Methods for manufacturing radioactive linear components, hardened films, representation elements, and hardened films.

Abstract

The primary objective of this invention is to provide a radiation-sensitive composition that has a low dielectric constant, excellent bending resistance, excellent melt resistance, and can form a cured film with minimal developing residue. [Solution] The present invention relates to a radiation-sensitive composition comprising a polymer component (A), a quinone diazide compound (B), and a solvent (C), wherein the polymer component (A) contains, in the same polymer or different polymers, at least one structural unit (I) selected from the group consisting of structural units having acid groups and structural units derived from maleimide, a structural unit (II) containing an alicyclic epoxy group, a structural unit (III) derived from (meth)acrylate having an alicyclic structure (excluding structural unit (II)), and a structural unit (IV) having a cyclic ether structure and a methylene group bonded to a carbon atom constituting the cyclic ether structure in its main chain.

Description

Technical Field

[0001] The present invention relates to a radiation-sensitive composition, a cured film, a display element, and a method for producing a cured film.

Background Art

[0002] In display elements, insulating cured films such as interlayer insulating films for insulating between wirings and substrates or between wirings, planarization films, and partition walls are provided. Generally, the cured film is formed by subjecting a coating film formed from a radiation-sensitive composition to exposure and development treatments and then performing a heat treatment to thermally cure it.

[0003] As a material for forming such a cured film, a photosensitive resin composition containing an acrylic copolymer obtained by copolymerizing an unsaturated carboxylic acid, an epoxy group-containing unsaturated compound, and an olefinic unsaturated compound at a specific ratio, a quinonediazide compound, a solvent, and a specific silane-based surfactant is known (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In recent years, cured films (for example, planarization films and interlayer insulating films) used in display devices such as organic light-emitting diodes (OLEDs) are required to have even lower dielectric constants and better bending resistance due to changes in panel and element structures. However, a highly flexible cured film with excellent bending resistance may have low melt resistance, and there have been problems such as hole patterns being filled during the baking process. Also, reducing development residues has become increasingly important in order to improve productivity.

[0006] This invention has been made in view of the above problems, and its main objective is to provide a radiation-sensitive composition that has a low dielectric constant, excellent bending resistance, excellent melt resistance, and can form a cured film with little developing residue. [Means for solving the problem]

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

[0008] In one embodiment, the present invention is Polymer component (A), Quinone diazide compound (B) and, Solvent (C) and, A radiation-sensitive composition containing, The polymer component (A) is At least one structural unit (I) selected from the group consisting of structural units having an acid group and structural units derived from maleimide, Structural unit (II) containing an alicyclic epoxy group, Structural unit (III) derived from (meth)acrylate having an alicyclic structure (excluding structural unit (II)), A structural unit (IV) having a cyclic ether structure and a methylene group bonded to the carbon atoms constituting the cyclic ether structure as its main chain is included in the same polymer or different polymers. This relates to radiation-sensitive compositions.

[0009] In another embodiment, the present invention is The steps include: applying the radiation-sensitive composition onto a substrate; A step of removing the solvent from the coated radiation-sensitive composition, A step of irradiating the radiation-sensitive composition from which the solvent has been removed with radiation, A step of developing the radiation-sensitive composition that has been irradiated with the aforementioned radiation, The process involves thermally curing 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 radiation-sensitive composition, and a display element comprising the cured film. [Effects of the Invention]

[0011] The present invention provides a radiation-sensitive composition that has a low dielectric constant, excellent bending resistance, excellent melt resistance, and can form a cured film with minimal developing residue. [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 two or more units.

[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 curable composition according to this embodiment (hereinafter also referred to as "this composition") Polymer component (A), Quinone diazide compound (B) and, Solvent (C) and, A radiation-sensitive composition containing, The polymer component (A) is At least one structural unit (I) selected from the group consisting of structural units having an acid group and structural units derived from maleimide, Structural unit (II) containing an alicyclic epoxy group, Structural unit (III) derived from (meth)acrylate having an alicyclic structure (excluding structural unit (II)), A structural unit (IV) having a cyclic ether structure and a methylene group bonded to the carbon atoms constituting the cyclic ether structure as its main chain is included in the same polymer or different polymers. This relates to radiation-sensitive compositions.

[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.

[0018] <Polymer component (A)> Polymer component (A) is an aggregate of polymers containing structural units (I) to (IV). These structural units may be contained in the same polymer, or they may be contained in different polymers. It is sufficient that the polymers constituting polymer component (A) as a whole contain structural units (I) to (IV). Therefore, polymer component (A) may consist of one type of polymer or two or more types of polymers, as long as it contains structural units (I) to (IV). Polymer component (A) may also contain structural units other than structural units (I) to (IV). Furthermore, polymer component (A) may further contain polymers that do not have any of the structural units (I) to (IV).

[0019] (Structural Unit (I)) By including a polymer containing structural unit (I) in polymer component (A), good alkali solubility can be imparted to the polymer component. In this specification, "alkali solubility" means dissolving in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0020] Structural unit (I) is at least one structural unit selected from the group consisting of structural units having an acid group (I-1) and structural units derived from maleimide (I-2).

[0021] Structural unit (I-1) is not particularly limited as long as it has an acid group. Examples of acid groups include carboxyl groups, sulfonic acid groups, and phenolic hydroxyl groups. Specifically, structural unit (I) is preferably at least one selected from the group consisting of structural units having a carboxyl group, structural units having a phenolic hydroxyl group, and structural units having a sulfonic acid group, and more preferably at least one selected from the group consisting of structural units having a carboxyl group and structural units having a phenolic hydroxyl group. In this specification, "phenolic hydroxyl group" means a hydroxyl group directly bonded to an aromatic ring (e.g., a benzene ring, naphthalene ring, anthracene ring, etc.).

[0022] The structural unit (I-1) is not particularly limited, but from the viewpoint of copolymerizability, it is preferable that it is a structural unit derived from an unsaturated monomer having an acid group.

[0023] Specific examples of monomers that provide structural unit (I-1) include, as monomers that provide structural units having a carboxyl group, 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; as monomers that provide structural units having a sulfonic acid group, for example, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, and (meth)acryloyloxyethylsulfonic acid; and as monomers that provide structural units having a phenolic hydroxyl group, for example, 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, and hydroxyphenyl(meth)acrylate.

[0024] Structural unit (I-2) is a structural unit derived from maleimide. A structural unit derived from maleimide is a structural unit derived from unsubstituted maleimide as shown in the following formula.

[0025] [ka]

[0026] As for structural unit (I), from the viewpoint of storage stability and thermal morphological stability, it is preferable to use a combination of a structural unit having a carboxyl group and a structural unit that gives a phenolic hydroxyl group or a structural unit derived from maleimide.

[0027] In polymer component (A), the content of structural unit (I) (total content if multiple types are included) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and particularly preferably 10% by mass or more, relative to the total structural units constituting polymer component (A), from the viewpoint of providing good solubility in alkaline developer. Furthermore, from the viewpoint of sufficiently creating a difference in solubility in alkaline developer between the exposed and unexposed areas and obtaining a good shape pattern, the content of structural unit (I) is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer component (A).

[0028] (Structural Unit (II)) By including a polymer component (A) containing structural unit (II), a cured film with excellent melt flow resistance and chemical resistance can be formed.

[0029] An alicyclic epoxy group is a group having a structure in which the epoxy group is formed by two adjacent carbon atoms and an oxygen atom that constitute the alicyclic group. Examples of alicyclic epoxy groups include 2,3-epoxycyclobutyl group, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decane-yl group, 5,6-epoxytricyclo[5.2.1.0 2,6 ] Decane-yl group, 2,3-epoxytricyclo[4.2.1.0 2,5 Examples include the nonan-yl group. Among these, the 3,4-epoxycyclohexyl group and the 3,4-epoxytricyclo[5.2.1.0 2,6 A decane-yl group is preferred.

[0030] Examples of monomers that provide structural unit (II) include vinyl compounds having alicyclic epoxy groups and (meth)acrylates having alicyclic epoxy groups, but among these, (meth)acrylates having alicyclic epoxy groups are preferred.

[0031] As the structural unit (II), a structural unit represented by any of the following formulas (II-1) to (II-3) is preferred. [ka]

[0032] R 1 Each of these is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, with hydrogen atoms and methyl groups being preferred.

[0033] L 1 Each of these is independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.

[0034] Examples of divalent hydrocarbon groups having 1 to 20 carbon atoms include divalent chain hydrocarbon groups having 1 to 20 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0035] Examples of divalent chain hydrocarbon groups having 1 to 20 carbon atoms include alkanediyl groups such as methanediyl, ethanediyl, propanediyl, and butanediyl groups; alkenediyl groups such as ethendiyl, propendiyl, and butendiyl groups; and alkynediyl groups such as ethingiyl, propindiyl, and butyndiyl groups.

[0036] Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include divalent monocyclic alicyclic saturated hydrocarbon groups such as a cyclopentanediyl group and a cyclohexanediyl group, divalent monocyclic alicyclic unsaturated hydrocarbon groups such as a cyclopentenediyl group and a cyclohexenediyl group, divalent polycyclic alicyclic saturated hydrocarbon groups such as a norbornanediyl group, an adamantanediyl group, and a tricyclodecanediyl group, and divalent polycyclic alicyclic unsaturated hydrocarbon groups such as a norbornenediyl group and a tricyclodecenediyl group.

[0037] Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include arenediyl groups such as a benzenediyl group, a toluenediyl group, a xylenediyl group, a naphthalenediyl group, and an anthracenediyl group, and arenediylalkanediyl groups such as a benzenediylmethanediyl group, a benzenediylethanediyl group, a naphthalenediylmethanediyl group, and an anthracenediylmethanediyl group.

[0038] n is an integer of from 1 to 5, preferably an integer of from 1 to 3, more preferably 1 or 2.

[0039] k1 is 0 or 1.

[0040] X 1 is a hydroxy group, a halogen atom, a cyano group, a nitro group, an alkyl group, or an alkoxy group.

[0041] As the alkyl group, an alkyl group having 1 to 10 carbon atoms represented by R 11 ~R 13 in the following formula (VI) can be preferably employed. As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms represented by R 11 ~R 13 in the following formula (VI) can be preferably employed.

[0042] a1 is an integer of from 0 to 3. When a"1" is 2 or more, a plurality of X 1 [[ID=3⑥]]are the same as or different from each other.

[0043] Specific examples of structural unit (II) include, but are not limited to, those listed below. [ka] (In the formula, R 1 This is equivalent to equations (II-1) to (II-3) above.

[0044] The content of the above structural unit (II) (total content if multiple types are included) is preferably 10% by mass or more, more preferably 12% by mass or more, and even more preferably 15% by mass or more, relative to the total structural units constituting polymer component (A). The above content is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. By setting the content of structural unit (II) within the above range, a cured film with excellent melt flow resistance and chemical resistance can be formed.

[0045] (Structural Unit (III)) By including polymer component (A) with a polymer containing structural unit (III), a cured film with excellent dielectric constant and chemical resistance can be formed.

[0046] Structural unit (III) is a structural unit derived from (meth)acrylate having an alicyclic structure, excluding those that fall under structural unit (II).

[0047] Examples of alicyclic structures include those with 3 to 20 ring members.

[0048] The alicyclic structure with 3 to 20 ring members is not particularly limited as long as it has an alicyclic structure, and may have monocyclic, bicyclic, tricyclic, tetracyclic, or polycyclic structures with more members, and may be a bridged ring structure, a spirocyclic structure, a ring aggregate structure in which multiple rings are directly linked by single or double bonds, or a combination thereof. Among these, it is preferable to have a bridged ring structure of monocyclic, bicyclic, or tricyclic, such as cyclopentane, cyclohexane, norbornane, adamantane, and tricyclo[5.2.1.0 2,6 Decane is preferred, and among these, tricyclo[5.2.1.02,6 Decane, norbornane, and cyclohexane are more preferred.

[0049] As the structural unit (III), a structural unit represented by any of the following formulas (III-1) to (III-4) is preferred. [ka]

[0050] R 2 Each of these is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, with hydrogen atoms and methyl groups being preferred.

[0051] L 2 Each of these is independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of divalent hydrocarbon groups having 1 to 20 carbon atoms are L in formulas (II-1) to (II-3) above. 1 The same divalent hydrocarbon group having 1 to 20 carbon atoms as represented by can be suitably used.

[0052] p is an integer between 1 and 5, preferably between 1 and 3, and more preferably 1 or 2.

[0053] k2 is either 0 or 1.

[0054] X 2 X is a hydroxyl group, halogen atom, cyano group, nitro group, alkyl group, or alkoxy group. Examples of alkyl groups and alkoxy groups are X in formulas (II-1) to (II-3) above. 1 The items listed above can be suitably adopted.

[0055] a2 is an integer between 0 and 3. If a2 is 2 or greater, multiple X 2 They are either identical or different from one another.

[0056] Specific examples of structural unit (III) include, but are not limited to, those listed below. [ka] (In the formula, R 2 This is equivalent to equations (III-1) to (III-4) above.

[0057] The content of the above structural unit (III) (total content if multiple types are included) is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer component (A). The above content is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less. By setting the content of structural unit (III) within the above range, a cured film with excellent dielectric constant and radiation sensitivity can be formed.

[0058] (Structural Unit (IV)) By including a polymer component (A) that contains a polymer having a cyclic ether structure and a structural unit (IV) in its main chain that has a methylene group bonded to a carbon atom constituting the cyclic ether structure, a cured film with excellent bending resistance can be formed.

[0059] The cyclic ether structure of structural unit (IV) preferably has 5 or 6 ring members, specifically a tetrahydrofuran ring structure or a tetrahydropyran structure. Structural unit (IV) may have a substructure in which a cyclic ether structure and a methylene group bonded to the carbon atoms constituting the cyclic ether structure are introduced into the polymer main chain. A preferred specific example is a structure in which structural unit (IV) has one or two methylene groups constituting the polymer main chain, and the main chain portion of the polymer constituting structural unit (IV) is a repeating unit of a structure consisting of a cyclic ether structure and one or two methylene groups. The cyclic ether structure of structural unit (IV) may have substituents on the ring portion.

[0060] More specifically, structural unit (IV) is preferably a structural unit represented by the following formula (IV). [ka] (In formula (IV), R A1 This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R A2 is a hydrogen atom or -COOR A3 That is. R A3 This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. m is either 0 or 1.

[0061] In the above equation (IV), R A1 or R A3 Examples of monovalent hydrocarbon groups having 1 to 30 carbon atoms represented by include linear or branched saturated hydrocarbon groups having 1 to 30 carbon atoms, linear or branched unsaturated hydrocarbon groups having 2 to 30 carbon atoms, alicyclic hydrocarbon groups having 3 to 30 carbon atoms, and aromatic hydrocarbon groups having 6 to 30 carbon atoms.

[0062] Specific examples of linear or branched saturated hydrocarbon groups having 1 to 30 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Specific examples of linear or branched unsaturated hydrocarbon groups having 2 to 30 carbon atoms include alkenyl groups such as ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, and 2-butenyl; and alkynyl groups such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl.

[0063] Examples of alicyclic hydrocarbon groups having 3 to 30 carbon atoms include groups having either an alicyclic monocyclic hydrocarbon structure with 3 to 30 carbon atoms or an alicyclic polycyclic hydrocarbon structure with 6 to 30 carbon atoms as their ring structure. The alicyclic monocyclic hydrocarbon structure with 3 to 30 carbon atoms and the alicyclic polycyclic hydrocarbon structure with 6 to 30 carbon atoms may be either saturated or unsaturated. Specific examples of rings possessed by alicyclic hydrocarbon groups include cyclopentane rings, cyclohexane rings, cycloheptane rings, cyclooctane rings, cyclopentene rings, cyclohexene rings, cycloheptene rings, cyclooctene rings, cyclodecene rings, norbornane rings, bicyclo[2.2.2]octane rings, adamantane rings, and the like.

[0064] Aromatic hydrocarbon groups having 6 to 30 carbon atoms include groups having either a monocyclic aromatic hydrocarbon structure or a polycyclic aromatic hydrocarbon structure with 6 to 30 carbon atoms as their ring structure. Specific examples of rings possessed by aromatic hydrocarbon groups include benzene rings, naphthalene rings, anthracene rings, indene rings, and fluorene rings.

[0065] R A1 or R A3 Each of the above is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.

[0066] Specific examples of structural units (IV) include the structural units represented by equations (IV-1) to (IV-11) below. [ka]

[0067] For example, the structural unit represented by formula (IV) can be introduced into the polymer by polymerization using a diene compound represented by formula (IVA) as a monomer. Preferred specific examples of the diene compound include methyl 2-(allyloxymethyl)(meth)acrylate, ethyl 2-(allyloxymethyl)(meth)acrylate, and n-propyl 2-(allyloxymethyl)(meth)acrylate. [ka] (In formula (IVA), R A1 and R A2 This is equivalent to equation (IV) above.

[0068] The content of structural unit (IV) in polymer (A) (total content if multiple types are included) is preferably 1 to 40% by mass relative to the total structural units constituting polymer component (A). By setting the content of structural unit (IV) within the above range, a cured film with superior heat resistance and bending resistance can be obtained. From the viewpoint of obtaining a cured film with superior heat resistance and bending resistance, the content of structural unit (IV) in polymer component (A) is more preferably 2% by mass or more, and even more preferably 5% by mass or more. Furthermore, from the viewpoint of suppressing melting of the composition and pattern collapse when heated at a relatively high temperature during film formation (post-bake), the content of structural unit (IV) is more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer component (A).

[0069] (Structural units other than structural units (I) to structural units (IV)) Polymer component (A) may further contain structural units other than structural units (I) to (IV) described above. Examples of other structural units include structural unit (V) derived from N-substituted maleimide compounds, structural unit (VI) having an alkoxysilyl group, structural unit (VII) derived from aromatic vinyl compounds, structural unit (VIII) having a hydroxyl group, structural unit (IX) derived from alkyl methacrylate compounds, and structural unit (X) having an epoxy group (excluding those corresponding to structural unit (II)).

[0070] (Structural unit (V)) Examples of N-substituted maleimide compounds constituting structural unit (V) include compounds in which a hydrogen atom bonded to the nitrogen atom of maleimide is replaced by a monovalent hydrocarbon group. Examples of such monovalent hydrocarbon groups include monovalent linear hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups. Of these, in order to further improve heat resistance, it is preferable that the N-substituted maleimide compound constituting structural unit (V) has a monovalent cyclic hydrocarbon group, and more preferably has a monovalent alicyclic hydrocarbon group having a monocyclic, cross-linked, or spirocyclic ring.

[0071] The structural unit (V) is preferably a structural unit represented by the following formula (V). [ka] (In formula (V), R 5 It is a monovalent cyclic hydrocarbon group. R 6 and R 7 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0072] In the above equation (V), R 5 The cyclic hydrocarbon group may have a ring structure that is directly bonded to the nitrogen atom, or the ring structure may be bonded via a divalent linking group. Examples of divalent linking groups include methylene groups, ethylene groups, and alkanediyl groups such as 1,3-propanediyl groups. Of these, R 5 Preferably, the ring structure of the cyclic hydrocarbon group is directly bonded to the nitrogen atom, and more preferably, the alicyclic hydrocarbon group is directly bonded to the nitrogen atom. 6 and R 7 The atom is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0073] Specific examples of N-substituted maleimide compounds include, as compounds having an alicyclic hydrocarbon group, 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, etc.; and as compounds having an aromatic hydrocarbon group, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. The N-substituted maleimide compound is preferably at least one selected from the group consisting of N-cyclohexylmaleimide, N-(4-methylcyclohexyl)maleimide, N-phenylmaleimide, and N-(4-methylphenyl)maleimide, and more preferably at least one selected from the group consisting of N-cyclohexylmaleimide and N-phenylmaleimide.

[0074] When polymer component (A) contains the above structural unit (V), the content ratio of the above structural unit (V) (total content ratio if multiple types are included) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer component (A), from the viewpoint of improving melt flow resistance. From the viewpoint of radiation sensitivity, the above content ratio is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0075] (Structural Unit VI) Polymer component (A) may further contain structural units (VI) having an alkoxysilyl group. Examples of alkoxysilyl groups include the group represented by the following formula (VI). [ka] (In formula (VI), R 11 , R 12 and R 13 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 11 , R 12 and R 13 One or more of these are alkoxy groups having 1 to 6 carbon atoms. The asterisk (*) represents a bonding operation.

[0076] In the above equation (VI), R 11 ~R 13 Examples of alkoxy groups having 1 to 6 carbon atoms represented by include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy groups. Of these, R 11 ~R 13 The alkoxy group represented by preferably has 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group.

[0077] R 11 ~R 13 The alkyl group having 1 to 10 carbon atoms represented by R may be linear or branched. 11 ~R 13 Examples of alkyl groups having 1 to 10 carbon atoms represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. Of these, R 11 ~R 13 The alkyl group represented is preferably a methyl group, an ethyl group, or a propyl group.

[0078] R 11 ~R 13One of the groups represented is an alkoxy group having 1 to 6 carbon atoms. The remaining 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, more preferably a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms.

[0079] R 11 ~R 13 Preferably, two or more of these are alkoxy groups having 1 to 6 carbon atoms, and more preferably, all of them are alkoxy groups having 1 to 6 carbon atoms.

[0080] The structural unit (VI) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as an "unsaturated monomer"). Specifically, it is preferably at least one selected from the group consisting of the structural unit represented by the following formula (VI-1) and the structural unit represented by the following formula (VI-2). [ka] (In equations (VI-1) and (VI-2), R A This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R 7 and R 8 Each of these is independently a divalent aromatic ring group or a chain-like hydrocarbon group. R 11 , R 12 and R 13 This is equivalent to equation (VI) above.

[0081] In the above equations (VI-1) and (VI-2), R 7 , R 8The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group. The divalent linear hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms, and even more preferably a linear alkanediyl group having 1 to 4 carbon atoms.

[0082] Specific examples of monomers that give structural unit (VI) include styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc.; trimethoxy(4-vinylnaphthyl) Examples include silanes, 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. Among these, styryltrimethoxysilane, styryltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and 4-(meth)acryloxybutyltrimethoxysilane are preferred, and 3-(meth)acryloxypropyltrimethoxysilane and 3-(meth)acryloxypropyltriethoxysilane are more preferred.

[0083] When polymer component (A) contains the above structural unit (VI), the content of the above structural unit (VI) (total content if multiple types are included) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, relative to the total structural units constituting polymer component (A). The above content is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. It is preferable to set the content of structural unit (VI) within the above range because it is possible to obtain a cured film with superior radiation sensitivity and chemical resistance.

[0084] (Structural Unit (VII)) The aromatic vinyl compounds constituting structural unit (VII) are not particularly limited, but examples include styrene compounds such as 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, and diphenylethylene; vinylnaphthalene compounds such as vinylnaphthalene and divinylnaphthalene; and heterocyclic vinyl compounds such as vinylpyridine. Of these, styrene compounds are preferred among the aromatic vinyl compounds.

[0085] When polymer component (A) contains the above structural unit (VII), the content ratio of the above structural unit (VII) (total content ratio if multiple types are included) is preferably 0.5% by mass or more, and more preferably 1% by mass or more, relative to all structural units constituting polymer component (A). The above content ratio is preferably 30% by mass or less, and more preferably 25% by mass or less. Setting the content ratio of structural unit (VII) within the above range is preferable because it is possible to obtain a cured film with a better pattern shape, the glass transition temperature of polymer component (A) does not become too high, and a decrease in developability can be suppressed.

[0086] (Structural Unit (VIII)) The structural unit (VIII) is preferably derived from an unsaturated monomer having a hydroxyl group (alcoholic hydroxyl group). Specifically, this includes structural units derived from monomers having one or more hydroxyl groups bonded to a saturated chain hydrocarbon group. The polymer component (A) containing structural unit (VIII) is preferable because it can suppress the decrease in pattern-forming ability caused by variations in pre-bake temperature during film formation, enabling the formation of a good pattern, and also from the viewpoint of radiation sensitivity. Structural unit (VIII) is not particularly limited, but examples include (meth)acrylic compounds and maleimide compounds.

[0087] Specific examples of structural unit (VIII) include (meth)acrylic compounds such as hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, glycerol mono(meth)acrylate, etc.; and maleimide compounds such as N-(hydroxymethyl)maleimide, N-(2-hydroxyethyl)maleimide, N-(3-hydroxypropyl)maleimide, etc.

[0088] When polymer component (A) contains the above structural unit (VIII), the content ratio of the above structural unit (VIII) (total content ratio if multiple types are included) is 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to all structural units constituting polymer component (A), from the viewpoint of suppressing a decrease in pattern formation ability due to variations in pre-bake temperature. From the viewpoint of suppressing a decrease in developability, the above content ratio is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0089] (Structural Unit (IX)) Structural unit (IX) can be included in polymer component (A) for purposes such as adjusting the glass transition temperature of the polymer. The monomer constituting structural unit (IX) is preferably a methacrylate compound in which the alkyl group bonded to the ester group has 1 to 10 carbon atoms. Examples include alkyl acrylate compounds such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, tert-butyl acrylate, and 2-ethylhexyl acrylate.

[0090] When polymer component (A) contains the above structural unit (IX), the content of the above structural unit (IX) (total content if multiple types are included) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, relative to all structural units constituting polymer component (A). The above content is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

[0091] (Structural unit (X)) Structural unit (X) is a structural unit derived from an unsaturated monomer having an oxyranyl group or an oxetanyl group, excluding those corresponding to structural unit (II). Specific examples of structural unit (X) include at least one selected from the group consisting of structural units represented by the following formula (X-1) and structural units represented by the following formula (X-2).

[0092] [ka] (In equations (X-1) and (X-2), R 20 This refers to a group having an oxiranil group or an oxetanil group (excluding alicyclic epoxy groups). R A1 This is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. L 3 (This is a single bond or a divalent linking group.)

[0093] In equations (X-1) and (X-2) above, R 20 Examples include the oxyranyl group, oxetanyl group, and 3-ethyloxetanyl group.

[0094] L 3 Examples of divalent linking groups include methylene groups, ethylene groups, alkanediyl groups such as 1,3-propanediyl groups, and divalent groups in which any methylene group of an alkanediyl group is replaced with -O-.

[0095] Specific examples of monomers having an epoxy group include glycidyl (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, and the like.

[0096] When polymer component (A) contains the above structural unit (X), the content ratio of the above structural unit (X) (total content ratio if multiple types are included) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer component (A). The above content ratio is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

[0097] (Other structural units) Other structural units include, in addition to those mentioned above, unsaturated dicarboxylic acid dialkyl ester compounds such as diethyl itaconate; unsaturated dicarboxylic acid anhydrides such as phthalic anhydride; conjugated diene compounds such as 1,3-butadiene and isoprene; nitrogen-containing vinyl compounds such as (meth)acrylonitrile, (meth)acrylamide, N-vinylalkylamide, and N-vinylpyrrolidone; and structural units derived from monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate. In polymer component (A), the content of other structural units is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, relative to the total structural units constituting polymer component (A).

[0098] The proportion of each structural unit is typically equivalent to the proportion of monomers used in the production of polymer component (A).

[0099] To adjust solubility and taper angle, embodiments can be adopted in which polymer component (A) contains two or more polymers. For example, by mixing a polymer (A1) that does not contain structural unit (IV), which has a cyclic ether structure and a methylene group bonded to the carbon atoms constituting the cyclic ether structure in its main chain, with a polymer (A2) that contains structural unit (IV), solubility is improved compared to the case in which a single polymer is included, and as a result, sensitivity may be improved. When two or more polymers are used in combination, it is preferable that polymer component (A) includes a polymer (A1) containing structural units (I), (II), and (III), and a polymer (A2) containing structural units (I), (II), and (IV).

[0100] The mixing ratio (mass ratio) of polymer (A1) and polymer (A2) is preferably 50:50 to 98:2, more preferably 60:40 to 95:5, and even more preferably 70:30 to 90:10.

[0101] In polymer component (A), the weight-average molecular weight (Mw) 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 acquisition of a cured film with sufficiently high chemical resistance and good developability. More preferably, Mw is 5,000 or more, even more preferably 6,000 or more, and particularly preferably 8,000 or more. Furthermore, from the viewpoint of improving film formation, Mw is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, even more preferably 18,000 or less, and particularly preferably 15,000 or less. When polymer component (A) consists of two or more polymers, it is preferable that each polymer satisfies the above range.

[0102] In polymer component (A), 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 2.7 or less. If polymer component (A) consists of two or more polymers, it is preferable that each polymer satisfies the above ranges for Mw and Mw / Mn.

[0103] The content of polymer component (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 component (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 component (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.

[0104] Polymer component (A) 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, etc., according to a known method such as radical polymerization. Specifically, examples of polymerization initiators to be used include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl. The ratio 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. Examples of polymerization solvents include alcohols, ethers, ketones, esters, hydrocarbons, etc.

[0105] In the polymerization reaction described above, the reaction temperature is typically 30°C to 180°C. The reaction time varies depending on the type of initiator and monomer and the reaction temperature, but is usually 0.5 to 10 hours. The amount of organic 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 reaction solution. The polymer obtained by the polymerization reaction can be isolated using 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 distilling the reaction solution under reduced pressure using an evaporator.

[0106] <Quinone diazide compound (B)> The quinone diazide compound (B) is a radiation-sensitive acid generator that produces a carboxylic acid upon irradiation with radiation. Preferably, the quinone diazide compound used is a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as the "nucleus") and a 1,2-naphthoquinone diazidosulfonic acid halide.

[0107] Examples of the above-mentioned nuclei include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkanes, and other nuclei.Specific examples of these include trihydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone; and tetrahydroxybenzophenones such as 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, and 2,3,4,4'-tetrahydroxybenzophenone. Examples include xy-3'-methoxybenzophenone, pentahydroxybenzophenone (e.g., 2,3,4,2',6'-pentahydroxybenzophenone), hexahydroxybenzophenone (e.g., 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone), and (polyhydroxyphenyl)alkanes (e.g., bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane). , tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)- Examples of other parent compounds include 2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirovidene-5,6,7,5',6',7'-hexanol, and 2,2,4-trimethyl-7,2',4'-trihydroxyflavan; and other parent compounds such as 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman and 2-[bis{(5-isopropyl-4-hydroxy-2-methyl)phenyl}methyl].

[0108] Of these, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol are preferred as the core.

[0109] As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferred. Specifically, examples include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. Of these, 1,2-naphthoquinone diazide-5-sulfonic acid chloride can be preferably used as the 1,2-naphthoquinone diazide sulfonic acid halide.

[0110] In the condensation reaction to obtain the above condensate, the ratio of the parent nucleus to 1,2-naphthoquinone diazidosulfonic acid halide is such that the amount of 1,2-naphthoquinone diazidosulfonic acid halide used corresponds to 30 to 85 mol%, more preferably 50 to 70 mol%, of the number of OH groups in the parent nucleus. The above condensation reaction can be carried out according to known methods. A 1,2-quinone diazide compound is obtained by the condensation reaction of the parent nucleus and 1,2-naphthoquinone diazidosulfonic acid halide.

[0111] The content of quinone diazide compound (B) in the radiation-sensitive composition is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of polymer component (A). Furthermore, the content of quinone diazide compound (B) is preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of polymer component (A). A content of quinone diazide compound (B) of 2 parts by mass or more is preferable because sufficient acid is generated by irradiation with radiation, and the difference in solubility between the irradiated and unirradiated portions in the alkaline solution can be sufficiently large. This allows for good patterning. It is also preferable because the amount of acid involved in the reaction with polymer component (A) can be increased, and sufficient chemical resistance can be ensured. On the other hand, limiting the content of quinone diazide compound (B) to 100 parts by mass or less is preferable because it allows for a sufficiently small amount of unreacted quinone diazide compound (B), thereby suppressing a decrease in developability due to residual quinone diazide compound (B).

[0112] <Solvent (C)> The radiation-sensitive composition of this disclosure is a liquid composition in which a polymer component (A), a quinone diazide compound (B), and other components as may be added are preferably dissolved or dispersed in a solvent (C). The solvent used is preferably an organic solvent that dissolves each component of the radiation-sensitive composition and does not react with each component.

[0113] The solvent (C) is not particularly limited and includes, for example, alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, etc. Solvent (C) may be used alone or in combination of two or more types.

[0114] 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.

[0115] 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.

[0116] Examples of ester-based 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; and polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.

[0117] Examples of ketone-based solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0118] Among these, ether-based solvents and ester-based solvents are preferred, ester-based solvents are more preferred, and polyhydric alcohol partial ether carboxylate-based solvents are even more preferred. Furthermore, among the ether-based and ester-based solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate are preferred.

[0119] The content of solvent (C) in this composition is not particularly limited, but it is preferable that the composition be prepared so that the solid content (components other than solvent (C)) concentration is within the following ranges. The lower limit of the solid content 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 solid content concentration is preferably 60% by mass, more preferably 40% by mass, and still more preferably 30% by mass. A solid content concentration of 5% by mass or more in the radiation-sensitive composition is preferable because it ensures sufficient film thickness when the radiation-sensitive composition is applied to a substrate. Furthermore, a solid content 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.

[0120] <Solvent (C1)> The compositions of this disclosure may include, in addition to the solvent (C) above, a solvent (C1) having a boiling point of 180°C or higher and a Hansen solubility parameter δH of 3.0 or more and 13.0 or less. Here, the Hansen solubility parameter (HSP value) is an index that takes into account the polarity of physical properties by dividing the Hildebrandt solubility parameter (SP value) into three components: dispersion force term δD, polarity term δP, and hydrogen bonding term δH. 2 =δD2 +δP 2 +δH 2 The relationship is as follows: In this specification, the Hansen solubility parameters are values ​​calculated using the calculation software HSPiP ver.5. The boiling point of the solvent is the value at 1 atmosphere.

[0121] The solvent (C1) is not particularly limited in type, as long as it has a boiling point of 180°C or higher and an HSP value of hydrogen bonding term δH of 3.0 or higher and 13.0 or lower. Among these, the solvent (C1) is preferably at least one selected from the group consisting of alcohols, carbonates, ethers, and esters. The solvent (C1) may be a compound having a chain structure or a compound having a cyclic structure.

[0122] Specific examples of solvents (C1) include dihydroterpineol (δH=6.69, boiling point=210°C), (S)-4-methyl-1,3-dioxolan-2-one (δH=7.35, boiling point=242°C), diethylene glycol monobutyl ether (δH=10.46, boiling point=231°C), dipropylene glycol methyl ether acetate (δH=5.78, boiling point=213°C), triethylene glycol monobutyl ether (δH=9.14, boiling point=278°C), propyl lactate (δH=11.7, boiling point=188°C), and benzyl alcohol (δH=12.5, boiling point=205°C).

[0123] If solvent (C) contains solvent (C1), it is preferable that the content of solvent (C1) be 10% by mass or less relative to the total amount of solvent.

[0124] <Adhesion enhancer (D)> This composition may further contain an adhesion aid (D). By using this composition containing an adhesion aid (D), the adhesion between the formed cured product and the substrate (adhesion object) can be improved, thereby improving the development adhesion and suppressing peeling of unexposed areas from the substrate during the development process. Examples of adhesion aid (D) include functional silane coupling agents having reactive functional groups and functional cardi compounds having reactive functional groups.

[0125] Reactive functional groups found in functionalized silane coupling agents include carboxyl groups, (meth)acryloyl groups, amino groups, epoxy groups, vinyl groups, and isocyanate groups.

[0126] Reactive functional groups found in functional cardo compounds include alkoxysilyl groups, oxyranyl groups, oxetanyl groups, mercapto groups, (meth)acryloyl groups, vinyl groups, and amino groups.

[0127] Specific examples of functional silane coupling agents include trimethoxysilyl benzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-isocyanatetopropyltrimethoxysilane.

[0128] The functionalized cardo compound may be a cardo compound described in Japanese Patent Publication No. 2023-58025 or a commercially available product. Examples of commercially available cardo compounds include, by trade name, Ogusol SC-001, EA-0200, EA-0300, and CR-1030 (all manufactured by Osaka Gas Chemical Co., Ltd.); WR-301 (manufactured by ADEKA Corporation); V-259ME (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); and Oncoat EX series (manufactured by Nagase ChemteX Corporation).

[0129] When the composition contains an adhesion aid (D), the content of the adhesion aid (D) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the polymer component (A) contained in the composition. Furthermore, the content of the adhesion aid (D) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the polymer component (A) contained in the composition. By setting the content of the adhesion aid (D) to 0.1 parts by mass or more, sufficient improvements in the developability, curing adhesion, and chemical resistance of the film formed by the composition can be obtained. On the other hand, by setting the content of the adhesion aid (D) to 20 parts by mass or less, it is preferable to obtain the effects of adding the adhesion aid while suppressing a decrease in the sensitivity of the composition.

[0130] <Other ingredients> The radiation-sensitive composition of this disclosure may further contain other components (hereinafter also referred to as "other components") in addition to the polymer component (A), quinone diazide compound (B), solvent (C), and the adhesion aid (D) added as needed. Examples of other components include reaction initiators (photoradical polymerization initiators, photocationic polymerization initiators, etc.), polyfunctional polymerizable compounds (polyfunctional (meth)acrylates, etc.), surfactants (fluorinated surfactants, silicone surfactants (silane surfactants), nonionic surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, etc. The blending ratio of these components is appropriately selected according to each component within a range that does not impair the effects of this disclosure. Furthermore, the radiation-sensitive composition of this disclosure may contain silane surfactants, but it is preferable that it does not contain them.

[0131] The radiation-sensitive composition of this disclosure has a solid content concentration (the ratio of the total mass of components other than the solvent (C) in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) which is appropriately selected considering viscosity, volatility, etc.

[0132] (Dielectric constant of the cured film obtained by the radiation-sensitive composition) By curing this composition, a cured film with a sufficiently low dielectric constant can be obtained. Specifically, the dielectric constant of the obtained cured film at a frequency of 10 kHz is preferably less than 3.2, more preferably less than 3.1, and even more preferably less than 3.0. For details on the method for measuring the dielectric constant of the cured film, please refer to the method described in the examples below.

[0133] The radiation-sensitive composition of this disclosure, by using a quinone diazide compound (B) as a radiation-sensitive acid generator together with a polymer component (A), can raise the glass transition temperature of the polymer while maintaining high radiation sensitivity. As a result, it can form a cured film with excellent melt resistance, good pattern shape, sufficiently low dielectric constant, and excellent bending resistance. Furthermore, by further including an adhesion aid (D), the radiation-sensitive composition of this disclosure can form a film with excellent developability in addition to the above effects. Such a radiation-sensitive composition of this disclosure is useful as a composition for forming a planarization film of a display element or for forming an interlayer insulating film.

[0134] ≪Method for manufacturing a cured film≫ The cured film of this disclosure is formed from the radiation-sensitive composition prepared as described above. The cured film obtained from the radiation-sensitive composition of this disclosure has a low dielectric constant, excellent bending resistance, excellent melt resistance, and low developing residue.

[0135] By using the above-mentioned radiation-sensitive composition in the manufacture of the cured film, a positive-type cured film can be formed by irradiation with radiation (ultraviolet light, far-ultraviolet light, visible light, etc.). The cured film of this disclosure can be manufactured, for example, by a method including the following steps (1) to (5). (Step 1) A step of applying a radiation-sensitive composition onto a substrate to form a coating film. (Step 2) Step of removing the solvent from the coating film. (Step 3) A step of irradiating the coating film from which the solvent has been removed with radiation. (Step 4) The process of developing the irradiated coating. (Step 5) A process to heat-cur the developed coating film. The following provides a detailed explanation of each step.

[0136] <Steps 1 and 2: Paint film formation process> In this process, the 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 the solvent is removed by heat treatment (pre-baking) to 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.

[0137] 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.

[0138] <Step 3: Exposure Process> In this step, at least a portion of the coating film formed in steps 1 and 2 above is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured film with a pattern (e.g., an interlayer insulating film) can be formed. Examples of radiation include charged particle beams such as ultraviolet rays, far ultraviolet rays, visible light, X-rays, and electron beams. Among these, ultraviolet rays are 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.

[0139] <Step 4: Development step> In this step, the coating film irradiated with radiation in step 3 is developed. Specifically, the coating film irradiated with radiation in step 3 is developed with a developer to remove the irradiated areas, performing positive-type development. Examples of the developer include aqueous solutions of alkali (basic compounds). Examples of alkalis include sodium hydroxide, tetramethylammonium hydroxide, and alkalis exemplified in paragraph

[0127] of Japanese Patent Publication No. 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. Appropriate development methods include the liquid-filling method, dipping method, agitation immersion method, and shower method. The development time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. After the development step, it is preferable to rinse the patterned coating film with running water.

[0140] <Step 5: Heating step> In this step, the coating developed in step 4 is subjected to a heating process (post-bake). This promotes the hardening reaction of the film, 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 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.

[0141] Furthermore, a post-exposure step may be included between steps 4 and 5. 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.

[0142] ≪Cured film≫ The cured film of this disclosure is formed using the radiation-sensitive composition. Formed using the radiation-sensitive composition of this disclosure, the resulting cured film has a low dielectric constant, excellent bending resistance, excellent melt resistance, and low development residue. Therefore, the cured film is useful as an insulating film for organic EL display elements and liquid crystal display elements. Specifically, the cured film can be used in organic EL display elements and liquid crystal display elements as a planarizing film to flatten surface irregularities caused by thin-film transistors (TFTs), an interlayer insulating film to insulate between wirings, partitions and banks that define regions for forming light-emitting layers, a protective film to protect TFTs, a spacer, an adhesive layer for color filters, etc. In this specification, "partition" refers to a component used for color separation such as a color filter or a color conversion layer using quantum dots, and "bank" refers to a component that divides the light-emitting layer. Among these, the cured film of this disclosure is particularly useful as an interlayer insulating film or a planarizing film.

[0143] ≪Display Elements≫ The display element of this disclosure comprises a cured film formed using the above-mentioned radiation-sensitive composition. Examples of display elements include liquid crystal display elements, organic electroluminescent (EL) display elements, micro-LED display elements, and the like.

[0144] The display element disclosed herein can be effectively applied to a variety of uses, and can be used as various display devices such as clocks, portable game consoles, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, LCD televisions, and information displays. [Examples]

[0145] 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.

[0146] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)] The Mw and Mn of the polymer were measured by the following method. • Measurement method: Gel permeation chromatography (GPC) method • Equipment: GPC-101 manufactured by Showa Denko Corporation • GPC columns: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 manufactured by Shimadzu GLC Co., Ltd. • 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

[0147] [monomer] The monomers used in the synthesis of the copolymer are as follows: (Structural Unit (I)) MA: Methacrylic acid PIPE: p-isopropenylphenol MI: Maleimide (Structural Unit (II)) ECHMA:3,4-Epoxycyclohexylmethyl methacrylate ETCDA:3,4-Epoxytricyclo[5.2.1.0 2,6 ] Decane-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 ] A mixture of decane-8-yl acrylate [50:50 (molar ratio)] (Structural Unit (III)) CHMA: Cyclohexyl methacrylate IBA: Isobornyl Acrylate DCM: Dicyclopentanyl methacrylate (Structural Unit (IV)) AOMA: 2-(allyloxymethyl)methyl acrylate (Structural unit (V)) CHMI:N-Cyclohexylmaleimide PMI: N-phenylmaleimide (Structural Unit (VI)) MPTES:3-Methacryloxypropyltriethoxysilane (Structural Unit (VII)) ST: Styrene (Structural Unit (VIII)) HEMA: 2-hydroxyethyl methacrylate (Structural Unit (IX)) MMA: Methyl methacrylate EHA: Ethylhexyl acrylate (Structural unit (X)) GMA: Glycidyl methacrylate OXMA: (3-ethyloxetan-3-yl)methyl methacrylate

[0148] [Synthesis Example 1: Synthesis of Polymer A1] In a flask equipped with a condenser and a stirrer, 13 parts of 2,2'-azobis(isobutyrate)dimethyl and 200 parts of diethylene glycol methyl ethyl ether were charged. Subsequently, 11 parts of methacrylic acid (MA), 9 parts of p-isopropenylphenol (PIPE), 3 parts of maleimide (MI), 25 parts of 3,4-epoxycyclohexylmethyl methacrylate (ECHMA), 14 parts of cyclohexyl methacrylate (CHMA), 9 parts of 2-(allyloxymethyl)methyl acrylate (AOMA), 15 parts of N-cyclohexylmaleimide (CHMI), and 14 parts of methyl methacrylate (MMA) 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 A1. The solid content concentration of this polymer solution was 35.3% by mass, the Mw of polymer A1 was 9,500, and the molecular weight distribution (Mw / Mn) was 2.2.

[0149] [Synthesis of Polymers A2-A31 and CA1-CA5] Polymers A2-A31 and CA1-CA5, having the same solid content concentration, molecular weight, and molecular weight distribution as polymer A1, were obtained using the same method as in Synthesis Example 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 monomer was not used.

[0150] [Table 1]

[0151] <Preparation of radiation-sensitive composition> The polymer component (A), quinone diazide compound (B), solvent (C), and adhesion promoter (D) used in the preparation of the radiation-sensitive composition are shown below.

[0152] (Polymer (A)) Polymers A1 to A31: The synthesized polymers A1 to A31 described above. Polymers CA1 to CA5: The synthesized polymers CA1 to CA5 described above. (Quinone diazide (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) (Solvent (C)) C-1: Diethylene glycol methyl ethyl ether (EDM) C-2: Propylene glycol monomethyl ether (PGME) C-3: Propylene glycol monomethyl ether acetate (PGMEA) (Adhesion enhancer (D)) D-1: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane D-2:3-Acryloyloxypropyltriethoxysilane D-3:3-Isocyanate-propyltriethoxysilane D-4: Ogusol SC-001 (manufactured by Osaka Gas Chemical Co., Ltd.) D-5: Ogusol CR-1030 (manufactured by Osaka Gas Chemical Co., Ltd.) D-6: WR-301 (Manufactured by ADEKA Corporation) D-7: V-259ME (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.)

[0153] <Preparation of radiation-sensitive composition> [Example 1] To a polymer solution containing polymer A1, 20 parts of quinone diazide compound (B-1), 5 parts of silane coupling agent (glycidyloxypropyltrimethoxysilane), and 0.1 parts of surfactant (DUWSIL® SH8400) were mixed in an amount equivalent to 100 parts (solids) of polymer A1. Diethylene glycol methyl ethyl ether (EDM, C-1), propylene glycol monomethyl ether (PGME, C-2), and propylene glycol monomethyl ether acetate (PGMEA, C-3) were added to achieve a final solids concentration of 15% by mass. The ratio of solvents in the radiation-sensitive composition was (C-1):(C-2):(C-3) = 20:70:10. The mixture was then filtered through a membrane filter with a pore size of 0.05 μm to prepare the radiation-sensitive composition of Example 1.

[0154] [Examples 2-41, Comparative Examples 1-5] The radiation-sensitive compositions of Examples 2-41 and Comparative Examples 1-5 were prepared using the same method as in Example 1, except that the components used were of the types and amounts (parts by mass) shown in Table 2. In Table 2 below, "-" in the adhesion aid (D) column indicates that the adhesion aid (D) was not used, and "-" in the developability column indicates that no measurement was performed.

[0155] [Table 2]

[0156] <Rating> Cured films were formed from the radiation-sensitive compositions of Examples 1-41 and Comparative Examples 1-5, and the following items were evaluated using the method described below. The results are shown in Table 2.

[0157] <Relative permittivity> Using a spinner, a radiation-sensitive composition was applied to a glass substrate coated with ITO (indium tin oxide). The solvent was then removed from the radiation-sensitive composition on the substrate under vacuum with the target pressure set to 100 Pa. The coating was then pre-baked on a hot plate at 100°C for 2 minutes to form a film. The spinner's rotation speed was adjusted to achieve a coating film thickness of 2.0 μm after heating at 230°C for 30 minutes, as described later. Subsequently, development was performed using the liquid-leveling method with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C for 80 seconds. Next, the substrate was rinsed with ultrapure water for 1 minute and then dried. An exposure unit (Canon's "MPA-600FA": using an ultra-high pressure mercury lamp) was used, with an integrated irradiation dose of 300 mJ / cm². 2 The above coating film was fully exposed to light, and the exposed substrate was heated in a clean oven at 230°C for 30 minutes to form a cured film on the ITO substrate. Next, an aluminum electrode pattern was formed on the cured film by vapor deposition to prepare a sample for dielectric constant measurement. The dielectric constant of this substrate with the electrode pattern was measured at a frequency of 10 kHz using an electrode (Yokogawa-Hewlett-Packard's "HP16451B") and a precision LCR meter (Yokogawa-Hewlett-Packard's "HP4284A"). (Evaluation Criteria) ◎: Less than 3.0 (Excellent) ○: 3.0 or higher and less than 3.1 (Good) △: 3.1 or higher and less than 3.2 (acceptable) ×: 3.2 or more (impossible)

[0158] <Bending resistance> A radiation-sensitive composition was applied to a polyimide film substrate using a spin coater. The solvent was then removed from the radiation-sensitive composition on the substrate under vacuum with the final pressure set to 100 Pa, and the film was pre-baked at 100°C for 2 minutes to form a coating. Next, the film was developed using a developer (2.38% by mass aqueous solution of tetramethylammonium hydroxide) at 25°C for 80 seconds, followed by rinsing with ultrapure water for 1 minute. The resulting coating was then exposed using an exposure machine (Canon's "MPA-600FA": using an ultra-high pressure mercury lamp) to an integrated irradiation dose of 300 mJ / cm². 2 The above coating film was fully exposed to light and heated at 230°C for 1 hour in a nitrogen-purged clean oven to form a cured film with an average thickness of 2.0 μm on the substrate. The resulting cured film-coated substrate was cut to a size of 50 mm x 50 mm. Next, with the side where the cured film was formed facing outwards, the cured film-coated substrate was folded so that the polyimide film substrates were in contact with each other, and held in that position for 10 minutes. After 10 minutes, the folded cured film-coated substrate was unfolded, and the folded portion of the cured film surface was observed using an optical microscope to evaluate the bending resistance (resistance to bending) based on the change in appearance. (Evaluation Criteria) ◎: No cracks (Excellent) ○: 1 to 5 cracks (good) △: 6 to 10 cracks (acceptable) ×: More than 10 cracks (not allowed)

[0159] <Melting resistance during post-baking> Using a spinner, a radiation-sensitive composition was applied to a silicon substrate that had been HMDS-treated at 60°C for 60 seconds. Then, the solvent was removed from the radiation-sensitive composition on the substrate under vacuum with the final pressure set to 100 Pa, and the coating was pre-baked on a hot plate at 100°C for 2 minutes to form a coating film. The spinner's rotation speed was adjusted to achieve a coating film thickness of 2.0 μm after heating at 230°C for 30 minutes, as described later. This coating film was irradiated with a predetermined amount of ultraviolet light from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, development was performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer at 25°C for 80 seconds, followed by rinsing with ultrapure water for 1 minute. The line width of the line-and-space pattern obtained at this time was defined as X1. Then, using an exposure machine (Canon's "MPA-600FA": using an ultra-high pressure mercury lamp), the cumulative irradiation dose was 300 mJ / cm². 2 The above coating film was fully exposed to light and heated at 230°C for 30 minutes to form a cured film. The line width of the resulting line-and-space pattern was defined as X2. The value obtained by subtracting X2 from X1 (=X1-X2) was calculated and evaluated according to the following criteria. (Evaluation Criteria) ◎: Less than 0.1 μm (Excellent) ○: 0.1 μm or larger and less than 0.2 μm (good) △: 0.2 μm or more and less than 0.3 μm (acceptable) ×: 0.3μm or more (not allowed)

[0160] <developing residue> Using a spinner, a radiation-sensitive composition was applied to a silicon substrate that had been HMDS-treated at 60°C for 60 seconds. Then, the solvent was removed from the radiation-sensitive composition on the substrate under vacuum with the final pressure set to 100 Pa, and the coating was pre-baked on a hot plate at 100°C for 2 minutes to form a film. The spinner's rotation speed was adjusted to achieve a coating film thickness of 2.0 μm after heating at 230°C for 30 minutes, as described later. This coating film was irradiated with a predetermined amount of ultraviolet light from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, development was performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer at 25°C for 80 seconds, followed by rinsing with ultrapure water for 1 minute. Finally, using an exposure machine (Canon's "MPA-600FA": using an ultra-high pressure mercury lamp), the cumulative irradiation dose was 300 mJ / cm². 2 The above coating was exposed to light across its entire surface and heated at 230°C for 30 minutes to form a cured film. The resulting substrate was then observed using a scanning electron microscope to determine the presence or absence of residue on the substrate. (Evaluation Criteria) ◎: No residue was found (Excellent) ○: Very little residue (good) ×: Residue present (not acceptable)

[0161] <Evaluation of adhesion during alkaline development (development adhesion)> Using a spinner, a radiation-sensitive composition was applied to a silicon substrate that had not undergone HMDS treatment. The mixture was then 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 400 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 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used as the developer, and development was performed at 25°C for 60 seconds, followed by rinsing with ultrapure water for 1 minute. After rinsing, the minimum width of the line-and-space pattern remaining on the substrate without peeling was measured and evaluated according to the following evaluation criteria. ◎: The minimum width of the line-and-space pattern remaining on the substrate without peeling is measured at 2 μm or less (Excellent). ○: Larger than 2 μm and 5 μm or less (Good) △: Greater than 5 μm and 10 μm or less (acceptable) ×: Larger than 10 μm (not allowed)

[0162] As shown in Table 2, each radiation-sensitive composition in Examples 1 to 27 exhibited good practical properties in terms of dielectric constant, bending resistance, melt resistance during melt flow, and development residue, demonstrating a good balance of various properties. Furthermore, Examples 28 to 41, which included adhesion enhancer (D), showed excellent development adhesion in addition to dielectric constant, bending resistance, melt resistance during melt flow, and development residue. In contrast, Comparative Examples 1 to 5 all received a "×" rating in at least one of the properties, and were all inferior to Examples 1 to 27.

Claims

1. Polymer component (A), Quinone diazide compound (B) and Solvent (C) and A radiation-sensitive composition containing, The polymer component (A) is At least one structural unit (I) selected from the group consisting of structural units having an acid group and structural units derived from maleimide, Structural unit (II) containing an alicyclic epoxy group, Structural units (III) derived from (meth)acrylates having an alicyclic structure (excluding structural unit (II)), A structural unit (IV) having a cyclic ether structure and a methylene group bonded to the carbon atoms constituting the cyclic ether structure as its main chain is included in the same polymer or different polymers. Radiation sensitive composition.

2. The radiation-sensitive composition according to claim 1, wherein the structural unit (II) is represented by the following formula (II-1), formula (II-2), or formula (II-3). 【Chemistry 1】 (Formula (II-1) to formula (II-3), R １ These are, independently, a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. L １ Each of these is independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. n is an integer between 1 and 5. k1 is either 0 or 1. X １ Each of these is independently a hydroxyl group, a halogen atom, a cyano group, a nitro group, an alkyl group, or an alkoxy group. a1 is an integer between 0 and 3, independently of each other. If a1 is 2 or greater, multiple X １ They are either identical or different from one another.

3. The radiation-sensitive composition according to claim 1, wherein the alicyclic structure is a monocyclic alicyclic structure.

4. The radiation-sensitive composition according to claim 1, wherein the (meth)acrylate having the alicyclic structure is cyclohexyl (meth)acrylate.

5. The radiation-sensitive composition according to claim 1, wherein the structural unit (IV) is represented by the following formula (IV). 【Chemistry 2】 (In formula (IV), R Ａ１ This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R Ａ２ is a hydrogen atom or -COOR Ａ３ That is. R Ａ３ This is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. m is either 0 or 1.

6. The radiation-sensitive composition according to claim 1, wherein the dielectric constant at 10 kHz of the cured film formed by curing the radiation-sensitive composition is less than 3.

2.

7. A step of applying the radiation-sensitive composition according to any one of claims 1 to 6 onto a substrate, A step of removing the solvent from the coated radiation-sensitive composition, A step of irradiating the radiation-sensitive composition from which the solvent has been removed with radiation, A step of developing the radiation-sensitive composition that has been irradiated with the aforementioned radiation, The process involves thermally curing the developed radiation-sensitive composition, A method for manufacturing a cured film, including the following:

8. A cured film formed using the radiation-sensitive composition described in any one of claims 1 to 6.

9. The cured film according to claim 8, which is an interlayer insulating film or a planarizing film.

10. A display element comprising the cured film described in claim 9.

11. The display element according to claim 10, which is for use with organic EL.

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