Methods for manufacturing linearly induced radiation components, curing films, liquid crystal display devices, organic EL display devices, and curing films.

Abstract

The present invention has been made in view of the above problems, and aims to provide a radiation-sensitive composition that can form a cured film with excellent radiation sensitivity, storage stability, and development adhesion. The present invention also aims to provide a cured film formed using the above radiation-sensitive composition, a method for manufacturing the cured film, and a liquid crystal display device and an organic EL display device equipped with the above cured film. [Solution] The present invention relates to a radiation-sensitive composition containing an alkali-soluble polymer (A), a radiation-sensitive compound (B), a solvent (E), and an imino group-containing organoxysilane compound (D).

Description

[Technical Field]

[0001] The present invention relates to a radiation-sensitive composition, a cured film, a liquid crystal display device, an organic EL display device, and a method for manufacturing a cured film. [Background technology]

[0002] Display devices are provided with insulating cured films such as interlayer insulating films that insulate between wiring and the substrate, as well as between wiring itself, planarization films, and partitions. Generally, these cured films are formed by exposing and developing a coating film made of a radiation-sensitive composition, followed by heat treatment to thermally cure it.

[0003] The cured film constituting such a display device requires good adhesion to the substrate, and it has been known to improve adhesion using adhesion aids such as silane coupling agents. Examples of such photosensitive resin compositions include those containing an alkali-soluble resin and a silane coupling agent having a specific structure (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-138254 [Overview of the project] [Problems that the invention aims to solve]

[0005] When a silane coupling agent is added to a radiation-sensitive composition to improve adhesion, the storage stability of the radiation-sensitive composition may decrease depending on the type of silane coupling agent used. Therefore, radiation-sensitive compositions are required to possess both adhesion and storage stability.

[0006] The present invention has been made in view of the above problems, and aims to provide a radiation-sensitive composition that can form a cured film with excellent radiation sensitivity, storage stability, and development adhesion. The present invention also aims to provide a cured film formed using the above radiation-sensitive composition, a method for manufacturing the cured film, and a liquid crystal display device and an organic EL display device equipped with the above cured film. [Means for solving the problem]

[0007] According to the present invention, the following radiation-sensitive composition, cured film, liquid crystal display device, organic EL display device, and method for manufacturing the cured film are provided.

[0008] In one embodiment, the present invention is Alkali-soluble polymer (A), Radiation-sensitive compound (B) and, Solvent (E) and, imino group-containing organoxysilane compound (D) and This relates to a radiation-sensitive composition containing [a specific substance].

[0009] In another embodiment, the present invention is The process involves applying the above-mentioned radiation-sensitive composition onto a substrate, A step of removing the solvent from the above-mentioned applied radiation-sensitive composition, A step of irradiating the radiation-sensitive composition from which the above solvent has been removed with radiation, A step of developing the radiation-sensitive composition that has been irradiated with the above radiation, The process involves heating the developed radiation-sensitive composition, This relates to a method for producing a cured film, including the present invention.

[0010] In another embodiment, the present invention is The present invention relates to a cured film formed using the above-mentioned radiation-sensitive composition, and to a liquid crystal display device and an organic EL display device equipped with the above-mentioned cured film. [Effects of the Invention]

[0011] The radiation-sensitive composition of the present invention, by containing an imino group-containing organoxysilane compound (D), can form a cured film with excellent radiation sensitivity, storage stability, and development adhesion. Furthermore, the method for producing the cured film of the present invention, by using the above-mentioned radiation-sensitive composition, can form a cured film with excellent radiation sensitivity, storage stability, and development adhesion. Moreover, the liquid crystal display device and organic EL display device of the present invention are of high quality because they are equipped with the above-mentioned cured film. [Modes for carrying out the invention]

[0012] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0013] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the values ​​indicated before and after "~" as the lower and upper limits, respectively. "Structural unit" refers to a unit that mainly constitutes the main chain structure and is included in the main chain structure in pairs or more.

[0014] In this specification, "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Linear hydrocarbon group" means a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in its main chain and consists only of a linear structure. However, linear hydrocarbon groups may be saturated or unsaturated. "Alicyclic hydrocarbon group" means a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as its ring structure and does not contain an aromatic ring structure. However, an alicyclic hydrocarbon group does not need to consist only of the structure of an alicyclic hydrocarbon; it may also include a linear structure as part of it. "Aromatic hydrocarbon group" means a hydrocarbon group that contains an aromatic ring structure as its ring structure. However, an aromatic hydrocarbon group does not need to consist only of an aromatic ring structure; it may also include a linear structure or an alicyclic hydrocarbon structure as part of it. The ring structure of an alicyclic hydrocarbon group and an aromatic hydrocarbon group may have substituents consisting of hydrocarbon structures. "Cyclic hydrocarbon" includes alicyclic hydrocarbons and aromatic hydrocarbons.

[0015] In this specification, "(meth)acryloyl" encompasses "acryloyl" and "methacryloyl," and "(meth)acrylic" encompasses "acrylic" and "methacrylic." "(meth)acrylate" encompasses "acrylate" and "methacrylate."

[0016] ≪Radiation-sensitive composition≫ The radiation-sensitive composition according to this embodiment (hereinafter also referred to as "the composition") contains an alkali-soluble polymer (A), a radiation-sensitive compound (B), a solvent (E), and an imino group-containing organoxysilane compound (D).

[0017] The following describes each component contained in this composition, as well as any other components that may be added as needed. Unless otherwise specified, each component may be used alone or in combination of two or more components.

[0018] <Imino group-containing organoxysilane compound (D)> The radiation-sensitive composition of this disclosure, by containing an imino group-containing organoxysilane compound (D), can achieve both development adhesion and storage stability.

[0019] Examples of the above-mentioned imino group-containing organoxysilane compound (D) include the compound represented by the following formula (1). [ka] (In formula (1), R 1 This refers to a hydrogen atom or an m-valent organic group having 1 to 20 carbon atoms. R 2 R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. 2 If multiple R 2 They are either the same or different. m is an integer between 1 and 10. However, the above R 1When it is a hydrogen atom, m is 1. R 3 is a divalent organic group having 1 to 20 carbon atoms. R 3 When there are a plurality of R 3 are the same or different from each other. R 4 and R 5 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. R 4 and R 5 When there are a plurality of R 4 and R 5 are the same or different from each other. n is an integer from 0 to 2.)

[0020] As the m-valent organic group having 1 to 20 carbon atoms represented by the above R 1 a group obtained by removing (m - 1) hydrogen atoms from a monovalent organic group having 1 to 20 carbon atoms can be preferably employed.

[0021] Examples of the monovalent organic group having 1 to 20 carbon atoms include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group having a divalent heteroatom-containing group between carbon-carbon bonds or at the end of a carbon chain of this hydrocarbon group, a group in which some or all of the hydrogen atoms of the above hydrocarbon group are substituted with a monovalent heteroatom-containing group, or a combination thereof.

[0022] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like.

[0023] Examples of monovalent linear hydrocarbon groups having 1 to 20 carbon atoms include monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, or monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of monovalent linear or branched saturated hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, isopentyl, and neopentyl groups. Examples of monovalent linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl, propenyl, and butenyl groups; and alkynyl groups such as ethynyl, propynyl, and butynyl groups.

[0024] Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include monocyclic or polycyclic saturated hydrocarbon groups, or monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic saturated hydrocarbon groups include bridged alicyclic hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl groups. Examples of monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups. Examples of polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norborneyl, tricyclodecenyl, and tetracyclododecenyl groups. A bridged alicyclic hydrocarbon group is a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other are bonded together by a linking group containing one or more carbon atoms.

[0025] Examples of the above-mentioned monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthyl groups; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl groups.

[0026] Examples of the monovalent heteroatom-containing groups mentioned above include hydroxyl groups, carboxyl groups, sulfanyl groups, cyano groups, nitro groups, halogen atoms, and the like.

[0027] Examples of the above-mentioned divalent heteroatom-containing groups include -CO-, -C(=O)O-, -CS-, -NR'-, -O-, -S-, -SO-, -SO2-, or combinations thereof. R' is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0028] Among these, R 1 Preferably, the group includes a cyclic structure. The cyclic structure may be an alicyclic structure, an aromatic ring structure, or a heterocyclic structure, and may be monocyclic or polycyclic, and may be saturated or unsaturated. It may also be formed solely of cyclic structures, or it may have a chain-like structure in part. If it has a chain-like structure in part, it may contain heteroatoms such as -O- or -S- between the carbon-carbon bonds in the chain-like structure. The heterocyclic structure is not particularly limited and includes lactone structures, cyclic carbonate structures, cyclic acetal structures, cyclic ether structures, sultone structures, and cyclic amine structures. The group having the above cyclic structure may have a combination of these cyclic structures. Among these, the aromatic ring structure is preferred as the cyclic structure, and the benzene ring is more preferred.

[0029] The above R 2 As a monovalent organic group having 1 to 20 carbon atoms, represented by the above R 1 A monovalent organic group having 1 to 20 carbon atoms can be suitably used in R. 2 A hydrogen atom is preferred as the element.

[0030] The above m is an integer between 1 and 10, preferably between 1 and 3, and more preferably 1.

[0031] The above R 3 As a divalent organic group having 1 to 20 carbon atoms represented by the above R 1A group obtained by removing one hydrogen atom from a monovalent organic group having 1 to 20 carbon atoms can be suitably adopted. Among these, R 3 Preferably, the group is a divalent chain hydrocarbon group having 1 to 20 carbon atoms, and more preferably an alkanediyl group having 1 to 10 carbon atoms.

[0032] The above R 4 and R 5 As a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, the above R 1 A monovalent hydrocarbon group having 1 to 20 carbon atoms can be suitably used. The hydrocarbon group may have substituents. Examples of substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; carboxyl groups; cyano groups; nitro groups; alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonyloxy groups, acyl groups, acyloxy groups, or groups in which the hydrogen atoms of these groups are substituted with halogen atoms; and substituents (T) such as oxo groups (=O).

[0033] The above n is an integer between 0 and 2, preferably 0 or 1, and more preferably 0.

[0034] Specific examples of the above imino group-containing organoxysilane compound (D) include compounds with the following structures. [ka] (In the formula, Et represents an ethyl group and Me represents a methyl group.)

[0035] Specific examples of the above imino group-containing organoxysilane compound (D) include, in addition to the above, Methyleneamino group-containing organoxysilane compounds such as methyleneaminomethyltrimethoxysilane, methyleneaminomethyldimethoxymethylsilane, methyleneaminomethylmethoxydimethylsilane, methyleneaminomethyltriethoxysilane, methyleneaminomethyldiethoxymethylsilane, methyleneaminomethylethoxydimethylsilane, 3-(methyleneamino)propyltrimethoxysilane, 3-(methyleneamino)propyldimethoxymethylsilane, 3-(methyleneamino)propylmethoxydimethylsilane, 3-(methyleneamino)propyltriethoxysilane, 3-(methyleneamino)propyldiethoxymethylsilane, and 3-(methyleneamino)propylethoxydimethylsilane; Benzylideneamino group-containing organoxysilane compounds such as benzylideneaminomethyltrimethoxysilane, benzylideneaminomethyldimethoxymethylsilane, benzylideneaminomethylmethoxydimethylsilane, benzylideneaminomethyltriethoxysilane, benzylideneaminomethyldiethoxymethylsilane, benzylideneaminomethylethoxydimethylsilane, 3-(benzylideneamino)propyldimethoxymethylsilane, 3-(benzylideneamino)propylmethoxydimethylsilane, 3-(benzylideneamino)propyldiethoxymethylsilane, and 3-(benzylideneamino)propylethoxydimethylsilane; Pyridylmethyleneamino group-containing organoxysilane compounds such as pyridylmethyleneaminomethyltrimethoxysilane, pyridylmethyleneaminomethyldimethoxymethylsilane, pyridylmethyleneaminomethylmethoxydimethylsilane, pyridylmethyleneaminomethyltriethoxysilane, pyridylmethyleneaminomethyldiethoxymethylsilane, pyridylmethyleneaminomethylethoxydimethylsilane, 3-(pyridylmethyleneamino)propyltrimethoxysilane, 3-(pyridylmethyleneamino)propyldimethoxymethylsilane, 3-(pyridylmethyleneamino)propylmethoxydimethylsilane, 3-(pyridylmethyleneamino)propyltriethoxysilane, 3-(pyridylmethyleneamino)propyldiethoxymethylsilane, and 3-(pyridylmethyleneamino)propylethoxydimethylsilane; Examples include bisorganoxysilyl group-containing 1,4-xylene-α,α'-diimine compounds such as N,N-bis(trimethoxysilylmethyl)-1,4-xylene-α,α'-diimine, N,N-bis(dimethoxymethylsilylmethyl)-1,4-xylene-α,α'-diimine, N,N-bis(triethoxysilylmethyl)-1,4-xylene-α,α'-diimine, N,N-bis(diethoxymethylsilylmethyl)-1,4-xylene-α,α'-diimine, and N,N-bis(ethoxydimethylsilylmethyl)-1,4-xylene-α,α'-diimine.

[0036] The lower limit of the content of compound (D) is preferably 0.1 parts by mass, more preferably 0.3 parts by mass, and still more preferably 0.5 parts by mass, per 100 parts by mass of polymer (A) incorporated into this composition. The upper limit of the content of compound (D) is preferably 10 parts by mass, more preferably 5 parts by mass, still more preferably 1 part by mass, and particularly preferably 0.9 parts by mass, per 100 parts by mass of polymer (A) incorporated into this composition. Setting the content of compound (D) within the above range is preferable from the viewpoint of radiation sensitivity, storage stability, and development adhesion.

[0037] <Alkali-soluble polymer (A)> The alkali-soluble polymer (A) is an aggregate of polymerization chains (hereinafter, this aggregate is also referred to as the "base polymer"). The alkali-soluble polymer (A) is preferably a polymer (A1) containing a structural unit (I) having an alkali-soluble group. Examples of alkali-soluble groups include acid groups and maleimide groups. Examples of acid groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, and phosphonic acid groups, among which carboxyl groups are preferred. Hereinafter, "alkali-soluble polymer" refers to a polymer that can dissolve or swell in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 25°C. Polymer (A1) will be described below.

[0038] (polymer (A1)) The polymer (A1) described above is preferably a (meth)acrylic polymer containing structural unit (I) having an alkali-soluble group. Polymer (A1) may also contain structural units other than structural unit (I). The following describes each structural unit included in polymer (A1).

[0039] [Structural Unit (I)] By including structural units (I) having alkali-soluble groups in polymer (A1), the solubility (alkali solubility) of polymer (A1) in an alkaline developer can be increased, and the curing reactivity can be enhanced.

[0040] Structural unit (I) is not particularly limited as long as it has an alkali-soluble group, but it is preferably at least one selected from the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units. In this specification, "phenolic hydroxyl group" means a hydroxyl group that is directly bonded to an aromatic ring (e.g., a benzene ring, naphthalene ring, anthracene ring, etc.).

[0041] Structural unit (I) is preferably a structural unit derived from an unsaturated monomer having an acid group. Specific examples of unsaturated monomers having an acid group include: Examples of monomers constituting structural units having a carboxyl group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; and unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Examples of monomers constituting structural units having a sulfonic acid group include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acryloyloxyethyl sulfonic acid, etc. Examples of monomers constituting structural units having phenolic hydroxyl groups include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acrylate, etc. Each of these can be listed.

[0042] Furthermore, maleimide can be used as the monomer constituting the structural unit (I).

[0043] Among these, monomers constituting structural units having a carboxyl group and monomers constituting structural units having a phenolic hydroxyl group are preferred, and (meth)acrylic acid and p-isopropenylphenol are more preferred.

[0044] The base polymer may contain one or more structural units (I) in combination.

[0045] When polymer (A1) contains structural unit (I), the lower limit of the content of structural unit (I) (total content if multiple types are included) is preferably 1% by mass, more preferably 3% by mass, and still more preferably 5% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 60% by mass, more preferably 50% by mass, still more preferably 40% by mass, and particularly preferably 30% by mass. Setting the content of structural unit (I) within the above range is preferable because it can impart good solubility to alkaline developing solutions.

[0046] [Structural Units (II)] Polymer (A1) preferably contains structural unit (II) having a crosslinkable group, as this can further enhance radiation sensitivity and adhesion of the cured film. The crosslinkable group is not particularly limited as long as it undergoes a curing reaction by heat treatment, but at least one selected from the group consisting of oxyranyl group, oxetanyl group, and ethylenically unsaturated group is preferred in terms of high thermosetting properties, and at least one selected from the group consisting of oxyranyl group and oxetanyl group is more preferred.

[0047] (Structural units having oxetanyl and oxyranyl groups) When the above crosslinkable groups are an oxetanyl group and an oxyranyl group, structural unit (II) is preferably a structural unit derived from an unsaturated monomer having an oxetanyl group and an oxyranyl group. Specifically, for example, a structural unit represented by the following formula (a1) or formula (a2) is preferred.

[0048] [ka] (In formulas (a1) and (a2), R 21 This is a monovalent group having an oxyranyl group or an oxetanyl group. R α This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X 1 (This is a single bond or a divalent linking group.)

[0049] In the above equations (a1) and (a2), R 21 Examples include oxyranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl groups, 3-methyloxetanyl groups, and 3-ethyloxetanyl groups.

[0050] X 1 Examples of divalent linking groups include alkanediyl groups such as methanediyl, ethanediyl, and 1,3-propanediyl groups, as well as groups containing -O- between the carbon-carbon bonds of the alkanediyl group.

[0051] Specific examples of monomers that give structural unit (II) represented by the above formulas (a1) and (a2) include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6Examples include decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, etc.

[0052] Among these, glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate are preferred.

[0053] (Structural units containing ethylenically unsaturated groups) When the above crosslinkable group is an ethylenically unsaturated group, structural unit (II) preferably has an ethylenically unsaturated group in its side chain, and more preferably has a side chain structure with 3 to 20 carbon atoms having an ethylenically unsaturated group at its terminal. Specifically, for example, a structural unit represented by the following formula (a3) ​​is preferred.

[0054] [ka] (In formula (a3), R 22 This is either a hydrogen atom or a methyl group. R α This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X 2 (This is a divalent linking group.)

[0055] X in the above formula (a3) 2Examples of divalent linking groups represented by include divalent hydrocarbon groups having 1 to 12 carbon atoms, divalent groups having -O-, -COO-, -OCO-, -NHCO-, -CONH-, -OCONH-, or -NHCOO- between any carbon-carbon bonds or at any terminal of the divalent hydrocarbon group (hereinafter also referred to as "divalent heteroatom-containing groups"), and divalent groups in which any hydrogen atom in the divalent hydrocarbon group or divalent heteroatom-containing group is substituted with a hydroxyl group, a carboxyl group, etc.

[0056] The base polymer may contain one or more structural units (II) in combination.

[0057] When polymer (A1) contains structural unit (II), the lower limit of the content of structural unit (II) (total content if multiple types are included) is preferably 1% by mass, more preferably 5% by mass, even more preferably 10% by mass, and particularly preferably 15% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. Setting the content of structural unit (II) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured film to have sufficiently high heat resistance and chemical resistance.

[0058] The polymer (A1) preferably contains the structural unit (II), but may further contain a polymer (A') that is different from polymer (A1) and contains the structural unit (II) having a crosslinkable group. Polymer (A') only needs to contain the structural unit (II), and is not particularly limited to other structural units, but may contain the structural unit (I) or structural units (III) to (IV) described later.

[0059] [Structural Unit (III)] The polymer (A1) described above may further contain structural units (III) derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic rings, aromatic vinyl compounds, N-substituted maleimide compounds, heterocyclic vinyl compounds, conjugated dienes, nitrogen-containing vinyl compounds, and unsaturated dialkyl dicarboxylate compounds. Introducing these structural units (III) into the polymer is preferable because it allows for adjusting the glass transition temperature of the polymer (A1) components and improving the pattern shape of the resulting cured film.

[0060] Examples of the alkyl (meth)acrylate esters mentioned above include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate.

[0061] Examples of (meth)acrylic acid esters having the above alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and tricyclo(meth)acrylate. 2,6 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.0 2,5 Examples include decane-8-yloxyethyl and isobornyl (meth)acrylate.

[0062] Examples of (meth)acrylic acid esters having the above aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0063] Examples of the above aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, and the like.

[0064] Examples of the above N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, and N-naphthylmaleimide.

[0065] Examples of vinyl compounds having the above heterocyclic structure include tetrahydrofuranylmethyl (meth)acrylate, tetrahydropyranylmethyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 5-methyl-1,3-dioxan-5-ylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (meth)acrylate (γ-butyrolactone-2-yl), (meth)acrylate glycerin carbonate, (meth)acrylate (γ-lactam-2-yl), and N-(meth)acryloxyethylhexahydrophthalimide.

[0066] Examples of the above-mentioned conjugated diene compounds include 1,3-butadiene and isoprene; examples of the above-mentioned nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; and examples of the above-mentioned unsaturated dicarboxylate dialkyl ester compounds include diethyl itaconate. In addition to the above, other monomers constituting the structural units include, for example, vinyl chloride, vinylidene chloride, and vinyl acetate.

[0067] The monomer that gives the above structural unit (III) preferably includes at least one selected from the group consisting of alkyl (meth)acrylates, N-substituted maleimide compounds, and vinyl compounds having a heterocyclic structure.

[0068] The base polymer may contain one or more structural units (III) in combination.

[0069] When polymer (A1) contains structural unit (III), the lower limit of the content of structural unit (III) (or the total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, even more preferably 20% by mass, and particularly preferably 30% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 90% by mass, and more preferably 80% by mass. Setting the content of structural unit (III) within the above range is preferable because it allows the glass transition temperature of polymer (A1) to be raised to a moderate level.

[0070] [Structural Units (IV)] In the case of the radiation-sensitive composition of the present invention being a chemically amplified composition, it is preferable from the viewpoint of forming a coating film with excellent developability that the polymer (A1) further comprises a structural unit (IV) having one or more groups selected from the group consisting of a group represented by the following formula (iv) and an acid-dissociable group. [ka] (In formula (iv), R B1 , R B2 and R B3 Each of these is independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. However, R B1 , R B2 and R B3 At least one of them is an alkoxy group having 1 to 6 carbon atoms. The asterisk (*) indicates a bonding operation.

[0071] R B1 ~R B3 Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, and tert-butoxy groups. Of these, R B1 ~R B3 The alkoxy group is preferably a methoxy group or an ethoxy group.

[0072] R B1 ~RB3 The C1-C10 alkyl group may be linear or branched. Examples of C1-C10 alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, and tert-butyl groups. Of these, methyl, ethyl, or propyl groups are preferred.

[0073] From the viewpoint of obtaining a heat-resistant cured film by forming a cross-linked structure, and from the viewpoint of improving the storage stability of the radiation-sensitive composition, R B1 ~R B3 Preferably, at least one of them is an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all are alkoxy groups.

[0074] Among the above, R B1 The group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, and even more preferably a methoxy group or an ethoxy group. B2 and R B3 The group is preferably a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, and more preferably a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0075] Structural unit (IV) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as "unsaturated monomer"), and more specifically, it is preferably at least one selected from the group consisting of structural units represented by the following formula (iv-1) and structural units represented by the following formula (iv-2). [ka] (In equations (iv-1) and (iv-2), R β1 This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R B21 and RB22 Each of these is independently a divalent aromatic ring group or a chain-like hydrocarbon group. R B1 , R B2 and R B3 This is equivalent to equation (iv) above.

[0076] In equations (iv-1) and (iv-2) above, R B21 , R B22 The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalenediyl group. The divalent chain hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.

[0077] The above R B21 , R B22 Among the above, a divalent chain-like hydrocarbon group is preferred, and an alkanediyl group having 1 to 4 carbon atoms is more preferred.

[0078] Specific examples of monomers constituting structural unit (IV) include, for example, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethyldimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc.; trimethoxy(4-vinyl naphthyl Examples include (4-)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloxynaphthyltrimethoxysilane, etc.; 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, etc.

[0079] The above-mentioned "acid-dissociable group" refers to a group in which a hydrogen atom in an acidic functional group, such as a phenolic hydroxyl group, carboxyl group, or sulfonic acid group, has been substituted, and which dissociates upon the action of an acid. For example, the acid generated from a photoacid generator upon exposure dissociates the acid-dissociable group, generating a carboxyl group, etc. This creates a difference in solubility in the developer between the exposed and unexposed areas of the coating film, enabling pattern formation.

[0080] The above acid-dissociable group is preferably a group represented by the following formula (iv-3) or a group represented by the following formula (iv-4). [ka] (In formula (iv-3), R B4 and R B5 Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which at least some of the hydrogen atoms of the hydrocarbon group are substituted with a hydroxyl group, a halogen atom, or a cyano group. However, R B4 and R B5 It is impossible for both to be hydrogen atoms. R B6 This refers to a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom or a sulfur atom between carbon atoms or at the end of the bond of this hydrocarbon group, or a group in which at least some of the hydrogen atoms of these groups are substituted with a hydroxyl group, a halogen atom, or a cyano group. R B7 It is a carbon atom or a silicon atom. In formula (iv-4), R B8 ~R B14 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. m is either 1 or 2. If m is 2, there are multiple R B11 and R B12 These may be the same or different. In equations (iv-3) and (iv-4), "*" indicates the site of bonding.

[0081] R B4 ~R B6 As the hydrocarbon group having 1 to 30 carbon atoms of ~R above, a group obtained by expanding the number of carbon atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R in the above formula (1) can be preferably adopted. 1

[0082] R in the above formula (iv-3) B4 ~R B6 are each independently preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

[0083] R B8 ~R B14 As the hydrocarbon group having 1 to 12 carbon atoms of ~R above, a group corresponding to 1 to 12 carbon atoms among the hydrocarbon groups having 1 to 30 carbon atoms of ~R above can be preferably adopted. B4 ~R B6

[0084] As the structural unit having the acid dissociable group, for example, the structural units represented by the following formulas (iv-3-1) and (iv-4-1) are preferable. [Chemical formula] 〔

[0085] In the above formulas (iv-3-1) and (iv-4-1), m1 is 0 or 1. R β1 is synonymous with R in the above formulas (iv-1) and (iv-2). R β1 is synonymous with R in the above formulas (iv-3) and (iv-4). R B4 ~R B14 is synonymous with ~R in the above formulas (iv-3) and (iv-4). R B4 ~R B14 is synonymous with ~R in the above formulas (iv-3) and (iv-4).

[0086] L in the above formulas (iv-3-1) and (iv-4-1) B1 、L B2 are each independently a single bond or a divalent linking group.

[0087] The above L B1 , L B2 Examples of divalent linking groups in this compound include alkanediyl groups, cycloalkanediyl groups, alkenediyl groups, and arenediyl groups.

[0088] Examples of monomers that give rise to the structural unit represented by the above formula (iv-4-1) include tetrahydrofurfuryl (meth)acrylate and tetrahydrofuranyl (meth)acrylate.

[0089] The base polymer may contain one or more structural units (IV).

[0090] When polymer (A1) contains structural unit (IV), the lower limit of the content of structural unit (IV) (total content if multiple types are included) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 12% by mass, relative to the total structural units constituting the base polymer. The upper limit of the above content is preferably 70% by mass, more preferably 60% by mass, and even more preferably 50% by mass. Setting the content of structural unit (IV) within the above range is preferable in that the coating film exhibits better resolution.

[0091] (Method for synthesizing polymer (A1)) Polymer (A1) can be produced, for example, by using an unsaturated monomer into which each of the above-mentioned structural units can be introduced, in a suitable solvent in the presence of a polymerization initiator, according to known methods such as radical polymerization.

[0092] Examples of polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl. The amount of polymerization initiator used is preferably 0.01 to 30 parts by mass per 100 parts by mass of the total amount of monomers used in the reaction.

[0093] Examples of polymerization solvents include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1 to 60% by mass of the total amount of the reaction solution.

[0094] In polymerization, the reaction temperature is typically 30°C to 180°C. The reaction time varies depending on the type of polymerization initiator and monomer and the reaction temperature, but is usually 0.5 to 10 hours. The polymer obtained by the polymerization reaction may be used in the preparation of the radiation-sensitive composition while still dissolved in the reaction solution, or it may be isolated from the reaction solution before being used in the preparation of the radiation-sensitive composition. The polymer can be isolated by known isolation methods, such as pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator.

[0095] The weight-average molecular weight (Mw) of the polymer (A) in terms of polystyrene, determined by gel permeation chromatography (GPC), is preferably 2,000 or more. An Mw of 2,000 or more is preferable because it allows for the production of a cured film with sufficiently high heat resistance and chemical resistance, as well as good developability. The Mw of the polymer is more preferably 5,000 or more, even more preferably 6,000 or more, and particularly preferably 7,000 or more. Furthermore, from the viewpoint of improving film-forming properties, the Mw is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 15,000 or less.

[0096] Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. When the base polymer consists of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above ranges.

[0097] The content of polymer (A) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, based on the total amount of solids contained in the radiation-sensitive composition. Furthermore, the content of polymer (A) is preferably 95% by mass or less, and more preferably 90% by mass or less, based on the total amount of solids contained in the radiation-sensitive composition. Setting the content of polymer (A) within the above range is preferable because it allows for the production of a cured film that exhibits sufficiently high chemical resistance, as well as good developability and transparency.

[0098] <Radiation sensitive compound (B)> The radiation-sensitive composition contains a radiation-sensitive compound (B) together with the polymer (A) described above. By irradiating the radiation-sensitive composition with radiation (visible light, ultraviolet light, far ultraviolet light, etc.), a positive or negative pattern can be formed. Examples of the radiation-sensitive compound (B) include photoacid generators, photopolymerization initiators, and photobase generators. Of these, at least one selected from the group consisting of quinone diazide compounds (B-1), photopolymerization initiators (B-2), and photoacid generators (B-3) can preferably be used as the radiation-sensitive compound (B).

[0099] Here, when a photoacid generator or photobase generator is used as the radiation-sensitive compound (B), a positive or negative pattern can be formed by changing the solubility of the exposed area in the developer. Furthermore, when the photoacid generator or photobase generator functions as a curing catalyst and accelerates the curing of the exposed area, a negative pattern can also be formed by decreasing the solubility of the exposed area in the developer. On the other hand, when a photopolymerization initiator is used as the radiation-sensitive compound, for example, the curing of the exposed area is accelerated by reaction with a compound having a vinyl group or a (meth)acryloyl group, and a negative pattern can be formed by decreasing the solubility of the exposed area in the developer.

[0100] (Quinone diazide compound (B-1)) Quinone diazide compounds (B-1) are compounds that generate carboxylic acids upon irradiation with radiation. Examples of quinone diazide compounds (B-1) include condensates of a phenolic compound or an alcoholic compound (hereinafter also referred to as the "nucleus") and an orthonaphthoquinone diazide compound. Of these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the nucleus and an orthonaphthoquinone diazide compound. Specific examples of the nucleus include, for example, the compounds described in paragraphs

[0065] to

[0070] of Japanese Patent Publication No. 2014-186300.

[0101] Specific examples of quinone diazide compounds (B-1) include 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, and 1,4-bis[1-(4-hydroxyphenyl)-1- Examples include ester compounds of a phenolic hydroxyl group-containing compound selected from methylethylbenzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Among these, a condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinone diazide-5-sulfonic acid chloride is preferred as the quinone diazide compound (B-1).

[0102] These quinone diazide compounds (B-1) may be used alone or in combination of two or more. The lower limit of the quinone diazide compound (B-1) content is preferably 0.01 parts by mass, more preferably 1 part by mass, and even more preferably 5 parts by mass, per 100 parts by mass of polymer (A) incorporated into the composition. The upper limit of the quinone diazide compound (B-1) content is preferably 40 parts by mass, more preferably 30 parts by mass, and even more preferably 25 parts by mass, per 100 parts by mass of polymer (A) incorporated into the composition. A quinone diazide compound (B-1) content of 0.01 parts by mass or more is preferable because sufficient carboxylic acid is generated upon irradiation of the composition, allowing for a sufficiently large difference in solubility between the irradiated and unirradiated portions in the developer, and enabling good patterning. It is also preferable because it allows for a larger amount of carboxylic acid involved in the reaction with the polymer components, ensuring sufficient heat resistance and chemical resistance. On the other hand, by limiting the quinone diazide compound content to 40 parts by mass or less, the amount of unreacted quinone diazide compound after exposure can be sufficiently reduced, which is preferable in that it can suppress the decrease in developability due to residual quinone diazide compound.

[0103] (Photopolymerization initiator (B-2)) As the photopolymerization initiator (B-2), a compound that is sensitive to active light with a wavelength of 300 nm or more (preferably 300 to 450 nm) and initiates and promotes the polymerization of the polymerizable monomer (X1) described later can be preferably used. When using a photopolymerization initiator (B-2) that is not directly sensitive to active light with a wavelength of 300 nm or more, it may be used in combination with a sensitizer to enable it to be sensitive to active light with a wavelength of 300 nm or more and to initiate and promote the polymerization of the polymerizable monomer (X1).

[0104] Known compounds can be used as the photopolymerization initiator (B-2). Specific examples include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboric acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, at least one selected from the group consisting of oxime ester compounds, α-aminoketone compounds, and hexaarylbiimidazole compounds is preferred, with oxime ester compounds or α-aminoketone compounds being more preferred, in order to increase the sensitivity of the composition. Furthermore, commercially available products may be used as the photopolymerization initiator (B-2), such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF).

[0105] These photopolymerization initiators (B-2) may be used alone or in combination of two or more. The lower limit of the content of the photopolymerization initiator (B-2) is preferably 1 part by mass, more preferably 5 parts by mass, and even more preferably 10 parts by mass, per 100 parts by mass of the polymerizable monomer (X1) described later. The upper limit of the content of the photopolymerization initiator (B-2) is preferably 45 parts by mass, more preferably 35 parts by mass, and even more preferably 25 parts by mass, per 100 parts by mass of the polymerizable monomer (X1).

[0106] When this composition contains a photopolymerization initiator (B-2) as the radiation-sensitive compound (B), it becomes a negative-type radiation-sensitive composition containing a polymerizable monomer (X1).

[0107] The polymerizable monomer (X1) described above is a compound having one or more polymerizable groups, preferably two or more. Examples of polymerizable groups include ethylenically unsaturated groups, oxyranyl groups, oxetanyl groups, and N-alkoxymethylamino groups. Of these, ethylenically unsaturated groups and N-alkoxymethylamino groups are preferred in terms of high polymerizability, and vinyl group-containing groups such as (meth)acryloyl groups, vinyl groups, and vinylphenyl groups are more preferred. Specifically, the polymerizable monomer (X1) is preferably a compound having two or more (meth)acryloyl groups, or a compound having two or more N-alkoxymethylamino groups, and a compound having two or more (meth)acryloyl groups is particularly preferred.

[0108] The polymerizable monomer (X1) may be used alone or in combination of two or more types. The lower limit of the polymerizable monomer (X1) content is preferably 20 parts by mass, more preferably 25 parts by mass, and even more preferably 30 parts by mass, per 100 parts by mass of polymer (A) contained in this composition. The upper limit of the polymerizable monomer (X1) content is preferably 300 parts by mass, more preferably 200 parts by mass, and even more preferably 100 parts by mass, per 100 parts by mass of polymer (A).

[0109] (Photoacid generator (B-3)) When the radiation-sensitive compound (B) includes a photoacid generator (B-3), it becomes a chemically amplified radiation-sensitive composition. In this case, the polymer (A) includes the above structural unit (IV).

[0110] The photoacid generator (B-3) can be any compound that generates acid in response to radiation (i.e., a radiation-sensitive acid generator), and is not particularly limited. Examples of photoacid generators (B-3) include oximesulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and the like.

[0111] Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds include, for example, the compounds described in paragraphs

[0078] to

[0106] of Japanese Patent Publication No. 2014-157252 and the compounds described in International Publication No. 2016 / 124493. From the viewpoint of radiation sensitivity, at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds can be preferably used as the photoacid generator.

[0112] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (t1). [ka] (In formula (t1), R 40 This refers to a monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are substituted with substituents. The asterisk (*) indicates a bonding operation.

[0113] In the above equation (t1), R 40 Examples of monovalent hydrocarbon groups include C1-C20 alkyl groups, C4-C12 cycloalkyl groups, and C6-C20 aryl groups. Examples of substituents include C1-C5 alkyl groups, C1-C5 alkoxy groups, oxo groups, and halogen atoms.

[0114] Examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (2-[2-(4-methylphenylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493. Examples of commercially available oximesulfonate compounds include Irgacure PAG121 from BASF.

[0115] Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphasulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphasulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphasulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide.

[0116] These photoacid generators (B-3) may be used alone or in combination of two or more. The lower limit of the photoacid generator (B-3) content is preferably 0.01 parts by mass, more preferably 0.1 parts by mass, and even more preferably 2 parts by mass, per 100 parts by mass of polymer (A) incorporated into the composition. The upper limit of the photoacid generator (B-3) content is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 10 parts by mass, per 100 parts by mass of polymer (A) incorporated into the composition. A photoacid generator (B-3) content of 0.01 parts by mass or more is preferable because it allows for good patterning and ensures sufficient heat resistance. Furthermore, a photoacid generator (B-3) content of 30 parts by mass or less is preferable because it sufficiently reduces the amount of unreacted photoacid generator after exposure, thereby suppressing a decrease in developability due to residual photoacid generator.

[0117] <Solvent (E)> The radiation-sensitive composition of this disclosure is a liquid composition in which a polymer (A), a radiation-sensitive compound (B), and a compound (D), and other components as may be added, are preferably dissolved or dispersed in a solvent (E). The solvent used is preferably an organic solvent that dissolves each component of the radiation-sensitive composition and does not react with each component.

[0118] The solvent (E) is not particularly limited and can include, for example, alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, etc. Solvent (E) may be used alone or in combination of two or more types.

[0119] Examples of alcohol-based solvents include methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1-methoxy-2-propanol, alkyl alcohols such as diacetone alcohol, and aromatic alcohols such as benzyl alcohol.

[0120] Examples of ether-based solvents include ethylene glycol monoalkyl ethers such as diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether; and dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.

[0121] Examples of ester solvents include carboxylic acid esters such as ethyl acetate, i-propyl acetate, n-butyl acetate, amyl acetate, ethyl lactate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; polyhydric alcohol carboxylate solvents such as propylene glycol diacetate; polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; and lactone solvents such as γ-butyrolactone and valerolactone.

[0122] Examples of ketone-based solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0123] Among these, ether-based solvents and ester-based solvents are preferred, with diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate being more preferred.

[0124] The content of solvent (E) in this composition is not particularly limited, but it is preferable that the concentration of solids (components other than solvent (E)) in this composition be adjusted to be within the following ranges. The lower limit of the solids concentration in this composition is preferably 5% by mass, more preferably 8% by mass, and still more preferably 15% by mass. On the other hand, the upper limit of the solids concentration is preferably 60% by mass, more preferably 40% by mass, and still more preferably 30% by mass. A solids concentration of 5% by mass or more in the radiation-sensitive composition is preferable because it ensures a sufficient film thickness when the radiation-sensitive composition is applied to a substrate. Furthermore, a solids concentration of 60% by mass or less is preferable because it prevents the film thickness from becoming excessively large, and allows for a moderately high viscosity of the radiation-sensitive composition, ensuring good coatability.

[0125] <Adhesion enhancer (F)> The radiation-sensitive composition of this disclosure may contain an adhesion aid (F) to improve the adhesion between the substrate and the cured film.

[0126] Examples of the adhesion aid (F) include functional silane coupling agents such as silane coupling agents having reactive functional groups such as carboxyl groups, methacryloyl groups, vinyl groups, isocyanate groups, epoxy groups, and amino groups. Specifically, examples include trimethoxysilylbenzoic acid, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. As the adhesion aid (F), for example, compounds described in Japanese Patent Publication No. 2006-126397 and Japanese Patent Publication No. 2009-204865 can also be used. Adhesion enhancer (F) can be used alone or in combination of two or more types.

[0127] If the composition contains an adhesion aid (F), the lower limit of the adhesion aid (F) content is preferably 0.1 parts by mass, more preferably 1 part by mass, and still more preferably 5 parts by mass, per 100 parts by mass of polymer (A) blended in the composition. The upper limit of the adhesion aid (F) content is preferably 40 parts by mass, more preferably 30 parts by mass, and still more preferably 20 parts by mass, per 100 parts by mass of polymer (A) blended in the composition. It is preferable to set the adhesion aid (F) content within the above ranges because it provides excellent adhesion.

[0128] <Other ingredients> The radiation-sensitive composition of this disclosure may further contain, in addition to the polymer (A), radiation-sensitive compound (B), compound (D), and solvent (E) described above, other components (hereinafter also referred to as "other components"). Examples of other components include surfactants, polymerization inhibitors, antioxidants, and chain transfer agents. The proportions of these components are appropriately selected according to each component, within a range that does not impair the effects of this disclosure.

[0129] The radiation-sensitive composition of this disclosure, comprising a polymer (A), a radiation-sensitive compound (B), and a compound (D), can exhibit excellent radiation sensitivity, development adhesion, and storage stability. Such a radiation-sensitive composition of this disclosure is useful as a radiation-sensitive composition for liquid crystal display devices and organic EL display devices.

[0130] ≪Method for manufacturing a cured film≫ The method for manufacturing a cured film according to this embodiment is: (Step 1) A step of forming a coating film using a radiation-sensitive composition, (Step 2) A step of irradiating at least a portion of the above coating film with radiation, (Step 3) A step of developing the above coating film after irradiation with radiation, (Step 4) The process includes heating the developed coating film.

[0131] The following provides a detailed explanation of each step.

[0132] <Process 1: Paint film formation process> In this process, a radiation-sensitive composition is applied to the surface on which the coating film will be formed (hereinafter also referred to as the "film-forming surface"), and preferably a heat treatment (pre-bake) is performed to remove the solvent and form a coating film on the film-forming surface. The material of the film-forming surface is not particularly limited. For example, when forming a planarization film using a radiation-sensitive composition, the radiation-sensitive composition is applied to a substrate on which switching elements such as TFTs are provided, and a coating film is formed. As the substrate, for example, a glass substrate or a resin substrate can be used.

[0133] Methods for applying the radiation-sensitive composition include, for example, spray coating, roll coating, spin coating, slit die coating, bar coating, and inkjet coating. Among these, spin coating, slit die coating, or bar coating are preferred. Pre-baking conditions vary depending on the type and proportion of each component in the radiation-sensitive composition, but for example, 60 to 130°C for 0.5 to 10 minutes is preferred. The thickness of the formed coating film (i.e., the film thickness after pre-baking) is preferably 1 to 12 μm.

[0134] <Process 2: Exposure Process> In this process, at least a part of the coating film formed in the above Process 1 is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured film (for example, an interlayer insulating film) having a pattern can be formed. Examples of the radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible light rays, X-rays, and electron beams. Among these, ultraviolet rays are preferable, and for example, g-line (wavelength 436 nm), i-line (wavelength 365 nm) can be mentioned. The exposure amount of the radiation is preferably 0.1 to 20,000 J / m 2 is preferable.

[0135] <Process 3: Development Process> In this process, the coating film irradiated with radiation in the above Process 2 is developed. Specifically, positive development is performed in which the coating film irradiated with radiation in the above Process 2 is developed with a developer to remove the irradiated portion of the radiation. Examples of the developer include an aqueous solution of an alkali (basic compound). Examples of the alkali include sodium hydroxide, tetramethylammonium hydroxide, and the alkalis exemplified in paragraph

[0127] of JP-A-2016-145913. From the viewpoint of obtaining appropriate developability, the alkali concentration in the aqueous alkali solution is preferably 0.1 to 5.0% by mass. Examples of the developing method include appropriate methods such as the puddle method, dipping method, rocking immersion method, and shower method. The development time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. In addition, after the development process, it is preferable to perform a rinsing process by running water washing on the patterned coating film.

[0136] <Process 4: Heating Process> In this step, the coating developed in step 3 is subjected to a heating process (post-bake). This allows the hardening reaction of the film to proceed, resulting in a cured film exhibiting good chemical resistance. Post-bake can be performed using a heating device such as an oven or a hot plate. Regarding the post-bake conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when heating on a hot plate, and 10 to 80 minutes when heating in an oven. In this way, a cured film having the desired pattern can be formed on the substrate.

[0137] Furthermore, a post-exposure step may be included between steps 3 and 4 described above. By irradiating the developed coating with radiation, a cured film with excellent melt flow resistance and transparency during the heating process can be formed. Examples of radiation include charged particle beams such as ultraviolet light, far ultraviolet light, visible light, X-rays, and electron beams. Among these, ultraviolet light is preferred, for example, g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m 2 It is preferable.

[0138] ≪Cured film≫ The cured film of this disclosure is formed using the above-mentioned radiation-sensitive composition. The radiation-sensitive composition of this disclosure has high radiation sensitivity, excellent storage stability, and can form a cured film with good developability. Therefore, the cured film can be preferably used, for example, as an interlayer insulating film, planarizing film, spacer, protective film, colored pattern film for color filters, partition wall, etc., in a display device, and is particularly suitable as an interlayer insulating film.

[0139] ≪Display device≫ The display device of this disclosure comprises a cured film formed using the above-mentioned radiation-sensitive composition. Examples of display devices include liquid crystal displays and organic electroluminescent (EL) displays. Examples of cured films for liquid crystal displays formed with the above-mentioned radiation-sensitive composition include interlayer insulating films, planarization films, protective films for color filters, and spacers. Examples of cured films for organic EL displays formed with the above-mentioned radiation-sensitive composition include interlayer insulating films, banks, planarization films, partitions, and pixel separation insulating films. [Examples]

[0140] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are based on mass unless otherwise specified.

[0141] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were measured by the following method. • Measurement method: Gel permeation chromatography (GPC) method • Equipment: HLC-8420GPC manufactured by Tosoh Corporation • Mobile phase: tetrahydrofuran Column temperature: 40°C ·Flow rate: 1.0mL / min • Sample concentration: 1.0% by mass • Sample injection volume: 100 μL • Detector: Differential refractometer • Standard material: Monodisperse polystyrene

[0142] <Synthesis of polymer (A)> [Synthesis Example A-1] Synthesis of (meth)acrylic polymer (A-1) In a flask equipped with a condenser and a stirrer, 12 parts of 2,2'-aziobis(isobutyrate)dimethyl and 100 parts of diethylene glycol ethyl methyl ether were charged. Subsequently, 5 parts of methacrylic acid, 20 parts of 4-isopropenylphenol, 25 parts of glycidyl methacrylate, 10 parts of 3,4-epoxycyclohexylmethyl methacrylate, 9 parts of N-cyclohexylmaleimide, 17 parts of N-phenylmaleimide, 10 parts of (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, and 4 parts of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 80°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-1). The solid content concentration of this polymer solution was 33% by mass, the Mw of polymer (A-1) was 10000, and the molecular weight distribution (Mw / Mn) was 2.2.

[0143] [Synthesis Examples A-2~A-3] Synthesis of polymers (A-2)~(A-3) A polymer solution containing polymers (A-2) to (A-3) having the same solid content concentration, molecular weight, and molecular weight distribution as polymer (A-1) was obtained using the same method as in Synthesis Example A-1, except that the components used were of the types and amounts (parts by mass) shown in Table 1. In Table 1 below, "-" indicates that the corresponding component was not used. The same applies to subsequent tables.

[0144] The monomers used in the synthesis of the polymers (A-1) to (A-3) described above are as follows. (Monomers that give structural units (I)) • MA: Methacrylic acid • 4IPP: 4-Isopropenylphenol

[0145] (Monomers that give structural unit (II)) GMA: Glycidyl methacrylate ECHMA: 3,4-Epoxycyclohexylmethyl methacrylate

[0146] (Monomers that give structural unit (III)) • CHMI:N-cyclohexylmaleimide • PMI: N-phenylmaleimide • MMA: Methyl methacrylate DOXA: (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate

[0147] (Monomers that give structural unit (IV)) • MPTES: 3-Methacryloxypropyltriethoxysilane

[0148] [Table 1]

[0149] <Synthesis example D-1> In a flask equipped with a stirrer, reflux apparatus, dropping funnel, and thermometer, 509.3 g (4.8 mol) of benzaldehyde and 1,200 ml of toluene were charged. At 20-40°C, 717.2 g (4.0 mol) of 3-aminopropyltrimethoxysilane was added dropwise over 2 hours, and the mixture was stirred at that temperature for 1 hour. The reaction mixture was transferred to a separatory funnel, and the lower aqueous layer, which had separated into two layers, was removed. The upper layer was distilled to obtain 768.8 g of 3-(benzylideneamino)propyltrimethoxysilane (compound (D-3)) as a fraction with a boiling point of 149°C / 0.4 kPa.

[0150] <Preparation of radiation-sensitive composition> The polymer (A), radiation-sensitive compound (B), compound (D), solvent (E), and adhesion promoter (F) used in the preparation of the radiation-sensitive composition are shown below.

[0151] ≪Potassium polymerization (A)≫ • A-1~A-3: Polymers synthesized in synthesis examples A-1~A-3 (A-1)~(A-3)

[0152] ≪Radiation-sensitive compound (B)≫ · B-1: Condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) B-2: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol)

[0153] ≪Compound (D)≫ • D-1: 1-Phenyl-N-[3-(triethoxysilyl)propyl]methanymine (X-12-1172ES, manufactured by Shin-Etsu Chemical Co., Ltd.) D-2: 3-Triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (KBE-9103P, manufactured by Shin-Etsu Chemical Co., Ltd.) • D-3: Compound synthesized in example D-1 (D-3) d-1: Triethoxysilylaminopropane ·d-2:N-2-(aminoethyl)-8-aminooctyltrimethoxysilane

[0154] ≪Solvent (E)≫ • E-1: Diethylene glycol methyl ethyl ether (EDM) • E-2: Propylene glycol monomethyl ether (PGME) • E-3: Propylene glycol monomethyl ether acetate (PGMEA)

[0155] ≪Adhesion enhancer (F)≫ ·F-1: Glycidyloxypropyltrimethoxysilane

[0156] [Example 1] To a polymer solution containing polymer (A-1), 20 parts of radiation-sensitive compound (B-1), 0.3 parts of compound (D-1), and 10 parts of adhesion promoter (F-1) were mixed in an amount equivalent to 100 parts (solids) of polymer (A-1). Solvents (E-1) and (E-2) were then added to achieve a final solids content of 20% by mass. The ratio of solvents in the radiation-sensitive composition was (E-1):(E-2)=50:50% by mass. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare the radiation-sensitive composition.

[0157] [Examples 2-11, Comparative Examples 1-3] The radiation-sensitive compositions of Examples 2-11 and Comparative Examples 1-3 were prepared using the same method as in Example 1, except that the types and amounts (parts by mass) of each component shown in Table 2 were used.

[0158] [Table 2]

[0159] <Rating> Cured films were formed from the radiation-sensitive compositions of Examples 1-11 and Comparative Examples 1-3, and the following items were evaluated using the method described below. The evaluation results are shown in Table 3.

[0160] [Radiation sensitivity] Hexamethyldisilazane (HMDS) was applied to a silicon substrate using a spinner and heated at 60°C for 1 minute (HMDS treatment). A radiation-sensitive composition was applied to the HMDS-treated silicon substrate using a spinner and the pressure was reduced to 50 Pa in a vacuum drying apparatus. Next, a coating film with a thickness of 3.0 μm was formed by pre-baking on a hot plate at 90°C for 2 minutes. This coating film was exposed using an exposure machine (Canon's "PLA-501F": using an ultra-high pressure mercury lamp) through a mask with a line-and-space pattern of 10 μm width, varying the exposure amount. Subsequently, it was developed by the liquid-build method at 25°C with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. The development time was 60 seconds. Next, it was washed with ultrapure water for 1 minute and then dried to form a pattern on the HMDS-treated silicon substrate. At this time, the minimum exposure dose required to form a 10 μm line-and-space pattern was measured, and this measurement was defined as the radiation sensitivity.

[0161] [Development adhesion] Using a spinner, a radiation-sensitive composition was applied to a silicon substrate that had not undergone hexamethyldisilazane (HMDS) treatment, and then the pressure was reduced to 50 Pa in a vacuum drying apparatus. Next, it was pre-baked on a hot plate at 90°C for 2 minutes to form a coating with an average thickness of 3.0 μm. This coating was then exposed to a mercury lamp at 365 nm with an exposure dose of 2000 J / m² through a pattern mask having a line-and-space pattern with a width of 1 to 50 μm. 2 The substrate was irradiated with ultraviolet light. Next, a developing solution consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used, and development was performed at 25°C for 60 seconds, followed by rinsing with ultrapure water for 1 minute. At this time, the minimum width of the line-and-space pattern that remained on the substrate without peeling off was measured. The following evaluation criteria were used. A smaller minimum width indicates better development adhesion. ○: Minimum width measurement is 10 μm or less △: When the measured minimum width is greater than 10 μm and less than or equal to 50 μm. ×: If the minimum width measurement is greater than 50 μm, or if the image could not be resolved and evaluation could not be performed.

[0162] [Storage stability] A hardened film was formed using the radiation-sensitive composition immediately after preparation, and the radiation sensitivity was measured using the method described above. Separately, the radiation-sensitive composition immediately after preparation was sealed in a light-shielded, airtight container and stored at 25°C for 7 days. After 7 days, the container was opened, and the radiation sensitivity was measured in the same manner as before storage, except that the radiation-sensitive composition inside the container was used. Furthermore, the rate of increase in radiation sensitivity (minimum exposure) before and after storage (sensitivity increase rate) was calculated using the following formula (Y) from the radiation sensitivity before and after the 7-day storage period. A lower sensitivity increase rate indicates better storage stability. Sensitivity increase rate = [(Sensitivity after storage - Sensitivity before storage) / Sensitivity before storage] × 100 …(Y) The following evaluation criteria were used for evaluation. ○: When the calculated sensitivity increase rate is less than 10% △: When the calculated sensitivity increase rate is between 10% and less than 30% ×: If the calculated sensitivity increase rate is 30% or more, or if the image could not be resolved and therefore could not be evaluated.

[0163] [Table 3]

[0164] As shown in Table 3, each of the radiation-sensitive compositions in Examples 1 to 11 exhibited good practical properties in terms of radiation sensitivity, development adhesion, and storage stability, demonstrating a good balance of various characteristics. In contrast, Comparative Examples 1 to 3 received a "×" rating in at least one of these characteristics, and all were inferior to Examples 1 to 11.

Claims

1. Alkali-soluble polymer (A), Radiation-sensitive compound (B), Solvent (E) and, Imino group-containing organoxysilane compound (D) and A radiation-sensitive composition containing the following:

2. The radiation-sensitive composition according to claim 1, wherein the above compound (D) is represented by the following formula (1). 【Chemistry 1】 (In formula (1), R １ This is a hydrogen atom or an m-valent organic group having 1 to 20 carbon atoms. R ２ R is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. ２ If multiple R ２ They are either the same or different. m is an integer between 1 and 10. However, the above R １ If it is a hydrogen atom, then m is 1. R ３ R is a divalent organic group having 1 to 20 carbon atoms. ３ If multiple R ３ They are either the same or different. R ４ and R ５ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. R ４ and R ５ When there are a plurality of R ４ and R ５ they may be the same or different from each other. n is an integer between 0 and 2.

3. The above R ２ The radiation-sensitive composition according to claim 2, wherein the atom is a hydrogen atom.

4. The radiation-sensitive composition according to claim 1, wherein the content of compound (D) is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of polymer (A).

5. The radiation-sensitive composition according to claim 1, wherein the polymer (A) is a polymer (A1) containing a structural unit (I) having an alkali-soluble group.

6. The radiation-sensitive composition according to claim 1, wherein the polymer (A) contains a structural unit (II) having a crosslinkable group, or further comprises a polymer (A') different from the polymer (A) that contains a structural unit (II) having a crosslinkable group.

7. The radiation-sensitive composition according to claim 6, wherein the above-mentioned crosslinkable group is at least one selected from the group consisting of an oxyranyl group, an oxetanyl group, and an ethylenically unsaturated group.

8. The above R １ The radiation-sensitive composition according to claim 2, wherein the composition includes a cyclic structure.

9. A step of applying the radiation-sensitive composition according to any one of claims 1 to 8 onto a substrate, A step of removing the solvent from the above-mentioned applied radiation-sensitive composition, A step of irradiating the radiation-sensitive composition from which the above solvent has been removed with radiation, A step of developing the radiation-sensitive composition that has been irradiated with the above radiation, The process involves heating the developed radiation-sensitive composition, A method for manufacturing a cured film, including [the specified element].

10. A cured film formed using the radiation-sensitive composition according to any one of claims 1 to 8.

11. The cured film according to claim 10, which is an interlayer insulating film.

12. A liquid crystal display device comprising the cured film described in claim 10.

13. An organic EL display device comprising the cured film described in claim 10.

Images