Radiation-sensitive composition, cured film, display element, and pattern forming method

Abstract

An object of the present invention is to provide a radiation-sensitive composition capable of forming a cured film having excellent radiation sensitivity and development adhesion and capable of suppressing foaming and foreign matter precipitation during development. Another object of the present invention is to provide a cured film formed using the radiation-sensitive composition of the present invention, and a display element including the cured film. Furthermore, another object of the present invention is to provide a pattern forming method capable of suppressing foaming or foreign matter precipitation during development and forming a pattern (cured film) having excellent radiation sensitivity and development adhesion.SOLUTION: The present invention relates to a positive-type radiation-sensitive composition comprising a polymer (A), a photoacid generator (B), a surfactant (C) and a solvent (S), wherein the surfactant (C) comprises a specific polyoxyalkylene-based surfactant (C1) or a specific antifoaming agent (C2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a radiation-sensitive composition, a cured film, a display element, and a pattern forming method. [Background technology]

[0002] Display elements are provided with insulating cured films such as interlayer insulating films that insulate between wiring and a substrate or between wirings, planarizing films, partition walls, etc. The cured films are generally formed by subjecting a coating film formed from a radiation-sensitive composition to exposure and development treatments, and then subjecting the coating film to heat treatment for thermal curing.

[0003] Known materials for forming such cured films include negative photosensitive resin compositions containing a specific acrylic copolymer, a photoinitiator, a polyfunctional monomer, a silicon compound, an antifoaming agent, and a solvent (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Korean Patent Publication No. 10-2010-0063540 Summary of the Invention [Problem to be solved by the invention]

[0005] When a coating film formed from a radiation-sensitive composition is exposed and developed, the developer may foam, which may cause the problem of foreign matter deposition, which is thought to occur when the foam dries.

[0006] From the viewpoint of suppressing foaming, adding an antifoaming agent or the like to the developer has been considered, but it has been newly discovered that depending on the type and amount of the antifoaming agent, foaming may become worse. Furthermore, it has been thought that when an antifoaming agent is added to a radiation-sensitive composition, the antifoaming agent may reduce the development adhesion, radiation sensitivity, and the like of the radiation-sensitive composition. That is, with conventional radiation-sensitive compositions, it has been difficult to achieve excellent cured film properties such as radiation sensitivity and development adhesion, while suppressing foaming and deposition of foreign matter during development.

[0007] The present invention has been made in view of the above-mentioned problems, and aims to provide a radiation-sensitive composition that can form a cured film having excellent radiation sensitivity and development adhesion, and that can suppress foaming and deposition of foreign matter during development. Another aim of the present invention is to provide a cured film formed using the radiation-sensitive composition, and a display element including the cured film. A further aim of the present invention is to provide a pattern-forming method that can suppress foaming and deposition of foreign matter during development, and that can form a pattern (cured film) having excellent radiation sensitivity and development adhesion. [Means for solving the problem]

[0008] According to the present invention, there are provided the following radiation-sensitive composition, cured film, display element, and pattern forming method.

[0009] In one embodiment, the present invention provides A polymer (A), a photoacid generator (B); a surfactant (C); a solvent (S); Contains The surfactant (C) A polyoxyalkylene surfactant (C1) having an HLB value of 0 or more and 3.5 or less, or Contains an antifoaming agent (C2) containing one or more selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl ethers, polyolefins, and modified or unmodified polydimethylsiloxanes; The present invention relates to a positive-working radiation-sensitive composition.

[0010] In another embodiment, the present invention provides applying a radiation-sensitive composition to a substrate; a step of irradiating the coated radiation-sensitive composition with radiation; developing the radiation-irradiated radiation-sensitive composition using a developer; A pattern forming method comprising: at least one of the radiation-sensitive composition and the developer contains a surfactant (C); The surfactant (C) A polyoxyalkylene surfactant (C1) having an HLB value of 0 or more and 3.5 or less, or Contains an antifoaming agent (C2) containing one or more selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl ethers, polyolefins, and modified or unmodified polydimethylsiloxanes; It relates to a pattern formation method.

[0011] In another embodiment, the present invention provides The present invention also relates to a cured film formed using the radiation-sensitive composition, and a display device including the cured film. [Effects of the Invention]

[0012] The radiation-sensitive composition of the present invention contains a specific surfactant (C), which allows the formation of a cured film having excellent radiation sensitivity and adhesion upon development, and further allows the suppression of foaming and deposition of foreign matter during development. Furthermore, the cured film and display element of the present invention are of high quality because they are formed from the radiation-sensitive composition. Furthermore, the pattern-forming method of the present invention allows the suppression of foaming and deposition of foreign matter during development, and allows the formation of a pattern (cured film) having excellent radiation sensitivity and adhesion upon development. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments.

[0014] Matters related to the embodiments will be explained in detail below. In this specification, a numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure.

[0015] In this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed solely of a chain structure. However, the chain hydrocarbon group may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, the alicyclic hydrocarbon group does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and also includes groups that have a chain structure as part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, the aromatic hydrocarbon group does not necessarily have to be composed solely of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure as part of it. The ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent composed of a hydrocarbon structure. The term "cyclic hydrocarbon" refers to both alicyclic hydrocarbons and aromatic hydrocarbons.

[0016] In this specification, "(meth)acryloyl" is intended to encompass "acryloyl" and "methacryloyl", "(meth)acrylic" is intended to encompass "acrylic" and "methacrylic", and "(meth)acrylate" is intended to encompass "acrylate" and "methacrylate".

[0017] ≪Radiation-sensitive composition≫ The radiation-sensitive composition according to this embodiment (hereinafter also referred to as "the composition") is A polymer (A), a photoacid generator (B); a surfactant (C); a solvent (S); Contains The surfactant (C) A polyoxyalkylene surfactant (C1) having an HLB value of 0 or more and 3.5 or less, or It contains an antifoaming agent (C2) containing one or more selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl ethers, polyolefins, and modified or unmodified polydimethylsiloxanes.

[0018] The present composition is a positive-working radiation-sensitive composition. The term "positive-working radiation-sensitive composition" refers to a radiation-sensitive composition in which the non-irradiated portions of a coating film obtained from the radiation-sensitive composition remain as a pattern after development. The components contained in the present composition and other components that may be blended as needed are described below. Unless otherwise specified, each component may be used alone or in combination of two or more.

[0019] <Polymer (A)> The polymer (A) is an aggregate of polymer chains (hereinafter, this aggregate will also be referred to as the "base polymer"). The polymer is not particularly limited, but is preferably an acrylic polymer, and more preferably an acrylic polymer containing a structural unit (I) having an acid group. The polymer (A) may also contain a structural unit other than the structural unit (I). When the polymer (A) contains two or more different structural units, the two or more structural units may be contained in the same polymer chain or may be contained separately in multiple different polymer chains, and the two or more structural units may be contained as a mixture of polymer chains. Each structural unit contained in the polymer (A) will be described below.

[0020] Structural Units The polymer (A) containing the structural unit (I) having an acid group can increase the solubility (alkali solubility) of the polymer (A) in an alkaline developer and can increase the curing reactivity. In this specification, "alkali soluble" means that the polymer (A) can be dissolved or swelled in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0021] The structural unit (I) is not particularly limited as long as it has an acid group, but is preferably at least one selected from the group consisting of a structural unit having a carboxy group, a structural unit having a sulfonic acid group, a structural unit having a phenolic hydroxyl group, and a maleimide unit. In this specification, the term "phenolic hydroxyl group" refers to a hydroxyl group directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.).

[0022] The structural unit (I) is preferably a structural unit derived from an unsaturated monomer having an acid group. Specific examples of the unsaturated monomer having an acid group include: Examples of monomers constituting structural units having a carboxy group include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and 4-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; Examples of monomers constituting a structural unit having a sulfonic acid group include vinyl sulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, and (meth)acryloyloxyethylsulfonic acid; Examples of monomers constituting structural units having a phenolic hydroxyl group include 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, and hydroxyphenyl (meth)acrylate. can be cited respectively.

[0023] Furthermore, maleimide can also be used as a monomer constituting the structural unit (I).

[0024] Among these, monomers constituting structural units having a carboxy group and monomers constituting structural units having a phenolic hydroxyl group are preferred, and (meth)acrylic acid and p-isopropenylphenol are more preferred.

[0025] The base polymer may contain one type of structural unit (I) or a combination of two or more types.

[0026] When the polymer (A) contains the structural unit (I), the lower limit of the content of the structural unit (I) (the total content when multiple types are contained) is preferably 1% by mass, more preferably 2% by mass, and even more preferably 5% by mass, based on all structural units constituting the base polymer. The upper limit of the content is preferably 40% by mass, more preferably 35% by mass, even more preferably 30% by mass, and particularly preferably 20% by mass. By keeping the content of the structural unit (I) within the above range, good solubility in an alkaline developer can be imparted, which is preferable.

[0027] [Structural unit (II)] The polymer (A) may contain a structural unit (II) having one or more groups selected from the group consisting of an oxetanyl group and an oxiranyl group. The polymer (A) preferably contains the structural unit (II), since this can further improve the film resolution and adhesion. Furthermore, the epoxy group acts as a crosslinkable group, allowing the formation of a pattern (cured film) that is highly heat-resistant and inhibits deterioration over a long period of time. The structural unit (II) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, and more specifically, a structural unit represented by the following formula (1): [ka] (In formula (1), R 21 is a monovalent group having an oxiranyl group or an oxetanyl group. R α is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. X 1 is a single bond or a divalent linking group.

[0028] In the above formula (1), R 21 Examples include oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl group, 3-methyloxetanyl group, 3-ethyloxetanyl group, and the like.

[0029] X 1 The divalent linking group is preferably an alkanediyl group such as a methanediyl group, an ethanediyl group, or a 1,3-propanediyl group.

[0030] Specific examples of the monomer that provides the structural unit (II) represented by the above formula (1) include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]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, and the like.

[0031] Among these, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and (3-ethyloxetan-3-yl)methyl (meth)acrylate are preferred.

[0032] The base polymer may contain one type of structural unit (II) or a combination of two or more types.

[0033] When polymer (A) contains structural unit (II), the lower limit of the content of structural unit (II) (total content when multiple types are contained) is preferably 5% by mass, more preferably 15% by mass, and even more preferably 25% by mass, based on all structural units constituting the base polymer. The upper limit of the content is preferably 90% by mass, more preferably 85% by mass, and even more preferably 80% by mass. By keeping the content of structural unit (II) within the above range, the coating film exhibits better resolution, and the resulting pattern (cured film) can be sufficiently improved in heat resistance and chemical resistance. This is preferable.

[0034] [Structural unit (III)] When the radiation-sensitive composition of the present invention is a chemically amplified composition, it is preferable that the polymer (A) further contains a structural unit (III) having one or more groups selected from the group consisting of a group represented by the following formula (2) and an acid-dissociable group, from the viewpoint of forming a coating film having excellent development adhesion: [ka] (In formula (2), R 1 , R 2 and R 3 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. 1 , R 2 and R 3 At least one of them is an alkoxy group having 1 to 6 carbon atoms. "*" indicates a bond.)

[0035] R 1 ~R 3 Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a tert-butoxy group. 1 ~R 3 The alkoxy group is preferably a methoxy group or an ethoxy group.

[0036] R 1 ~R 3 The alkyl group having 1 to 10 carbon atoms may be either linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a tert-butyl group. Of these, a methyl group, an ethyl group, or a propyl group is preferred.

[0037] From the viewpoint of obtaining a cured film having excellent heat resistance by forming a crosslinked structure and enhancing the storage stability of the radiation-sensitive composition, R 1 ~R 3At least one of them is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably two or more are alkoxy groups, and particularly preferably all are alkoxy groups.

[0038] Among the above, R 1 R 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. 2 and R 3 is preferably a hydroxy 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 hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms.

[0039] In the structural unit (III), the group represented by the above formula (2) is preferably bonded to an aromatic ring group or a chain hydrocarbon group. In this specification, the term "aromatic ring group" refers to a group obtained by removing n hydrogen atoms (n is an integer) from the ring portion of an aromatic ring. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. The ring may have a substituent such as an alkyl group. Examples of the chain hydrocarbon group to which the group represented by the above formula (2) is bonded include an alkanediyl group and an alkenediyl group.

[0040] The group represented by the formula (2) is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain, among the above. That is, the structural unit (III) preferably has at least one selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), and a group represented by the following formula (2-3). [ka] (In formula (2-1), formula (2-2), and formula (2-3), A 1 and A 2 are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. n1 is an integer from 0 to 4. n2 is an integer from 0 to 6. However, if n1 is 2 or more, multiple A 1 are the same or different groups. When n2 is 2 or more, multiple A 2 are the same or different groups. R 31 is an alkanediyl group. R 1 , R 2 and R 3 is synonymous with the above formula (2). "*" indicates a bond.)

[0041] A 1 and A 2 The alkoxy group having 1 to 6 carbon atoms includes R 1 ~R 3 The alkoxy groups having 1 to 6 carbon atoms mentioned above can be preferably used. 1 and A 2 The alkyl group having 1 to 6 carbon atoms includes R 1 ~R 3 Among the alkyl groups having 1 to 10 carbon atoms, groups having 1 to 6 carbon atoms can be suitably used.

[0042] The group "-SiR" that binds to the aromatic ring 1 R 2 R 3 " is located at A 1 and A 2 For example, in the case of the above formula (2-1), the group "-SiR 1 R 2 R 3 The position of " may be any of the ortho, meta, and para positions, and is preferably the para position.

[0043] n1 is preferably 0 or 1, and more preferably 0. n2 is preferably 0 to 2, and more preferably 0.

[0044] In the above formula (2-3), R 31From the viewpoint of increasing the heat resistance of the resulting cured film, R 31 The alkyl group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 4 carbon atoms.

[0045] The structural unit (III) preferably has at least one selected from the group consisting of the group represented by the formula (2-1) and the group represented by the formula (2-2) among the above formulas (2-1) to (2-3). 1 R 2 R 3 When " is directly bonded, it is possible to stabilize the silanol groups generated in the presence of water. This is preferable in that the solubility of the exposed area in an alkaline developer can be increased, and a good pattern can be formed. Among these, the structural unit (III) is particularly preferably a structural unit having a group represented by the above formula (2-1).

[0046] The structural unit (III) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond (hereinafter also referred to as "unsaturated monomer"), and specifically, it is preferably at least one selected from the group consisting of structural units represented by the following formula (2a-1) and structural units represented by the following formula (2a-2). [ka] (In formula (2a-1) and formula (2a-2), R α1 is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R 32 and R 33 are each independently a divalent aromatic ring group or a chain hydrocarbon group. R 1 , R 2 and R 3 is the same as the above formula (2).

[0047] In the above formula (2a-1) and formula (2a-2), R 32 , R 33The divalent aromatic ring group is preferably a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthylene 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.

[0048] R is advantageous in that it can produce a pattern (cured film) with higher heat resistance and hardness, and can increase the solubility of the exposed area in alkaline developer. 32 , R 33 Among the above, is preferably a divalent aromatic ring group, and particularly preferably a substituted or unsubstituted phenylene group.

[0049] Specific examples of the structural unit represented by the formula (2a-1) include structural units represented by the following formulas (2a-1-1) and (2a-1-2): Specific examples of the structural unit represented by the formula (2a-2) include structural units represented by the following formulas (2a-2-1) and (2a-2-2): [ka] (Formula (2a-1-1), Formula (2a-1-2), Formula (2a-2-1), and Formula (2a-2- 2) Medium, R 34 and R 35 are each independently an alkyl group having 1 to 4 carbon atoms, and R 36 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. n3 is an integer of 1 to 4. A 1 , A 2 , n1 and n2 have the same meanings as in the above formulas (2-1) and (2-2). R α1 has the same meaning as the above formula (2a-1) and formula (2a-2).

[0050] Specific examples of the monomer constituting the structural unit (III) include styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethyldimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, and the like; trimethoxy(4-vinylnaphthyl)silane; (meth)acryloxypropyl)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.

[0051] The "acid-dissociable group" refers to a group in which a hydrogen atom in an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group is substituted, and refers to a group that dissociates under the action of an acid. For example, an acid generated from a photoacid generator upon exposure dissociates the acid-dissociable group to generate a carboxyl group or the like. This results in a difference in solubility in a developer between the exposed and unexposed areas of the coating film, making it possible to form a pattern.

[0052] The acid-dissociable group is preferably a group represented by the following formula (3-1) or a group represented by the following formula (3-2). [ka] (In formula (3-1), R 4 and R 5are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which at least a portion of the hydrogen atoms in the hydrocarbon group have been substituted with a hydroxy group, a halogen atom, or a cyano group. 4 and R 5 are never both hydrogen atoms. R 6 is 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 bond-side terminal of this hydrocarbon group, or a group in which at least some of the hydrogen atoms of these groups have been substituted with hydroxy groups, halogen atoms or cyano groups. R 7 is a carbon atom or a silicon atom. In formula (3-2), R 8 ~R 14 are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. m is 1 or 2. When m is 2, multiple R 11 and R 12 may be the same or different. In formula (3-1) and formula (3-2), "*" indicates the bonding site.

[0053] R 4 ~R 6 Examples of the hydrocarbon group having 1 to 30 carbon atoms include a chain hydrocarbon having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0054] Examples of the linear hydrocarbon group having 1 to 30 carbon atoms include linear or branched saturated hydrocarbon groups having 1 to 30 carbon atoms, and linear or branched unsaturated hydrocarbon groups having 2 to 20 carbon atoms. Examples of the linear or branched saturated hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-hexyl, 3-hexyl, n-octyl, n-dodecyl, n-tetradecyl, and n-octadecyl. Examples of the monovalent linear or branched unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl.

[0055] Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic or polycyclic saturated hydrocarbon groups, and monocyclic or polycyclic unsaturated hydrocarbon groups. Examples of monocyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic saturated hydrocarbon groups include bridged alicyclic hydrocarbon groups such as bornyl, norbornyl, adamantyl, tricyclodecyl, and tetracyclododecyl. Examples of monocyclic unsaturated hydrocarbon groups include monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. Examples of polycyclic unsaturated hydrocarbon groups include polycyclic cycloalkenyl groups such as norbornenyl, tricyclodecenyl, and tetracyclododecenyl. The bridged alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group in which two carbon atoms that are not adjacent to each other among the carbon atoms that constitute the alicyclic ring are linked by a linking group containing one or more carbon atoms.

[0056] The aromatic hydrocarbon group having 6 to 30 carbon atoms may have a structure in which monocyclic rings are linked, a condensed ring, or a structure in which an aromatic ring is linked to an aliphatic hydrocarbon group. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthryl; and aralkyl groups such as benzyl, phenethyl, and naphthylmethyl.

[0057] R in the above formula (3-1) 4 ~R 6 are each independently preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

[0058] R 8 ~R 14 The hydrocarbon group having 1 to 12 carbon atoms is the above-mentioned R 4 ~R 6 Among the hydrocarbon groups having 1 to 30 carbon atoms, groups corresponding to those having 1 to 12 carbon atoms can be suitably used.

[0059] As the structural unit having the acid-dissociable group, for example, structural units represented by the following formulae (3-1-1) and (3-1-2) are preferred. [ka]

[0060] In the above formulas (3-1-1) and (3-1-2), m1 is 0 or 1. α1 is R in the above formula (2a-1) and formula (2a-2). α1 It is synonymous with R. 4 ~R 14 is R in the above formulas (3-1) and (3-2). 4 ~R 14 is synonymous with.

[0061] L in the above formulas (3-1-1) and (3-1-2) 1 , L 2 are each independently a single bond or a divalent linking group.

[0062] The above L 1 , L 2 Examples of the divalent linking group in include an alkanediyl group, a cycloalkanediyl group, an alkenediyl group, and an arenediyl group.

[0063] The alkanediyl group includes X in formula (1). 1 Examples of the divalent linking group include the same as those described above.

[0064] Examples of the cycloalkanediyl group include monocyclic cycloalkanediyl groups such as a cyclopentanediyl group and a cyclohexanediyl group; and polycyclic cycloalkanediyl groups such as a norbornanediyl group and an adamantanediyl group.

[0065] Examples of the alkenediyl group include an ethenediyl group, a propenediyl group, and a butenediyl group.

[0066] Examples of the arenediyl group include a phenylene group, a tolylene group, a naphthylene group, etc. The arenediyl group is preferably an arenediyl group having 6 to 15 carbon atoms.

[0067] The base polymer may contain one type of structural unit (III) or a combination of two or more types.

[0068] When polymer (A) contains structural unit (III), the lower limit of the content of structural unit (III) (total content when multiple types are contained) is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass, based on all structural units constituting the base polymer. The upper limit of the content is preferably 60% by mass, more preferably 50% by mass, and even more preferably 40% by mass. By keeping the content of structural unit (III) within the above range, the coating film exhibits better resolution, which is preferable.

[0069] Structural Unit (IV) The polymer (A) may further contain a structural unit (IV) derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic (meth)acrylates, aromatic vinyl compounds, N-substituted maleimide compounds, heterocyclic vinyl compounds, conjugated diene compounds, nitrogen-containing vinyl compounds, and unsaturated dicarboxylic acid dialkyl ester compounds. Introducing these structural units (IV) into the polymer is advantageous in that it adjusts the glass transition temperature of the polymer (A) component and improves the pattern shapeability of the resulting cured film.

[0070] Examples of the (meth)acrylic acid alkyl ester 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.

[0071] Examples of the (meth)acrylic acid ester having the alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, and the like. 2,6 ] decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 2,5 ] decan-8-yloxyethyl, isobornyl (meth)acrylate, and the like.

[0072] Examples of the (meth)acrylic acid ester having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0073] Examples of the aromatic vinyl compound 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, and vinylpyridine.

[0074] Examples of the N-substituted maleimide compound 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.

[0075] Examples of vinyl compounds having a heterocyclic structure include tetrahydrofurfuryl (meth)acrylate, tetrahydrofuranyl (meth)acrylate, tetrahydropyranyl (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, γ-butyrolactone-2-yl (meth)acrylate, glycerin carbonate (meth)acrylate, γ-lactam-2-yl (meth)acrylate, and N-(meth)acryloxyethylhexahydrophthalimide.

[0076] Examples of the conjugated diene compound include 1,3-butadiene, isoprene, etc., examples of the nitrogen-containing vinyl compound include (meth)acrylonitrile, (meth)acrylamide, etc., and examples of the unsaturated dicarboxylic acid dialkyl ester compound include diethyl itaconate, etc. In addition to the above, examples of the monomers constituting the other structural units include monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, etc.

[0077] The monomer that provides the structural unit (IV) preferably includes at least one selected from the group consisting of (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having an alicyclic structure, aromatic vinyl compounds, N-substituted maleimide compounds, and vinyl compounds having a heterocyclic structure.

[0078] The base polymer may contain one type of structural unit (IV) or a combination of two or more types.

[0079] When polymer (A) contains structural unit (IV), the lower limit of the content of structural unit (IV) (the total content when multiple types are contained) is preferably 1 mass %, more preferably 5 mass %, and even more preferably 10 mass %, based on all structural units constituting the base polymer. The upper limit of the content is preferably 60 mass %, more preferably 50 mass %. By keeping the content of structural unit (IV) within the above range, the glass transition temperature of polymer (A) can be suitably increased, which is preferable.

[0080] (Method for synthesizing polymer (A)) The polymer (A) can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in a suitable solvent in the presence of a polymerization initiator.

[0081] Examples of the polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyrate) dimethyl, etc. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the total amount of the monomers used in the reaction.

[0082] Examples of the polymerization solvent include alcohols, ethers, ketones, esters, hydrocarbons, etc. The amount of the polymerization solvent used is preferably an amount such that the total amount of the monomers used in the reaction is 0.1 to 60% by mass relative to the total amount of the reaction solution.

[0083] In the polymerization, the reaction temperature is usually 30 to 180°C. The reaction time varies depending on the types 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 for preparing the radiation-sensitive composition while still dissolved in the reaction solution, or may be used for preparing the radiation-sensitive composition after being isolated from the reaction solution. The polymer can be isolated by known isolation methods, such as a method of pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or a method of distilling the reaction solution under reduced pressure using an evaporator.

[0084] The weight average molecular weight (Mw) of the polymer contained in the polymer component, as calculated in terms of polystyrene by gel permeation chromatography (GPC), is preferably 2,000 or more. An Mw of 2,000 or more is preferable in that a cured film having sufficiently high heat resistance and chemical resistance and exhibiting good developability can be obtained. 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.

[0085] The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the 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 is composed of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above ranges.

[0086] 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, more preferably 90% by mass or less, based on the total amount of solids contained in the radiation-sensitive composition. By setting the content of polymer (A) within the above range, it is possible to obtain a cured film that has sufficiently high chemical resistance and exhibits good developability and transparency.

[0087] <Photoacid generator (B)> The composition contains a photoacid generator (B) in addition to the polymer (A). A positive pattern can be formed by irradiating the composition with radiation (visible light, ultraviolet light, far ultraviolet light, etc.). The photoacid generator (B) may be any compound that generates an acid upon irradiation with radiation, and examples thereof include quinone diazide compounds, oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, and carboxylate ester compounds. Among these, quinone diazide compounds and oxime sulfonate compounds are preferred because of their high radiation sensitivity.

[0088] (Quinone diazide compounds) A quinone diazide compound is a compound that generates a carboxylic acid upon irradiation with radiation. Examples of the quinone diazide compound include a condensation product of a phenolic compound or an alcoholic compound (hereinafter also referred to as a "mother nucleus") with an orthonaphthoquinone diazide compound. Among these, the quinone diazide compound used is preferably a condensation product of a compound having a phenolic hydroxyl group as a mother nucleus with an orthonaphthoquinone diazide compound. Specific examples of the mother nucleus include the compounds described in paragraphs

[0065] to

[0070] of JP 2014-186300 A.

[0089] Specific examples of quinone diazide compounds 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, 1,4-bis[1-(4-hydroxyphenyl)-1-methyl and ester compounds of a phenolic hydroxyl group-containing compound selected from the group consisting of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride. Among these, the quinonediazide compound is preferably a condensate of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

[0090] These quinone diazide compounds may be used alone or in combination of two or more.

[0091] (Oxime sulfonate compounds) The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (5). [ka] (In formula (5), R 40 is a monovalent hydrocarbon group or a monovalent group in which some or all of the hydrogen atoms in the hydrocarbon group have been substituted with substituents. "*" indicates a bond.)

[0092] In the above formula (5), R 40Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an oxo group, and a halogen atom.

[0093] Examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, [2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in WO 2016 / 124493. Commercially available oxime sulfonate compounds include Irgacure PAG121 manufactured by BASF.

[0094] (Sulfonimide compounds) Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide.

[0095] Specific examples of the onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, and carboxylate ester compounds include the compounds described in paragraphs

[0078] to

[0106] of JP2014-157252A and the compounds described in WO2016 / 124493A.

[0096] The photoacid generator (B) may be used alone or in combination of two or more. When a photoacid generator other than a quinone diazide compound is used, the lower limit of the content of the photoacid generator is preferably 0.01 parts by mass, more preferably 0.1 parts by mass, and even more preferably 0.3 parts by mass, relative to 100 parts by mass of the polymer (A) blended in the composition. The upper limit of the content of the photoacid generator (B) is preferably 5 parts by mass, more preferably 4 parts by mass, and even more preferably 3 parts by mass, relative to 100 parts by mass of the polymer (A) blended in the composition. A content of the photoacid generator (B) of 0.01 parts by mass or more is preferable in terms of achieving good patterning. Furthermore, by limiting the content of the photoacid generator (B) to 5 parts by mass or less, the amount of unreacted photoacid generator (B) after exposure can be sufficiently reduced.

[0097] When a quinone diazide compound is used as the photoacid generator (B), the lower limit of the quinone diazide compound content is preferably 1 part by mass, more preferably 10 parts by mass, and even more preferably 15 parts by mass, per 100 parts by mass of the polymer (A) incorporated in the composition. The upper limit of the quinone diazide compound content is preferably 50 parts by mass, more preferably 30 parts by mass, per 100 parts by mass of the polymer (A) incorporated in the composition. A quinone diazide compound content of 1 part by mass or more is preferred because sufficient carboxylic acid is generated upon irradiation of the composition, thereby sufficiently increasing the difference in solubility between the irradiated and unirradiated portions in the developer, thereby enabling good patterning. It is also preferred because it increases the amount of carboxylic acid involved in the reaction with the polymer component, thereby ensuring sufficient heat resistance and chemical resistance. On the other hand, by setting the content of the quinone diazide compound to 50 parts by mass or less, the amount of unreacted quinone diazide compound after exposure can be sufficiently reduced, and a decrease in developability due to the remaining quinone diazide compound can be suppressed, which is preferable.

[0098] <Surfactant (C)> The surfactant (C) may be: A polyoxyalkylene surfactant (C1) having an HLB value of 0 or more and 3.5 or less, or It contains an antifoaming agent (C2) containing one or more selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl ethers, polyolefins, and modified or unmodified polydimethylsiloxanes.

[0099] (Polyoxyalkylene surfactant (C1)) The polyoxyalkylene surfactant (C1) may be any surfactant having a polyoxyalkylene structure, such as polyethylene oxide or polypropylene oxide, and may, for example, be at least one compound selected from the group consisting of the following formulae (C1-1) and (C1-2):

[0100] R 11 O[(C3H6O) k (C2H4O)l ]H (C1-1) (In formula (C1-1), R 11 is a hydrogen atom or a hydrocarbon group having 10 to 22 carbon atoms. k is an integer from 0 to 70, and l is an integer from 0 to 25, provided that k+l≧1. The ethylene oxide and propylene oxide may be bonded in a block form or in a random form.

[0101] Q-[(R 12 O) p -(C2H4O) q -(R 13 O) r -H] x (C1-2) (In formula (C1-2), Q is a group having a structure in which X hydrogen atoms have been removed from the hydroxy groups of an organic hydroxy compound having 3 to 8 hydroxy groups, and the adjacent R 12 is a group that bonds to R 12 , R 13 are each independently an alkylene group having 3 to 4 carbon atoms. X is a number corresponding to the number of hydroxy groups in the organic hydroxy compound. p and r each independently represent an integer of 2 to 30. q is 1 to 20.

[0102] R in the above formula (C1-1) 11 is a hydrocarbon group having 10 to 22 carbon atoms, and examples thereof include a dodecyl group, a tridecyl group, a hexadecyl group, an octadecyl group, a docosyl group, and an oleyl group.

[0103] In the formula (C1-1), k is the average number of moles of propylene oxide added and is 0 to 70, preferably 0 to 50. The l is the average number of moles of ethylene oxide added and is 0 to 25, preferably 0 to 10.

[0104] Examples of the organic hydroxy compound having 3 to 8 hydroxy groups in Q of the above formula (C1-2) include glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitol, glucose, fructose, sucrose, and sorbitan.

[0105] R in the above formula (C1-2) 12 , R 13 Examples of the alkylene group having 3 to 4 carbon atoms in the formula include an n-propylene group, an isopropylene group, an n-butylene group, and a sec-butylene group.

[0106] The HLB value of the polyoxyalkylene surfactant (C1) is from 0 to 3.5, preferably from 0.2 to 3.0.

[0107] The ratio (mol %) of ethylene oxide (EO) to propylene oxide (PO) contained in the polyoxyalkylene surfactant (C1), where the total amount of EO and PO is 100 mol %, is preferably EO:PO=0:100 to 30:70, more preferably 5:95 to 27.5:72.5, and even more preferably 10:90 to 25:75. A ratio within the above range is preferred because it provides excellent defoaming properties and precipitation suppression capabilities and can suppress the generation of foreign matter.

[0108] The polyoxyalkylene surfactant (C1) is 18 H 35 O-[(C3H6O) 40 -(C2H4O)5]H (HLB value: 1.6), C 18 H 37 O-[(C3H6O) 37 -(C2H4O)2]H (HLB value: 0.7), C 16 H 33 O-[(C3H6O) 36 -(C2H4O)6]H (HLB value: 2.0), C 10 H 21 O-[(C3H6O) 35 -(C2H4O)6]H (HLB value: 2.2), C 16 H 33O-[(C3H6O) 15 -(C2H4O)5]H (HLB value: 3.3), C 16 H 33 O-[(C3H6O) 70 -(C2H4O)5]H (HLB value: 1.0), C 18 H 35 O-[(C3H6O) 40 / (C2H4O)5]H (HLB value: 1.6), HO-[(C3H6O) 35 ]H(HLB value: 0.3), C3H5O3[(C3H6O) 48 -(C2H4O)9H]3(HLB value: 2.4), C3H5O3[(C3H6O)5-(C2H4O)5-(C3H6O) 13 H]3(HLB value: 3.5), C5H8O4[(C3H6O)5-(C2H4O)2-(C3H6O)5H]4(HLB value: 2.6), C3H5O3[(C3H6O) 13 -(C2H4O)3-(C3H6O)5H]3 (HLB value: 2.3), etc. In the above formula, " / " indicates a random bond.

[0109] The polyoxyalkylene surfactants can be synthesized by known methods, for example, by the methods described in Japanese Patent No. 3945278 and Japanese Patent Laid-Open No. 52-69881.

[0110] The polyoxyalkylene surfactant (C1) is preferably used in combination with a polyoxyalkylene surfactant (C3) having an HLB value of more than 3.5 and 10 or less, from the viewpoint of suppressing foaming of the developer.

[0111] Examples of the polyoxyalkylene surfactant (C3) include HO—[(C3H6O) 10 / (C2H4O)5]H (HLB value: 5.8), C 16 H 33 O-[(C3H6O) 43 -(C2H4O) 30 ]H (HLB value: 6.5), HO-[(C3H6O) 10.5 / (C2H4O) 7.5]H (HLB value: 7.3), HO-[(C3H6O)5 / (C2H4O)5]H (HLB value: 9.0), HO-[(C3H6O) 17.5 / (C2H4O) 12.5 ]H (HLB value: 7.2), HO-[(C3H6O) 1.2 / (C2H4O) 0.8 ]H (HLB value: 8.7) and the like.

[0112] When the polyoxyalkylene surfactant (C3) is used, its content is preferably 2% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 20% by mass or less, and even more preferably 10% by mass or more and 18% by mass or less, based on the total amount of the surfactants (C).

[0113] (Antifoaming agent (C2)) The antifoaming agent (C2) may include one or more selected from the group consisting of poly(meth)acrylic acid esters, polyolefins, polyvinyl ethers, and modified or unmodified polydimethylsiloxanes.

[0114] As the defoaming agent containing one or more selected from the group consisting of poly(meth)acrylic acid ester, polyolefin, polyvinyl ether, and modified or unmodified polydimethylsiloxane, commercially available products can be used.

[0115] Examples of the defoaming agent containing the poly(meth)acrylic acid ester, polyolefin, or polyvinyl ether include FLORENE AC-300VF (manufactured by Kyoeisha Chemical Co., Ltd.) and BYK-054 (manufactured by BYK Japan KK).

[0116] An example of the defoaming agent containing the modified or unmodified polydimethylsiloxane is BYK-1770 (manufactured by BYK Japan), which is a polyether-modified polydimethylsiloxane.

[0117] The surfactant (C) may be used singly or in combination of two or more kinds.

[0118] The lower limit of the content of the surfactant (C) (total content when multiple types are included) is preferably 0.1 parts by mass, more preferably 0.2 parts by mass, and even more preferably 0.3 parts by mass, per 100 parts by mass of the polymer (A). The upper limit of the content of the surfactant (C) is preferably 10 parts by mass, more preferably 8 parts by mass, and even more preferably 5 parts by mass, per 100 parts by mass of the polymer (A). Setting the content of the surfactant (C) within the above range is preferable because it can further suppress foaming of the developer and deposition of foreign matter during development.

[0119] <Compound (D)> The present composition preferably contains at least one compound (D) selected from the group consisting of amine compounds, imidazole compounds, and isocyanate compounds. The inclusion of compound (D) is preferred in that the resulting cured film can have higher development adhesion.

[0120] As the amine compound, a silane coupling agent having an amino group (including a primary amino group, a secondary amino group, and a tertiary amino group) can be preferably used. When the radiation-sensitive composition contains an amino-group-containing silane coupling agent, peeling of the film after development can be suppressed when a pattern film is formed on a substrate using the radiation-sensitive composition, which is preferable. The silane coupling agent contains a group "-Si(OR 51 ) a (R 52 ) 3-a ” (However, R 51 and R 52 are each independently a monovalent hydrocarbon group, and a is an integer of 1 to 3. 51 and R 52 is preferably an alkyl group or a phenyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. a is preferably 2 or 3 in that it can enhance the effect of improving development adhesion.

[0121] As the imidazole-based compound, a compound used as a curing catalyst for an epoxy group can be preferably used. By incorporating such a curing catalyst into the radiation-sensitive composition, it is possible to provide the resulting cured film with excellent chemical resistance, which is preferable.

[0122] As the isocyanate-based compound, a compound used as an adhesion promoter or an epoxy group curing catalyst can be preferably used, and a silane coupling agent can be particularly preferably used. By incorporating such an isocyanate-based compound into the radiation-sensitive composition, it is possible to further improve the effect of suppressing peeling of the pattern film and the chemical resistance, which is preferable.

[0123] Specific examples of the compound (D) include: Examples of amine compounds include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-methyl-3-(trimethoxysilyl)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, and 3-ureidopropyltriethoxysilane; Imidazole compounds include imidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxy-imidazole adduct curing agents; Examples of the isocyanate compound include 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, hexamethylene diisocyanate-based polyisocyanate, and toluene diisocyanate-based polyisocyanate.

[0124] Among these, 2-phenyl-4-methylimidazole, N-phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferred as compound (D).

[0125] The compound (D) may be used either individually or in combination of two or more.

[0126] When the composition contains compound (D), the lower limit of its content (total content when multiple types are contained) is preferably 0.01 parts by mass, more preferably 0.05 parts by mass, and even more preferably 0.1 parts by mass relative to 100 parts by mass of polymer (A), from the viewpoint of further improving the development adhesion of the resulting cured film. The upper limit of the content of compound (D) is preferably 10 parts by mass, more preferably 5 parts by mass, and even more preferably 1 part by mass relative to 100 parts by mass of polymer (A).

[0127] <Phenolic hydroxyl group-containing compound (E)> The present composition may further contain a compound (E) having a phenolic hydroxyl group. Inclusion of the compound (E) is preferred in that it can improve the radiation sensitivity of the radiation-sensitive composition. The compound (E) is preferably a compound having 2 to 5 benzene rings in one molecule, and preferably a compound having 2 to 6 phenolic hydroxyl groups. The molecular weight of the compound (E) is preferably 1,000 or less, more preferably 700 or less, and even more preferably 550 or less. The molecular weight of the compound (E) is preferably 200 or more.

[0128] Examples of the compound (E) include compounds represented by the following formulas (E-1), (E-2), (E-3), (E-4) and (E-5). [ka] (In formula (E-1), R e1 is a hydrogen atom or a methyl group. R e2 ~R e4 are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms. a1, a3 and a5 each independently represent an integer of 0 to 2, and a2, a4 and a6 each independently represent an integer of 1 to 3. a7 is 0 or 1.) [ka] (In formula (E-2), R e5 ~R e7 are each independently a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. R e8 and R e9 are each independently a methylene group, an ethane-1,1-diyl group, a propane-2,2-diyl group, or a perfluoropropane-2,2-diyl group. b1, b3, b5, and b6 each independently represent an integer of 0 to 2, and b2 and b4 each independently represent an integer of 0 to 3, provided that b2+b4+b6≧2 is satisfied. b7 is an integer from 0 to 3. [ka] (In formula (E-3), R e10 and R e11 are each independently a hydrogen atom or a methyl group. R e12 ~R e16 are each independently an alkyl group or alkoxy group having 1 to 4 carbon atoms. c1, c3, c5, c7, and c9 each independently represent an integer of 0 to 2, c2, c4, c6, and c8 each independently represent an integer of 1 to 3, and c10 is 1 or 2. [ka] (In formula (E-4), R e17 and R e18 are each independently an alkyl group or an alkoxy group having 1 to 4 carbon atoms. X 2 is a carbonyl group, a sulfonyl group, a 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group, —CH(COCH3)—, or —CH═CH—CO—CH2—CO—CH═CH—. d1 and d3 are each independently an integer of 0 to 2, and d2 and d4 are each independently an integer of 1 to 3. [ka] (In formula (E-5), R e19 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a (meth)acryloyl group, a vinyl group, or a methylvinyl group. e1 is an integer between 0 and 2.)

[0129] Examples of the compound (E) include 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, 1,1,1-tris(4-hydroxyphenyl)ethane, bisphenol AF, and bisphenol S.

[0130] Of these, the compound (E) is preferably the compound represented by formula (E-1) because it has a greater effect of improving radiation sensitivity.

[0131] The compound (E) may be used either individually or in combination of two or more.

[0132] When the composition contains compound (E), the lower limit of its content (total content when multiple types are contained) is preferably 1 part by mass, more preferably 3 parts by mass, and even more preferably 5 parts by mass per 100 parts by mass of polymer (A) from the viewpoint of further improving radiation sensitivity. The upper limit of the content of compound (E) is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 15 parts by mass per 100 parts by mass of polymer (A).

[0133] <Solvent (S)> The radiation-sensitive composition of the present disclosure is a liquid composition in which the polymer (A), the photoacid generator (B), the surfactant (C), and other components that are blended as needed are dissolved or dispersed, preferably in a solvent (S). The solvent used is preferably an organic solvent that dissolves each of the components blended in the radiation-sensitive composition but does not react with each of the components.

[0134] The solvent (S) is not particularly limited, and examples thereof include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, etc. The solvent (S) may be used alone or in combination of two or more.

[0135] Examples of alcohol-based solvents include alkyl alcohols such as 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, and diacetone alcohol; and aromatic alcohols such as benzyl alcohol.

[0136] 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.

[0137] 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-based solvents such as propylene glycol diacetate; and polyhydric alcohol partial ether carboxylate-based solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.

[0138] Examples of ketone solvents include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and cycloheptanone.

[0139] Among these, ether-based solvents and ester-based solvents are preferred, ester-based solvents are more preferred, and polyhydric alcohol partially etherified carboxylate-based solvents are even more preferred. Furthermore, among the ether-based solvents 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.

[0140] The content of the solvent (S) in the composition is not particularly limited, but it is preferable that the solids concentration (components other than the solvent (S)) of the composition be adjusted to be within the following range. The lower limit of the solids concentration in the composition is preferably 5% by mass, more preferably 8% by mass, and even 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 even more preferably 30% by mass. A solids concentration of 5% by mass or more in the radiation-sensitive composition is preferable in that a sufficient coating thickness can be ensured when the radiation-sensitive composition is applied to a substrate. Furthermore, a solids concentration of 60% by mass or less is preferable in that the coating thickness does not become too large, and furthermore, the viscosity of the radiation-sensitive composition can be appropriately increased, ensuring good coatability.

[0141] <Other ingredients> The radiation-sensitive composition of the present disclosure may further contain components other than the above-described polymer (A), photoacid generator (B), surfactant (C), and solvent (S) (hereinafter also referred to as "other components"). Examples of other components include a reaction initiator (a photoradical polymerization initiator, a photocationic polymerization initiator, etc.), a polyfunctional polymerizable compound (a polyfunctional (meth)acrylate, etc.), an adhesion aid (a functional silane coupling agent, etc.), a surfactant other than surfactant (C), a polymerization inhibitor, an antioxidant, a chain transfer agent, etc. The blending ratio of these components is appropriately selected depending on each component within a range that does not impair the effects of the present disclosure.

[0142] The solids concentration of the radiation-sensitive composition of the present disclosure (the proportion of the total mass of components other than the solvent (S) in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) is appropriately selected in consideration of viscosity, volatility, etc.

[0143] The radiation-sensitive composition of the present disclosure contains a polymer (A), a photoacid generator (B), and a specific surfactant (C), and thereby exhibits excellent radiation sensitivity and development adhesion, and furthermore, can suppress foaming and deposition of foreign matter during development. Such a radiation-sensitive composition of the present disclosure is useful as a radiation-sensitive composition for display devices such as organic electroluminescence (EL) display devices.

[0144] <Pattern formation method> The pattern forming method according to this embodiment includes the steps of: (Step 1) applying a radiation-sensitive composition to a substrate; (Step 2) irradiating the coated radiation-sensitive composition with radiation; (Step 3) developing the radiation-irradiated radiation-sensitive composition using a developer; at least one of the radiation-sensitive composition and the developer contains a surfactant (C); The surfactant (C) A polyoxyalkylene surfactant (C1) having an HLB value of 0 or more and 3.5 or less, or It contains an antifoaming agent (C2) containing one or more selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl ethers, polyolefins, and modified or unmodified polydimethylsiloxanes.

[0145] The surfactant (C) can be suitably the same as that described in the radiation-sensitive composition. The content of the surfactant (C) in the radiation-sensitive composition can also be suitably the same as that described above.

[0146] Each step will be described in detail below.

[0147] <Process 1: Paint film formation process> In this step, a radiation-sensitive composition is applied to a surface on which a coating film is to be formed (hereinafter also referred to as "film-forming surface"), and the solvent is preferably removed by a heat treatment (pre-bake) to form a coating film on the film-forming surface. The material of the film-forming surface is not particularly limited. For example, when a planarizing film is formed using a radiation-sensitive composition, the radiation-sensitive composition is applied to a substrate provided with switching elements such as TFTs to form a coating film. For example, a glass substrate or a resin substrate is used as the substrate.

[0148] Examples of methods for applying the radiation-sensitive composition include spraying, roll coating, spin coating, slit die coating, bar coating, and inkjet coating. Among these, spin coating, slit die coating, and bar coating are preferred. Pre-baking conditions vary depending on the types and content ratios of each component in the radiation-sensitive composition, but are, for example, 60 to 130°C for 0.5 to 10 minutes. The thickness of the coating film formed (i.e., the film thickness after pre-baking) is preferably 1 to 12 μm.

[0149] As the radiation-sensitive composition, it is preferable to use the present composition from the viewpoint of suppressing foaming and deposition of foreign matter during development.

[0150] <Step 2: Exposure step> In this step, at least a portion of the coating film formed in step 1 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 having a pattern (for example, an interlayer insulating film) 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, and examples thereof include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m 2 is preferred.

[0151] <Process 3: Development process> In this step, the coating film irradiated in step 2 above is developed. Specifically, the coating film irradiated in step 2 above is developed with a developer to remove the irradiated portions, resulting in positive development. Examples of the developer include an aqueous solution of an alkali (basic compound). Examples of alkali include sodium hydroxide, tetramethylammonium hydroxide, and the alkalis exemplified in paragraph

[0127] of JP 2016-145913 A. The alkali concentration in the aqueous alkali solution is preferably 0.1 to 5.0% by mass to obtain adequate developability. Examples of development methods include a puddle method, a dipping method, a swinging immersion method, and a 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, the patterned coating film is preferably rinsed with running water.

[0152] In the present invention, from the viewpoint of suppressing foaming during development and suppressing deposition of foreign matter, it is preferable to add the surfactant (C) to the developer. The concentration of the surfactant (C) in the developer is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 1% by mass.

[0153] <Step 4: Heating step> In this step, the coating film developed in step 3 above can be subjected to a heating treatment (post-baking). This promotes the curing reaction of the film, resulting in a cured film that exhibits good chemical resistance. Post-baking can be performed using a heating device such as an oven or a hot plate. Regarding post-baking conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when the heat treatment is performed on a hot plate, and 10 to 80 minutes when the heat treatment is performed in an oven. In this manner, a cured film having a desired pattern can be formed on a substrate.

[0154] A post-exposure step may be further included between the above steps 3 and 4. By irradiating the developed coating film with radiation, a cured film having excellent melt flow resistance and transparency in the heating step 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, and examples thereof include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m 2 is preferred.

[0155] The pattern forming method of the present invention preferably includes a step of recovering and reusing the developer after development. When the radiation-sensitive composition contains a surfactant (C), the developer after development becomes a developer containing the surfactant (C) by transferring the surfactant (C) from the radiation-sensitive composition to the developer.

[0156] ≪Cured film≫ The cured film of the present disclosure is formed using the radiation-sensitive composition. The radiation-sensitive composition of the present disclosure has high radiation sensitivity, can suppress thermal melt flow after patterning, and has good dielectric constant and chemical resistance. Therefore, the cured film is useful as an insulating film for liquid crystal display devices or organic electroluminescence (EL) devices. Specifically, the cured film can be used as an organic interlayer insulating film formed on thin film transistors (TFTs) in liquid crystal display devices, a planarizing film that smooths surface irregularities caused by thin film transistors (TFTs) in organic EL devices, an interlayer insulating film that insulates between wirings, a partition wall and bank that define the area where the light-emitting layer is formed, a protective film that protects TFTs, a spacer, an adhesive layer for color filters, etc. In this specification, a "partition wall" refers to a member used for color separation, such as a color filter or a color conversion layer using quantum dots, and a "bank" refers to a member that separates light-emitting layers. Among these, the cured film of the present disclosure is particularly useful as an interlayer insulating film or a planarizing film.

[0157] <Display element> The display device of the present disclosure includes a cured film formed using the radiation-sensitive composition. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, and a micro LED display device.

[0158] The display element of the present disclosure can be effectively applied to a variety of applications, and can be used as various display devices such as watches, portable game machines, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays. [Example]

[0159] The present invention will be described in more 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 by mass unless otherwise specified.

[0160] [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 Apparatus: GPC-101 manufactured by Showa Denko Co., Ltd. GPC column: Shimadzu GLC GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 Mobile phase: Tetrahydrofuran Column temperature: 40℃ ·Flow rate: 1.0mL / min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: Differential refractometer Standard material: Monodisperse polystyrene

[0161] <Synthesis of Polymer (A)> [Synthesis Example A-1] Synthesis of Polymer (A-1) A flask equipped with a condenser and a stirrer was charged with 8 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol ethyl methyl ether. Subsequently, 13 parts of methacrylic acid, 40 parts of glycidyl methacrylate, 10 parts of dicyclopentanyl methacrylate, and 37 parts of methyl methacrylate were charged, and after nitrogen substitution, the temperature of the solution was raised to 70°C with gentle stirring and maintained at this temperature for 5 hours, yielding a polymer solution containing polymer (A-1). The solids concentration of this polymer solution was 35.0% by mass, and the Mw of polymer (A-1) was 9200, Mn was 4000, and the molecular weight distribution (Mw / Mn) was 2.3.

[0162] [Synthesis Examples A-2 to A-5] Synthesis of polymers (A-2) to (A-5) Polymer solutions containing polymers (A-2) to (A-5) having the same solid content concentration, molecular weight, and molecular weight distribution as polymer (A-1) were obtained in the same manner as in Synthesis Example A-1, except that the types and amounts (parts) of each component were used as shown in Table 1. In Table 1 below, "-" indicates that the corresponding component was not used. The same applies to the following tables.

[0163] The monomers used in the synthesis of the above polymers (A-1) to (A-5) are as follows. (Monomer that provides structural unit (I)) ·MA: methacrylic acid PIPE: p-Isopropenylphenol

[0164] (Monomer providing structural unit (II)) GMA: Glycidyl methacrylate ECHMA: 3,4-epoxycyclohexylmethyl methacrylate OXMA: 3-ethyl-3-oxetanylmethyl methacrylate

[0165] (Monomers that give structural units (III) and (IV)) CHMI: N-cyclohexylmaleimide DCM: dicyclopentanyl methacrylate MMA: Methyl methacrylate ST: Styrene MATHF: 2-Tetrahydrofuranyl methacrylate STMS: p-Styryltrimethoxysilane

[0166] [Table 1]

[0167] <Synthesis of surfactant (C)> [Synthesis Examples C-1 to C-3] Synthesis of surfactants (C-1) to (C-3) Similar to Production Example 1 of Compound (I)a1 in Japanese Patent No. 3945278, surfactant (C-1) was synthesized using octadecenyl alcohol and potassium hydroxide as a catalyst, propylene oxide, and ethylene oxide. Similarly, surfactants (C-2) and (C-3) were synthesized in the same manner as compounds (I) a2 and a3 of Japanese Patent No. 3945278. The structures and HLB values ​​of surfactants (C-1) to (C-3) are as follows. (C-1):C 18 H 37 O-[(C3H6O) 40 -(C2H4O)5]H, HLB value: 1.6 (C-2):C 18 H 37 O-[(C3H6O) 37 -(C2H4O)2]H, HLB value: 0.7 (C-3):C 16 H 33 O-[(C3H6O) 36 -(C2H4O)6]H, HLB value: 2

[0168] [Synthesis Examples C-4 and C-6] Synthesis of surfactants (C-4) and (C-6) Surfactants (C-4) and (C-6) were synthesized using diethylene glycol, potassium hydroxide as a catalyst, propylene oxide, and ethylene oxide in the same manner as in Production Example 2 of Japanese Patent No. 3945278. The structures and HLB values ​​of surfactants (C-4) and (C-6) are as follows: (C-4): HO-[(C3H6O) 35 ]H, HLB value: 0.3 (C-6): HO-[(C3H6O) 10 / (C2H4O)5]H, HLB value: 5.8 In the above formula, " / " indicates a random bond.

[0169] [Synthesis Example C-5] Synthesis of surfactant (C-5) Surfactant (C-5) was synthesized according to the synthesis example (sample No. 1) of JP-A-52-069881. The structure and HLB value of surfactant (C-5) are as follows: (C-5):C3H5O3[(C3H6O) 48 -(C2H4O)9H]3, HLB value: 2.4

[0170] The above HLB values ​​are calculated by the Griffin method described in "J. Soc. Cosmetic Chemists, 1, 311 (1949) Journal of the Federation of Japanese Cosmetic Chemists, Vol. 8, No. 2 (1973) 22." HLB value = 20 × (mass of hydrophilic part) / (molecular weight) The hydrophilic part is made up of ethylene oxide and alcohol.

[0171] <Preparation of Radiation-Sensitive Composition> The polymer (A), photoacid generator (B), surfactant (C), compound (D), compound (E), and solvent (S) used in the preparation of the radiation-sensitive composition are shown below.

[0172] Polymer (A) Polymers (A-1) to (A-5) synthesized in Synthesis Examples A-1 to A-5

[0173] Photoacid generator (B) B-1: Condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) B-2: Irgacure PAG121 (BASF)

[0174] Surfactants (C) C-1 to C-6: Polyoxyalkylene surfactants (C-1) to (C-6) synthesized in the above Synthesis Examples C-1 to C-6 C-7: AC-300VF (acrylic polymer / vinyl ether polymer) (Kyoeisha Chemical Co., Ltd.) C-8: BYK-054 (polyolefin) (manufactured by BYK Japan) C-9: BYK-1770 (polyether-modified polydimethylsiloxane) (BYK Japan) C-10: Ionet DS-300 (Sanyo Chemical Industries, Ltd.) (Structure: C 17 H 35 CO2-[(C3H6O)6]COC 17 H 35 , HLB value: 7.3)

[0175] 《Compound (D)》 D-1: 2-phenyl-4-methylimidazole D-2: N-phenyl-3-aminopropyltrimethoxysilane D-3: 3-aminopropyltriethoxysilane D-4: 3-Isocyanatopropyltriethoxysilane

[0176] <Phenolic hydroxyl group-containing compound (E)> E-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol

[0177] Solvent (S) S-1: Diethylene glycol ethyl methyl ether S-2: 3-Methoxypropionic acid methyl ester

[0178] [Example 1] To the polymer solution containing the polymer (A-1) obtained in Synthesis Example A-1 above, 0.5 parts of surfactant (C-1) and 20 parts of photoacid generator (B-1) were mixed in amounts corresponding to 100 parts (solid content) of polymer (A), and (S-1) and (S-2) were added in a mass ratio of 50:50 so that the final solid content concentration was 20 mass %. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0179] [Examples 2 to 22, Comparative Examples 1 to 11] Radiation-sensitive compositions of Examples 2 to 22 and Comparative Examples 1 to 11 were prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of each component shown in Table 2 were used.

[0180] [Table 2]

[0181] <Evaluation> The radiation-sensitive compositions of Examples 1 to 22 and Comparative Examples 1 to 11 were evaluated for the following items by the methods described below. The evaluation results are shown in Table 3.

[0182] [Radiation sensitivity] Using a spinner, the radiation-sensitive composition was applied to a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 100°C for 3 minutes to form a coating film with an average thickness of 4.0 μm. This coating film was irradiated with a predetermined amount of ultraviolet light from a high-pressure mercury lamp through a mask with a 10 μm x 10 μm rectangular light-shielding pattern. Next, a development process was carried out at 23°C for 80 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide as a developer, and then the film was washed with running ultrapure water for 1 minute. The entire coating film was irradiated with 300 mJ / cm2 from a high-pressure mercury lamp. 2The substrate was then post-baked by heating it in a clean oven at 230°C for 30 minutes to obtain a pattern (cured film). The exposure dose required to form a 10µm x 10µm pattern was determined. The smaller the exposure dose, the better the radiation sensitivity can be evaluated. The sensitivity was evaluated according to the following criteria. (Evaluation criteria) A: 200mJ / cm 2 less than B: 200 mJ / cm 2 More than 250mJ / cm 2 less than C: 250 mJ / cm 2 End

[0183] [Developing Adhesion] Using a spinner, the radiation-sensitive composition was applied to a silicon substrate that had not been treated with hexamethyldisilazane (HMDS), and then the pressure was reduced to 50 Pa in a vacuum drying apparatus. The substrate was then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was 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 then exposed to ultraviolet light of 1000 kJ / s. The substrate was then developed for 60 seconds at 25°C using a developer consisting of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and then rinsed with running ultrapure water for 1 minute. The minimum width of the line and space pattern that remained on the substrate without peeling was measured. The smaller the minimum width, the better the development adhesion can be evaluated. (Evaluation criteria) A: The minimum width measurement is 10 μm or less B: More than 10 μm and less than 50 μm C: If it is larger than 50 μm or if it cannot be resolved and is not evaluated

[0184] [Evaluation of anti-foaming and precipitation suppression ability] The radiation-sensitive composition was applied to a 6-inch silicon substrate that had been treated with HMDS at 60°C for 60 seconds using a spinner, and then prebaked on a hot plate at 100°C for 3 minutes to form a coating film with an average thickness of 5.0 μm. This coating film was then irradiated with 300 mJ / cm 2 using a high-pressure mercury lamp. 2 The coating film was exposed to light and dissolved in 30 g of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. Dissolution of two substrates' worth of coating film was repeated to prepare a coating film solution. 10 g of this coating film solution was placed in a 100 mL glass bottle, and air was continuously blown into it using the air blowing method to generate bubbles. The state was observed after 120 minutes, and the defoaming and precipitation suppression abilities were evaluated according to the following criteria. (Evaluation criteria) AA: No bubbles, no deposits A: Foam height less than 2cm, no precipitates B: Foam height 2cm or more but less than 7cm, no precipitates C: Bubble height was 7cm or more, and precipitate was observed. AA indicates that the antifoaming and precipitation suppression capabilities are "very good," A indicates "good," B indicates "not good but acceptable for practical use," and C indicates "poor."

[0185] [Foreign matter evaluation] The prepared radiation-sensitive composition was weighed into a container and allowed to stand. The appearance of the radiation-sensitive composition was then visually observed. Next, using a spinner, the radiation-sensitive composition was applied to a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and the pressure was reduced to 23 Pa in a vacuum drying apparatus. The substrate was then prebaked on a hot plate at 100°C for 3 minutes to produce a coating film. Evaluation was performed according to the following criteria. (Evaluation criteria) A: No foreign matter was found on the coating or in the container. B: Foreign matter was visible on the container walls and lid. C: Foreign matter was visible on the coating film. A means that the suppression of foreign matter generation is "very good", B means "good", and C means "poor".

[0186] [Table 3]

[0187] As shown in Table 3, the radiation-sensitive compositions of Examples 1 to 22 were all good in terms of practical properties, such as radiation sensitivity, development adhesion, defoaming property, precipitation suppression ability, and foreign matter evaluation, and were well-balanced in terms of various properties. In contrast, the compositions of Comparative Examples 1 to 11 were rated "C" for one or more of the various properties, and were inferior to Examples 1 to 22.

Claims

1. Polymer (A), a photoacid generator (B); a surfactant (C); a solvent (S); Contains The surfactant (C) A polyoxyalkylene surfactant (C1) having an HLB value of 0 or more and 3.5 or less, or Contains an antifoaming agent (C2) containing one or more selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl ethers, polyolefins, and modified or unmodified polydimethylsiloxanes; Positive radiation-sensitive composition.

2. 2. The positive-working radiation-sensitive composition according to claim 1, wherein the polymer (A) is an acrylic polymer.

3. the surfactant (C) comprises the polyoxyalkylene surfactant (C1) and a polyoxyalkylene surfactant (C3) having an HLB value of more than 3.5 and not more than 10, 2. The positive-tone radiation-sensitive composition according to claim 1, wherein the content of the polyoxyalkylene surfactant (C3) is from 2% by mass to 20% by mass, both inclusive, based on the total amount of the surfactants (C).

4. The positive-tone radiation-sensitive composition according to any one of claims 1 to 3, further comprising at least one compound (D) selected from the group consisting of amine-based compounds, imidazole-based compounds, and isocyanate-based compounds.

5. 5. The positive-working radiation-sensitive composition according to claim 4, wherein the compound (D) is a silane coupling agent.

6. The positive-working radiation-sensitive composition according to any one of claims 1 to 3, further comprising a phenolic hydroxyl group-containing compound (E).

7. applying a radiation-sensitive composition to a substrate; a step of irradiating the coated radiation-sensitive composition with radiation; developing the radiation-irradiated radiation-sensitive composition using a developer; A pattern forming method comprising: at least one of the radiation-sensitive composition and the developer contains a surfactant (C); The surfactant (C) A polyoxyalkylene surfactant (C1) having an HLB value of 0 or more and 3.5 or less, or Contains an antifoaming agent (C2) containing one or more selected from the group consisting of poly(meth)acrylic acid esters, polyvinyl ethers, polyolefins, and modified or unmodified polydimethylsiloxanes; Pattern formation method.

8. The pattern forming method according to claim 7 , further comprising a step of recovering and reusing the developer after development.

9. A cured film formed using the positive-working radiation-sensitive composition according to any one of claims 1 to 3.

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

11. The display element according to claim 10, which is for organic electroluminescence.

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