohexyloxime, bis(p-toluenesulfonyl)-2,3-pentanedione oxime, bis(p-toluenesulfonyl)-2-methyl-3,4-pentanedione oxime, bis(n-butanesulfonyl)-α-dimethylglyoxime, bis(n-butanesulfonyl)-α-diphenyloxime, bis(n-butanesulfonyl)-α-dicyclohexyloxime, bis(n-butanesulfonyl)-2,3-pentanedione oxime, and bis(n-butanesulfonyl)-2-methyl-3,4-pentanedione oxime. Diketoxime, bis(methanesulfonyl)-α-dimethylglyoxime, bis(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis(tert-butanesulfonyl)-α-dimethylglyoxime, bis(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis( Cyclohexanesulfonyl)-α-dimethylglyoxime, bis(o-(benzenesulfonyl)-α-dimethylglyoxime, bis(o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis(o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis(o-(xylenesulfonyl)-α-dimethylglyoxime, bis(o-camphorsulfonyl)-α-dimethylglyoxime, etc.

[0134] Examples of the β-ketosulfonyl derivatives include 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane and 2-isopropylcarbonyl-2-(p-toluenesulfonyl)propane.

[0135] Examples of disulfone derivatives include diphenyl disulfone and dicyclohexyl disulfone.

[0136] Examples of the nitrobenzyl sulfonate derivatives include 2,6-dinitrobenzyl p-toluenesulfonic acid and 2,4-dinitrobenzyl p-toluenesulfonic acid.

[0137] Examples of such sulfonate derivatives include 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene.

[0138] Examples of the imide sulfonate derivatives include phthalimide trifluoromethanesulfonate, phthalimide toluenesulfonate, 5-norbornene-2,3-dicarboxyimide trifluoromethanesulfonate, 5-norbornene-2,3-dicarboxyimide toluenesulfonate, 5-norbornene-2,3-dicarboxyimide n-butylsulfonate, and n-trifluoromethanesulfonyloxynaphthylimide.

[0139] Examples of such oxime sulfonate derivatives include α-(phenylthionyloxyimino)-4-methylphenylacetonitrile.

[0140] Examples of iminosulfonate derivatives include (5-(4-methylphenyl)sulfonyloxyimino-5H-thiophen-2-ene)-(2-methylphenyl)acetonitrile and (5-(4-(4-methylphenylsulfonyloxy)phenylsulfonyloxyimino)-5H-thiophen-2-ene)-(2-methylphenyl)acetonitrile.

[0141] Examples of triazine derivatives include 2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, and 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine.

[0142] In addition, 2-methyl-2-[(4-methylphenyl)sulfonyl]-1-[(4-methylthio)phenyl]-1-propane, etc., can also be used appropriately.

[0143] As a photoacid generator of component (B), the onium salt is particularly preferred, and the thionium salt is more preferred.

[0144] The content of component (B) is preferably 0.05 to 20 parts by weight, more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of component (A). If the content of component (B) is within this range, sufficient photocurability is easily obtained. Furthermore, to obtain the desired transparency and lightfastness, the amount of photoacid generator in component (B), which has light-absorbing properties, should preferably be as low as possible without hindering its photocurability. One photoacid generator in component (B) can be used alone or two or more can be used simultaneously.

[0145] [(C) Quantum Dot]

[0146] Quantum dots are nanoscale semiconductor materials. Atoms form molecules, and molecules form clusters of molecules, which are small aggregates that form nanoparticles. When such nanoparticles exhibit semiconductor properties, they are called quantum dots (quantum dot particles).

[0147] If a quantum dot receives energy from the outside and reaches an excited state, it will autonomously (automatically) release energy from the corresponding band gap.

[0148] Red and green quantum dot particles can be classified according to their particle size, with the size decreasing from red to green. Specifically, red quantum dot particles have a particle size of 5–10 nm, while green quantum dot particles have a particle size of 3–5 nm. When illuminated, red quantum dot particles emit red light, and green quantum dot particles emit green light.

[0149] Quantum dot particles are not particularly limited to any quantum dot particles that can emit light upon photostimulation. For example, they can be selected from the group consisting of group II-VI semiconductor compounds, group III-V semiconductor compounds, group IV-VI semiconductor compounds, group IV elements or compounds containing such elements, and combinations thereof. These quantum dot particles can be used alone or in combination of two or more.

[0150] The group II-VI semiconductor compounds can be selected from the group consisting of binary, ternary, and quaternary compounds. The binary compounds are selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof. The ternary compounds are selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, and Hg... The group consisting of STe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; and the quaternary compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and combinations thereof.

[0151] The III-V semiconductor compounds can be selected from the group consisting of binary compounds, ternary compounds, and quaternary compounds. The binary compounds are selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof. The ternary compounds are selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof. The quaternary compounds are selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

[0152] The IV-VI semiconductor compounds can be selected from the group consisting of binary, ternary, and quaternary compounds, wherein the binary compounds are selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; the ternary compounds are selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and the quaternary compounds are selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

[0153] The group IV element or a compound containing the element can be selected from the group consisting of elemental compounds and binary compounds, wherein the elemental compound is selected from the group consisting of Si, Ge and mixtures thereof; and the binary compound is selected from the group consisting of SiC, SiGe and mixtures thereof.

[0154] Furthermore, semiconductor crystal particles can be either a core or a core-shell structure; the structure is not limited and can be chosen appropriately. Moreover, semiconductor crystal particles can be spherical, but can also be cubic or rod-shaped; the shape is not limited and can be freely chosen.

[0155] There are no particular limitations on the method of quantum dot doping. The desired method is to mix quantum dots in a colloidal solution with a solution containing other components. This mixing method, as described above, can suppress the aggregation of quantum dots.

[0156] From the perspective of luminescence intensity and the formation of fine patterns, the solid content of quantum dot particles is preferably 3 to 80% by mass of the total solid content of the photosensitive resin composition, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass. If the content of quantum dot particles is within the above range, fine patterns can be formed while maintaining good luminescence intensity.

[0157] [(D) Crosslinking agent]

[0158] The photosensitive resin composition of the present invention may further include a crosslinking agent as component (D). The crosslinking agent reacts with the epoxy groups of component (A), which is a component that facilitates pattern formation, and can further improve the strength of the resin coating after photocuring.

[0159] As the crosslinking agent, compounds having an average of two or more epoxy, alicyclic epoxy, oxetyl, or vinyl ether groups per molecule are preferred. For example, compounds listed below can be used. As such compounds, low-molecular-weight or high-molecular-weight compounds with a Mw of 100 to 20,000 are preferred, and compounds with a Mw of 200 to 10,000 are more preferred. Sufficient photocurability can be obtained if the Mw is 100 or higher, and the heat resistance of the composition after photocuring will not deteriorate if the Mw is 20,000 or lower, therefore these are preferred.

[0160] [Chemical Formula 14]

[0161]

[0162] In the above formula, n ranges from 1 to 50.

[0163] [Chemical Formula 15]

[0164]

[0165] The content of component (D) is 0 to 100 parts by weight relative to 100 parts by weight of component (A), but when component (D) is present, it is preferably 0.5 to 100 parts by weight, more preferably 1 to 50 parts by weight. If the content of component (D) is 0.5 parts by weight or more, sufficient curability can be obtained upon irradiation; if it is 100 parts by weight or less, the proportion of component (A) in the photosensitive resin composition will not decrease, thus allowing the cured product to fully exhibit the effects of the present invention. Component (D) can be used alone or in combination of two or more.

[0166] (E) Antioxidants

[0167] The photosensitive resin composition of the present invention can contain an antioxidant as an additive. By including an antioxidant, heat resistance can be improved. Examples of such antioxidants include hindered phenolic compounds and hindered amine compounds.

[0168] There are no particular limitations on the hindered phenolic compounds, but the compounds listed below are preferred. For example, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (product name: IRGANOX 1330), 2,6-di-tert-butyl-4-methylphenol (product name: Sumilizer BHT), 2,5-di-tert-butyl-hydroquinone (product name: Nocrac NS-7), 2,6-di-tert-butyl-4-ethylphenol (product name: Nocrac M-17), 2,5-di-tert-pentylhydroquinone (product name: Nocrac DAH), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (product name: Nocrac NS-6), 3,5-di-tert-butyl-4-hydroxy-phenyl phosphate diethyl ester (product name: IRGANOX 1222), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (product name: Nocrac 300), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (product name: Nocrac NS-5), 4,4'-butylenebis(3-methyl-6-tert-butylphenol) (product name: ADK STAB AO-40), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-

[0169] Methylbenzyl)-4-methylphenyl acrylate (Product Name: Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Product Name: Sumilizer GS), 2,2'-methylenebis[4-methyl-6-(α-methyl-cyclohexyl)phenol], 4,4'-methylenebis(2,6-di-tert-butylphenol) (Product Name: Cinnox 226M), 4,6-bis(octylthiomethyl)-o-cresol (Product Name: IRGANOX 1520L), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Product Name: IRGANOX) 1076), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (product name: ADK STAB AO-30), tetra[methylene-(3,5-di-tert-butyl-4-hydroxycinnamate)]methane (product name: ADK STAB AO-60), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (product name: IRGANOX 245), 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine (product name: IRGANOX 565), N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxycyanamide) (product name: IRGANOX) 1098), 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Product Name: IRGANOX 259), 2,2-thiodiethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Product Name: IRGANOX 1035), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]1,1-dimethylethyl]2,4,8,10-tetraoxaspiro[5.5]undecane (Product Name: Sumilizer GA-80), tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate (Product Name: IRGANOX 3114), bis(3,5-di-tert-butyl-4-hydroxyphenyl phosphate ethyl ester) calcium / polyethylene wax mixture (50:50) (Product Name: IRGANOX) 1425WL), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (product name: IRGANOX 1135), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (product name: Sumilizer WX-R), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetratert-butyldibenzo[d,f][1,3,2]dioxinazole (product name: Sumilizer GP), etc.

[0170] There are no particular limitations on the hindered amine compounds, but the compounds listed below are preferred. Examples include p,p'-dioctyldiphenylamine (product name: IRGANOX 5057), phenyl-α-naphthylamine (product name: NocracPA), poly(2,2,4-trimethyl-1,2-dihydroquinoline) (product name: Nocrac 224, 224-S), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (product name: Nocrac AW), N,N'-diphenyl-p-phenylenediamine (product name: NocracDP), N,N'-di-β-naphthyl-p-phenylenediamine (product name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (product name: Nocrac 810NA), N,N'-diallyl-p-phenylenediamine (product name: Nonflex TP), and 4,4'-(α,α-dimethylbenzyl)diphenylamine (product name: Nocrac). CD), p-(p-toluenesulfonylamino)diphenylamine (product name: Nocrac TD), N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine (product name: Nocrac G1), N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine (product name: Ozonon 35), N,N'-disec-butyl-p-phenylenediamine (product name: Sumilizer BPA), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (product name: Antigene 6C), alkylated diphenylamine (product name: Sumilizer 9A), dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine condensate (product name: Tinuvin) 622LD), poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]] (product name: CHIMASSORB 944), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-6-chloro-1,3,5-triazine condensate (product name: CHIMASSORB 119FL), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (product name: TINUVIN) 123), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (product name: TINUVIN 770), 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-Pentamethyl-4-piperidinyl (Product Name: TINUVIN 144), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Product Name: TINUVIN 765), tetra(1,2,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate (Product Name: LA-57), tetra(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate (Product Name: LA-52), mixed esterifications of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecyl alcohol (Product Name: LA-62),

[0171] A mixed esterification of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecyl alcohol (product name: LA-67), and a mixed esterification of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (product name: Products include: LA-63P, a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (product name: LA-68LD), (2,2,6,6-tetramethylene-4-piperidinyl)-2-propenylcarboxylic acid ester (product name: ADK STAB LA-82), (1,2,2,6,6-pentamethyl-4-piperidinyl)-2-propenylcarboxylic acid ester (product name: ADK STAB LA-87), etc.

[0172] The content of component (E) is not particularly limited, but when component (E) is present, it is preferably 0.01 to 1% by mass in the photosensitive resin composition of the present invention. The antioxidant of component (E) can be used alone or two or more at the same time.

[0173] [(F) solvent]

[0174] To improve the coatability of the photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention may also include a solvent as component (F). As the solvent (F), there are no particular limitations as long as it can dissolve and disperse the components (A) to (E) or other various additives described above.

[0175] Organic solvents are preferred as solvent (F). Specific examples 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; and 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 monotert-butyl ether acetate, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

[0176] As solvents for (F), ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, and mixed solvents thereof are particularly preferred as solvents with excellent solubility for photoacid generators.

[0177] From the perspective of the compatibility and viscosity of the photosensitive resin composition, the content of component (F) is preferably 200 to 20,000 parts by mass relative to a total of 100 parts by mass of components (A) and (C), more preferably 250 to 10,000 parts by mass, and even more preferably 350 to 3,500 parts by mass.

[0178] [Other Additives]

[0179] In addition to the components described above, the photosensitive resin composition of the present invention may also contain other additives. Examples of additives include surfactants commonly used to improve coatability.

[0180] As the surfactant, nonionic surfactants are preferred, such as fluorinated surfactants, specifically including perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkyl amino oxides, and fluorinated organosiloxane compounds. These surfactants can be commercially available products, such as Fluorad (registered trademark) "FC-430" (manufactured by 3M), Surflon (registered trademark) "S-141" and "S-145" (manufactured by AGC SEIMI CHEMICAL CO.,LTD.), UNIDYNE (registered trademark) "DS-401", "DS-4031" and "DS-451" (manufactured by DAIKIN INDUSTRIES,LTD.), MEGAFACE (registered trademark) "F-8151" (manufactured by DIC CORPORATION), and "X-70-093" (manufactured by Shin-Etsu Chemical Co.,Ltd.). Fluorad FC-430 and X-70-093 are preferred. The content of the surfactant is not particularly limited, but when a surfactant is present, the surfactant in the photosensitive resin composition of the present invention is preferably 0.01 to 1% by mass.

[0181] In addition, silane coupling agents can also be used as additives. By including silane coupling agents, the adhesion of the photosensitive resin composition to the adherend can be further improved. Examples of silane coupling agents include epoxy silane coupling agents and aromatic amino silane coupling agents. These can be used alone or in combination of two or more. The content of the silane coupling agent is not particularly limited, but when silane coupling agents are included, in the photosensitive resin composition of the present invention, the silane coupling agent is preferably 0.01 to 5% by mass.

[0182] [A method for pattern formation using a photosensitive resin composition]

[0183] The patterning method using the photosensitive resin composition of the present invention includes:

[0184] (i) The step of coating the photosensitive resin composition onto a substrate to form a photosensitive resin coating on the substrate.

[0185] (ii) The process of exposing the photosensitive resin coating, and

[0186] (iii) A process of developing the exposed photosensitive resin coating using a developing solution.

[0187] Step (i) is a step of coating the photosensitive resin composition onto a substrate to form a photosensitive resin coating on the substrate. The photosensitive resin coating is a dried form of the photosensitive resin composition. Examples of substrates include silicon wafers, glass wafers, quartz wafers, plastic circuit boards, and ceramic circuit boards.

[0188] As for the coating method, any known method can be used, such as dip coating, spin coating, and roller coating. The coating amount can be appropriately selected according to the target, but it is preferable to coat the resulting photosensitive resin film (the dried body of the photosensitive resin composition) with a film thickness of 1 to 5,000 nm, more preferably 50 to 4,000 nm.

[0189] To improve the uniformity of film thickness on the substrate surface, a solvent can be dropped onto the substrate before coating the photosensitive resin composition (pre-wetting). The solvent added can be appropriately selected depending on the purpose. As such solvents, alcohols such as isopropanol (IPA), ketones such as cyclohexanone, and diols such as propylene glycol monomethyl ether are preferred, but solvents that can be used in the photosensitive resin composition can also be used.

[0190] In order to achieve efficient photocuring, the solvent and other components can be pre-evaporated by preheating (pre-baking) as needed. Pre-baking can be carried out at 40-140°C for about 1 minute to 1 hour.

[0191] Next, (ii) the photosensitive resin coating is exposed. At this time, exposure is preferably performed with light of wavelength 10–600 nm, and more preferably with light of wavelength 190–500 nm. Examples of such wavelengths include light of various wavelengths generated by a radiation generator, such as gamma rays, h rays, i rays, and other ultraviolet light, as well as far-ultraviolet light (248 nm, 193 nm). Light of wavelength 248–436 nm is particularly preferred. The exposure dose is preferably 10–10,000 mJ / cm². 2 .

[0192] Exposure can also be performed through a photomask. The photomask can be, for example, a photomask with the desired pattern cut out. In addition, the material of the photomask is not particularly limited, but it is preferable to use a material that can block light of the wavelength, such as a chromium-based photomask suitable as a light-shielding film, but it is not limited to this.

[0193] Furthermore, to improve development sensitivity, post-exposure heat treatment (PEB) can be performed. Preferably, PEB is performed at 40–150°C for 0.5–10 minutes. Through PEB, cross-linking occurs in the exposed areas, forming insoluble patterns that are insoluble in the organic solvent used as the developer.

[0194] (iii) After exposure or PEB, the exposed photosensitive resin coating is developed using a developing solution to dissolve and remove the unexposed areas, thereby forming a pattern. As a developing solution, organic solvents such as alcohols like IPA, ketones like cyclohexanone, and glycols like propylene glycol monomethyl ether are preferred, but solvents that can be used in the photosensitive resin composition can also be used. Common methods can be listed as developing methods, such as immersing the patterned substrate in the developing solution. By developing with such an organic solvent, the unexposed areas can be dissolved and removed, thereby forming a pattern. Then, as needed, washing, rinsing, drying, etc., are performed to obtain a coating with the desired pattern.

[0195] Furthermore, (iv) an oven or heating plate can be used, preferably at 100–250°C, more preferably at 150–220°C, to post-cure the patterned coating. If the photosensitive resin composition of the present invention is used, even post-curing at a relatively low temperature of around 200°C can yield resin coatings with various excellent film properties. Additionally, a post-curing temperature of 100–250°C can increase the crosslinking density of the photosensitive resin composition and remove residual volatile components, which is preferable from the perspectives of adhesion to the substrate, heat resistance, strength, electrical properties, and bonding strength. The post-curing time is preferably 10 minutes to 10 hours, more preferably 10 minutes to 3 hours. The film thickness of the post-cured resin coating is typically 1–200 μm, preferably 5–50 μm. Through these processes, a film for a light-emitting element can be obtained as the final target.

[0196] [Photosensitive dry film]

[0197] The photosensitive dry film of the present invention comprises a support film and a photosensitive resin coating made of a photosensitive resin composition on the support film.

[0198] The photosensitive dry film (support film and photosensitive resin coating) is solid. Since the photosensitive resin coating does not contain solvent, air bubbles caused by solvent evaporation will not remain inside the photosensitive resin coating or between the uneven substrate. The thickness of the photosensitive resin coating is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 to 100 μm.

[0199] Furthermore, the viscosity and flowability of the photosensitive resin coating are closely related. The photosensitive resin coating can exhibit appropriate flowability within a suitable viscosity range, allowing it to penetrate deep into narrow crevices or enhance adhesion to the substrate by softening the resin. Therefore, from the perspective of the flowability of the photosensitive resin coating, its viscosity is preferably 10–5,000 Pa·s at 80–120°C, more preferably 30–2,000 Pa·s, and even more preferably 50–300 Pa·s. Additionally, the viscosity in this invention is a value measured using a rotational viscometer.

[0200] When the photosensitive dry film of the present invention is bonded to a substrate with uneven surfaces, the photosensitive resin coating adheres tightly to and covers the uneven surfaces, achieving a high degree of flatness. In particular, the photosensitive resin composition of the present invention is characterized by softening properties, thus enabling even higher flatness. Furthermore, if the photosensitive resin coating is bonded to the substrate under vacuum, gaps between them can be prevented more effectively.

[0201] The photosensitive dry film of the present invention can be manufactured by coating the photosensitive resin composition onto a substrate and drying it to form a photosensitive resin film. As the manufacturing apparatus for the photosensitive dry film, a coating machine commonly used in the manufacture of adhesive products can be used. Examples of such coating machines include comma coating machines, comma reverse coating machines, multilayer coating machines, die coating machines, lip coating machines, reverse lip coating machines, direct gravure coating machines, compensated gravure coating machines, 3-roll bottom-feed reverse coating machines, and 4-roll bottom-feed reverse coating machines.

[0202] When the support film is unwound from the unwinding spool of the coating machine and passed through the coating head of the coating machine, the photosensitive resin composition is coated onto the support film to a predetermined thickness. Then, the film is passed through a hot air circulating oven at a predetermined temperature and time to dry the photosensitive resin composition on the support film, thus producing a photosensitive dry film. Alternatively, if necessary, the photosensitive dry film, together with a protective film unwound from another unwinding spool of the coating machine, can be passed through laminating rollers under a predetermined pressure to bond the photosensitive resin coating on the support film to the protective film. Then, it is wound onto the take-up spool of the coating machine, thereby producing a photosensitive dry film with a protective film. In this case, the preferred temperature is 25–150°C, the preferred time is 1–100 minutes, and the preferred pressure is 0.01–5 MPa.

[0203] The support film used in the photosensitive dry film of the present invention can be a single-layer film composed of a single film, or a multilayer film composed of multiple films stacked together. Examples of materials for the film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate. Polyethylene terephthalate, which has moderate flexibility, mechanical strength, and heat resistance, is preferred. These films can also be materials that have undergone various treatments such as corona treatment or coating with a release agent. These films can also use commercially available products, such as Cerapeel WZ(RX), Cerapeel BX8(R) (manufactured by TORAY ADVANCED FILM CO.,LTD.), E7302, E7304 (manufactured by TOYOBO CO.,LTD.), Purex G31, Purex G71T1 (manufactured by Teijin DuPont Film Co., Ltd.), PET38×1-A3, PET38×1-V8, PET38×1-X08 (manufactured by NIPPA Co.,Ltd.), etc.

[0204] As the protective film, the same materials as the support film described above can be used, but polyethylene terephthalate and polyethylene, which have moderate flexibility, are preferred. Commercially available products can be used, including materials exemplified by polyethylene terephthalate, and polyethylene such as GF-8 (manufactured by TAMAPOLY CO.,LTD.) and PE film type O (manufactured by NIPPA Co.,Ltd.).

[0205] From the perspective of ensuring the stability of the photosensitive dry film and preventing the core from curling, the thickness of both the support film and the protective film is preferably 10 to 100 μm, and more preferably 25 to 50 μm.

[0206] [Patterning Method Using Photosensitive Dry Film]

[0207] The patterning method using the photosensitive dry film of the present invention includes:

[0208] (i') The process of forming a photosensitive resin coating on a substrate using the aforementioned photosensitive dry film.

[0209] (ii) The process of exposing the photosensitive resin coating, and

[0210] (iii) A process of developing the exposed photosensitive resin coating with a developing solution to dissolve and remove the unexposed areas, thereby forming a pattern.

[0211] First, (i') a photosensitive resin coating is formed on the substrate using a photosensitive dry film. That is, a photosensitive resin coating is formed on the substrate by attaching the photosensitive resin coating of the photosensitive dry film onto the substrate. Furthermore, when the photosensitive dry film has a protective film, the photosensitive resin coating of the photosensitive dry film is attached to the substrate after peeling off the protective film. For example, an attachment device can be used for attachment.

[0212] As the laminating apparatus, a vacuum laminator is preferred. For example, the protective film of the photosensitive dry film is peeled off, and the exposed photosensitive resin film is adhered to the substrate using an attachment roller at a specified pressure in a vacuum chamber with a specified vacuum level and on an operating table at a specified temperature. Furthermore, the temperature is preferably 60–120°C, the pressure is preferably 0–5.0 MPa, and the vacuum level is preferably 50–500 Pa.

[0213] To effectively perform the photocuring reaction of the photosensitive resin coating and improve the adhesion between the photosensitive resin coating and the substrate, pre-baking can be performed as needed. Pre-baking can, for example, be carried out at 40–140°C for about 1 minute to 1 hour.

[0214] The photosensitive resin coating attached to the substrate can be patterned by the same steps as the patterning method using the photosensitive resin composition: (ii) exposing the photosensitive resin coating, (iii) developing and dissolving the exposed photosensitive resin coating with a developer to remove the unexposed areas, thereby forming a pattern, and (iv) performing a post-curing heat treatment as needed. Furthermore, the support film of the photosensitive dry film can be peeled off before pre-baking or before PEB, or removed by other methods, depending on the process.

[0215] The patterning method of the present invention using a photosensitive resin composition or a photosensitive dry film makes it easy to form fine patterns in a thick film. For example, the photosensitive dry film of the present invention can be used to fill multiple blue microLEDs laid on a substrate, and then a photosensitive insulating film containing quantum dots such as red and green can be formed on the blue microLEDs in a patterned manner, thereby producing light emission of red and green.

[0216] Example

[0217] The following describes the invention in detail with examples of synthesis, embodiments, and comparative examples, but the invention is not limited to the examples described below. Furthermore, Mw was determined using a TSKgel Super HZM-H column (manufactured by Tosoh Corporation) and analytical conditions of 0.6 mL / min flow rate, tetrahydrofuran as the elution solvent, and 40°C column temperature, with GPC as the standard for monodisperse polystyrene.

[0218] The compounds (S-1) to (S-5) used in the following examples and comparative examples are as follows.

[0219] [Chemical Formula 16]

[0220]

[0221] [1] Synthesis of organosilicon resins containing acid crosslinking groups

[0222] [Synthesis Example 1] Synthesis of Resin A-1

[0223] Add 265.0 g (1.00 mol) of compound (S-5) to a 3 L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, and reflux cooler, then add 2,000 g of toluene and heat to 70 °C. Next, add 1.0 g (0.5 wt% platinum concentration) of toluene chloroplatinic acid solution, and dropwise add 164.9 g (0.85 mol) of compound (S-1) and 453.0 g (0.15 mol) of compound (S-2) over 1 hour. 1 =40, manufactured by Shin-Etsu Chemical Co., Ltd. (Total of hydrosilyl groups / Total of alkenyl groups = 1 / 1 (molar ratio)). After the addition is complete, heat to 100°C, mature for 6 hours, and then remove toluene from the reaction solution by vacuum distillation to obtain resin A-1. 1 H-NMR and 29 The structure of resin A-1 was confirmed by Si-NMR (manufactured by Bruker) and GPC analysis. Resin A-1 has a Mw of 65,000 and an organosilicon content of 51.3% by mass. Furthermore, in formulas (A1) to (A6), a = b = c = d = 0, e = 0.85, f = 0.15, z = 1, and m = 41.

[0224] In addition, the organosilicon content is obtained through 29 The result was obtained using Si-NMR (manufactured by Bruker).

[0225] [Synthesis Example 2] Synthesis of Resin A-2

[0226] Add 111.6 g (0.60 mol) of compound (S-3) and 156.8 g (0.40 mol) of compound (S-4) to a 3 L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, and reflux cooler, then add 2,000 g of toluene and heat to 70 °C. Next, add 1.0 g (0.5% by mass platinum) of toluene chloroplatinic acid solution, and dropwise add 135.8 g (0.70 mol) of compound (S-1) and 906.0 g (0.30 mol) of compound (S-2) over 1 hour. 1=40, manufactured by Shin-Etsu Chemical Co., Ltd. (Total of hydrosilyl groups / Total of alkenyl groups = 1 / 1 (molar ratio)). After the addition is complete, heat to 100°C, mature for 6 hours, and then remove toluene from the reaction solution by vacuum distillation to obtain resin A-2. 1 H-NMR and 29 The structure of resin A-2 was confirmed by Si-NMR (manufactured by Bruker) and GPC analysis. Resin A-2 has a Mw of 55,000 and an organosilicon content of 77.7% by mass. Furthermore, in formulas (A1) to (A6), a = 0.42, b = 0.18, c = 0.28, d = 0.12, e = f = 0, p = 1, x = 0, y = 1, g = h = 0, and m = 41.

[0227] [Synthesis Example 3] Synthesis of Resin A-3

[0228] Add 111.6 g (0.60 mol) of compound (S-3) and 106.0 g (0.40 mol) of compound (S-5) to a 3 L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, and reflux cooler, then add 2,000 g of toluene and heat to 70 °C. Next, add 1.0 g (0.5% by mass platinum) of toluene chloroplatinic acid solution, and dropwise add 174.6 g (0.90 mol) of compound (S-1) and 302.0 g (0.10 mol) of compound (S-2) over 1 hour. 1 =40, manufactured by Shin-Etsu Chemical Co., Ltd. (Total of hydrosilyl groups / Total of alkenyl groups = 1 / 1 (molar ratio)). After the addition is complete, heat to 100°C, mature for 6 hours, and then remove toluene from the reaction solution by vacuum distillation to obtain resin A-3. 1 H-NMR and 29 The structure of resin A-3 was confirmed by Si-NMR (manufactured by Bruker) and GPC analysis. Resin A-3 has a Mw of 50,000 and an organosilicon content of 59.6% by mass. Furthermore, in formulas (A1) to (A6), a = 0.54, b = 0.06, c = d = 0, e = 0.36, f = 0.04, p = 1, x = 0, z = 1, and m = 41.

[0229] [Synthesis Example 4] Synthesis of Resin A-4

[0230] Add 392.0 g (1.00 mol) of compound (S-4) to a 3 L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, and reflux cooler, then add 2,000 g of toluene and heat to 70 °C. Next, add 1.0 g (0.5% by mass platinum) of toluene chloroplatinic acid solution, followed by dropwise addition of 155.2 g (0.80 mol) of compound (S-1) and 317.0 g (0.20 mol) of compound (S-2) over 1 hour. 1 =20, manufactured by Shin-Etsu Chemical Co., Ltd. (Total of hydrosilyl groups / Total of alkenyl groups = 1 / 1 (molar ratio)). After the addition is complete, heat to 100°C, mature for 6 hours, and then remove toluene from the reaction solution by vacuum distillation to obtain resin A-4. 1 H-NMR and 29 The structure of resin A-4 was confirmed by Si-NMR (manufactured by Bruker) and GPC analysis. Resin A-4 has a Mw of 23,000 and an organosilicon content of 36.7% by mass. Furthermore, in formulas (A1) to (A6), a = b = 0, c = 0.8, d = 0.2, e = f = 0, y = 1, g = h = 0, and m = 21.

[0231] [Synthesis Example 5] Synthesis of Resin A-5

[0232] Add 274.4 g (0.70 mol) of compound (S-4) and 79.5 g (0.30 mol) of compound (S-5) to a 3 L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, and reflux cooler, then add 2,000 g of toluene and heat to 70 °C. Next, add 1.0 g (0.5 wt% platinum concentration) of toluene chloroplatinic acid solution, and dropwise add 58.2 g (0.30 mol) of compound (S-1) and 1,109.5 g (0.70 mol) of compound (S-2) over 1 hour. 1 =20, manufactured by Shin-Etsu Chemical Co., Ltd. (Total of hydrosilyl groups / Total of alkenyl groups = 1 / 1 (molar ratio)). After the addition is complete, heat to 100°C, mature for 6 hours, and then remove toluene from the reaction solution by vacuum distillation to obtain resin A-5. 1 H-NMR and 29 The structure of resin A-5 was confirmed by Si-NMR (manufactured by Bruker) and GPC analysis. Resin A-5 has a Mw of 42,000 and an organosilicon content of 72.9% by mass. Furthermore, in formulas (A1) to (A6), a = b = 0, c = 0.21, d = 0.49, e = 0.09, f = 0.21, y = 1, g = h = 0, z = 1, and m = 21.

[0233] [Synthesis Example 6] Synthesis of Resin A-6

[0234] Add 55.8 g (0.30 mol) of compound (S-3), 117.6 g (0.30 mol) of compound (S-4), and 106.0 g (0.40 mol) of compound (S-5) to a 3 L flask equipped with a stirrer, thermometer, nitrogen purging apparatus, and reflux cooler. Then add 2,000 g of toluene and heat to 70 °C. Next, add 1.0 g (0.5% by mass platinum concentration) of toluene chloroplatinic acid solution. After 1 hour, add 135.8 g (0.70 mol) of compound (S-1) and 475.5 g (0.30 mol) of compound (S-2) (y 1 =20, manufactured by Shin-Etsu Chemical Co., Ltd. (Total of hydrosilyl groups / Total of alkenyl groups = 1 / 1 (molar ratio)). After the addition is complete, heat to 100°C, mature for 6 hours, and then remove toluene from the reaction solution by vacuum distillation to obtain resin A-6. 1 H-NMR and 29 The structure of resin A-6 was confirmed by Si-NMR (manufactured by Bruker) and GPC analysis. Resin A-6 has a Mw of 31,000 and an organosilicon content of 59.6% by mass. Furthermore, in formulas (A1) to (A6), a = 0.21, b = 0.09, c = 0.21, d = 0.09, e = 0.28, f = 0.12, p = 1, x = 0, y = 1, g = h = 0, z = 1, and m = 21.

[0235] [Comparative Synthesis Example 1] Synthesis of Acrylic Resin 1

[0236] 70 g of propylene glycol monomethyl ether and 70 g of toluene were added to a flask equipped with a stirrer, reflux condenser, inert gas inlet, and thermometer. The mixture was heated to 80 °C under a nitrogen atmosphere. While maintaining the reaction temperature at 80 °C ± 2 °C, 90 g of methyl methacrylate, 10 g of methacrylic acid, and 2,2'-azobis(isobutyronitrile) were added dropwise over 4 hours. After the addition, the mixture was stirred for another 6 hours at 80 °C ± 2 °C to obtain a solution of acrylic resin 1 (resin 7). The Mw of acrylic resin 1 was 50,000.

[0237] [2] Preparation and evaluation of photosensitive resin compositions

[0238] [Examples 1-12 and Comparative Examples 1-17]

[0239] Each component was mixed according to the mixing amounts recorded in Tables 1 to 3, and then stirred, mixed, and dissolved at room temperature to obtain the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 17.

[0240] [Table 1]

[0241]

[0242] [Table 2]

[0243]

[0244] Resin 7: Acrylic Resin 1

[0245] Resin 8: Acrylic Resin 2

[0246] [Table 3]

[0247]

[0248] In Tables 1-3, the quantum dots are as follows:

[0249] Red-1 is S-BE030 manufactured by SHOEI CHEMICAL INC. (particle size 5-10nm, material InP:ZnS:SeZn = 25:50:25 colloid / PGMEA);

[0250] Red-2 is 900514-1ML (particle size 5-10nm, material CdSe (core) / CdS (shell) core-shell colloid / hexane) manufactured by Aldrich;

[0251] Green-1 is S-BE029 (particle size 3-5nm, material InP:ZnS:SeZn = 25:50:25 colloidal / PGMEA) manufactured by SHOEI CHEMICAL INC.

[0252] Green-2 is 900511-1ML manufactured by Aldrich (particle size 3-5nm, material CdSe (core) / CdS (shell) core-shell colloid / hexane).

[0253] In addition, tetraethoxysilane and (3,3,3-trifluoropropyl)triethoxysilane are manufactured by Shin-Etsu Chemical Co., Ltd.

[0254] In addition, the photoacid generator PAG-1, crosslinking agents D-1 to D-3, antioxidants E-1 and E-2, acrylic resin 2 (resin 8), and photopolymerization initiator Irgacure OXE02 are as follows.

[0255] • Photoacid generator PAG-1: CPI-210S (manufactured by San-Apro Ltd.)

[0256] Crosslinking agent D-1: (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0257] [Chemical Formula 17]

[0258]

[0259] Crosslinking agent D-2: (manufactured by SHIKOKU CHEMICALS CORPORATION)

[0260] [Chemical Formula 18]

[0261]

[0262] Crosslinking agent D-3: (manufactured by SHIKOKU CHEMICALS CORPORATION)

[0263] [Chemical Formula 19]

[0264]

[0265] • Antioxidant E-1: CHIMASSORB 119FL (manufactured by BASF)

[0266] [Chemical Formula 20]

[0267]

[0268] • Antioxidant E-2: IRGANOX 3114 (manufactured by BASF)

[0269] [Chemical Formula 21]

[0270]

[0271] • Acrylic Resin 2 (Resin 8): Manufactured by Nippon Kayaku Co., Ltd. (Product Name)

[0272] “DPCA-20” (an acrylate of ε-caprolactone-modified dipentaerythritol, see formula below)

[0273] [Chemical Formula 22]

[0274]

[0275] • Photopolymerization initiator Irgacure OXE02: Manufactured by BASF (ethane, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime))

[0276] (1) Preparation of photosensitive dry film and evaluation of dry film properties

[0277] Using a die-coating machine as the coating machine and a polyethylene terephthalate film (38 μm thick) as the support film, the photosensitive resin compositions described in Tables 1-3 were coated onto the support film. Next, the film was dried in a hot air circulating oven (4 m long) set to 100°C for 5 minutes to form a photosensitive resin coating on the support film, thereby obtaining a photosensitive dry film. A polyethylene film (100 μm thick) as a protective film was laminated onto the photosensitive resin coating using a laminating roller at a pressure of 1 MPa, thereby producing a 50 μm photosensitive dry film with a protective film. Then, photosensitive dry films that could be peeled off without separation or adhesion during the protective film peeling process were classified as 0, and photosensitive dry films with defects were classified as ×, as described in Tables 4-6.

[0278] (2) The formation and evaluation of patterns

[0279] Each photosensitive resin composition was coated onto a glass substrate using a spin coater at a thickness of 20 μm. The substrate was placed on a heated plate to remove the solvent from the composition and dried at 110°C for 3 minutes. The resulting photosensitive resin coating was exposed at 365 nm using a contact aligner-type exposure device to form a 20 mm × 20 mm pattern and contact hole pattern through a mask. After exposure, the substrate was subjected to PEB treatment at 120°C for 3 minutes on a heated plate, followed by cooling. The substrate was then spray-developed with PGMEA (propylene glycol monomethyl ether acetate) for 60 seconds to form the pattern. The limiting resolution of the formed pattern was evaluated as follows.

[0280] (3) Evaluation of the heat resistance of the pattern

[0281] The photosensitive resin coating on the substrate patterned by the above method was post-cured for 2 hours at 150°C under nitrogen blowing. Then, cross-sections of the formed contact hole patterns of 50μm, 30μm, 20μm, and 10μm were observed using a scanning electron microscope (SEM). The size of the smallest hole pattern that penetrates to the bottom of the film was defined as the limiting resolution (resolution limit F). Cases where the resolution (limit resolution) did not reach 50μm were marked as ×. The results are shown in Tables 4-6. Furthermore, after placing the 20mm × 20mm patterned area in air at 150°C for 100 hours (heat resistance evaluation), patterns showing peeling were marked as peeling, patterns showing cracking were marked as cracks, and patterns without any of the above conditions were marked as good (〇). The results are shown in Tables 4-6 below.

[0282] (4) Measurement of luminescence intensity and evaluation of heat resistance

[0283] The 20mm × 20mm pattern formed in (2) was irradiated with light using a 365nm Tube-type 4W UV irradiation machine (VL-4LC, VILBERLOURMAT). The luminescence intensity of the region of photoluminescence emission (640nm for red quantum dots Red-1 and Red-2, and 545nm for green quantum dots Green-1 and Green-2) was measured using a spectrometer (manufactured by Ocean Optics). For the values ​​shown in Tables 4 to 6 below, the luminescence intensity ratio of each sample containing red quantum dots is recorded when the luminescence intensity of Example 1 is used as standard 1.0, and the luminescence intensity ratio of each sample containing green quantum dots is recorded when the luminescence intensity of Example 7 is used as standard 1.0. In addition, the luminescence intensity ratio after placing the above-mentioned pattern at 150°C in air for 100 hours (heat resistance evaluation) is also shown in Tables 4 to 6 below.

[0284] [Table 4]

[0285]

[0286] [Table 5]

[0287]

[0288] [Table 6]

[0289]

[0290] As can be seen from the above results, the photosensitive resin composition of the present invention can provide a cured film with good dry film properties, resolution, luminescence characteristics, heat resistance (adhesion, crack resistance, and maintenance of luminescence intensity) and is suitable for light-emitting elements.

[0291] On the other hand, Comparative Example 1, which did not contain quantum dots, did not emit light. Comparative Examples 2-9, which used acrylic resin instead of component (A) of the present invention, were inferior to the present invention in all aspects, including dry film properties, resolution, luminescence characteristics, and heat resistance. Comparative Examples 10-17, which used silicone resin, were found to have cracks in the heat resistance evaluation, in addition to poor dry film properties and resolution.

[0292] Furthermore, the present invention is not limited to the above-described embodiments. The above embodiments are illustrative examples, and any technical solutions that have substantially the same composition and perform the same effects as the technical concept described in the claims of the present invention are included within the scope of protection of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, It includes: (A) Organosilicon resins containing acid crosslinking groups, (B) Photoacid generators, and (C) Quantum dot particles, The photosensitive resin composition further comprises a (D) crosslinking agent, wherein the (D) crosslinking agent is present in an amount of 30-60 parts by weight relative to 100 parts by weight of component (A). Component (A) comprises an organosilicon resin containing repeating units represented by the following formulas (A1) to (A6). In the formula, R 1 ~R 4 Each R is an independently selected monovalent hydrocarbon group containing 1 to 20 carbon atoms and containing heteroatoms, and m is an independently selected integer from 1 to 600. When m is an integer greater than 2, each R 3 Choose any two that are the same or different from each other, each R 4 Let X be any numbers that are the same or different from each other, where a, b, c, d, e, and f are numbers that satisfy 0 ≤ a ≤ 1, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, 0 ≤ d ≤ 1, 0 ≤ e ≤ 1, 0 ≤ f ≤ 1, 0 < c + d + e + f ≤ 1, and a + b + c + d + e + f = 1. 1 X is a divalent group represented by the following formula (X1), where X 2 X is a divalent group represented by the following formula (X2), where X 3 The divalent group represented by the following formula (X3) In the formula, R 11 ~R 14 Each is independently a arbitrarily chosen monovalent hydrocarbon group containing 1 to 20 carbon atoms, where p is an integer from 1 to 600. When p is an integer greater than 2, each R... 13 Choose any two that are the same or different from each other, each R 14 Choose either the same or different from each other, R 15 and R 16 Each atom is independently a hydrogen atom or a methyl group, and each x is an independent integer from 0 to 7. In the formula, Y 1 For single bonds, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 21 and R 22 Each is independently an alkyl or alkoxy group having 1 to 4 carbon atoms, and g and h are independently 0, 1, or 2. When g is 2, each R 21 Choose any two numbers that are the same or different from each other. When h is 2, each R... 22 Choose either the same or different from each other, R 23 and R 24 Each is independently a hydrogen atom or a methyl group, and each y is an independent integer from 0 to 7. In the formula, R 31 and R 32 Each is independently a hydrogen atom or a methyl group, z is independently an integer from 0 to 7, and R 33 It can be a monovalent hydrocarbon group with 1 to 8 carbon atoms, which may contain an ester bond or an ether bond, or a monovalent group represented by the following formula (X3-1). In the formula, R 34 The carbon group can be a divalent hydrocarbon group containing either an ester bond or an ether bond, with a carbon number of 1 to 8. The quantum dot particles (C) are InP / ZnS / SeZn or CdSe / CdS.

2. The photosensitive resin composition according to claim 1, characterized in that, The quantum dot particles (C) are either red quantum dot particles or green quantum dot particles.

3. The photosensitive resin composition according to claim 1, characterized in that, The total solid composition contains 3 to 80% by mass of the (C) quantum dot particles.

4. The photosensitive resin composition according to claim 2, characterized in that, The total solid composition contains 3 to 80% by mass of the (C) quantum dot particles.

5. The photosensitive resin composition according to claim 1, characterized in that, The photosensitive resin composition further comprises (E) an antioxidant.

6. The photosensitive resin composition according to claim 1, characterized in that, The photosensitive resin composition further comprises (F) solvent.

7. A photosensitive resin coating, characterized in that, It is the dried form of the photosensitive resin composition according to any one of claims 1 to 6.

8. A photosensitive dry film, characterized in that, It has a support film and a photosensitive resin coating as described in claim 7 on the support film.

9. A method for forming a pattern, comprising: (i) The step of coating the photosensitive resin composition of any one of claims 1 to 6 onto a substrate to form a photosensitive resin coating on the substrate; (ii) The process of exposing the photosensitive resin coating, and (iii) A process of developing and dissolving the unexposed areas of the exposed photosensitive resin coating using a developing solution to form a pattern.

10. A method for forming a pattern, comprising: (i') The process of forming a photosensitive resin coating on a substrate using the photosensitive dry film according to claim 8. (ii) The process of exposing the photosensitive resin coating, and (iii) A process of developing and dissolving the unexposed areas of the exposed photosensitive resin coating using a developing solution to form a pattern.

11. The pattern forming method according to claim 9 or 10, wherein, Further includes (iv) a process of post-curing the resin coating patterned by development at a temperature of 100 to 250°C.

12. A light-emitting element, characterized in that, The light-emitting element has the photosensitive resin coating as described in claim 7.

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