Photosensitive resin composition, cured film, and display device provided therewith

Abstract

Provided is a cured film wherein post-development residue is suppressed, development peeling is suppressed, and adhesion to a substrate is excellent. The present invention also addresses the problem of providing a cured film that is provided to a display device exhibiting good light emission characteristics and having excellent reliability.　Provided is a photosensitive resin composition including (A1) a siloxane resin, (B) a photosensitive agent, and (C) a silane compound, wherein the (C) silane compound is a compound that has a prescribed chemical structure. Also provided is a photosensitive resin composition including (A2) a siloxane resin and (B) a photosensitive agent, wherein the (A2) siloxane resin is a resin that has a repeating unit represented by a prescribed chemical structure.

Description

Photosensitive resin composition, cured film, and display device including the same

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

[0002] In recent years, technologies related to organic electroluminescence (hereinafter referred to as "organic EL") displays, quantum dot displays, and micro light-emitting diode (hereinafter referred to as "LED") displays have been actively researched for thin displays such as those used in smartphones, TVs, smartwatches, and AR / VR devices.

[0003] For example, pixel dividing layers in organic electroluminescent (EL) displays, partition layers and planarizing layers in mini-LEDs and micro-LEDs, planarizing layers for thin-film transistors (hereinafter "TFTs") in various displays, and insulating films for other peripheral components are formed from cured films of photosensitive resin compositions patterned by photolithography. Peeling of these cured films from adjacent components, such as other insulating layers, wiring, or light-emitting elements, can cause cracks in the wiring or damage to the elements, resulting in poor display light emission. Therefore, high adhesion between the cured film and each component is required. In particular, mini-LED and micro-LED displays require high adhesion between the cured film and the metals and metal oxides contained in the wiring and LED chips. Furthermore, in the display manufacturing process, excellent chemical resistance is required to prevent a decrease in adhesion due to chemicals used in processing peripheral components. Additionally, when forming patterns by photolithography using a photosensitive resin composition, it is necessary to simultaneously suppress development residues in openings and peeling of the remaining film.

[0004] For example, Patent Document 1 describes an example in which a cured film having excellent substrate adhesion is obtained using a photosensitive resin composition containing an acrylic resin, and Patent Document 2 describes an example in which a cured film having excellent substrate adhesion is obtained using a photosensitive resin composition containing a polyimide resin.

[0005] International Publication No. WO 2015 / 046296 International Publication No. WO 2017 / 122623

[0006] The resin compositions described in Patent Documents 1 and 2 have issues with adhesion to substrates other than those specified. They also have issues with both suppressing residue and film peeling during the development process, and with the chemical resistance of the cured film. Therefore, further improvements in the properties of photosensitive resin compositions are desired. The present invention aims to provide a cured film that suppresses both residue and film peeling during the development process, has excellent adhesion to various substrates, and is highly chemical-resistant. Another object of the present invention is to provide a cured film that exhibits good light-emitting properties and is used in highly reliable display devices.

[0007] The present invention has the following configuration: [1] A photosensitive resin composition containing (A1) a siloxane resin, (B) a photosensitizer, and (C) a silane compound, wherein the silane compound (C) has a structure represented by chemical formula (1).

[0008]

[0009] (In chemical formula (1), １ represents an oxygen atom or a sulfur atom, and Y １ represents a sulfur atom or an amino group. １ , R ２ each independently represents one selected from the group consisting of a monovalent or divalent organic group having 1 to 20 carbon atoms, a monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle, and a monovalent or divalent organic group having 1 to 20 carbon atoms and containing an alkoxysilyl group; R １ , R ２ [2] The photosensitive resin composition according to [1] above, wherein the content of the silane compound (C) is 0.01 to 5 parts by mass relative to 100 parts by mass of the siloxane resin. [3] In the chemical formula (1), X １ [4] The photosensitive resin composition according to the above [1] or [2], wherein R is a sulfur atom. １ , R ２[5] A photosensitive resin composition comprising (A2) a siloxane resin and (B) a photosensitizer, wherein the siloxane resin (A2) is a resin containing a repeating unit represented by chemical formula (2):

[0010]

[0011] (In chemical formula (2), ２ represents an oxygen atom or a sulfur atom, and Y ２ represents a sulfur atom or an amino group. ３ , R ４each independently represent any one selected from the group consisting of a monovalent or divalent organic group having 1 to 20 carbon atoms, a monovalent or divalent organic group having 1 to 20 carbon atoms containing a heterocycle, and a monovalent or divalent organic group having 1 to 20 carbon atoms and an alkoxysilyl group.) [6] The photosensitive resin composition according to [5] above, wherein the content of the repeating unit represented by chemical formula (2) in the (A2) siloxane resin is 0.01 to 5 mol % relative to 100 mol % of all repeating units consisting of siloxane structures contained in the siloxane resin. [7] The photosensitive resin composition according to any one of [1] to [6] above, wherein the (B) photosensitizer is a quinone diazide compound. [8] The photosensitive resin composition according to any one of [1] to [6] above, wherein the (B) photosensitizer is a photopolymerization initiator. [9] The photosensitive resin composition according to any one of [1] to [8] above, further comprising a silane coupling agent other than the (C) silane compound, the silane coupling agent having an epoxy group or an oxetanyl group.

[10] The photosensitive resin composition according to any one of [1] to [9] above, further comprising water, the content of water in the photosensitive composition being 0.1 to 5.0 mass%.

[11] The photosensitive resin composition according to any one of [1] to

[10] above, further comprising (D) particles, the (D) particles comprising one or more selected from the group consisting of titanium dioxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc oxide, barium carbonate, and composite compounds thereof.

[12] The photosensitive resin composition according to

[11] above, wherein the (D) particles are titanium dioxide.

[13] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to

[12] above.

[14] A display device comprising the cured film according to

[13] above.

[15] The display device according to

[14] above, comprising a mini LED or a micro LED.

[0012] The photosensitive resin composition of the present invention can suppress film peeling and residue generation during the development process. In addition, it is possible to provide a cured film that has excellent adhesion to various substrates and chemical resistance. Furthermore, the display device of the present invention can provide a display device that exhibits good light-emitting properties and is highly reliable.

[0013] 1A and 1B are schematic cross-sectional views of a micro LED display having a barrier layer and a planarization layer, respectively, and another type of micro LED display having a barrier layer and a planarization layer.

[0014] 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.

[0015] <Photosensitive Resin Composition> The "First Invention," one embodiment of the present invention, is a photosensitive resin composition having the configuration described above in [1]. A photosensitive resin composition having this configuration can suppress film peeling and residue generation during development. It can also provide a cured film with excellent adhesion to the substrate and chemical resistance. It can also suppress peeling of the cured film and corrosion of the substrate, exhibit good light-emitting properties, and provide a display device with excellent reliability. Insufficient chemical resistance reduces adhesion after immersion in a resist stripper during the device fabrication process. Insufficient adhesion can cause peeling between the cured film and adjacent components such as wiring and light-emitting elements, resulting in cracks in the wiring and damage to the elements, leading to poor light emission in the display. Therefore, high chemical resistance is required for the cured film, and chemical resistance is evaluated based on adhesion after a chemical resistance test described below.

[0016] The reason why the photosensitive resin composition of the first invention exhibits the above-mentioned effects is presumed to be as follows: The (C) silane compound contains an alkoxysilyl group. The alkoxysilyl group forms a bond through a condensation reaction with other alkoxy groups or hydroxy groups. Therefore, the (C) silane compound and the (A1) siloxane resin can form a bond through a condensation reaction. Furthermore, the partial structure of the (C) silane compound excluding the alkoxysilyl group is thought to have a strong interaction with the substrate, such as a metal, metal oxide, metal nitride, or organic film. Because the (C) silane compound bonds and interacts with both the (A1) siloxane resin and the substrate, it is presumed that the cured film obtained from the photosensitive resin of the present invention has excellent adhesion to the substrate.

[0017] In addition, since the (C) silane compound has bonding and interaction with the (A1) siloxane resin and the substrate, it is thought that a large amount is present at the interface between the (A1) siloxane resin and the substrate.In addition, since the (C) silane compound is highly hydrophobic, it is thought that it suppresses the penetration of the alkaline developer into the interface between the (A1) siloxane resin and the substrate in the development process, and has the effect of suppressing the peeling of the remaining film during development.In addition, it is thought that the substrate surface modification by the (C) silane compound prevents residue adhesion in the openings, and has the effect of suppressing residue after development.

[0018] Furthermore, in the cured film, the silane compound present at the interface between the substrate and the siloxane resin plays a role in protecting the substrate interface, thereby suppressing a decrease in adhesion due to chemicals. In addition, when a film is formed on wiring, corrosive substances generated during high-temperature and high-humidity tests and weather resistance tests of display devices can be prevented from contacting the wiring surface, thereby suppressing wiring corrosion. Therefore, a display device including a cured film obtained from the photosensitive resin composition of the present invention has high reliability.

[0019] Another embodiment of the present invention, "the second invention," is a photosensitive resin composition having the structure [5] above. Here, the siloxane resin (A2) in the structure [5] above can be considered as a resin obtained by reacting the siloxane resin (A1) in the structure [1] above with the silane compound (C). R in chemical formula (1) １ and R ２ The alkoxysilyl group contained in at least one of the (A1) and (C) compounds forms a siloxane structure upon condensation with another alkoxysilyl group or a hydroxysilyl group. That is, when a condensation reaction occurs between the (A1) siloxane resin and the (C) silane compound, a siloxane resin (A2) containing a repeating unit represented by chemical formula (2) is obtained. Therefore, the photosensitive resin composition having the structure [5] above exhibits the same effects as the photosensitive resin composition having the structure [1] above. The "first invention" and the "second invention" may be collectively referred to as the "present invention."

[0020] (Siloxane Resin) The photosensitive resin composition of the first invention contains (A1) a siloxane resin, and the photosensitive resin composition of the second invention contains (A2) a siloxane resin.

[0021] The siloxane resin (A1) and the siloxane resin (A2) in the present invention refer to polymers having siloxane bonds in the main chain skeleton, such as resins obtained by hydrolyzing and dehydrating condensation of one or more organosilanes selected from the group consisting of trifunctional organosilanes, tetrafunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes.

[0022] The (A1) siloxane resin and the (A2) siloxane resin preferably have a repeating unit represented by chemical formula (3). The repeating unit represented by chemical formula (3) is a trifunctional organosilane unit.

[0023]

[0024] In chemical formula (3), R ５ 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.

[0025] 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 thereof 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.

[0026] The content of trifunctional organosilane units in the siloxane resin (A1) and the siloxane resin (A2) is preferably 10 mol % to 100 mol %, more preferably 30 mol % to 100 mol %, and particularly preferably 50 mol % to 100 mol %, relative to 100 mol % of all repeating units consisting of siloxane structures contained in the resin. Within this range, the resin can be easily miscible with other components, thereby enabling excellent resolution to be achieved.

[0027] It is also preferable that the siloxane resin (A1) and the siloxane resin (A2) have a repeating unit represented by chemical formula (4). The repeating unit represented by chemical formula (4) is a tetrafunctional organosilane unit.

[0028]

[0029] Examples of compounds that provide tetrafunctional organosilane units include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

[0030] The siloxane resin (A1) and the siloxane resin (A2) preferably have a tetrafunctional organosilane unit content of 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, relative to 100 mol% of all repeating units consisting of siloxane structures contained in the resin. If the content is 1 mol% or more, the siloxane resin quickly crosslinks, suppressing fluidity, thereby suppressing fluctuations in processed dimensions before and after heating. Furthermore, the content is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less. If the content is 40 mol% or less, an excessive amount of silanol groups can be prevented, improving the storage stability of the photosensitive resin composition.

[0031] The (A1) siloxane resin and the (A2) siloxane resin may also contain a difunctional organosilane unit and / or a monofunctional organosilane unit.

[0032] Examples of compounds that provide bifunctional organosilane units include dimethyldimethoxysilane, dimethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, and octadecylmethyldimethoxysilane.

[0033] Examples of compounds that provide a monofunctional organosilane unit include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triphenylmethoxysilane, diphenylmethylmethoxysilane, and diphenylmethylethoxysilane.

[0034] The content of bifunctional organosilane units in the (A1) siloxane resin and the (A2) siloxane resin is preferably 1 mol% or more, more preferably 5 mol% or more, and even more 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 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. If it is 1 mol% or more, the storage stability of the photosensitive resin composition can be improved. If it is 30 mol or less, a cured film with high crosslink density can be produced.

[0035] The content of monofunctional organosilane units in the (A1) siloxane resin and the (A2) siloxane resin is preferably 1 mol% or more, more preferably 5 mol% or more, and even more 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 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. If it is 1 mol% or more, the storage stability of the photosensitive resin composition can be improved. If it is 30 mol or less, a cured film with high crosslink density can be produced.

[0036] The siloxane resin (A2) is a resin containing a repeating unit represented by chemical formula (2).

[0037]

[0038] In chemical formula (2), X ２ represents an oxygen atom or a sulfur atom, and Y ２ represents a sulfur atom or an amino group. ３ , R ４ each independently represents one selected from the group consisting of a monovalent or divalent organic group having 1 to 20 carbon atoms, a monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle, and a monovalent or divalent organic group having 1 to 20 carbon atoms and containing an alkoxysilyl group.

[0039] In chemical formula (2), X ２ If Y is a sulfur atom, it has a strong interaction with the substrate and the adhesion of the cured film is improved, which is preferable. ２is preferably an amino group. From the viewpoint of preventing film peeling during development, R ３ , R ４ At least one of R is preferably a monovalent or divalent organic group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. ３ , R ４ At least one of the groups is preferably a monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle, since this has a strong interaction with the substrate and further improves the adhesion of the cured film.

[0040] The repeating unit represented by chemical formula (2) is a repeating unit derived from the silane compound represented by chemical formula (1).

[0041]

[0042] In chemical formula (1), X １ represents an oxygen atom or a sulfur atom, and Y １ represents a sulfur atom or an amino group. １ , R ２ each independently represents one selected from the group consisting of a monovalent or divalent organic group having 1 to 20 carbon atoms, a monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle, and a monovalent or divalent organic group having 1 to 20 carbon atoms and an alkoxysilyl group; R １ , R ２ At least one of the groups is a monovalent or divalent organic group having 1 to 20 carbon atoms and an alkoxysilyl group. Examples and preferred descriptions regarding the silane compound represented by chemical formula (1) are as described below in the section on silane compound (C).

[0043] The content of the repeating unit represented by chemical formula (2) in the (A2) siloxane resin is preferably 0.01 mol% or more, more preferably 0.02 mol% or more, and particularly preferably 0.05 mol% or more, relative to 100 mol% of all repeating units consisting of siloxane structures contained in the resin. Also, it is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 1 mol% or less. When the content of the repeating unit represented by chemical formula (2) is 0.01 mol% or more, the adhesion between the cured film and the substrate is excellent. When it is 5 mol% or less, the effect of suppressing film peeling during development is excellent.

[0044] From the viewpoint of pattern processability in an alkaline developer, the siloxane resin (A1) and the siloxane resin (A2) preferably have an organosilane unit containing an acidic group. Examples of the acidic group include a carboxy group, a carboxylic acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, and a mercapto 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.

[0045] In the siloxane resin (A1) and the siloxane resin (A2), the content of organosilane units containing acidic groups is preferably 1 mol% or more, more preferably 5 mol% or more, and even more 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 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less. If it is 1 mol% or more, the effect of the alkali solubility of the acidic groups can be obtained. If it is 40 mol% or less, it is possible to prevent the resin composition from being excessively dissolved in an alkaline developer due to the acidic groups.

[0046] From the viewpoint of improving chemical resistance, the siloxane resin (A1) and the siloxane resin (A2) preferably have an organosilane unit containing a radically polymerizable group.

[0047] 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.

[0048] Examples of compounds that provide organosilane units containing a radical polymerizable 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 γ-(meth)acryloylpropyltriethoxysilane, γ-(meth)acryloylpropyltriethoxysilane, γ-(meth)acryloylpropyltriethoxysilane, γ-(meth)acryloylpropyltri(methoxyethoxy)silane, γ-(meth)acryloylpropylmethyldimethoxysilane, γ-(meth)acryloylpropylmethyldiethoxysilane, and γ-(meth)acryloylpropyl(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.

[0049] From the viewpoint of improving chemical resistance, the (A1) siloxane resin and the (A2) siloxane resin preferably have an organosilane unit containing an epoxy group or an oxetanyl group, and more preferably have an organosilane unit containing a cyclohexylepoxy group, a glycidyl group, or an oxetanyl group.

[0050] Examples of compounds that provide these organosilane units include 3-(N,N-glycidyl)aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, butyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, σ-glycidoxybutyltrimethoxysilane, σ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, and the like.

[0051] From the viewpoint of improving sensitivity during exposure, the siloxane resin (A1) and the siloxane resin (A2) preferably have an organosilane unit containing a condensed polycyclic structure, a condensed polycyclic heterocyclic structure, or an aromatic structure, more preferably have an organosilane unit containing a naphthyl group, an anthracenyl group, a biphenyl group, a phenyl group, a tolyl group, or a methoxyphenyl group, and even more preferably have an organosilane unit containing a naphthyl group or an anthracenyl group.

[0052] Examples of compounds that provide these organosilane units include naphthyltrimethoxysilane, naphthyltriethoxysilane, and naphthyltrippropoxysilane.

[0053] From the viewpoint of suppressing residues after development, the (A1) siloxane resin and the (A2) siloxane resin preferably have organosilane units to which the (D) particles described below are bonded. Hereinafter, the (A1) siloxane resin or the (A2) siloxane resin having such organosilane units may be collectively referred to as the "particle-containing siloxane resin." The particle-containing siloxane resin is preferably a resin obtained by hydrolyzing one or more selected from the group consisting of trifunctional organosilanes, tetrafunctional organosilanes, bifunctional organosilanes, and monofunctional organosilanes in the presence of the (D) particles, followed by dehydration condensation. Examples and preferred descriptions of the (D) particles are as described below for the (D) particles.

[0054] The (A1) siloxane resin and the (A2) siloxane resin 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. The various conditions for the hydrolysis can be set to suit the physical properties appropriate for the intended application, taking into account the reaction scale, the size and shape of the reaction vessel, etc. Examples of the various conditions include acid concentration, reaction temperature, and reaction time. Acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, and ion exchange resins can be used for the hydrolysis reaction. Among these, an acid catalyst preferably includes an acidic aqueous solution containing one or more selected from the group consisting of formic acid, acetic acid, and phosphoric acid. 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 all organosilane compounds used in the hydrolysis reaction, in order to promote the hydrolysis more rapidly. On the other hand, from the viewpoint of appropriately controlling the progress of the hydrolysis reaction, the amount of the 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. 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.

[0055] 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; ethers such as 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, ethylene glycol dibutyl ether, and diethyl ether; methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ether, and the like. Examples of suitable solvents include ketones such as methyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; esters 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; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used.

[0056] 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.

[0057] When a solvent is produced by the hydrolysis reaction, it is also 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, etc. can be distilled and removed by heating and / or under reduced pressure, and then a suitable solvent can be added.

[0058] 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.

[0059] 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 hydrolysis, an appropriate amount of the produced alcohol may be distilled and removed by heating and / or under reduced pressure, followed by the addition of a suitable solvent.

[0060] 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, and then washed several times with water, 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.

[0061] The weight average molecular weight of the (A1) siloxane resin and the (A2) siloxane resin is preferably 1,000 or more, more preferably 2,000 or more, from the viewpoint of coating properties. If it is 1,000 or more, the viscosity necessary for controlling the film thickness during coating of the resin composition can be obtained. On the other hand, from the viewpoint of developability, 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).

[0062] In the photosensitive resin composition of the present invention, the content of the (A1) siloxane resin or (A2) siloxane resin can be arbitrarily set depending on the desired film thickness and application, but is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, relative to 100 parts by mass of the total solid content of the photosensitive resin composition. Also, it is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 80 parts by mass or less. When it is 10 parts by mass or more, good pattern processability can be obtained. When it is 80 parts by mass or less, high storage stability can be obtained.

[0063] (Photosensitizer) The photosensitive resin composition of the present invention contains a (B) photosensitizer. The (B) photosensitizer refers to a compound that undergoes bond cleavage, reaction, or structural change upon exposure to generate another compound, thereby imparting positive or negative photosensitivity to the composition. The (B) photosensitizer preferably contains one or more compounds selected from the group consisting of a (B1) quinone diazide compound, a (B2) photopolymerization initiator, a (B3) photoacid generator, and a (B4) photobase generator.

[0064] 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 (A1) siloxane resin and the (A2) siloxane resin, 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.

[0065] When the composition is to be imparted with positive photosensitivity, it preferably contains a quinone diazide compound (B1) or a photoacid generator (B3), and more preferably contains a quinone diazide compound (B1).When the composition is to be imparted with negative photosensitivity, it preferably contains a photopolymerization initiator (B2) or a photoacid generator (B3), and more preferably contains a photopolymerization initiator (B2).

[0066] The quinone diazide compound (B1) undergoes a structural change upon exposure to generate an indene carboxylic acid and / or a sulfoindene carboxylic acid. Therefore, the inclusion of the quinone diazide compound (B1) is suitable for forming a positive-tone pattern. During exposure, the acidic compound resulting from the structural change of the quinone diazide compound (B1) selectively solubilizes the exposed portions of the film of the composition in an alkaline developer, resulting in a significant improvement in resolution after development.

[0067] 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 here 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, and BisP. -IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (TekP-4HBPA) TrachysP-DO-BPA), TrisP-HAP, TrisP-PA, Phcc-AP, BisOFP-Z, BisRS-2P, BisPG-26X, Bi Examples of such an isomer include sRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, methylenetrith-FR-CR, BisRS-26X, and BisRS-OCHP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, and TEP-BIP-A (trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), 4,4'-sulfonyldiphenol (manufactured by Wako Pure Chemical Industries Co., Ltd.), and BPFL (trade name, manufactured by JFE Chemical Corporation).

[0068] Among these, preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, Phcc-AP, 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, 4,4'-sulfonyldiphenol, and BPFL. Among these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, Phcc-AP, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR-BIPC-F, 4,4'-sulfonyldiphenol, and BPFL.

[0069] 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.

[0070] The (B2) photopolymerization initiator is a compound that generates radicals by bond cleavage and / or reaction upon exposure. The inclusion of the (B2) photopolymerization initiator is suitable for negative pattern formation from the viewpoint of promoting radical polymerization, etc. In particular, when other monomer compounds are contained, even if only a small amount of radicals are generated upon exposure, radical polymerization of the monomer compounds etc. proceeds in a chain reaction, which is preferable because the effect of improving sensitivity upon exposure is significant.

[0071] The (B2) photopolymerization initiator 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 benzoate ester compound. From the viewpoints 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.

[0072] The above-mentioned α-hydroxyketone compounds, α-aminoketone compounds, biimidazole compounds, phosphine oxide compounds, and oxime ester compounds have the effect of improving the degree of crosslinking of the cured film and accelerating the ring-closing reaction of the resin due to the generation of radicals upon heating and the interaction of the hydroxy group, amino group, imidazole structure, phosphine oxide structure, or oxime ester structure, and therefore have a significant effect of improving the reliability of the light-emitting device.

[0073] The (B3) photoacid generator is a compound that generates an acid by bond cleavage and / or reaction upon exposure. When a resin or the like has a cationically polymerizable group, the (B3) photoacid generator is suitable for negative pattern formation from the viewpoint of promoting cationic polymerization upon exposure. On the other hand, when a resin or the like has an acidic group protected by an acid-dissociable group, the (B3) photoacid generator is suitable for positive pattern formation from the viewpoint of liberating the acidic group upon exposure, and the effect of improving sensitivity upon exposure is significant.

[0074] Examples of the photoacid generator (B3) include ionic compounds and nonionic compounds. Preferred examples of the ionic compound include triorganosulfonium salt compounds. Preferred examples of the nonionic compound include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, carboxylate ester compounds, sulfonimide compounds, phosphate ester compounds, and sulfonebenzotriazole compounds.

[0075] The photobase generator (B4) is a compound that generates a base by bond cleavage and / or reaction upon exposure. The inclusion of the photobase generator (B4) is suitable for negative pattern formation from the viewpoint of promoting anionic polymerization, etc. On the other hand, when a resin or the like has a base-dissociable protected acidic group, it is suitable for positive pattern formation from the viewpoint of liberating the acidic group upon exposure, and the effect of improving sensitivity upon exposure is remarkable.

[0076] Examples of the photobase generator (B4) include ionic compounds and nonionic compounds. Preferred examples of the ionic compound include 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 examples of the nonionic compound include nitrobenzyl carbamate compounds, anthracenyl carbamate compounds, benzoin carbamate compounds, anthraquinone carbamate compounds, hydroxycinnamamide compounds, and coumarinamide compounds.

[0077] (Silane Compound) One of the photosensitive resin compositions of the present invention contains a silane compound (C). The silane compound (C) has a structure represented by chemical formula (1).

[0078]

[0079] In chemical formula (1), X １ represents an oxygen atom or a sulfur atom, and Y １ represents a sulfur atom or an amino group. １ , R ２ each independently represents one selected from the group consisting of a monovalent or divalent organic group having 1 to 20 carbon atoms, a monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle, and a monovalent or divalent organic group having 1 to 20 carbon atoms and an alkoxysilyl group; R １ , R ２ At least one of the groups is a monovalent or divalent organic group having 1 to 20 carbon atoms and an alkoxysilyl group.

[0080] In chemical formula (1), R１ and / or R ２ Examples of the monovalent or divalent organic group having 1 to 20 carbon atoms that gives the formula (I) include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an aryl group, an allyl group, a vinyl group, and combinations thereof.

[0081] In chemical formula (1), R １ and / or R ２ The monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle, which gives the formula (I), may consist solely of a heterocycle, or may consist of a heterocycle and another organic group. Examples of heterocycles include triazole groups, pyrrole groups, furan groups, thiophene groups, imidazole groups, oxazole groups, thiazole groups, pyrazole groups, isoxazole groups, isothiazole groups, tetrazole groups, pyridine groups, pyridazine groups, pyrimidine groups, pyrazine groups, piperidine groups, piperazine groups, morpholine groups, 2H-pyran groups, 6H-pyran groups, triazine groups, imidazoline groups, oxazoline groups, thiazoline groups, pyrazoline groups, and isoxazoline groups. Examples of other organic groups include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, aryl groups, allyl groups, vinyl groups, and combinations thereof.

[0082] In chemical formula (1), R １ and / or R ２ The monovalent or divalent organic group having 1 to 20 carbon atoms and having an alkoxysilyl group, which gives the formula (I), may be composed solely of an alkoxysilyl group, or may be composed of an alkoxysilyl group and another organic group. Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a tributoxysilyl group, a dimethoxymethylsilyl group, a dimethoxyphenylsilyl group, and a methoxydimethylsilyl group. Examples of the other organic group include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an aryl group, an allyl group, a vinyl group, and combinations thereof.

[0083] In chemical formula (1), X １If Y is a sulfur atom, it has a strong interaction with the substrate, and the adhesion of the cured film is improved, which is preferable. In particular, it is preferable because it improves the adhesion to a metal oxide substrate such as alumina. Furthermore, from the viewpoint of suppressing residues during development, Y is preferably a sulfur atom. １ is preferably an amino group. From the viewpoint of preventing film peeling during development, R １ , R ２ At least one of R is preferably a monovalent or divalent organic group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. １ , R ２ At least one of the groups is preferably a monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle, since this has a strong interaction with the substrate and further improves the adhesion of the cured film.

[0084] Examples of the silane compound having the structure represented by chemical formula (1) include the silane compounds described below.

[0085]

[0086] The content of the silane compound having the structure represented by chemical formula (1) is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and particularly preferably 0.05 parts by mass or more, relative to a total of 100 parts by mass of the siloxane resin (A1) or the siloxane resin (A2). Also, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, particularly preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less. When the content of the silane compound having the structure represented by chemical formula (1) is 0.01 parts by mass or more, the adhesion between the cured film and the substrate is excellent. When it is 5 parts by mass or less, the effect of suppressing film peeling during development is excellent.

[0087] (Particles) The photosensitive resin composition of the present invention may contain (D) particles. The photosensitive resin composition of the present invention may contain (D) particles in either the particle-containing siloxane resin or the photosensitive resin composition. The photosensitive resin composition of the present invention preferably contains the particle-containing siloxane resin and further contains (D) particles, or preferably does not contain the particle-containing siloxane resin and contains (D) particles.

[0088] Examples of the (D) particles include compounds selected from the group consisting of titanium dioxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc 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 diffusion, the (D) particles preferably contain one or more selected from the group consisting of titanium dioxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc oxide, barium carbonate, and composite compounds thereof. Among these, titanium dioxide and / or zirconia, which have high light diffusion properties and are easily used industrially, are preferred, and titanium dioxide is most preferred.

[0089] From the viewpoint of light diffusion, the content of the (D) particles is preferably 5.0 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and particularly preferably 30 parts by mass or more, relative to 100 parts by mass of the total solid content of the photosensitive resin composition. Also, from the viewpoint of suppressing residue after development, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less. The content ratio of the (D) particles refers to the sum of the (D) particles in the particle-containing siloxane resin and the (D) particles added to the photosensitive resin composition.

[0090] Furthermore, from the viewpoint of light diffusion, the particle size of the (D) particles preferably has a median diameter of 100 to 400 nm, more preferably 200 to 400 nm, and even more preferably 250 to 350 nm. A median diameter of 100 nm or more provides good light diffusion properties for the cured film, while a median diameter of 400 nm or less facilitates pattern processing of the thin film. The median diameter refers to the average primary particle diameter calculated from the particle size distribution measured by laser diffraction.

[0091] (Solvent) The photosensitive resin composition of the present invention may contain a solvent. By containing a solvent, the viscosity can be easily adjusted to a level suitable for application, and the uniformity of the coated film can be improved. 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 150°C or less. By containing a solvent having a boiling point of more than 150°C and not more than 250°C, the solvent volatilizes appropriately during application, allowing the coating film to dry more rapidly, 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, it is possible to suppress the solvent from remaining in the cured film, thereby improving chemical resistance and adhesion. It is preferable that the solvent having a boiling point of not more than 150°C at atmospheric pressure be contained in an amount of 50% by mass or more of the total solvent.

[0092] Examples of solvents having a boiling point of 150°C or less under atmospheric pressure include ethanol, isopropanol, 1-propanol, 1-butanol, 2-butanol, isopentanol, 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.

[0093] 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.

[0094] 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.

[0095] (Crosslinking Agent) The photosensitive resin composition of the present invention may contain a crosslinking agent. The crosslinking agent refers to a compound having a crosslinkable group, a cationically polymerizable group, or an anionically polymerizable group that can react with a resin or the like. From the viewpoint of improving sensitivity during exposure and improving the 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 an alkoxyalkyl group, a hydroxyalkyl group, an epoxy group, an oxetanyl group, and a blocked isocyanate group (hereinafter referred to as "specific crosslinkable group"). 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.

[0096] From the viewpoint of improving the sensitivity during exposure and the reliability of the light-emitting device, the number of specific crosslinkable groups contained 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 the reliability of the light-emitting device, the number of specific crosslinkable groups contained in the crosslinking agent is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less per molecule.

[0097] The content of the crosslinking agent is preferably 1.0 part by mass or more relative to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoints of improving sensitivity during exposure and improving the reliability of the light-emitting device, while it is preferably 30 parts by mass or less from the viewpoints of suppressing residues after development and improving the reliability of the light-emitting device.

[0098] (Radical Polymerizable Compound) The photosensitive resin composition of the present invention may contain a radical polymerizable compound. The radical polymerizable compound refers to a compound having a radical polymerizable group. The radical polymerizable group preferably has an ethylenically unsaturated double bond group. Examples of the radical 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.

[0099] 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.

[0100] The content of the radical polymerizable compound is preferably 15 parts by mass or more relative to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoint of reducing the taper of the pattern shape and improving the reliability of the light-emitting device, and is preferably 75 parts by mass or less from the viewpoint of improving the sensitivity during exposure and suppressing residues after development.

[0101] (Curing Agent) The photosensitive resin composition of the present invention may contain a curing agent. Examples of curing agents include nitrogen-containing organic compounds, silicone resin curing agents, various metal alkoxylates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more of these may be contained. Among these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferred from the viewpoints of the stability of the curing agent and the processability of the siloxane resin composition.

[0102] (Surfactant) The photosensitive resin composition of the present invention may contain a surfactant. By containing a surfactant, flow properties during application can be improved. 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.), and 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 Co., Ltd.); polyalkylene oxide-based surfactants; and poly(meth)acrylate-based surfactants. Two or more of these may be contained.

[0103] (Silane Coupling Agent) The photosensitive resin composition of the present invention may contain a silane coupling agent other than the silane compound (C). By containing a silane coupling agent, adhesion can be improved. The silane coupling agent is preferably a compound containing at least one selected from the group consisting of an amino group, an epoxy group, an oxetanyl group, a mercapto group, an acid anhydride group, and an imide group, and more preferably a compound containing an epoxy group or an oxetanyl group. Examples of silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Examples of suitable silanes include silane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, and N-(t-butyl)-3-(3-trimethoxysilylpropyl)succinimide. Among these, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, and [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane are preferred.

[0104] (Water) From the viewpoint of improving adhesion, the photosensitive composition of the present invention preferably further contains water. From the viewpoint of improving adhesion, the content of water in the photosensitive composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more. Furthermore, from the viewpoint of improving storage stability, it is preferably 5.0% by mass or less, more preferably 4.0% by mass or less. It is believed that by setting the content of water in the photosensitive composition within the above range, the hydrolysis reaction of the silane compound (C) can be promoted, and adhesion can be further improved. It is also believed that the silanol groups in the siloxane resin (A) can be stabilized, and storage stability can be improved.

[0105] (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.

[0106] 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 mass % or more and 50 mass % or less.

[0107] (Method for producing photosensitive resin composition) Next, a method for producing the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention can be obtained by mixing the above-mentioned (A1) siloxane resin or (A2) siloxane resin, (B) photosensitive material, and, if necessary, (C) silane compound with other components.

[0108] More specifically, for example, a method can be mentioned in which (B) the photosensitizer, and optionally (C) the silane compound and other additives, are added to an arbitrary solvent and stirred to dissolve, and then (A1) the siloxane resin or (A2) the siloxane is added, followed by stirring for an additional 20 minutes to 3 hours, and the resulting solution is filtered.

[0109] <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 obtained by curing the above-mentioned photosensitive resin composition of the present invention. There are no particular restrictions on the film thickness of the cured film, but it is preferably 0.1 to 30 μm.

[0110] The cured film of the present invention can be obtained, for example, by applying the above-mentioned photosensitive resin composition of the present invention in the form of a film, patterning it as necessary, and then curing it. The cured film of the present invention is preferably obtained by applying the above-mentioned photosensitive resin composition of the present invention to a substrate, prebaking it, exposing it to light, developing it to form a positive or negative pattern, and then thermally curing it. It is also preferable to expose it again before thermal curing.

[0111] Examples of substrate materials include silicon, gallium arsenide, glass, metals (copper, aluminum, chromium, titanium, molybdenum, gold, indium, etc.), metal oxides (alumina, ITO, etc.), silicon oxide, silicon nitride, ceramics, and resins. These substrates may be made of a single material, or a substrate having a plurality of materials formed thereon may be used depending on the product form. Among these, the photosensitive resin composition of the present invention has excellent adhesion to metals, silicon oxide, and metal oxides, so it is preferable to use a substrate containing these materials.

[0112] Examples of the coating method for coating the photosensitive resin composition on the substrate include microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating.

[0113] 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. The film thickness after pre-baking is preferably 0.1 to 50 μm. If the film thickness is 0.1 μm or more, film peeling during development can be suppressed, and if it is 50 μm or less, light rays during exposure can easily reach deep into the film, resulting in high resolution in pattern processing.

[0114] The exposure may be performed through a desired mask or without a mask. Examples of the exposure device 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 The exposure light source may be a mercury lamp (i-line, g-line, h-line, etc.), a KrF laser (wavelength 248 nm), or an ArF laser (wavelength 193 nm).

[0115] 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 also be subsequently dry baked at a temperature in the range of 50 to 130°C.

[0116] The re-exposure method uses an ultraviolet-visible exposure device such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA), and is performed at 100 to 20,000 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).

[0117] Heating devices used for thermal curing include hot plates, ovens, etc. The thermal curing temperature is preferably 80 to 300° C., and the thermal curing time is preferably about 15 minutes to 2 hours.

[0118] <Display Device> Next, the display device of the present invention will be described.

[0119] 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 EL 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 a large number of LED cells with vertical and horizontal dimensions of 100 μm to 10 mm are arranged. A micro LED display refers to a display device having a light source in which a large number of LED cells with vertical and horizontal dimensions of less than 100 μm are arranged.

[0120] 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.

[0121] The photosensitive resin composition of the present invention is also preferably used to form a partition layer or a planarizing layer in a micro LED display or a mini LED display. The partition 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 partition layer preferably has light reflectivity to improve the light extraction efficiency of the display. Furthermore, to achieve light reflectivity, the partition layer preferably contains the (D) particles. The planarizing layer has the function of flattening unevenness generated during the manufacturing process of the display device, and is preferably formed so as to cover at least a portion of the light-emitting element. The light-emitting element is preferably a semiconductor chip. That is, the photosensitive resin composition of the present invention is particularly preferably used to form a partition layer formed between adjacent light-emitting elements or a planarizing layer formed so as to cover at least a portion of the light-emitting element.

[0122] The display device of the present invention is preferably a micro LED display or a mini LED display. When the area of ​​the redistribution layer is larger than the area of ​​the light-emitting element, which is a semiconductor chip, in a planar view, the display device of the present invention has a fan-out wafer-level package structure or a fan-out panel-level package structure. The substrate, the redistribution layer, the interlayer insulating layer of the redistribution layer, the light-emitting element, the semiconductor chip, the partition layer, and the planarization layer may be made of known materials.

[0123] 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.

[0124] FIG. 1 is a schematic cross-sectional view of a micro LED display having a barrier layer and a planarization layer.

[0125] The display device 1a includes a plurality of light-emitting elements 2 and a plurality of partition layers 15 on an opposing substrate 5, a planarization layer 21 provided on the light-emitting elements 2, an interlayer insulating layer 3 provided on the planarization layer 21, and a drive substrate 8 provided on the interlayer insulating layer 3. The light-emitting elements 2 are preferably semiconductor chips. "On the light-emitting elements 2" does not only mean the surface of the light-emitting elements 2, but may also mean the upper side of the opposing substrate 5 or the light-emitting elements 2. In the embodiment shown in FIG. 1 , the partition layer 15 is provided between adjacent light-emitting elements 2, the planarization layer 21 is formed so as to cover the light-emitting elements 2, and a configuration in which a plurality of interlayer insulating layers 3 are stacked on the planarization layer 21 is illustrated, but the interlayer insulating layer 3 may be a single layer.

[0126] The light-emitting element 2 has a pair of electrode terminals 6 on the surface opposite to the surface in contact with the counter substrate 5, and each electrode terminal 6 is electrically connected to a wiring 4 extending in the planarization layer 21 and the interlayer insulating layer 3. If the plurality of wirings 4 are covered with the planarization layer 21 or the interlayer insulating layer 3, these layers function as insulating films, and thus the wirings 4 are configured to maintain electrical insulation. The metal wiring being configured to maintain electrical insulation means that the portions of the metal wiring that require electrical insulation are covered with a cured film formed by curing a resin-containing composition.

[0127] In the display device 1a, the side of the light-emitting element 2 that contacts the counter substrate 5 (the lower side in FIG. 1) is the light extraction side. The method for manufacturing the display device 1a is preferably a chip-first (RDL-last) structure in which the light-emitting element 2, which is a semiconductor chip, is placed on a separately prepared support substrate, and then the wiring 4 and the interlayer insulating layer 3 are formed. That is, in the manufacturing process of the display device 1a, it is preferable to place the light-emitting element 2 on a support substrate not shown in FIG. 1, and then form or bond the interlayer insulating layer 3, drive substrate 8, etc. thereon, and then peel off the support substrate and bond the counter substrate 5.

[0128] FIG. 2 is a schematic cross-sectional view of another type of micro LED display having a partition layer and a planarization layer. In the display device 1b, the side of the light-emitting element 2 that contacts the counter substrate 5 (the upper side in FIG. 2) is the light extraction side. A preferred method for manufacturing the display device 1b is to form wiring 4 and an interlayer insulating layer 3 on a separately prepared support substrate, and then arrange the light-emitting element 2, which is a semiconductor chip, using an RDL-first (chip-last) structure. That is, in the manufacturing process of the display device 1b, the interlayer insulating layer 3, planarization layer 21, etc. are preferably formed on a support substrate (not shown in FIG. 2), and after the support substrate is peeled off, a drive substrate 8 is bonded to the interlayer insulating layer 3 instead of the support substrate, and the counter substrate 5 is bonded to the planarization layer 21.

[0129] 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 5 to 700 μm, more preferably 5 to 100 μm. The interlayer insulating layer 3, the partition layer 15, 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 15 is also preferred. A configuration in which the planarizing layer 21 covers a portion of the surface of the partition layer 15 opposite to the surface that contacts the opposing substrate 5 is also preferred, and a configuration in which the planarizing layer 21 covers the entire surface of the partition layer 15 opposite to the surface that contacts the opposing substrate 5 is more preferred. From the viewpoint of improving reliability, the partition layer 15 and the planarizing layer 21 are preferably the cured film of the present invention. From the viewpoint of improving luminance, the partition layer 15 preferably contains the above-mentioned (D) particles.

[0130] The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. First, the measurements, evaluations, tests, etc. performed in the following examples and comparative examples will be described. Note that unless otherwise specified, the number of measurements (n) is 1.

[0131] (Item 1: Adhesion) The laminate of the cured film and the substrate obtained in each example was evaluated for substrate adhesion by the following method in accordance with JIS "K5600-5-6 (established on April 20, 1999)." The substrate was a glass substrate coated with copper, SiO ２ or alumina (hereinafter, Cu substrate, SiO ２ The Cu substrate and the alumina substrate were used. ２ On the surface of the cured film on each of the substrate and the alumina substrate, 11 parallel lines, each perpendicular to the other, were drawn at 1 mm intervals using a cutter knife to create 100 1 mm x 1 mm grids. Cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) was attached to the surface of the cured film and rubbed with an eraser (JIS S6050 compliant) to adhere it. One end of the tape was held perpendicular to the plate and instantly peeled off, and the number of remaining grids was counted visually. The peeled area of ​​the grids was evaluated according to the following criteria: A: peeled area is 0%; B: peeled 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: peeled area is 35% or more but less than 65%; F: peeled area is 65% or more.

[0132] (Item 2: Adhesion after chemical resistance test) The laminate of the cured film and substrate obtained in each example was immersed in a resist stripping solution (a mixed solution of monoethanolamine and diethylene glycol monobutyl ether) for 120 seconds at 50° C. Subsequently, after rinsing with pure water, the adhesion to the substrate was evaluated in the same manner as in item 1.

[0133] (Item 3: Adhesion after PCT test) The laminate of the cured film and substrate obtained in each example was subjected to PCT treatment for 12 hours using a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD, manufactured by SSPEC Corporation) under conditions of 121°C, 2.1 atm, and 100% humidity, and then the adhesion to the substrate was evaluated in the same manner as in item 1.

[0134] (Item 4: Peeling during development) The developed film obtained in each example was observed for peeling during development. As an index of peeling during development, the area of ​​the peeled film relative to the remaining film due to patterning was calculated. The area of ​​the peeled film was judged according to the following criteria. A: The area of ​​the peeled film was less than 1%. B: The area of ​​the peeled film was 1% or more and less than 3%. C: The area of ​​the peeled film was 3% or more and less than 5%. D: The area of ​​the peeled film was 5% or more and less than 20%. E: The area of ​​the peeled film was 20% or more and less than 100%.

[0135] (Item 5: Development Residue) The resolved pattern was observed for the developed film obtained in each Example. As an index of development residue, the presence or absence of residue in a 20 μm line and space pattern was observed, and the area occupied by the residue in the opening was calculated. The residue area was evaluated according to the following criteria: A: The residue area was less than 1% B: The residue area was 1% or more and less than 3% C: The residue area was 3% or more and less than 5% D: The residue area was 5% or more and less than 20% E: The residue area was 20% or more and less than 100%.

[0136] (Item 6: Sensitivity) The resolution pattern of the developed film obtained in each Example was observed. As an index of sensitivity, the optimum exposure dose at which a space pattern corresponding to an opening in a 20 μm line and space pattern could be formed with a dimensional width of 20 μm was determined.

[0137] (Item 7: Evaluation of display light emission) A voltage was applied to the micro LED displays obtained in each example via a drive circuit to cause them to emit light. At this time, the number of non-emitting LED chips was observed, and the ratio of non-emitting chips to all LED chips was calculated and judged as follows: A. Non-emitting ratio: 0% B. Non-emitting ratio: more than 0% but less than 1% C. Non-emitting ratio: 1% or more but less than 3% D. Non-emitting ratio: 3% or more but less than 10% E. Non-emitting ratio: 10% or more

[0138] (Item 8: 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 left in an environment of 85°C and 85% RH for 7 days as a high-temperature, high-humidity treatment, and the light extraction efficiency was measured again. The relative value of the light extraction efficiency after the high-temperature, high-humidity treatment was calculated, assuming the initial light extraction efficiency to be 1.00, and the evaluation was made as follows: A: The relative value of the light extraction efficiency was 0.95 or more; B: The relative value of the light extraction efficiency was 0.80 or more but less than 0.95; C: The relative value of the light extraction efficiency was 0.70 or more but less than 0.80; D: The relative value of the light extraction efficiency was 0.50 or more but less than 0.70; E: The relative value of the light extraction efficiency was less than 0.50.

[0139] <Compounds> In the examples and comparative examples, the compounds shown below are used as appropriate. Each compound and its abbreviation are as follows: MeTMS: methyltrimethoxysilane PhTMS: phenyltrimethoxysilane EpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane SucTMS: (3-trimethoxysilyl)propylsuccinic anhydride StTMS: 4-styryltrimethoxysilane AcrTMS: 3-acryloxypropyltrimethoxysilane TEOS: tetraethoxysilane SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane MAP: m-aminophenol ODPA: 4,4'-oxydiphthalic anhydride DFA: N,N'-dimethylformamide dimethyl acetal NA: 5-norbornene-2,3-dicarboxylic anhydride OBBOC: 4,4'-oxydibenzoyl chloride DPHA: dipentaerythritol hexaacrylate (trade name "Kayarad (registered trademark)" DPHA, manufactured by Shin Nippon Kayaku Co., Ltd.) BPEFA: 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (trade name "BPEFA", manufactured by Osaka Gas Chemicals) Irgacure 907: 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (trade name "Irgacure 907", manufactured by Ciba Specialty Chemicals) PGMEA: propylene glycol monomethyl ether acetate NMP: N-methyl-2-pyrrolidone.

[0140] The structures of the compounds used in each of the Examples and Comparative Examples are shown below.

[0141]

[0142]

[0143]

[0144]

[0145] The weight-average molecular weights of the siloxane resin, polyimide precursor, polybenzoxazole precursor, and acrylic resin 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 weight in terms of polystyrene. Tetrahydrofuran was used as the fluidized bed for the siloxane resin and acrylic resin, and NMP was used for the polyimide precursor and polybenzoxazole precursor.

[0146] <Synthesis Examples> (Synthesis Example 1) In a 500 ml three-necked flask, under a dry nitrogen stream, 40.86 g (0.30 mol) of MeTMS, 99.15 g (0.50 mol) of PhTMS, 24.64 g (0.1 mol) of EpoTMS, 20.83 g (0.1 mol) of TEOS, and 171.27 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution prepared by dissolving 0.927 g of phosphoric acid (0.50 mass% relative to the charged monomers) in 55.80 g of water was added over 30 minutes. Thereafter, the three-necked flask was immersed in an oil bath at 70 ° C. and stirred for 90 minutes, and then the oil bath was heated to 115 ° 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, and 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 127.10 g of by-products, methanol and water, was distilled off. PGMEA was added to the obtained siloxane resin solution so that the solids concentration was 40% by mass, yielding a siloxane resin solution.

[0147] (Synthesis Example 2) In a 500ml three-neck flask, under dry nitrogen flow, MeTMS 54.48g (0.40mol), PhTMS 99.15g (0.50mol), EpoTMS 24.64g (0.10mol), PGMEA 163.91g are charged, and while stirring at room temperature, the phosphoric acid aqueous solution that dissolves 0.891g (0.50% by mass relative to charged monomer) in 54.00g water is added over 30 minutes. Thereafter, by the same procedure as in Synthesis Example 1, obtain a siloxane resin solution with a solid content concentration of 40% by mass.

[0148] (Synthesis Example 3) In a 500ml three-necked flask, under dry nitrogen gas flow, MeTMS 47.67g (0.35mol), PhTMS 99.15g (0.50mol), SucTMS 13.12g (0.05mol), TEOS 20.83g (0.10mol), PGMEA 165.55g were charged, and while stirring at room temperature, an aqueous phosphoric acid solution obtained by dissolving 0.904g of phosphoric acid (0.50% by mass relative to charged monomer) in 56.70g of water was added over 30 minutes. Thereafter, by the same procedure as in Synthesis Example 1, a siloxane resin solution with a solid content concentration of 40% by mass was obtained.

[0149] (Synthesis Example 4) In a 500ml three-necked flask, under dry nitrogen flow, MeTMS 27.24g (0.20mol), PhTMS 99.15g (0.50mol), StTMS 13.12g (0.05mol), TEOS 20.83g (0.10mol), PGMEA 150.43g are charged, and while stirring at room temperature, the phosphoric acid aqueous solution obtained by dissolving 0.802g of phosphoric acid (0.50% by mass relative to charged monomer) in 48.60g of water is added over 30 minutes. Thereafter, by the same procedure as in Synthesis Example 1, obtain a siloxane resin solution with a solid content concentration of 40% by mass.

[0150] (Synthesis Example 5) In a 500 ml three-necked flask, under a dry nitrogen stream, 54.44 g (0.3997 mol) of MeTMS, 99.15 g (0.50 mol) of PhTMS, 0.09 g (0.0003 mol) of C-1, 20.83 g (0.10 mol) of TEOS, and 154.81 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution obtained by dissolving 0.873 g of phosphoric acid (0.50% by mass relative to the charged monomer) in 55.80 g of water was added over 30 minutes. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain a siloxane resin solution having a solids concentration of 40% by mass.

[0151] (Synthesis Example 6) In a 500 ml three-necked flask, under a dry nitrogen stream, 54.21 g (0.398 mol) of MeTMS, 99.15 g (0.50 mol) of PhTMS, 0.59 g (0.02 mol) of C-1, 20.83 g (0.10 mol) of TEOS, and 155.21 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution obtained by dissolving 0.874 g of phosphoric acid (0.50% by mass relative to the charged monomer) in 55.80 g of water was added over 30 minutes. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain a siloxane resin solution having a solids concentration of 40% by mass.

[0152] (Synthesis Example 7) In a 500 ml three-necked flask, under a dry nitrogen stream, 53.12 g (0.39 mol) of MeTMS, 99.15 g (0.50 mol) of PhTMS, 2.94 g (0.01 mol) of C-1, 20.83 g (0.10 mol) of TEOS, and 157.11 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution obtained by dissolving 0.880 g of phosphoric acid (0.50 mass% relative to the charged monomer) in 50.80 g of water was added over 30 minutes. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain a siloxane resin solution having a solids concentration of 40 mass%.

[0153] (Synthesis Example 8) In a 500 ml three-necked flask, under a dry nitrogen stream, 50.39 g (0.37 mol) of MeTMS, 99.15 g (0.50 mol) of PhTMS, 8.83 g (0.03 mol) of C-1, 20.83 g (0.10 mol) of TEOS, and 161.86 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution obtained by dissolving 0.896 g of phosphoric acid (0.50% by mass relative to the charged monomer) in 55.80 g of water was added over 30 minutes. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain a siloxane resin solution having a solids concentration of 40% by mass.

[0154] (Synthesis Example 9) In a 500 ml three-necked flask, under a dry nitrogen stream, 40.86 g (0.30 mol) of MeTMS, 99.15 g (0.50 mol) of PhTMS, 29.45 g (0.10 mol) of C-1, 20.83 g (0.10 mol) of TEOS, and 178.48 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution obtained by dissolving 0.951 g of phosphoric acid (0.50% by mass relative to the charged monomer) in 55.80 g of water was added over 30 minutes. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain a siloxane resin solution having a solids concentration of 40% by mass.

[0155] (Synthesis Example 10) In a 500 ml three-necked flask, under a dry nitrogen stream, 47.67 g (0.35 mol) of MeTMS, 39.66 g (0.20 mol) of PhTMS, 26.23 g (0.10 mol) of SucTMS, 82.01 g (0.35 mol) of AcrTMS, and 192.55 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution prepared by dissolving 0.978 g of phosphoric acid (0.50 mass% relative to the charged monomer) in 55.80 g of water was added over 30 minutes. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain a siloxane resin solution with a solids concentration of 40 mass%.

[0156] (Synthesis Example 11) In a 500 ml three-necked flask, under a dry nitrogen stream, 46.31 g (0.34 mol) of MeTMS, 39.66 g (0.20 mol) of PhTMS, 2.94 g (0.01 mol) of C-1, 26.23 g (0.10 mol) of SucTMS, 82.01 g (0.35 mol) of AcrTMS, and 194.93 g of PGMEA were charged, and while stirring at room temperature, an aqueous phosphoric acid solution obtained by dissolving 0.986 g of phosphoric acid (0.50% by mass relative to the charged monomer) in 55.80 g of water was added over 30 minutes. Thereafter, the same procedure as in Synthesis Example 1 was followed to obtain a siloxane resin solution having a solids concentration of 40% by mass.

[0157] (Synthesis Example 12) In a 500 ml three-neck flask, 18.61 g (0.06 mol) of ODPA and 200 g of NMP were added and dissolved under a dry nitrogen stream. 27.20 g (0.045 mol) of HFHA and 0.75 g (0.003 mol) of SiDA were added together with 20 g of NMP, and the mixture was allowed to react at 20 ° C. for 1 hour, and then at 50 ° C. for 2 hours. Next, 2.62 g (0.024 mol) of MAP was added as an end-capping agent together with 20 g of NMP, and the mixture was allowed to react at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 14.30 g (0.12 mol) of DFA with 20 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50 ° C. for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a polyimide precursor.

[0158] Synthesis Example 13: 34.78 g (0.09 mol) of BAHF, 3.12 g (0.018 mol) of NAOH, and 150 g of NMP were added to a 500 ml three-neck flask under a dry nitrogen stream and stirred at 70°C for 1 hour. The solution was then cooled to -15°C. A solution of 25.22 g (0.081 mol) of OBBOC dissolved in 60 g of NMP was added dropwise to the flask, ensuring that the internal temperature did not exceed 0°C. After the dropwise addition, stirring was continued for 6 hours at -15°C. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polybenzoxazole precursor.

[0159] Synthesis Example 14: 2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) and 150 g of PGMEA were charged into a 500 ml flask 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 obtained acrylic resin solution so that the solids concentration was 40% by mass, thereby obtaining an acrylic resin solution.

[0160] The resins obtained in each of Synthesis Examples 1 to 14 are shown in Table 1. In Synthesis Example 12, the amic acid structural unit in the resin was reacted with DFA as an esterifying agent, resulting in structural conversion to an amic acid ester structural unit having a methyl group.

[0161]

[0162] <Preparation of Photosensitive Resin Compositions> Compositions 1 to 36 were prepared according to the formulations shown in Tables 2-1, 2-2, and 2-3. In Tables 2-1, 2-2, and 2-3, the values ​​in parentheses indicate the parts by mass of each component. When the composition contained particles, a preparation not containing a particle dispersion was first prepared, and then the particle dispersion and the preparation were mixed to prepare the composition. The particle dispersion contained titanium dioxide (R-960; SiO ２ / Al ２ O ３ 50.00 g of the siloxane resin solution used in each composition was mixed with 50.00 g of the (surface-treated, median diameter 210 nm) and dispersed using a mill-type disperser filled with zirconia beads to obtain a particle dispersion. The resulting composition solution was filtered through a 0.45 μmφ filter before use.

[0163] <Examples> (Example 1) Composition 1, which is a photosensitive resin composition, was spin-coated onto a substrate 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 film with a thickness of 1.0 μm. The substrates used were glass substrates, Cu substrates, SiO ２ A substrate was appropriately selected from a glass substrate and an alumina substrate depending on the evaluation.

[0164] The prepared film was exposed to light by contact lens using a parallel light mask aligner (product 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 with widths of 50 μm, 40 μm, 30 μm, 20 μm, 15 μm, 10 μm, 7 μm, 5 μm, and 4 μm. The film was then shower-developed for 120 seconds with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (hereinafter abbreviated as "TMAH") (product name: ELM-D, manufactured by Mitsubishi Gas Chemical Company, Inc.) using an automatic developing apparatus (product name: "AD-2000" manufactured by Takizawa Sangyo Co., Ltd.), followed by rinsing with water for 30 seconds. The resulting developed film was evaluated for peeling during development using the method described in item 4 above, for development residue using the method described in item 5 above, and for sensitivity using the method described in item 6 above.

[0165] Thereafter, bleaching exposure was performed using a parallel light mask aligner (trade name PLA-501F, manufactured by Canon Inc.) at an exposure dose of 1000 mJ / cm ２ The resulting cured film on the substrate was exposed to 1000 kJ / cm² (equivalent to i-line radiation) and cured in air at 170°C for 30 minutes using an oven (IHPS-222; manufactured by Espec Corporation). The resulting cured film on the substrate was evaluated for adhesion by the method in item 1 above, for adhesion after a chemical resistance test by the method in item 2 above, and for adhesion after a PCT test by the method in item 3. Note that evaluations for items 1, 2, and 3 were each performed using a different laminate of cured film and substrate.

[0166] (Examples 2 to 24 and Comparative Examples 1 to 12) In Examples 2 to 24 and Comparative Examples 1 to 12, evaluations were performed in the same manner as in Example 1, except that the photosensitive resin composition used was changed from composition 1 to any of compositions 2 to 36 as shown in Tables 2-1, 2-2, and 2-3, and that the developer was changed from a 2.38 mass% TMAH aqueous solution to a 0.4 mass% TMAH aqueous solution in Examples 19, 20, and Comparative Example 6. The evaluation results for Examples 1 to 24 and Comparative Examples 1 to 12 are shown in Tables 3-1 and 3-2.

[0167]

[0168]

[0169]

[0170]

[0171]

[0172] Example 101: An alkali-free glass substrate with a temporary adhesive formed thereon was used as a support substrate, and an interlayer insulating layer and metal wiring were formed on the support substrate. The interlayer insulating layer was formed by applying and pre-baking a photosensitive resin composition containing polyimide, patterning exposure through a photomask with a predetermined pattern, developing, rinsing, and then heating and thermal curing to form an interlayer insulating layer with a thickness of approximately 10 μm. Next, a titanium barrier metal was formed on the interlayer insulating layer by sputtering, and a copper seed layer was further formed on the barrier metal by sputtering. Next, a photoresist layer was formed, and copper wiring was formed by plating. The photoresist layer, seed layer, and barrier metal were then removed from areas where metal wiring was not to be formed. The thickness of the formed wiring was 5 μm. The above-mentioned interlayer insulating layer formation and wiring formation were then repeated twice to form three interlayer insulating layers. SiO was then formed on the surface of the interlayer insulating layer in a manner that allowed the wiring to be opened. ２ The total thickness of the three interlayer insulating layers was 30 μm.

[0173] Next, LEDs, which are light-emitting elements, were placed on the interlayer insulating layer so as to be electrically connected to the metal wiring. The LEDs were 2 μm thick, 10 μm long on one side, and 20 μm long on the other side, and contained an alumina substrate. Next, to form a partition layer, Composition 21 was applied to the interlayer insulating layer and the LEDs, pre-baked, patterned and 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 measuring 25 μm. In the matrix pattern, the pattern dimension between openings with a side length of 15 μm was 5 μm, and the pattern dimension between openings with a side length of 25 μm was also 5 μm. The composition was then heated and thermally cured to form a partition layer with a thickness of approximately 4 μm. The thermal curing conditions were as follows: in a nitrogen atmosphere with an oxygen concentration of 20 mass ppm or less, the temperature was raised to 200°C at a rate of 3.5°C / min, heat treatment was carried out at 200°C for 60 minutes, and then cooling to 50°C.

[0174] Next, to form a planarizing layer, Composition 1 was applied and prebaked on the interlayer insulating layer and the LEDs using the method described above. The composition was then patterned and exposed through a photomask having a predetermined pattern, developed, and rinsed to form a plurality of opening patterns extending through the thickness direction up to the LEDs. The opening patterns were circular, with the smallest pattern having a bottom diameter of 2 μm. The resulting material was then heated and thermally cured to form a planarizing layer with a thickness of approximately 4 μm. The thermal curing conditions were as follows: the temperature was increased to 200°C at a rate of 3.5°C / min in a nitrogen atmosphere with an oxygen concentration of 20 ppm by mass or less, and the material was then heated at 200°C for 60 minutes, followed by cooling to 50°C.

[0175] Finally, a counter substrate was attached to the planarizing layer and the partition layer, the support substrate was peeled off, and a drive substrate was attached to fabricate a micro LED display equipped with a plurality of LEDs as light-emitting elements. The light emission of the obtained micro LED display was evaluated by the method described in item 7 above, and the reliability of the display was evaluated by the method described in item 8 above.

[0176] (Examples 102 to 106 and Comparative Examples 101 to 107) In Examples 102 to 106 and Comparative Examples 101 to 107, evaluations were performed in the same manner as in Example 1, except that the photosensitive resin compositions used in the partition wall layer and the planarizing layer were changed to other compositions as shown in Table 3. However, when a composition having negative photosensitivity was used, a photomask in which the light-transmitting and light-shielding portions were reversed was used. The evaluation results of Examples 101 to 106 and Comparative Examples 101 to 107 are shown in Table 4.

[0177]

[0178] Comparative Examples 1 to 6 do not contain the (C) silane compound, and therefore have poor properties. Comparative Examples 7 to 12 do not contain the (A-1) siloxane resin or the (A-2) siloxane resin, and Comparative Examples 8, 9, and 11 do not contain the (C) silane compound, and therefore Comparative Examples 7 to 12 have poor properties. Furthermore, in Comparative Examples 101 to 107, the photosensitive resin composition used in the partition wall layer does not contain the (C) silane compound. In addition, in Comparative Examples 101 to 104, the photosensitive resin composition used in the planarization layer does not contain the (C) silane compound, and in Comparative Examples 105 to 107, the photosensitive resin composition used in the planarization layer does not contain the (A-1) siloxane resin or the (A-2) siloxane resin. Therefore, Comparative Examples 101 to 107 have poor properties.

[0179] The photosensitive resin composition and cured film according to the present invention can be used in display devices and the like.

[0180] 1a, 1b Display device 2 Light-emitting element 3 Interlayer insulating layer 4 Wiring 5 Counter substrate 6 Electrode terminal 8 Driving substrate 15 Partition layer 21 Planarization layer

Claims

1. A photosensitive resin composition comprising (A1) a siloxane resin, (B) a photosensitizer, and (C) a silane compound, the silane compound (C) having a structure represented by chemical formula (1). (In chemical formula (1), １ represents an oxygen atom or a sulfur atom, Y １ R represents a sulfur atom or an amino group. １ , R ２ each independently represents any one selected from the group consisting of a monovalent or divalent organic group having 1 to 20 carbon atoms, a monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle, and a monovalent or divalent organic group having 1 to 20 carbon atoms and an alkoxysilyl group; R １ , R ２ At least one of the above is a monovalent or divalent organic group having 1 to 20 carbon atoms and an alkoxysilyl group.) 2. The photosensitive resin composition according to claim 1, wherein the content of the silane compound (C) is 0.01 to 5 parts by mass per 100 parts by mass of the siloxane resin.

3. In chemical formula (1), X １ The photosensitive resin composition according to claim 1 , wherein is a sulfur atom.

4. In chemical formula (1), R １ , R ２ 2. The photosensitive resin composition according to claim 1, wherein at least one of the above is a monovalent or divalent organic group having 1 to 20 carbon atoms and containing a heterocycle.

5. A photosensitive resin composition comprising (A2) a siloxane resin and (B) a photosensitizer, wherein the (A2) siloxane resin is a resin containing a repeating unit represented by chemical formula (2). (In chemical formula (2), ２ represents an oxygen atom or a sulfur atom, Y ２ R represents a sulfur atom or an amino group. ３ , R ４ each independently represents any one selected from the group consisting of a monovalent or divalent organic group having 1 to 20 carbon atoms, a monovalent or divalent organic group having 1 to 20 carbon atoms containing a heterocycle, and a monovalent or divalent organic group having 1 to 20 carbon atoms and an alkoxysilyl group.

6. The photosensitive resin composition according to claim 5, wherein in the (A2) siloxane resin, the content of the repeating unit represented by chemical formula (2) is 0.01 to 5 mol % relative to 100 mol % of all repeating units consisting of a siloxane structure contained in the siloxane resin.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the photosensitizer (B) is a quinone diazide compound.

8. The photosensitive resin composition according to any one of claims 1 to 6, wherein the photosensitizer (B) is a photopolymerization initiator.

9. The photosensitive resin composition according to any one of claims 1 to 6, further comprising a silane coupling agent other than the silane compound (C), the silane coupling agent having an epoxy group or an oxetanyl group.

10. The photosensitive resin composition according to any one of claims 1 to 6, further comprising water, the content of the water in the photosensitive composition being 0.1 to 5.0% by mass.

11. The photosensitive resin composition according to any one of claims 1 to 6, further comprising particles (D), the particles (D) comprising at least one member selected from the group consisting of titanium dioxide, zirconium oxide, aluminum oxide, talc, mica, white carbon, magnesium oxide, zinc oxide, barium carbonate, and composite compounds thereof.

12. The photosensitive resin composition according to claim 11, wherein the particles (D) are titanium dioxide.

13. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 6.

14. A display device comprising the cured film according to claim 13.

15. The display device of claim 14, comprising a mini LED or a micro LED.

Images