Photosensitive resin composition, cured film, and display device

Abstract

To provide: a cured film having excellent adhesion to a substrate and capable of maintaining high substrate adhesion even after immersion in a resist stripping solution used in a device manufacturing process; and a display device exhibiting good luminescent properties and excellent reliability.SOLUTION: A photosensitive resin composition comprises (a) a siloxane resin, (b) a photosensitizer, (c) a silane compound containing a sulfur atom, and (d) a compound containing an epoxy group, where the silane compound (c) containing a sulfur atom has a functional group of a structure represented by the general formula (1) in the figure. (X represents hydrogen or an organic group having 1 to 18 carbon atoms, and * denotes a bonding site.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a cured film, and a display device including the same. [Background technology]

[0002] In recent years, there has been active research into technologies related to organic electroluminescence (hereinafter referred to as "OLED") displays, quantum dot displays, and micro light-emitting diode (hereinafter referred to as "LED") displays for thin displays such as TVs, smartphones, smartwatches, and AR / VR devices.

[0003] For example, pixel dividing layers in organic EL displays, partition layers and planarizing layers in micro LEDs, planarizing layers in thin film transistors (hereinafter "TFTs") in various displays, and insulating films in other peripheral components are formed from cured films of photosensitive resin compositions patterned by photolithography. These cured films are required to have excellent light resistance because they are exposed to light emission for long periods of time. Cured films of resin compositions using siloxane resins are known to have high light resistance (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2006 / 178436 A [Patent Document 2] International Publication No. 2023 / 054226 Summary of the Invention [Problem to be solved by the invention]

[0005] The cured film of the resin composition using the siloxane resin described in Patent Document 1 or 2 has a problem in that the adhesion to the substrate decreases after immersion in a resist stripping solution during the device fabrication process. Specifically, when the cured film is immersed in a resist stripping solution, the adhesion to certain substrates such as alumina substrates decreases. Peeling between the cured film and adjacent components such as wiring or light-emitting elements can cause cracks in the wiring or damage to the elements, resulting in poor light emission in the display.

[0006] Therefore, an object of the present invention is to provide a cured film that has excellent substrate adhesion and maintains high substrate adhesion even after immersion in a resist stripper used in the device manufacturing process, and to provide a display device that exhibits good light-emitting properties and is highly reliable. [Means for solving the problem]

[0007] The present invention has the following configuration. [1] A photosensitive resin composition comprising (a) a siloxane resin, (b) a photosensitizer, (c) a silane compound containing a sulfur atom, and (d) a compound containing an epoxy group, wherein the (c) silane compound containing a sulfur atom is a compound having a functional group having a structure represented by the following general formula (1):

[0008] [ka]

[0009] X is hydrogen or an organic group having 1 to 18 carbon atoms. * indicates a bond. [2] The photosensitive resin composition according to claim 1, wherein the (a) siloxane resin has a polymerizable carbon-carbon double bond. [3] The photosensitive resin composition according to claim 2, wherein the polymerizable carbon-carbon double bond is a functional group represented by the structure of the following general formula (2):

[0010] [ka]

[0011] (In general formula (2), R I is a single bond or a hydrocarbon group having 1 to 10 carbon atoms. II , R III , R IV are hydrogen or hydrocarbon groups with 1 to 10 carbon atoms. I , R II , R III , R IV Two or more of these may be bonded to form a ring. * indicates a bond to the Si atom.) [4] The photosensitive resin composition according to [1] above, wherein the (b) photosensitizer is a quinone diazide compound. [5] The photosensitive resin composition according to [1] above, wherein X in the general formula (1) is a group represented by the following general formula (3):

[0012] [ka]

[0013] (R V , R VI , R VII are alkyl or alkoxy groups having 1 to 6 carbon atoms. * indicates a bond to the sulfur atom.) [6] The photosensitive resin composition according to [1], further comprising (e) particles having a median diameter of 100 to 400 nm. [7] The photosensitive resin composition according to [6], wherein the particles (e) having a median diameter of 100 to 400 nm contain at least one selected from titanium oxide, zinc oxide, and zirconium oxide. [8] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [7] above. [9] A display device having the cured film according to [9] above.

[10] An information terminal having the display device according to [9] above. [Effects of the Invention]

[0014] The photosensitive resin composition of the present invention can provide a cured film having high adhesion to a substrate, and the display device of the present invention can provide a display device that exhibits good light-emitting properties and is highly reliable. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a schematic cross-sectional view of a micro LED display having a barrier layer and a planarization layer. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications depending on the purpose and application.

[0017] (Photosensitive resin composition) An embodiment of the present invention is a photosensitive resin composition having the configuration [1] above. The photosensitive resin composition having this configuration can provide a cured film with excellent adhesion to a substrate. Furthermore, by suppressing peeling of the cured film, a display device exhibiting good light-emitting properties and excellent reliability can be provided.

[0018] (siloxane resin) The photosensitive resin composition of the present invention contains (a) a siloxane resin.

[0019] The term "(a) siloxane resin" used in the present invention refers to a polymer having a siloxane bond in the main chain. Examples of the (a) siloxane resin include resins obtained by hydrolyzing and dehydrating condensation one or more compounds selected from the group consisting of compounds that provide trifunctional organosilane units, compounds that provide tetrafunctional organosilane units, compounds that provide difunctional organosilane units, and compounds that provide monofunctional organosilane units, as described below.

[0020] The (a) siloxane resin preferably has a repeating unit represented by chemical formula (4). The repeating unit represented by chemical formula (4) is a trifunctional organosilane unit. The inclusion of a trifunctional organosilane unit can impart the functionality of an organic group to the resin, while at the same time enabling the production of a cured film with a higher crosslink density than when a bifunctional organosilane unit or a monofunctional organosilane unit is used, and making it easier to control the molecular weight of the resin than when a tetrafunctional organosilane unit is used.

[0021] [ka]

[0022] In chemical formula (4), R VIII represents a monovalent organic group. Preferably, it is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated cycloalkyl group having 4 to 10 carbon atoms, or a halogenated aryl group having 6 to 15 carbon atoms. The above-mentioned substituents and structures may have a heteroatom, and may be either unsubstituted or substituted.

[0023] Examples of compounds that provide trifunctional organosilane units include methyltrimethoxysilane, methyltriethoxysilane, methyltri(methoxyethoxy)silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrippropoxysilane, and 3-aminopropyltrimethoxysilane. Examples of suitable silanes include silane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, and perfluoropentyltriethoxysilane.

[0024] Of all repeating units (100 mol%) in the (a) siloxane resin, the trifunctional organosilane unit is preferably 10 mol% or more, more preferably 30 mol% or more, and particularly preferably 50 mol% or more. If it is 10 mol% or more, it becomes easy to control the molecular weight.

[0025] Additionally, the (a) siloxane resin may have a repeating unit represented by chemical formula (5). The repeating unit represented by chemical formula (5) is a tetrafunctional organosilane unit. By including the tetrafunctional organosilane unit, the inorganic crosslink density of the cured film is increased, resulting in a cured film with high hardness.

[0026] [ka]

[0027] Examples of compounds that provide tetrafunctional organosilane units include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

[0028] The content of the tetrafunctional organosilane unit is preferably 1 mol% or more, more preferably 5 mol% or more, and particularly preferably 10 mol% or more, relative to 100 mol% of all repeating units consisting of siloxane structures contained in the resin. Also, it is preferably 80 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less. If it is 1 mol% or more, the inorganic crosslink density of the cured film increases, and the hardness of the cured film can be increased. If it is 80 mol% or less, a resin composition with excellent storage stability can be obtained.

[0029] Additionally, (a) the siloxane resin may contain a difunctional organosilane unit and / or a monofunctional organosilane unit.

[0030] Examples of compounds that provide bifunctional organosilane units include dimethyldimethoxysilane, dimethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, and octadecylmethyldimethoxysilane.

[0031] Examples of compounds that provide a monofunctional organosilane unit include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, and diphenylmethylmethoxysilane.

[0032] When the (a) siloxane resin contains a bifunctional organosilane unit and / or a monofunctional organosilane unit, the content thereof is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on 100 mol% of all repeating units consisting of siloxane structures contained in the resin. Also, the content is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. A content of 1 mol% or more can improve the storage stability of the photosensitive resin composition. A content of 30 mol% or less can produce a cured film with high crosslink density.

[0033] Furthermore, the (a) siloxane resin preferably has a polymerizable carbon-carbon double bond. By using the (a) siloxane resin having a polymerizable carbon-carbon double bond, the organic crosslink density is increased, and swelling of the cured film due to penetration of a resist stripper used in the process of manufacturing a display device can be suppressed. As the polymerizable carbon-carbon double bond, a double bond having a structure represented by the following general formula (2) is preferred.

[0034] [ka]

[0035] In formula (2), R I is a single bond or a hydrocarbon group having 1 to 10 carbon atoms. II , R III , R IV are hydrogen or hydrocarbon groups with 1 to 10 carbon atoms. I , R II , R III , R IV Two or more of these may be bonded to form a ring. * indicates a bond to the Si atom.

[0036] Examples of compounds that provide organosilane units containing a polymerizable double bond group include organosilane compounds having a vinyl group, such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltri(methoxyethoxy)silane; organosilane compounds having an α-methylvinyl group, such as vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldi(methoxyethoxy)silane; organosilane compounds having an allyl group, such as allyltrimethoxysilane, allyltriethoxysilane, allyltri(methoxyethoxy)silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, and allylmethyldi(methoxyethoxy)silane; styryltrimethoxysilane, styryltriethoxysilane, and styryltriethoxysilane. Organosilane compounds having a styryl group, such as styryltriethoxysilane, styryltri(methoxyethoxy)silane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, and styrylmethyldi(methoxyethoxy)silane; and organosilane compounds having a (meth)acryloyl group, such as γ-(meth)acryloylpropyltrimethoxysilane, γ-(meth)acryloylpropyltriethoxysilane, γ-(meth)acryloylpropyltri(methoxyethoxy)silane, γ-(meth)acryloylpropylmethyldimethoxysilane, γ-(meth)acryloylpropylmethyldiethoxysilane, and γ-(meth)acryloylpropyl(methoxyethoxy)silane. Among these, from the viewpoint of suppressing swelling of the cured film, organosilane compounds having a double bond group selected from vinyl, allyl, and styryl groups, which are functional groups with high thermal polymerizability and hydrophobicity, are preferred, and organosilane compounds having a double bond group selected from vinyl and styryl groups are more preferred. It is even more preferred to simultaneously use an organosilane compound having a highly hydrophobic vinyl group and an organosilane compound having a highly thermal polymerizable styryl group.

[0037] Furthermore, the content of organosilane units containing polymerizable double bonds is preferably 1 mol% or more, more preferably 10 mol% or more, and particularly preferably 30 mol% or more, relative to 100 mol% of all repeating units consisting of siloxane structures contained in (a) siloxane resin. Also, it is preferably 80 mol% or less, more preferably 60 mol% or less. If it is 5 mol% or more, it is effective in suppressing swelling of the cured film due to chemical solutions. If it is 80 mol% or less, polymerization at low temperatures is suppressed, resulting in a resin composition with high storage stability.

[0038] In the past, when (a) a siloxane resin having such a polymerizable double bond was used, there was a problem that the adhesion of the resulting cured film to the substrate was reduced. However, in the present invention, by using (c) a silane compound containing a sulfur atom, which will be described later, and (d) a compound containing an epoxy, which will be described later, it is possible to suppress the problem of reduced adhesion to the substrate.

[0039] The (a) siloxane resin preferably further contains an organosilane unit containing an acidic group. By including the (a) siloxane resin having an organosilane unit containing an acidic group in the photosensitive resin composition, the solubility in an alkaline developer can be controlled. Examples of acidic groups include a carboxy group, a carboxylic acid anhydride group, a sulfonic acid group, and a phenolic hydroxyl group. Examples of compounds that provide organosilane units containing an acidic group include organosilane compounds having a carboxylic acid anhydride group, such as 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride, and 3-trimethoxysilylpropyl phthalic anhydride.

[0040] The content of organosilane units containing acidic groups is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and even more preferably 1 mol% or more, relative to 100 mol% of all repeating units consisting of siloxane structures contained in (a) siloxane resin. Also, it is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less. If it is 0.1 mol% or more, the alkali solubility effect of the acidic groups can be obtained. If it is 10 mol% or less, it is possible to prevent the resin composition from being excessively dissolved in an alkaline developer due to the acidic groups.

[0041] In order to improve sensitivity during exposure, the (a) siloxane resin may have an organosilane unit containing a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, or an aromatic structure. Examples of the condensed polycyclic structure, the condensed polycyclic heterocyclic structure, or the aromatic structure include a naphthyl group, an anthracenyl group, a biphenyl group, a phenyl group, a tolyl group, and a methoxyphenyl group.

[0042] Examples of compounds that provide these organosilane units include naphthyltrimethoxysilane, naphthyltriethoxysilane, and naphthyltrippropoxysilane.

[0043] From the viewpoint of suppressing residues after development, the (a) siloxane resin may have organosilane units bonded to particles (e) having a median diameter of 100 to 400 nm, as described below. (a) siloxane resins having such particle-bonded organosilane units are collectively referred to as "particle-containing siloxane resins" below. Preferred particle-containing siloxane resins are those obtained by hydrolyzing and dehydrating condensation one or more compounds selected from the group consisting of compounds that provide trifunctional organosilane units, compounds that provide tetrafunctional organosilane units, compounds that provide bifunctional organosilane units, and compounds that provide monofunctional organosilane units, in the presence of (e) particles having a median diameter of 100 to 400 nm. Examples and preferred descriptions of (e) particles having a median diameter of 100 to 400 nm are as described below for (e) particles having a median diameter of 100 to 400 nm.

[0044] (a) Siloxane resins can be obtained by hydrolyzing an organosilane compound and then subjecting the hydrolyzate to a dehydration condensation reaction in the presence or absence of a solvent. Various conditions for the hydrolysis can be set to suit the physical properties appropriate for the intended application, taking into account factors such as the reaction scale and the size and shape of the reaction vessel. Examples of various conditions include acid concentration, reaction temperature, and reaction time. Acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, and ion exchange resins can be used in the hydrolysis reaction. Among these, an acidic aqueous solution containing one or more selected from formic acid, acetic acid, and phosphoric acid is preferred. When an acid catalyst is used in the hydrolysis reaction, the amount of the acid catalyst added is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, per 100 parts by mass of the total organosilane compounds used in the hydrolysis reaction, in order to promote rapid hydrolysis. At 0.01 parts by mass or more, the acid catalyst's effect can be achieved. On the other hand, from the viewpoint of appropriately controlling the progress of the hydrolysis reaction, the amount of acid catalyst added is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the total organosilane compounds. If the amount is 20 parts by mass or less, excessive condensation of the organosilanes can be suppressed. Here, the total amount of organosilane compounds refers to the amount including all of the organosilane compounds, their hydrolysates, and their condensates, and the same applies hereinafter.

[0045] The hydrolysis reaction can be carried out in a solvent. The solvent can be appropriately selected taking into consideration the stability, wettability, volatility, etc. of the photosensitive resin composition. Examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Examples of suitable solvents include ethers such as diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; and γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used.

[0046] Among these, from the viewpoints of the transmittance and crack resistance of the cured film, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, γ-butyrolactone, and the like are preferably used.

[0047] When a solvent is produced by the hydrolysis reaction, it is possible to carry out the hydrolysis without a solvent. After the hydrolysis reaction is completed, it is also preferable to add a solvent to adjust the concentration to an appropriate level for the photosensitive resin composition. Alternatively, after the hydrolysis, all or part of the produced alcohol may be distilled and removed by heating and / or under reduced pressure, and then a suitable solvent may be added.

[0048] When a solvent is used in the hydrolysis reaction, the amount of solvent added is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, per 100 parts by mass of all organosilane compounds, from the viewpoint of suppressing gel formation. On the other hand, the amount of solvent added is preferably 500 parts by mass or less, more preferably 200 parts by mass or less, per 100 parts by mass of all organosilane compounds, from the viewpoint of promoting hydrolysis more rapidly. Furthermore, ion-exchanged water is preferred as the water used in the hydrolysis reaction. The amount of water can be set as desired, but is preferably 1.0 to 4.0 moles per mole of all organosilane compounds.

[0049] Examples of methods for the dehydration condensation reaction include heating the silanol compound solution obtained by the hydrolysis reaction of the organosilane compound as is. The heating temperature is preferably 50°C or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. Furthermore, reheating or the addition of a base catalyst may be performed to increase the degree of polymerization of the siloxane resin. Depending on the purpose, after the dehydration condensation reaction, an appropriate amount of the produced alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

[0050] From the viewpoint of storage stability of the photosensitive resin composition, it is preferable that the siloxane resin solution after hydrolysis and dehydration condensation does not contain the catalyst, and the catalyst can be removed as necessary. From the viewpoint of ease of operation and removability, preferred catalyst removal methods include water washing and treatment with an ion exchange resin. Water washing is a method in which the siloxane resin solution is diluted with an appropriate hydrophobic solvent, washed several times with water, and then separated into layers, and the resulting organic layer is concentrated using an evaporator or the like. Ion exchange resin treatment is a method in which the siloxane resin solution is brought into contact with an appropriate ion exchange resin.

[0051] The weight-average molecular weight of the (a) siloxane resin is preferably 1,000 or more, more preferably 2,000 or more, in order to obtain sufficient viscosity. If it is 1,000 or more, the viscosity necessary to control the film thickness when applying the resin composition can be obtained. On the other hand, in order to obtain alkali solubility, the weight-average molecular weight is preferably 50,000 or less, more preferably 20,000 or less. If the weight-average molecular weight is 50,000 or less, the solubility in an alkaline developer necessary for pattern processing can be obtained. Here, the weight-average molecular weight in the present invention refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0052] In the photosensitive resin composition of the present invention, the content of (a) siloxane resin can be set arbitrarily depending on the desired film thickness and application, but is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to 100% by mass of the total solids content of the photosensitive resin composition. Also, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. When it is 10% by mass or more, good pattern processability can be obtained. When it is 80% by mass or less, high storage stability can be obtained. The solid content is the component that remains as a solid when the photosensitive resin composition is thermally cured at 250°C or higher, based on the weight of the photosensitive resin composition.

[0053] (photosensitizer) The photosensitive resin composition of the present invention contains (b) a photosensitizer. The (b) photosensitizer refers to a compound that imparts positive or negative photosensitivity to the composition by undergoing bond cleavage, reaction, or structural change upon exposure to light to generate another compound. The (b) photosensitizer preferably contains one or more compounds selected from the group consisting of (b1) quinone diazide compounds, (b2) photoradical generators, (b3) photoacid generators, and (b4) photobase generators.

[0054] The content of the (b) photosensitizer is preferably 1.0 part by mass or more, based on 100 parts by mass of the total of the (a) siloxane resins, from the viewpoint of improving sensitivity during exposure, while the content of the (b) photosensitizer is preferably 30 parts by mass or less from the viewpoint of suppressing residues after development.

[0055] When the composition is to be imparted with positive photosensitivity, it preferably contains (b1) a quinone diazide compound or (b3) a photoacid generator, and more preferably contains (b1) a quinone diazide compound.When the composition is to be imparted with negative photosensitivity, it preferably contains (b2) a photoradical generator or (b3) a photoacid generator, and more preferably contains (b2) a photoradical generator.

[0056] The (b1) quinone diazide compound undergoes a structural change upon exposure to generate an indene carboxylic acid and / or a sulfoindene carboxylic acid. Therefore, the inclusion of the (b1) quinone diazide compound is suitable for forming positive-tone patterns. During exposure, the acidic compound resulting from the structural change of the (b1) quinone diazide compound selectively solubilizes the exposed areas of the composition film in an alkaline developer, resulting in a significant improvement in resolution after development.

[0057] The quinone diazide compound (b1) is not particularly limited, but is preferably a compound in which a compound having a phenolic hydroxyl group and a naphthoquinone diazide having a sulfonic acid group are bonded to form a sulfonate ester group. Examples of the compound having a phenolic hydroxyl group used herein include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakisP-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, and BisRS -3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (all trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), 4,4'-sulfonyldiphenol (manufactured by Wako Pure Chemical Industries Co., Ltd.), and BPFL (trade name, manufactured by JFE Chemical Corporation).

[0058] Among these, preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F, etc. Among these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F, 4,4'-sulfonyldiphenol, and BPFL. These compounds having a phenolic hydroxyl group are preferably those to which 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid has been introduced via an ester bond.

[0059] (b2) Photoradical generator is a compound that generates radicals by bond cleavage and / or reaction upon exposure. The inclusion of (b2) photoradical generator promotes radical polymerization in exposed areas, making it suitable for negative pattern formation. In particular, when other monomer compounds are included, even if only a small amount of radicals are generated upon exposure, radical polymerization of the monomer compounds etc. proceeds in a chain reaction, resulting in a significant effect of improving sensitivity upon exposure, which is preferable.

[0060] (b2) The photoradical generator is preferably a benzyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a biimidazole compound, a phosphine oxide compound, an oxime ester compound, an acridine compound, a titanocene compound, a benzophenone compound, an acetophenone compound, an aromatic ketoester compound, or a benzoic acid ester compound. From the viewpoint of improving sensitivity during exposure and improving the reliability of the light-emitting device, an α-hydroxyketone compound, an α-aminoketone compound, a biimidazole compound, a phosphine oxide compound, or an oxime ester compound is more preferred, and an oxime ester compound is even more preferred.

[0061] The above-mentioned α-hydroxyketone compounds, α-aminoketone compounds, biimidazole compounds, phosphine oxide compounds, and oxime ester compounds are expected to improve the hardness of the cured film by generating radicals when heated and by facilitating interactions between the hydroxy group, amino group, imidazole structure, phosphine oxide structure, or oxime ester structure, thereby improving the degree of crosslinking in the cured film and promoting the ring-closing reaction of the resin.

[0062] (b3) Photoacid generators are compounds that undergo bond cleavage and / or reaction upon exposure to generate strong acids such as sulfonic acids. The inclusion of (b3) photoacid generators promotes cationic polymerization in exposed areas, making them suitable for negative-tone pattern formation. On the other hand, resins or other materials containing acidic groups protected by acid-dissociable groups are suitable for positive-tone pattern formation because the acidic groups are liberated by exposure, resulting in a significant improvement in sensitivity during exposure.

[0063] (b3) Examples of the photoacid generator include ionic compounds and nonionic compounds. As the ionic compound, a triorganosulfonium salt compound is preferred. As the nonionic compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate ester compound, a carboxylate ester compound, a sulfonimide compound, a phosphate ester compound, or a sulfonebenzotriazole compound is preferred.

[0064] (b4) The photobase generator is a compound that generates a base by bond cleavage and / or reaction upon exposure to light. The inclusion of (b4) the photobase generator is suitable for negative pattern formation from the viewpoint of promoting anionic polymerization, etc.

[0065] (b4) Examples of photobase generators include ionic compounds and nonionic compounds. Preferred ionic compounds are diazabicycloalkene salt compounds, triazabicycloalkene salt compounds, α-keto quaternary ammonium salt compounds, benzyl quaternary ammonium salt compounds, guanidine salt compounds, and biguanide salt compounds. Preferred ionic compounds have a ketoprofen structure, an oxoxanthene structure, a benzofuran structure, or a naphthalene structure. Preferred nonionic compounds are nitrobenzyl carbamate compounds, anthracenyl carbamate compounds, benzoin-based carbamate compounds, anthraquinone-based carbamate compounds, hydroxycinnamamide-based compounds, and coumarinamide-based compounds.

[0066] (Silane compounds containing sulfur atoms) The photosensitive resin composition of the present invention contains (c) a silane compound containing a sulfur atom. (c) The silane compound containing a sulfur atom is a silane compound containing a sulfur atom as a constituent element in the molecule, and the sulfur atom is contained in the silane compound as a functional group represented by general formula (1).

[0067] [ka]

[0068] In general formula (1), X is hydrogen or an organic group having 1 to 18 carbon atoms. The organic group having 1 to 18 carbon atoms may contain, in addition to carbon and hydrogen atoms, an atom selected from silicon, oxygen, sulfur, and nitrogen atoms. * indicates a bond.

[0069] The photosensitive resin composition of the present invention contains (c) a silane compound containing a sulfur atom and (d) an epoxy-containing compound described below, which can improve the substrate adhesion of a cured film of the photosensitive resin composition after immersion in a chemical solution. Furthermore, as described above, the use of (a) a siloxane resin having a polymerizable double bond and excellent swelling resistance can also suppress a decrease in the substrate adhesion of the cured film. In other words, the use of a cured film obtained from the photosensitive resin composition of the present invention can enable the production of a highly reliable display device.

[0070] The reason why the photosensitive resin composition of the present invention exhibits the aforementioned effect of improving substrate adhesion is presumed to be as follows: The functional group represented by chemical formula (1) of the (c) sulfur-containing silane compound reacts with the (d) epoxy-containing compound (described below) through heat treatments such as pre-baking and curing. The partial structure generated by this reaction is thought to have a strong interaction with the substrate, such as a metal, metal oxide, metal nitride, or organic film. Furthermore, if the (c) sulfur-containing silane compound has an alkoxy group, it can form a bond with the (a) siloxane resin through a condensation reaction. In this case, the (c) sulfur-containing silane compound bonds and interacts with both the (a) siloxane resin and the substrate, and therefore, it is presumed that the cured film obtained from the photosensitive resin of the present invention exhibits excellent adhesion to the substrate.

[0071] Furthermore, X in general formula (1) is hydrogen or an organic group having 1 to 18 carbon atoms. When X is hydrogen, general formula (1) represents a thiol group. X is preferably an organic group having 1 to 18 carbon atoms rather than hydrogen. Here, the organic group having 1 to 18 carbon atoms is preferably a protecting group for a thiol group. A protecting group for a thiol group refers to a substituent that does not react at room temperature, but generates a thiol group by elimination (deprotection) under heat treatment conditions such as pre-baking and curing. If X is a protecting group for a thiol group, this is preferable because it can suppress the reaction at room temperature between (c) a silane compound containing a sulfur atom and (d) an epoxy-containing compound, etc., described below, and improve the storage stability of the photosensitive resin composition. From the viewpoints of compatibility with (a) siloxane resin and ease of deprotection, X is more preferably a group represented by the following general formula (3):

[0072] [ka]

[0073] In general formula (3), R V , R VI , R VII are alkyl or alkoxy groups having 1 to 6 carbon atoms, and * indicates a bond to the sulfur atom.

[0074] From the viewpoint of compatibility with siloxane resin and improved adhesion, R V , R VI , R VII is preferably an alkoxy group, because if the protecting group has an alkoxy group, the protecting group liberated from the sulfur atom is bound to and incorporated into the (a) siloxane resin, and is therefore less likely to undergo side reactions with other compounds than a protecting group without an alkoxy group, and does not affect the properties of the photosensitive resin composition.

[0075] Examples of the silane compound having the structure represented by chemical formula (1) include the silane compounds shown below.

[0076] [ka]

[0077] The content of (c) the sulfur atom-containing silane compound is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 1 part by mass or more, relative to 100 parts by mass of the total amount of (a) the siloxane resin. Also, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less. When it is 0.01 parts by mass or more, the effect of improving substrate adhesion can be obtained. When it is 20 parts by mass or less, residues during development can be suppressed.

[0078] In addition, some or all of the (c) sulfur-containing silane compound in the photosensitive resin composition may be incorporated into the (a) siloxane resin by a condensation reaction. When the (c) sulfur-containing silane compound and the (a) siloxane resin are mixed in a solvent and allowed to stand at low temperature for a long period of time, the (c) sulfur-containing silane compound may bond with the (a) siloxane resin by a condensation reaction. The chemical species produced by such a condensation reaction may be the (c) sulfur-containing silane compound.

[0079] (compounds containing epoxy groups) The photosensitive resin composition of the present invention contains (d) a compound containing an epoxy group. As described above, (d) the epoxy-containing compound reacts with (c) a silane compound containing a sulfur atom by heat treatment such as pre-baking or curing. The chemical species generated by this reaction have a strong interaction with the surface of the substrate.

[0080] (d) Examples of compounds containing an epoxy group include 2-(3,4-epoxycyclohexyl)trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, n-butyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, Glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, water Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol A bis(propylene glycol glycidyl ether) ether, hydrogenated bisphenol A bis(ethylene glycol glycidyl ether) ether, epoxycyclohexane, 1,4-cyclohexanedicarboxylate diglycidyl, 1,4-cyclohexanedimethanol diglycidyl ether, 3,4-epoxycyclohexylmethyl, (3,4-epoxycyclohexyl)methyl acrylate, bis(2,3-epoxypropyl) sulfide, bis (2,3-epoxypropyl) disulfide, bis(2,3-epoxypropylthio)methane, 1,2-bis(2,3-epoxypropylthio)ethane, 1,2-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)propane, 1,3-bis(2,3-epoxypropylthio)-2-methylpropane, 1,4-bis(2,3-epoxypropylthio)butane, 1,4-bis(2,3-epoxypropylthio)-2-methylbutane, 1,3-bis(2,3-epoxypropylthio)butane, 1,5-bis(2,1,5-bis(2,3-epoxypropylthio)pentane, 1,5-bis(2,3-epoxypropylthio)-2-methylpentane, 1,5-bis(2,3-epoxypropylthio)-3-thiapentane, 1,6-bis(2,3-epoxypropylthio)hexane, 1,6-bis(2,3-epoxypropylthio)-2-methylhexane, 3,8-bis(2,3-epoxypropylthio)-3,6-dithiaoctane, 1,2,3-tris(2,3-epoxypropylthio)propane, 2,2-bis(2,3-epoxypropylthio)-1,3-bis(2,3-epoxypropylthio) 1,5-bis(2,3-epoxypropylthio)-2-(2,3-epoxypropylthiomethyl)-3-thiapentane, 1,5-bis(2,3-epoxypropylthio)-2,4-bis(2,3-epoxypropylthiomethyl)-3-thiapentane, 1-(2,3-epoxypropylthio)-2,2-bis(2,3-epoxypropylthiomethyl)-4-thiahexane, 1,5,6-tris(2,3-epoxypropylthio) )-4-(2,3-epoxypropylthiomethyl)-3-thiahexane, 1,8-bis(2,3-epoxypropylthio)-4-(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(2,3-epoxypropylthio)-4,5-bis(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(2,3-epoxypropylthio)-4,4-bis(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(2,3-epoxypropylthio)-2,5-bis(2,3-epoxypropylthiomethyl) propylthiomethyl)-3,6-dithiaoctane, 1,8-bis(2,3-epoxypropylthio)-2,4,5-tris(2,3-epoxypropylthiomethyl)-3,6-dithiaoctane, 1,1,1-tris[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]-2-(2,3-epoxypropylthio)ethane, 1,1,2,2-tetrakis[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]ethane, 1,11-bis(2,3-epoxypropylthio)-4,8-bis(2,3-epoxypropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(2,3-epoxypropylthio)-4,7-bis(2,3-epoxypropylthiomethyl)-3,6,9-trithiaundecane, 1,11-bis(2,3-epoxypropylthio)-5,7-bis(2,3-epoxypropylthiomethyl)-3,6,9-trithiaundecane, 1,3-bis(2,3-epoxypropylthio)cyclohexane, 1,4-bis(2,3-epoxypropylthio)cyclohexane, 1,3-bis(2,3-epoxypropylthiomethyl)cyclohexane, 1,4-bis(2,3-epoxypropylthiomethyl)cyclohexane, 2,5-bis(2,3-epoxypropylthiomethyl)-1,4-dithiane, 2,5-bis[[2-(2,3-epoxypropylthio)ethyl]thiomethyl]-1,4-dithiane, 2,5-bis(2,3-epoxypropylthiomethyl)-2,5-dimethicone Examples of bis(2,3-epoxypropylthio)phenyl include 1,4-dithiane, 1,2-bis(2,3-epoxypropylthio)benzene, 1,3-bis(2,3-epoxypropylthio)benzene, 1,4-bis(2,3-epoxypropylthio)benzene, 1,2-bis(2,3-epoxypropylthiomethyl)benzene, 1,3-bis(2,3-epoxypropylthiomethyl)benzene, 1,4-bis(2,3-epoxypropylthiomethyl)benzene, bis[4-(2,3-epoxypropylthio)phenyl]methane, 2,2-bis[4-(2,3-epoxypropylthio)phenyl]propane, bis[4-(2,3-epoxypropylthio)phenyl]sulfide, bis[4-(2,3-epoxypropylthio)phenyl]sulfone, 4,4'-bis(2,3-epoxypropylthio)biphenyl, and 1,6-bis(2',3'-epoxypropyl)perfluoro-n-hexane.

[0081] From the viewpoint of further improving adhesion, it is more preferable that the compound containing an epoxy group (d) is a silane compound containing an epoxy group. Examples of silane compounds containing an epoxy group include the above-mentioned (d) compounds containing an epoxy group, such as 2-(3,4-epoxycyclohexyl)trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylethyldimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. Some or all of these epoxysilanes may be incorporated into the (a) siloxane resin by a condensation reaction.

[0082] The content of the (d) epoxy group-containing compound is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 1 part by mass or more, relative to 100 parts by mass of the total amount of the (a) siloxane resin. Also, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less. If it is 0.01 parts by mass or more, the effect of improving substrate adhesion can be obtained. Also, if it is 20 parts by mass or less, a cured film with good resolution in pattern processing can be obtained.

[0083] (Particles with a median diameter of 100 to 400 nm) The photosensitive resin composition of the present invention may contain (e) particles having a median diameter of 100 to 400 nm. By containing (e) particles having a median diameter of 100 to 400 nm in the cured film, optical functions can be imparted. For example, imparting reflectivity can reflect light from a light source, thereby improving the light extraction efficiency of a display.

[0084] The photosensitive resin composition of the present invention may contain (e) particles having a median diameter of 100 to 400 nm either as part of the particle-containing siloxane resin or as particles having a median diameter of 100 to 400 nm added to the photosensitive resin composition. The photosensitive resin composition of the present invention may contain both the particle-containing siloxane resin and the particles having a median diameter of 100 to 400 nm, or it may contain only particles having a median diameter of 100 to 400 nm without containing the particle-containing siloxane resin.

[0085] Examples of materials for (e) particles having a median diameter of 100 to 400 nm include titanium dioxide, zirconium oxide, zinc oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, barium carbonate, silica, vanadium oxide, chromium oxide, iron oxide, cobalt oxide, copper oxide, zinc oxide, niobium oxide, tin oxide, cerium oxide, and composite compounds thereof. Two or more of these may be contained. From the viewpoint of light reflectivity, preferred (e) particles having a median diameter of 100 to 400 nm include particles containing a compound selected from titanium oxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc oxide, barium carbonate, and composite compounds thereof. Among these, particles containing one or more selected from titanium oxide, zinc oxide, and zirconium oxide are preferred because of their high light reflectivity and ease of industrial use, and titanium oxide particles are most preferred.

[0086] The content of (e) particles having a median diameter of 100 to 400 nm is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more, relative to 100% by mass of the total solids content of the photosensitive resin composition. If it is 5% by mass or more, light reflectivity can be obtained. Furthermore, it is preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. If it is 90% by mass or less, residues during development can be suppressed. The content ratio of (e) particles having a median diameter of 100 to 400 nm refers to the sum of (e) particles having a median diameter of 100 to 400 nm in the particle-containing siloxane resin and (e) particles having a median diameter of 100 to 400 nm added to the photosensitive resin composition.

[0087] Furthermore, the particle size of (e) particles having a median diameter of 100 to 400 nm is preferably 200 to 400 nm, and more preferably 250 to 350 nm. If the median diameter is 100 nm or more, good light reflectivity of the cured film can be obtained, and if the median diameter is 400 nm or less, patterning of the thin film becomes easy.

[0088] (solvent) The photosensitive resin composition of the present invention may contain a solvent. By containing a solvent, the viscosity of the photosensitive resin composition can be easily adjusted to a value suitable for application, thereby improving the uniformity of the coated film. The solvent may be one type or a mixture of two or more types. It is preferable to combine a solvent having a boiling point of more than 150°C and not more than 250°C at atmospheric pressure with a solvent having a boiling point of not more than 150°C at atmospheric pressure. By containing a solvent having a boiling point of more than 150°C and not more than 250°C at atmospheric pressure, the solvent volatilizes appropriately during application, promoting drying of the coated film, thereby suppressing coating unevenness and improving film thickness uniformity. Furthermore, by containing a solvent having a boiling point of not more than 150°C at atmospheric pressure, residual solvent in the cured film can be suppressed, improving the hardness of the cured film. It is preferable that the solvent having a boiling point of not more than 150°C at atmospheric pressure be contained in 50% by mass or more of the total solvent.

[0089] Examples of solvents having a boiling point of 150°C or less under atmospheric pressure include ethanol, isopropyl alcohol, 1-propyl alcohol, 1-butanol, 2-butanol, isopentyl alcohol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, methoxymethyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, acetol, acetylacetone, methyl isobutyl ketone, methyl ethyl ketone, methyl propyl ketone, methyl lactate, toluene, cyclopentanone, cyclohexane, normal heptane, benzene, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2-pentanone. Two or more of these may be used.

[0090] Examples of solvents having a boiling point under atmospheric pressure of more than 150 ° C. and not more than 250 ° C. include ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-tert-butyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 2-ethoxyethyl acetate, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, diisobutyl ketone, diacetone alcohol, ethyl lactate, butyl lactate, dimethylformamide, dimethylacetamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, diethylene glycol monobutyl ether, and ethylene glycol dibutyl ether. Two or more of these may be used.

[0091] The content of the solvent can be set arbitrarily depending on the application method, etc. For example, when forming a film by spin coating, the content of the solvent in the photosensitive resin composition is generally set to 50% by mass or more and 95% by mass or less.

[0092] (Crosslinking agent) The photosensitive resin composition of the present invention may contain a crosslinking agent. A crosslinking agent refers to a compound having a crosslinkable group, a cationically polymerizable group, or an anionically polymerizable group capable of reacting with a resin or the like. Addition of a crosslinking agent increases the crosslink density in the cured film of the photosensitive resin composition, and is expected to improve hardness and swelling resistance after immersion in a chemical solution. From the viewpoint of improving sensitivity during exposure and reliability of the light-emitting device, the crosslinking agent is preferably a compound having one or more crosslinkable groups selected from the group consisting of alkoxyalkyl groups, hydroxyalkyl groups, epoxy groups, oxetanyl groups, and blocked isocyanate groups (hereinafter referred to as "specific crosslinkable groups"). As the alkoxyalkyl group, an alkoxymethyl group is preferred, and a methoxymethyl group is more preferred. As the hydroxyalkyl group, a methylol group is preferred. Other examples of crosslinking agents include silicone resin curing agents, various metal alkoxylates, and various metal chelate compounds. Two or more of these may be contained.

[0093] From the viewpoint of improving sensitivity during exposure, the number of specific crosslinkable groups in the crosslinking agent is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 6 or more per molecule. On the other hand, from the viewpoint of improving reliability of the light-emitting device, the number of specific crosslinkable groups in the crosslinking agent is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less per molecule.

[0094] The content of the crosslinking agent is preferably 1.0% by mass or more relative to 100% by mass of the total solid content of the photosensitive resin composition from the viewpoint of improving sensitivity during exposure, and is preferably 30% by mass or less from the viewpoint of suppressing residues after development.

[0095] (Radical polymerizable compound) The photosensitive resin composition of the present invention may contain a radically polymerizable compound in addition to the (a) siloxane resin. The radically polymerizable compound refers to a compound having a radically polymerizable group. The radically polymerizable group preferably has an ethylenically unsaturated double bond group. Examples of the radically polymerizable group include a styryl group, a cinnamoyl group, a maleimide group, a nadimide group, a (meth)acryloyl group, a vinyl group, an allyl group, a 2-methyl-2-propenyl group, a crotonyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a 2,3-dimethyl-2-butenyl group, an ethynyl group, and a 2-propargyl group.

[0096] The radical polymerizable group is preferably a (meth)acryloyl group from the viewpoints of promoting radical polymerization, improving sensitivity during exposure, and improving the reliability of the light-emitting device. The number of radical polymerizable groups possessed by the radical polymerizable compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more per molecule from the viewpoints of improving sensitivity during exposure and improving the reliability of the light-emitting device. On the other hand, the number of radical polymerizable groups is preferably 12 or less, more preferably 10 or less, even more preferably 8 or less, and particularly preferably 6 or less per molecule from the viewpoint of improving the reliability of the light-emitting device.

[0097] The content of the radical polymerizable compound is preferably 15% by mass or more relative to 100% by mass of the total solid content of the photosensitive resin composition from the viewpoints of reducing the taper of the pattern shape and improving the reliability of the light-emitting device, and is preferably 75% by mass or less from the viewpoints of improving the sensitivity during exposure and suppressing residues after development.

[0098] (surfactant) The photosensitive resin composition of the present invention may contain a surfactant. The inclusion of a surfactant can improve flow properties during application. Examples of surfactants include fluorine-based surfactants such as "Megafac" (registered trademark) F142D, F172, F173, F183, F445, F470, F475, and F477 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), NBX-15, and FTX-218 (all trade names, manufactured by Neos Corporation); silicone-based surfactants such as "Disperbyk" (registered trademark) 333, 301, 331, 345, and 207 (all trade names, manufactured by BYK-Chemie Corporation); polyalkylene oxide-based surfactants; and poly(meth)acrylate-based surfactants. The composition may contain two or more of these surfactants.

[0099] (Silane coupling agent) The photosensitive resin composition of the present invention may contain a silane coupling agent other than the (c) sulfur-atom-containing silane compound. The inclusion of a silane coupling agent can prevent peeling during development and further improve adhesion. Examples of silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-trimethoxysilylpropyl succinic acid, and N-(t-butyl)-3-(3-trimethoxysilylpropyl)succinimide.

[0100] (Other additives) The photosensitive resin composition of the present invention may further contain, as necessary, a thermal color former, an oxidative color former, a dissolution promoter, a dissolution inhibitor, an adhesion improver, a stabilizer, an antifoaming agent, an ink repellent, a sensitizer, a chain transfer agent, a polymerization inhibitor, etc. Known additives may be used as these additives.

[0101] The solid content concentration of the photosensitive resin composition of the present invention can be set arbitrarily depending on the application method, etc. For example, when forming a film by spin coating as described below, the solid content concentration is generally set to 5% by mass or more and 50% by mass or less.

[0102] (Method for producing photosensitive resin composition) Next, a method for producing the photosensitive resin composition of the present invention will be described.

[0103] The photosensitive resin composition of the present invention can be obtained by mixing the aforementioned (a) siloxane resin, (b) photosensitizer, (c) sulfur atom-containing silane compound, (d) epoxy group-containing compound, and, if necessary, (e) particles with a median diameter of 100 to 400 nm and other components.

[0104] More specifically, for example, a method can be used in which (b) a photosensitizer and, if necessary, materials selected from (c) a silane compound containing a sulfur atom, (d) a compound containing an epoxy group, and other additives are added to any solvent and stirred to dissolve, and then (a) a siloxane resin is added, followed by stirring for a further 20 minutes to 3 hours, and the resulting solution is filtered.

[0105] (cured film) Next, the cured film of the present invention will be described. The cured film of the present invention is made of a cured product of the photosensitive resin composition of the present invention. There are no particular restrictions on the thickness of the cured film, but it is preferably 0.1 to 30 μm.

[0106] The cured film of the present invention can be obtained, for example, by applying the above-described photosensitive resin composition of the present invention in the form of a film to form a coating film, patterning the coating film as necessary, and then curing the coating film.

[0107] The coating film is preferably formed by applying the photosensitive resin composition of the present invention onto a substrate. Examples of the coating method for applying the photosensitive resin composition onto a substrate include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating.

[0108] After forming the coating film, it is preferable to pre-bake the coating film before patterning. Examples of pre-baking devices include heating devices such as hot plates and ovens. The pre-baking temperature is preferably 50 to 130°C, and the pre-baking time is preferably 30 seconds to 30 minutes. If the pre-baking temperature is 50°C or higher or the pre-baking time is 30 seconds or longer, film loss during patterning can be suppressed. Furthermore, if the pre-baking temperature is 130°C or lower or the pre-baking time is 30 minutes or less, excessive condensation of the siloxane resin is suppressed, and resolution during patterning is improved.

[0109] The thickness of the coating film after pre-baking is preferably 0.1 to 50 μm. If the thickness is 0.1 μm or more, peeling of the film during development can be suppressed, and if it is 50 μm or less, light rays during exposure can easily penetrate deep into the film, resulting in high resolution in pattern processing.

[0110] After pre-baking, a positive or negative pattern is formed by exposure and development. The exposure may be performed through a desired mask or without a mask. Examples of exposure devices include a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (PLA). The exposure intensity is 10 to 40,000 mJ / cm. 2 (converted into exposure dose at a wavelength of 365 nm) Examples of exposure light sources include mercury lamps (h-line, g-line, i-line, etc.), KrF lasers (wavelength 248 nm), and ArF lasers (wavelength 193 nm).

[0111] Examples of the development method include showering, dipping, and puddling. The immersion time in the developer is preferably 5 seconds to 10 minutes. Examples of the developer include alkaline developers such as inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and aqueous solutions containing quaternary ammonium salts such as tetramethylammonium hydroxide and choline. After development, the film is preferably rinsed with water, and can be subsequently dry baked at a temperature in the range of 50 to 130°C.

[0112] Re-exposure may be performed after development. As a method of re-exposure, a UV-visible exposure device such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA) is used at 100 to 200,000 mJ / cm. 2 It is preferable to expose the entire surface with an exposure intensity of about 1000 nm (equivalent to the exposure dose at a wavelength of 365 nm).

[0113] The coated film after pattern formation is thermally cured. Examples of heating devices used for thermal curing include a hot plate and an oven. The thermal curing temperature is preferably 80 to 300°C, and the thermal curing time is preferably about 15 minutes to 2 hours. If the thermal curing temperature is 80°C or higher or the thermal curing time is 15 minutes or longer, a cured film with high hardness can be obtained. If the thermal curing temperature is 200°C or lower or the thermal curing time is 2 hours or shorter, thermal decomposition of chemical species in the cured film can be suppressed.

[0114] (display device) Next, the display device of the present invention will be described.

[0115] The display device of the present invention comprises the cured film of the present invention. Examples of the display device include a liquid crystal display, an organic electroluminescence display, a quantum dot display, a mini LED display, and a micro LED display. Here, a mini LED display refers to a display device having a light source in which many LEDs with vertical and horizontal lengths of 100 μm to 10 mm are arranged. A micro LED display refers to a display device having a light source in which many LEDs with vertical and horizontal lengths of less than 100 μm are arranged.

[0116] The cured film of the present invention is suitable for use as a pixel dividing layer, a TFT planarizing layer, a TFT protective layer, a TFT interlayer insulating layer, or a gate insulating layer in display devices such as liquid crystal displays, organic EL displays, quantum dot displays, mini LED displays, and micro LED displays.

[0117] The substrates used in the display device of the present invention are mainly Cu substrates, SiO2 substrates, SiN substrates, alumina substrates, and the like.

[0118] The photosensitive resin composition of the present invention is also preferably used to form a barrier layer or a planarizing layer in a micro LED display or a mini LED display. A barrier layer is a layer formed between adjacent light-emitting elements in a display device and has the function of separating the light-emitting elements. The barrier layer preferably has light reflectivity to improve the light extraction efficiency of the display. In order to obtain light reflectivity, the barrier layer preferably contains the above-mentioned (e) particles having a median diameter of 100 to 400 nm.

[0119] The planarization layer is a layer formed to cover at least a part of the light-emitting element in order to flatten out irregularities that occur during the manufacturing process of the display device. From the viewpoint of flatness, the planarization layer preferably does not contain the (e) particles having a median diameter of 100 to 400 nm.

[0120] The display device of the present invention will be described below with reference to the drawings, but the display device of the present invention is not limited to this embodiment.

[0121] FIG. 1 is an example of a schematic cross-sectional view of a micro LED display having a barrier layer and a planarization layer.

[0122] The display device 1 has wiring 4 and an interlayer insulating layer 3 on a drive substrate 8, and has a plurality of light-emitting elements 2 and a partition layer 11 on top of that. The drive substrate 8 can be a TFT substrate provided with TFTs for driving the display. A planarization layer 21 is provided so as to cover the light-emitting elements 2. Here, "covering the light-emitting elements 2" means that the planarization layer 21 covers at least the side surfaces of the light-emitting elements 2, but the planarization layer 21 may also cover the upper side of the light-emitting elements 2. A wiring layer 7 that constitutes a touch panel or the like is provided on the planarization layer 21, and a counter substrate 5 is provided on top of that. The light extraction side of the display device 1 is the side of the counter substrate 5 when viewed from the light-emitting elements 2.

[0123] In the embodiment shown in FIG. 1 , a partition layer 11 is provided between adjacent light-emitting elements 2, and a planarization layer 21 is formed to cover the light-emitting elements 2. While the illustrated configuration shows an interlayer insulating layer 3 made up of multiple layers stacked below the planarization layer, the interlayer insulating layer 3 may be a single layer. The light-emitting elements 2 are preferably LED chips. The light-emitting elements 2 are provided with a pair of electrode terminals 6 facing the drive substrate 8, and each electrode terminal 6 is electrically connected to the planarization layer 21 and the wiring 4 in the interlayer insulating layer 3. When the wiring 4 is covered by the planarization layer 21 or the interlayer insulating layer 3, these layers function as insulating films, thereby maintaining electrical insulation. The term "metal wiring maintaining electrical insulation" refers to the fact that the portions of the metal wiring that require electrical insulation are covered with a cured film formed by curing a resin-containing composition.

[0124] A preferred method for manufacturing such a display device 1 is to use an RDL-first (Chip-last) structure in which wiring 4 and an interlayer insulating layer 3 are formed on a separately prepared support substrate, and then the light-emitting elements 2 are arranged on the support substrate. After that, the support substrate is peeled off, and then a drive substrate 8 is bonded to the interlayer insulating layer 3, and then a wiring layer 7 is arranged, and then an opposing substrate 5 is bonded.

[0125] The light-emitting element 2 is preferably a PN junction diode in which a P-type semiconductor and an N-type semiconductor are joined. The light-emitting element 2 preferably has a side length of 1 to 700 μm, more preferably 2 to 100 μm. The interlayer insulating layer 3, the partition layer 11, and the planarizing layer 21 are preferably cured films of a patterned photosensitive resin composition. A configuration in which the thickness of the planarizing layer 21 is greater than the thickness of the partition layer 11 is also preferred. A configuration in which the planarizing layer 21 covers a portion of the surface of the partition layer 11 opposite to the surface facing the counter substrate 5 is also preferred, and a configuration in which the planarizing layer 21 covers the entire surface of the partition layer 11 opposite to the surface facing the counter substrate 5 is more preferred. From the viewpoint of improving reliability, the partition layer 11 and the planarizing layer 21 are preferably the cured film of the present invention. From the viewpoint of improving luminance of light emitted from a display device, the partition layer 11 preferably contains the above-mentioned (e) particles having a median diameter of 100 to 400 nm. (Information terminal) An information terminal is an electronic device whose main functions include inputting, outputting, storing, processing, and transmitting information, and if it has a display device, it outputs information such as pictures and text to the display device. The information terminal of the present invention is equipped with the display device of the present invention as its display device. Examples of information terminals include mobile phones such as smartphones, tablet devices, TVs, PCs, digital signage, game consoles, AR / VR devices, watches, portable music players, and calculators. [Example]

[0126] The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. First, measurements, evaluations, tests, etc. carried out in the following examples and comparative examples will be described.

[0127] (Item 1: Evaluation of swelling resistance of cured film after immersion in chemical solution) For the laminate of the cured film and alumina substrate obtained in each example, the film thickness T1 of the cured film was measured using a stylus film thickness meter (product name SURFCOM 1500DX, manufactured by Tokyo Seimitsu Co., Ltd.). The laminate of the cured film and alumina substrate was then immersed in a resist stripping solution (a mixed solution of monoethanolamine and diethylene glycol monobutyl ether) at 50°C for 120 seconds. After rinsing with pure water, the film thickness T2 was measured again. The film thickness change rate was calculated from T1 and T2 using the following formula: Film thickness change rate (%) = (T2 / T1-1) x 100 Based on this rate of change in film thickness, the swelling resistance was evaluated according to the following criteria. A: Film thickness change rate is less than 0.5% B: Film thickness change rate is 0.5% or more and less than 3% C: Film thickness change rate is 3% or more and less than 5% D: Film thickness change rate is 5% or more and less than 10% E: Film thickness change rate is 10% or more but less than 15% F: Film thickness change rate is 15% or more (Item 2: Evaluation of substrate adhesion after immersion of cured film in chemical solution) Next, for each laminate treated with the resist stripper described above, substrate adhesion after immersion in the chemical solution was evaluated using the following method in accordance with JIS K5600-5-6 (established April 20, 1999). Eleven parallel lines, each perpendicular to each other, were drawn at 1 mm intervals on the cured film of each laminate using a utility knife to create 100 1 mm x 1 mm grids. Cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) was applied to the surface of the cured film and rubbed with an eraser (JIS S6050 compliant) to adhere the tape to the cured film. Then, one end of the tape was held and peeled off while maintaining a right angle between the tape and the laminate. The number of peeled and remaining grids was visually counted. Substrate adhesion was evaluated based on the peeled area of ​​the grids according to the following criteria. A rating of C or lower was deemed unsuitable due to reduced reliability of the display device containing the cured film. A: Peeling area is 0% B: Peeling area is 1% or more but less than 5% C: Peeled area is 5% or more but less than 15% D: Peeled area is 15% or more but less than 35% E: Peeling area is 35% or more but less than 65% F: Peeling area is 65% or more.

[0128] (Item 3: Evaluation of storage stability of resin composition) The storage stability of the photosensitive resin compositions prepared in each example was evaluated. Specifically, a line-and-space pattern with a line width of 20 μm was processed using the photosensitive resin composition after 7 days of frozen storage after preparation, and the residue in the patterned area was evaluated. As an index, the area occupied by the residue in the opening was calculated, and the storage stability was evaluated from the area of ​​the residue according to the following criteria. A: Residue area is less than 1% B: Residue area is 1% or more but less than 3% C: Residue area is 3% or more but less than 5% D: Residue area is 5% or more but less than 20% E: Residue area is 20% or more (Item 4: Display luminescence evaluation) The micro LED displays obtained in each example were subjected to voltage application via the driving substrate to emit light. At this time, the number of non-emitting LED chips was observed, and the ratio of non-emitting chips to the total LED chips was calculated and evaluated as follows: A. Non-luminous ratio is 0% B. Non-luminous ratio is greater than 0% and less than 1% C. Non-luminescent ratio is 1% or more but less than 3% D. Non-luminous ratio is 3% or more but less than 10% E. Non-luminous ratio is 10% or more.

[0129] (Item 5: Display reliability evaluation) The micro LED display fabricated by the method described in Example 1 below was allowed to emit light, and the light extraction efficiency was measured as an index of luminance using an external quantum efficiency measurement device (Hamamatsu Photonics; C9920). Next, the display was subjected to high temperature and high humidity treatment by leaving it in an environment of 85°C and 85% RH for 7 days, after which the light extraction efficiency was measured again. The initial light extraction efficiency was set to 1.00, and the relative value of the light extraction efficiency after the high temperature and high humidity treatment was calculated and evaluated as follows: A: The relative value of light extraction efficiency is 0.95 or more B: The relative value of the light extraction efficiency is 0.80 or more and less than 0.95 C: The relative value of the light extraction efficiency is 0.70 or more and less than 0.80 D: The relative value of light extraction efficiency is 0.50 or more and less than 0.70 E: The relative value of the light extraction efficiency is less than 0.50.

[0130] <Compound> In the examples and comparative examples, the compounds shown below are used as appropriate. and their abbreviations are as follows: MeTMS: methyltrimethoxysilane StTMS: 4-styryltrimethoxysilane PhTMS: phenyltrimethoxysilane SucTMS: (3-trimethoxysilyl)propylsuccinic anhydride MerTMS: 3-mercaptopropyltrimethoxysilane Promer TMS: O,O,O-triethyl S-[3-(trimethoxysilyl)propyl] ester thiosilicic acid EpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane MacTMS: 3-methacryloxypropyltrimethoxysilane ViTMS: vinyltrimethoxysilane BDD: 1,4-butanediol diglycidyl ether (product name "BD(D)", manufactured by Yokkaichi Chemical Co., Ltd.) TEOS: Tetraethoxysilane PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol BHT: Dibutylhydroxytoluene PGE: Phenyl glycidyl ether PTT: p-toluenethiol NQD: A compound containing a naphthoquinone diazide skeleton represented by chemical formula (6) The structures of the compounds used in each of the Examples and Comparative Examples are shown below.

[0131] [ka]

[0132] [ka]

[0133] The weight-average molecular weights of the siloxane resins and acrylic resins in the following synthesis examples were determined by the following method. GPC analysis was performed using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) in accordance with JIS K7252-3 (established on March 20, 2008) to measure the weight-average molecular weights in terms of polystyrene. Tetrahydrofuran was used as the mobile phase for the siloxane resins and acrylic resins.

[0134] The content ratio of each repeating unit in the polysiloxane in Synthesis Examples 1, 2, and 3 was determined by the following method. The polysiloxane solution was poured into an NMR sample tube made of "Teflon" (registered trademark) with a diameter of 10 mm. 29 Si-NMR measurements were performed, and the content ratio of each repeating unit was calculated from the ratio of the integral value of Si derived from a specific organosilane to the integral value of all Si derived from organosilanes. 29 The Si-NMR measurement conditions are as follows: Equipment used: Nuclear magnetic resonance equipment (ECZ-600R (manufactured by JEOL Ltd.)) Measurement method: Single pulse with inverse gated 1h decoupling Measurement frequency: 119.2MHz Pulse width: 5.0 μs Lock solvent: DMSO-d6 Chemical shift reference: Tetramethylsilane (TMS) (0 ppm) Observation range: -200 to 100 ppm Accumulation count: 4800 times Measurement temperature: room temperature (about 20~21℃) Number of data points: 32768 Waiting time: 10 seconds Sample rotation speed: 15Hz <Synthesis example> (Synthesis Example 1) In a 500 ml three-neck flask, under a dry nitrogen stream, 51.76 g (0.38 mol) of MeTMS, 112.15 g (0.50 mol) of StTMS, 14.82 g (0.1 mol) of ViTMS, 5.25 g (0.02 mol) of SucTMS, 156.97 g of PGMEA, and 1.27 g of BHT (1 part by mass per 100 parts by mass of silane monomer containing a polymerizable double bond) were charged, and while stirring at room temperature, an aqueous phosphoric acid solution prepared by dissolving 0.184 g of phosphoric acid in 54.36 g of water (0.10 parts by mass per 100 parts by mass of total silane monomers) was added over 30 minutes. Then, the three-neck flask was immersed in a 70 ° C. oil bath and stirred for 60 minutes, after which the oil bath was heated to 120 ° C. over 30 minutes. One hour after the start of the temperature increase, the internal temperature (solution temperature) of the three-neck flask reached 100°C. The mixture was then heated and stirred for two hours (internal temperature 100-110°C) to obtain a siloxane resin solution. During the reaction, a total of 135.43 g of by-products, methanol and water, was distilled. PGMEA was added to the resulting siloxane resin solution to adjust the solids concentration to 40% by mass, yielding a siloxane resin solution. The weight-average molecular weight of the resulting siloxane resin (P-1) was 2,000. The molar ratios of the repeating units derived from MeTMS, StTMS, ViTMS, and SucTMS in the siloxane resin (P-1) were 38 mol%, 50 mol%, 10 mol%, and 2 mol%, respectively. (Synthesis Example 2) A 500 ml three-neck flask was charged with 17.71 g (0.13 mol) of MeTMS, 99.15 g (0.50 mol) of PhTMS, 86.94 g (0.35 mol) of MacTMS, 5.25 g (0.02 mol) of SucTMS, 191.13 g of PGMEA, and 0.87 g of BHT (1 part by mass per 100 parts by mass of silane monomer containing a polymerizable double bond). While stirring at room temperature, an aqueous solution of phosphoric acid (1.045 g of phosphoric acid dissolved in 56.70 g of water, 0.50 parts by mass per 100 parts by mass of total silane monomer) was added over 30 minutes. The procedure was then repeated as in Synthesis Example 1, yielding a siloxane resin solution with a solids concentration of 40% by mass. The weight-average molecular weight of the resulting polysiloxane (P-2) was 4,000. In addition, the molar ratios of repeating units derived from MeTMS, PhTMS, MacTMS, and SucTMS in the siloxane resin (P-2) were 13 mol %, 50 mol %, 35 mol %, and 2 mol %, respectively. (Synthesis Example 3) In a 500 ml three-neck flask, under a dry nitrogen stream, 47.67 g (0.35 mol) of MeTMS, 99.15 g (0.50 mol) of PhTMS, 13.12 g (0.05 mol) of SucTMS, 20.83 g (0.10 mol) of TEOS, and 165.55 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution prepared by dissolving 0.904 g of phosphoric acid in 56.70 g of water (0.50 parts by weight per 100 parts by weight of total silane monomers) was added over 30 minutes. The procedure thereafter was the same as in Synthesis Example 1, resulting in a siloxane resin solution with a solids concentration of 40% by weight. The weight-average molecular weight of the resulting siloxane resin (P-3) was 4,100. In addition, the molar ratios of repeating units derived from MeTMS, PhTMS, SucTMS, and TEOS in the siloxane resin (P-3) were 35 mol %, 50 mol %, 5 mol %, and 10 mol %, respectively.

[0135] (Synthesis Example 4) A 500 ml flask was charged with 2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) and 150 g of PGMEA under a dry nitrogen stream. Then, 34.43 g (0.40 mol) of methacrylic acid, 26.69 g (0.27 mol) of methyl methacrylate, 56.85 g (0.40 mol) of glycidyl methacrylate, and 32.03 g (0.27 mol) of 4-hydroxystyrene were charged and heated with stirring at 70 °C for 5 hours. PGMEA was added to the resulting acrylic resin solution to adjust the solids concentration to 40% by mass, yielding an acrylic resin solution. The weight-average molecular weight of the resulting acrylic resin (P-4) was 15,000.

[0136] The resins obtained in Synthesis Examples 1 to 3 are shown in Table 1.

[0137] [Table 1]

[0138] <Preparation of Photosensitive Resin Composition> Compositions 1 to 15 were prepared by mixing the components according to the formulations listed in Table 2. In Table 2, the values ​​in parentheses indicate the parts by mass of each component. When a composition contained particles, a preparation not containing the particle dispersion was first prepared, and then the particle dispersion was mixed with the preparation to prepare the composition. The particle dispersion was prepared by mixing 50.00 g of titanium dioxide (R-960; manufactured by DuPont (SiO2 / Al2O3 surface treatment, median diameter 0.21 μm)) with 100.00 g of the siloxane resin solution used in each composition, and dispersing the mixture using a mill-type disperser filled with zirconia beads. The resulting composition solution was filtered through a 0.45 μm diameter filter before use.

[0139] <Example> Example 1 Composition 1, a photosensitive resin composition, was spin-coated onto an alumina substrate (a glass substrate on which an alumina film had been formed by sputtering) using a spin coater (product name 1H-360S, manufactured by Mikasa Co., Ltd.), and the coating was pre-baked at 100°C for 2 minutes using a hot plate (product name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.) to form a coating film with a thickness of 1.0 μm.

[0140] The prepared coating film was exposed to light by contact using a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as the light source through a grayscale mask having line and space patterns of 50 μm, 40 μm, 30 μm, 20 μm, 15 μm, 10 μm, 7 μm, 5 μm, and 4 μm widths. Then, using an automatic developing apparatus (manufactured by Takizawa Sangyo Co., Ltd., "AD-2000 (trade name)"), the film was shower-developed for 120 seconds with a 2.38 wt% tetramethylammonium hydroxide (hereinafter abbreviated as "TMAH") aqueous solution (trade name "ELM-D", manufactured by Mitsubishi Gas Chemical Co., Inc.), followed by rinsing with water for 30 seconds. The resulting developed film was bleached using a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) at an exposure dose of 1000 mJ / cm. 2 The film was exposed to 1000 kJ / cm² (equivalent to i-line radiation) and cured in an oven (IHPS-222, manufactured by Espec Corporation) at 170°C for 30 minutes in a nitrogen atmosphere to produce a cured film. The resulting cured film on the substrate was evaluated for swelling resistance and substrate adhesion after immersion in liquid as described above. The storage stability of the resin composition was also evaluated from the patterned portion of the cured film.

[0141] (Examples 2 to 7 and Comparative Examples 1 to 7) Examples 2 to 7 and Comparative Examples 1 to 7 were evaluated in the same manner as Example 1, except that the photosensitive resin composition used was changed from Composition 1 to any of Compositions 2 to 7, and 9 to 15, as shown in Table 2. The evaluation results for Examples 1 to 7 and Comparative Examples 1 to 7 are shown in Table 3.

[0142] [Table 2]

[0143] [Table 3]

[0144] Examples 1 to 7 contained both (c) a sulfur-containing silane compound and (d) an epoxy-containing compound, and therefore had excellent adhesion. Examples 2 to 7 also had excellent storage stability because (c) the sulfur-containing silane compound had a protecting group. Examples 1 to 6 also had excellent swelling resistance because (a) the siloxane resin had a polymerizable carbon-carbon double bond.

[0145] In Comparative Example 1, the resin was an acrylic resin rather than (a) a siloxane resin, and therefore the effects of (c) a silane compound containing a sulfur atom and (d) an epoxy-containing compound on improving substrate adhesion were not obtained, resulting in poor adhesion. Comparative Example 2 contained (c) a silane compound containing a sulfur atom, but did not contain (d) an epoxy-containing compound, resulting in poor adhesion. Comparative Examples 3 and 4 contained (d) an epoxy-containing compound, but did not contain (c) a silane compound containing a sulfur atom, resulting in poor adhesion. Comparative Example 5 contained a compound containing a sulfur atom, but was not a silane compound containing a sulfur atom, resulting in poor adhesion. Comparative Examples 6 and 7 contained neither (c) a silane compound containing a sulfur atom nor a compound containing an epoxy, resulting in poor adhesion.

[0146] Example 101 An alkali-free glass substrate with a temporary adhesive applied was used as the support substrate, and an interlayer insulating layer and metal wiring were formed on the support substrate. For the interlayer insulating layer, a photosensitive resin composition containing polyimide was applied and prebaked, followed by patterning exposure through a photomask with a predetermined pattern, development, rinsing, and then heated and thermally cured to form an approximately 10 μm thick interlayer insulating layer. A titanium barrier metal was then formed on the interlayer insulating layer by sputtering, and a copper seed layer was then formed on the barrier metal by sputtering. A photoresist layer was then formed, and copper metal wiring was formed by plating. The photoresist layer, seed layer, and barrier metal were then removed from areas where no metal wiring was to be formed. The resulting metal wiring was 5 μm thick. The above interlayer insulating layer and metal wiring formation were then repeated twice to form a triple-layer interlayer insulating layer. A protective film made of SiO2 was formed on the surface of the interlayer insulating layer, leaving openings for the metal wiring. The total thickness of the three interlayer insulating layers was 30 μm.

[0147] Next, a light-emitting diode (LED) was placed on the interlayer insulating layer, electrically connected to the metal wiring. The LED was 5 μm thick, 10 μm long on one side, and 20 μm long on the other, and contained an alumina substrate.

[0148] Next, to form the barrier layer, Composition 1 was applied over the interlayer insulating layer and LEDs, prebaked, patterned, exposed through a photomask with a predetermined pattern, developed, and rinsed to form a matrix pattern with multiple openings exposing the LEDs and their surroundings. The openings were rectangular, with one side measuring 15 μm and the other 25 μm. In the matrix pattern, the pattern dimensions between the 15 μm openings and the 25 μm openings were also 5 μm. The matrix pattern was then heated and thermally cured to form a barrier layer with a thickness of approximately 4 μm. The thermal curing conditions were a nitrogen atmosphere with an oxygen concentration of 20 ppm by mass or less, where the temperature was raised to 200°C at a rate of 3.5°C / min, followed by heating at 200°C for 60 minutes and cooling to 50°C.

[0149] Next, to form a planarizing layer, Composition 8 was applied and prebaked over the interlayer insulating layer, LED, and partition wall layer using the method described above. The resulting film was then patterned, exposed, developed, and rinsed using a photomask with a predetermined pattern to form an uncured film with multiple openings for connecting the touch panel wiring to the drive substrate. The openings were circular, with the smallest pattern having a bottom diameter of 2 μm. The uncured film was then heated and thermally cured to form a planarizing layer with a thickness of approximately 4 μm. The thermal curing conditions were a nitrogen atmosphere with an oxygen concentration of 20 ppm by mass or less, where the temperature was increased to 200°C at a rate of 3.5°C / min, followed by heating at 200°C for 60 minutes and then cooling to 50°C.

[0150] Next, a wiring layer was formed on the planarization layer by sputtering. A patterned photoresist layer was formed on the wiring layer, and the wiring layer was etched with an acidic solution to form a wiring layer pattern. The remaining photoresist layer was then removed with an alkaline resist remover.

[0151] Finally, the support substrate was peeled off from the laminated body prepared as described above, a drive substrate was attached, and an opposing substrate was then attached to the wiring layer to produce a micro LED display equipped with multiple LEDs, which are light-emitting elements. The obtained micro LED display was subjected to light emission evaluation and reliability evaluation.

[0152] (Examples 102 to 107 and Comparative Examples 101 to 107) In Examples 102 to 107 and Comparative Examples 101 to 107, evaluations were performed in the same manner as in Example 101, except that the photosensitive resin composition used in the partition wall layer was changed to another composition as shown in Table 3. The evaluation results of Examples 101 to 107 and Comparative Examples 101 to 107 are shown in Table 4.

[0153] [Table 4]

[0154] In Examples 101 to 107, the partition wall layer and the planarizing layer were made of a cured film of the photosensitive resin composition of the present invention, and therefore the light emitting properties and reliability were excellent.

[0155] In Comparative Example 101, the photosensitive resin composition used in the partition wall layer was (a) an acrylic resin rather than a siloxane resin. In Comparative Examples 102 to 107, the photosensitive resin composition used in the partition wall layer did not contain either (c) a silane compound containing a sulfur atom or (d) an epoxy-containing compound, or both. Therefore, Comparative Examples 101 to 107 were inferior in various properties. [Industrial Applicability]

[0156] The photosensitive resin composition and cured film according to the present invention can be used in display devices and information terminals having such devices. [Explanation of symbols]

[0157] 1 Display device 2 Light-emitting element 3 Interlayer insulation layer 4 Wiring 5 Opposing substrate 6 electrode terminal 7 wiring layer 8 Drive board 11 Partition layer 21 Planarization layer

Claims

1. A photosensitive resin composition comprising (a) a siloxane resin, (b) a photosensitizer, (c) a silane compound containing a sulfur atom, and (d) a compound containing an epoxy group, wherein the (c) silane compound containing a sulfur atom is a compound having a functional group having a structure represented by the following general formula (1): 【Chemical 1】 (X is hydrogen or an organic group having 1 to 18 carbon atoms. * indicates a bond.)

2. 2. The photosensitive resin composition according to claim 1, wherein the siloxane resin (a) has a polymerizable carbon-carbon double bond.

3. 3. The photosensitive resin composition according to claim 2, wherein the polymerizable carbon-carbon double bond is a functional group represented by the structure of the following general formula (2): 【Chemistry 2】 (In general formula (2), R Ｉ is a single bond or a hydrocarbon group having 1 to 10 carbon atoms. ＩＩ , R ＩＩＩ , R ＩＶ are each hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. Ｉ , R ＩＩ , R ＩＩＩ , R ＩＶ Two or more of these may be bonded to form a ring. * indicates a bond to the Si atom.)

4. 2. The photosensitive resin composition according to claim 1, wherein the (b) photosensitizer is a naphthoquinone diazide compound.

5. The photosensitive resin composition according to claim 1, wherein X in the general formula (1) is a group represented by the following general formula (3): 【Chemistry 3】 (R Ｖ , R ＶＩ , R ＶＩＩ are alkyl or alkoxy groups having 1 to 6 carbon atoms. * indicates a bond to the sulfur atom.)

6. 2. The photosensitive resin composition according to claim 1, further comprising: (e) particles having a median diameter of 100 to 400 nm.

7. 7. The photosensitive resin composition according to claim 6, wherein the particles (e) having a median diameter of 100 to 400 nm contain at least one selected from titanium oxide, zinc oxide, and zirconium oxide.

8. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 7.

9. A display device comprising the cured film according to claim 8.

10. An information terminal comprising the display device according to claim 9.

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