Radiation-sensitive composition, cured film and method for manufacturing the same, semiconductor element and display element

Abstract

To provide a radiation-sensitive composition that can form a cured film with excellent development adhesion. [Solution] A radiation-sensitive composition comprising a polymer containing a structural unit having an acidic group (excluding polymers having a structural unit represented by formula (1)), a quinone diazide compound, a silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and which does not have an alkoxy group, a basic compound, and a solvent. In formula (1), R 1 , R 2 and R 3 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 1 , R 2 and R 3 One or more of these are alkoxy groups with 1 to 6 carbon atoms. "*" indicates a bonding bond. TIFF2026063097000022.tif20169

Description

[Technical Field]

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

[0002] Cured films (e.g., interlayer insulating films, spacers, protective films, etc.) on semiconductor elements and display elements are generally formed using radiation-sensitive compositions containing polymer components and radiation-sensitive compounds (e.g., photoacid generators, photopolymerization initiators, etc.). For example, a patterned cured film can be obtained by forming a pattern on a coating film formed from a radiation-sensitive composition by irradiating and developing it, and then performing a heat treatment to thermally cure it.

[0003] As materials for forming cured films on semiconductor elements and display elements, Patent Documents 1 and 2 propose radiation-sensitive compositions containing silicon-containing polymers such as polymers having silicon-containing functional groups such as alkoxysilyl groups or siloxane polymers, and photoacid generators.

[0004] When a coating film is formed using the radiation-sensitive composition of Patent Document 1, exposure during pattern formation generates acid from the photoacid generator, and the generated acid decomposes the alkoxy groups, solubilizing the exposed areas in the developer. The unexposed areas are alkali-insoluble, and after development, dehydration condensation occurs by heating, and curing forms a cured film. In addition, with the radiation-sensitive composition of Patent Document 2, the acid generated from the photoacid generator upon exposure promotes the self-crosslinking of the siloxane polymer, thereby forming a cured film.

[0005] Furthermore, as a material for forming cured films on semiconductor elements and display elements, Patent Document 3 proposes a radiation-sensitive composition comprising a polymer containing structural units having acidic groups, a polymerizable monomer, and a photopolymerization initiator. Patent Document 4 proposes a chemically amplified radiation-sensitive composition comprising a polymer containing structural units having acid-dissociable groups and a photoacid generator. Patent Document 5 proposes a radiation-sensitive composition comprising a polymer containing structural units having acidic groups and a quinone diazide compound. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2017-107024 [Patent Document 2] International Publication No. 2011 / 065215 [Patent Document 3] Japanese Patent Publication No. 2003-5357 [Patent Document 4] Japanese Patent Publication No. 2011-232632 [Patent Document 5] Japanese Patent Publication No. 2014-186300 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] If the adhesion between the coating film and the substrate after irradiation is insufficient, the developer may penetrate from the interface between the film and the substrate during the developing process, causing the film pattern to peel off. In particular, in recent years, there has been a demand for even higher quality display devices, and as patterns become finer to meet the demand for higher quality display devices, there is a tendency for the film pattern to peel off more easily during the developing process. From the perspective of suppressing a decrease in manufacturing yield, radiation-sensitive compositions are required to be less prone to peeling between the film and the substrate during the developing process (i.e., have good developing adhesion).

[0008] The present invention has been made in view of the above problems, and one of its objectives is to provide a radiation-sensitive composition that can form a cured film with excellent developability. [Means for solving the problem]

[0009] The inventors have found that the above problems can be solved by incorporating a specific compound into a radiation-sensitive composition. That is, the present invention provides the following radiation-sensitive composition, cured film and method for producing the same, semiconductor element and display element.

[0010] [1] A radiation-sensitive composition comprising: a polymer selected from the group consisting of polymers and siloxane polymers, which include a structural unit (I) having a group represented by the following formula (1) or an acid-dissociable group; a photoacid generator; and a silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and which does not have an alkoxy group. [ka] (In formula (1), R 1 , R 2 and R 3 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 1 , R 2 and R 3 One or more of these are alkoxy groups with 1 to 6 carbon atoms. (* indicates a bonding bond.)

[0011] [2] A radiation-sensitive composition comprising a polymer containing a structural unit having an acidic group (excluding polymers having a structural unit represented by formula (1) above), a quinone diazide compound, a silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and which does not have an alkoxy group, a basic compound, and a solvent.

[0012] [3] A radiation-sensitive composition comprising a polymer containing a structural unit having an acidic group, a polymerizable monomer, a photopolymerization initiator, a silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and which does not have an alkoxy group, a basic compound, and a solvent.

[0013] [4] A method for producing a cured film, comprising the steps of: forming a coating film using any one of the radiation-sensitive compositions described in [1] to [3] above; irradiating at least a portion of the coating film with radiation; developing the radiation-irradiated coating film; and heating the developed coating film. [5] A cured film formed using any one of the radiation-sensitive compositions described in [1] to [3] above. [6] A semiconductor element comprising the cured film described in [5] above. [7] A display element comprising the cured film described in [5] above. [Effects of the Invention]

[0014] According to the radiation-sensitive composition of this disclosure, a cured film with excellent developability can be formed. [Modes for carrying out the invention]

[0015] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the values ​​indicated before and after "~" as the lower and upper limits, respectively. "Structural unit" refers to a unit that mainly constitutes the main chain structure and is included in the main chain structure in pairs or more.

[0016] 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, it 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, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, and it may also include those that have 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, it is not necessary to consist only of the structure of an aromatic ring, and it may also contain 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 group" includes alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0017] 《Radiation sensitive composition》 The radiation-sensitive composition of this disclosure (hereinafter also referred to as "the Composition") is used, for example, to form a cured film of a display element. The Composition is a resin composition containing [A] a polymer component and [B] a silanol compound. The following describes the components contained in the first, second, and third compositions, which are specific embodiments of the Composition, and 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] [First composition] The first composition is a positive-type resin composition containing [A] a polymer component, [B] a silanol compound, and [C] a photoacid generator.

[0019] <[A] Polymer component> [A] The polymer component contains at least one polymer selected from the group consisting of polymers and siloxane polymers that include a structural unit (I) having a group represented by the following formula (1) or an acid-dissociable group (hereinafter also referred to as "(A-1) polymer"). [Chemical formula] (In formula (1), 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. However, among R 1 , R 2 and R 3 , one or more are alkoxy groups having 1 to 6 carbon atoms. "*" represents a bond.)

[0020] Specific examples of the polymer component contained in the first composition include a polymer containing a structural unit (I-1) having a group represented by the above formula (1) (hereinafter, also referred to as "polymer (a1-1)"), a polymer containing a structural unit (I-2) having an acid dissociable group (hereinafter, also referred to as "polymer (a1-2)"), and a siloxane polymer. Among the (A-1) polymers, at least one selected from the group consisting of a polymer containing a structural unit having a group represented by the above formula (1) and a siloxane polymer is hereinafter also referred to as a "silicon-containing polymer".

[0021] Here, in the cured film formed using the radiation-sensitive compositions of Patent Documents 1 and 2 above, it is considered that water absorption occurs from the end of the unexposed portion during the development process, so that the alkoxy group in the unexposed portion becomes a silanol group, and the hydrophilicity of the unexposed portion increases. In this case, there is a concern that the adhesion of the unexposed portion to the substrate (development adhesion) decreases, and the pattern is likely to peel off from the substrate.

[0022] Furthermore, in a cured film formed using the radiation-sensitive compositions of Patent Documents 1 and 2 described above, there is a concern that if water absorption occurs from the edges of the unexposed areas during the developing process, and the alkoxy groups in the unexposed areas are changed to silanol groups, the dielectric constant of the cured film will increase due to the presence of hydroxyl groups in the polymer side chains. Therefore, one objective of this disclosure is to provide a radiation-sensitive composition that, when containing a silicon-containing polymer as a polymer component, can form a cured film with excellent developability and low dielectric constant.

[0023] In this regard, a radiation-sensitive composition comprising a silicon-containing polymer, which is at least one selected from the group consisting of polymers containing a structural unit having a group represented by formula (1) above and siloxane polymers, a photoacid generator, and the silanol compound above, can form a cured film with excellent developability and low dielectric constant.

[0024] [Regarding the polymer (a1-1)] • Structural unit (I-1) In the above equation (1), R 1 ~R 3 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 1 ~R 3 The alkoxy group represented by the above formula (1) is preferably having 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group. In particular, when the group represented by the above formula (1) is bonded to an aromatic ring group, R 1 ~R 3 The alkoxy group represented by the above formula (1) is preferably a methoxy group. When the group represented by the above formula (1) is bonded to a chain hydrocarbon group, R 1 ~R 3 The alkoxy group represented is preferably an ethoxy group.

[0025] R 1 ~R 3 The alkyl group having 1 to 10 carbon atoms represented by R may be linear or branched. 1 ~R 3Examples of alkyl groups represented by R 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 1 ~R 3 The alkyl group represented is preferably a methyl group, an ethyl group, or a propyl group.

[0026] R 1 ~R 3 One 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.

[0027] From the viewpoint of obtaining a cured film with excellent heat resistance by forming a cross-linked structure, R 1 ~R 3 Preferably, two or more of these are alkoxy groups having 1 to 6 carbon atoms, and it is particularly preferable that all of them are alkoxy groups having 1 to 6 carbon atoms.

[0028] In structural unit (I-1), the group represented by formula (1) is preferably bonded to an aromatic ring group or a linear hydrocarbon group. In this specification, "aromatic ring group" means a group obtained by removing n (where n is an integer) hydrogen atoms from the ring portion of an aromatic ring. Examples of such aromatic rings include benzene rings, naphthalene rings, and anthracene rings. These rings may have substituents such as alkyl groups. When the group represented by formula (1) is bonded to a linear hydrocarbon group, examples of such linear hydrocarbon groups include alkanediyl groups and alkenediyl groups.

[0029] The group represented by formula (1) above is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. Specifically, structural unit (I-1) preferably has at least one selected from the group consisting of the group represented by formula (3-1), the group represented by formula (3-2), and the group represented by formula (3-3). [ka] (In equations (3-1), (3-2), and (3-3), A 1 and A 2 Each of these is independently a halogen atom, a hydroxyl group, a C1-C6 alkyl group, or a C1-C6 alkoxy group. n1 is an integer from 0 to 4. n2 is an integer from 0 to 6. However, if n1 is 2 or greater, multiple A 1 They are either identical or different from each other. If n2 is 2 or more, there are multiple A 2 They are either identical or different from one another. 6 This is an alkanediyl group. 1 , R 2 and R 3 This is equivalent to equation (1) above. "*" indicates a bonding operation.

[0030] In equations (3-1) and (3-2) above, A 1 and A 2 Examples of alkoxy groups having 1 to 6 carbon atoms and alkyl groups having 1 to 6 carbon atoms represented by the above formula (1) are as follows: 1 ~R 3 Similar groups to those exemplified above can be cited. Groups that bond to aromatic rings "-SiR 1 R 2 R 3 The position of " is A 1 and A 2 The bond position of any of the other groups (i.e., the bond position represented by "*") may be any position. For example, in formula (3-1) above, "-SiR 1 R 2 R 3The position of the bond represented by "*" may be any of the ortho, meta, or para positions. The para position is preferred. n1 is preferably 0 or 1, more preferably 0. n2 is preferably 0 to 2, more preferably 0. In the above equation (3-3), R 6 It is preferable that it is linear. From the viewpoint of increasing the heat resistance of the resulting cured film, R 6 The carbon atoms preferably have 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

[0031] In order to improve the heat resistance, chemical resistance, and hardness of the cured film, it is preferable that the structural unit (I-1) has at least one selected from the group consisting of the group represented by formula (3-1) and the group represented by formula (3-2) among the above formulas (3-1) to (3-3). In addition, the aromatic ring may have the group "-SiR 1 R 2 R 3 When the group is directly bonded, it becomes possible to stabilize the silanol group that is generated in the presence of water. This is preferable because it allows for higher solubility of the exposed area in the alkaline developer and enables the formation of a good pattern. Among these, structural unit (I-1) is particularly preferably a structural unit having a group represented by the above formula (3-1).

[0032] The structural unit (I-1) is preferably a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond as a bond involved in polymerization (hereinafter also referred to as "unsaturated monomer"), and more specifically, it is preferably at least one selected from the group consisting of the structural unit represented by the following formula (4-1) and the structural unit represented by the following formula (4-2). [ka] (In equations (4-1) and (4-2), R A R is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. 7 and R 8 Each of these is independently a divalent aromatic ring group or a chain-like hydrocarbon group. 1 , R2 and R 3 This is equivalent to equation (1) above.

[0033] In equations (4-1) and (4-2) above, R 7 , R 8 The divalent aromatic ring group represented by is preferably a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalenediyl group. Substituents include one or more selected from the group consisting of halogen atoms, hydroxyl groups, C1-C6 alkyl groups, and C1-C6 alkoxy groups. The divalent chain hydrocarbon group is preferably an alkanediyl group having C1-C6, and more preferably an alkanediyl group having C1-C4.

[0034] In terms of obtaining a cured film with higher heat resistance, chemical resistance, and hardness, and in terms of increasing the solubility of the exposed area in alkaline developing solution, R 7 , R 8 Among the above, it is preferable that it be a divalent aromatic ring group, and particularly preferable that it be a substituted or unsubstituted phenylene group.

[0035] Specific examples of structural units represented by formula (4-1) above include the structural units represented by formulas (4-1-1) and (4-1-2) below. Furthermore, specific examples of structural units represented by formula (4-2) above include the structural units represented by formulas (4-2-1) and (4-2-2) below. [ka] (In equations (4-1-1), (4-1-2), (4-2-1), and (4-2-2), R 11 and R 12 Each of these is an alkyl group having 1 to 4 carbon atoms. 13 n3 is an integer between 1 and 4 carbon atoms, an alkyl group between 1 and 4 carbon atoms, an alkoxy group between 1 and 4 carbon atoms, or a hydroxyl group. 1 , A 2 n1 and n2 are equivalent to equations (3-1) and (3-2) above. AThis is equivalent to equations (4-1) and (4-2) above.

[0036] Specific examples of monomers constituting structural unit (I-1) include compounds having the group represented by formula (3-1) above, such as styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, (meth)acryloxyphenylethyldiethoxysilane, etc. Compounds having the group represented by the above formula (3-2) include trimethoxy(4-vinylnaphthyl)silane, triethoxy(4-vinylnaphthyl)silane, methyldimethoxy(4-vinylnaphthyl)silane, ethyldiethoxy(4-vinylnaphthyl)silane, (meth)acryloxynaphthyltrimethoxysilane, etc. Examples of compounds having the group represented by the above formula (3-3) include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and 4-(meth)acryloxybutyltrimethoxysilane. In this specification, "(meth)acrylic" encompasses both "acrylic" and "methacrylic".

[0037] The content of structural unit (I-1) in polymer (a1-1) is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more, relative to the total structural units constituting polymer (a1-1). Furthermore, the content of structural unit (I-1) is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, relative to the total structural units constituting polymer (a1-1). Setting the content of structural unit (I-1) within the above range is preferable because it allows for sufficiently high heat resistance and chemical resistance of the resulting cured film, enables high sensitivity, and allows the coating film to exhibit better resolution.

[0038] Other structural units The polymer (a1-1) may further contain structural units other than structural unit (I-1) (hereinafter also referred to as "other structural units (1)"). Examples of other structural units (1) include structural units (II-1) having one or more selected from the group consisting of oxiranyl groups and oxetanyl groups, and structural units having acidic groups (III-1). In this specification, oxiranyl groups and oxetanyl groups are collectively referred to as "epoxy groups".

[0039] • Structural unit (II-1) The polymer (a1-1) is preferable because it contains structural unit (II-1), which can further improve the resolution and adhesion of the film. Furthermore, the epoxy group acts as a crosslinking group, which is preferable because it can form a cured film with high chemical resistance and suppressed degradation over a long period of time. Structural unit (II-1) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, and more specifically, it is preferably at least one selected from the group consisting of structural units represented by the following formula (5-1) and structural units represented by the following formula (5-2). [ka] (In equations (5-1) and (5-2), R 20 R is a monovalent group having an oxyranyl group or an oxetanyl group. AX is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. 1 (This is a single bond or a divalent linking group.)

[0040] In equations (5-1) and (5-2) above, R 20 Examples include oxyranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl groups and 3-ethyloxetanyl groups. X 1 Preferred 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 by an oxygen atom.

[0041] Specific examples of monomers having an epoxy group include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, etc.

[0042] The content of structural unit (II-1) in polymer (a1-1) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to the total structural units constituting polymer (a1-1). Furthermore, the content of structural unit (II-1) is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to the total structural units constituting polymer (a1-1). Setting the content of structural unit (II-1) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured film to have sufficiently high heat resistance and chemical resistance.

[0043] • Structural unit (III-1) The polymer (a1-1) preferably further contains a structural unit (III-1) having an acidic group. The introduction of structural unit (III-1) can increase the solubility (alkali solubility) of the polymer (a1-1) in an alkaline developer or enhance its curing reactivity. In this specification, "alkali soluble" means that it is soluble in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

[0044] Structural unit (III-1) is not particularly limited as long as it has an acidic group. Preferably, structural unit (III-1) is at least one selected from the group consisting of structural units having a carboxyl group, structural units having a sulfonic acid group, structural units having a phenolic hydroxyl group, and maleimide units. In this specification, "phenolic hydroxyl group" means a hydroxyl group directly bonded to an aromatic ring (e.g., a benzene ring, naphthalene ring, anthracene ring, etc.).

[0045] The structural unit (III-1) is preferably derived from an unsaturated monomer having an acidic group. Specific examples of unsaturated monomers having an acidic group include, as monomers constituting a structural unit 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 constituting a structural unit having a sulfonic acid group, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, and (meth)acryloxyethylsulfonic acid; and as monomers constituting a structural unit having a phenolic hydroxyl group, 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, and hydroxyphenyl(meth)acrylate. Maleimide can also be used as the monomer constituting structural unit (III-1).

[0046] From the viewpoint of providing good solubility in alkaline developer, the content of structural unit (III-1) in polymer (a1-1) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, relative to the total structural units constituting polymer (a1-1). On the other hand, if the content of structural unit (III-1) is too high, there is a concern that the difference in solubility in alkaline developer between the exposed and unexposed areas will become small, making it difficult to obtain a good pattern shape. From this viewpoint, the content of structural unit (III-1) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer (a1-1).

[0047] Other structural units (1) include structural units derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, alicyclic (meth)acrylates, aromatic rings, aromatic vinyl compounds, N-substituted maleimide compounds, heterocyclic vinyl compounds, conjugated dienes, nitrogen-containing vinyl compounds, and unsaturated dialkyl dicarboxylic acid compounds. By introducing these structural units into the polymer, the glass transition temperature of the polymer components can be adjusted, improving the pattern shape and chemical resistance of the resulting cured film.

[0048] Specific examples of the above monomers include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, and n-stearyl methacrylate; As (meth)acrylic acid esters having an alicyclic structure, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(meth)acrylate [5.2.1.0 2,6 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.0 2,5 Decane-8-yloxyethyl, isoboronyl (meth)acrylate, etc. Examples of (meth)acrylic acid esters having an aromatic ring structure include phenyl (meth)acrylate and benzyl (meth)acrylate; Aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, etc. Examples of N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. Examples of vinyl compounds having a heterocyclic structure include tetrahydrofurfuryl (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, N-(meth)acryloxyethylhexahydrophthalimide, etc. Examples of conjugated diene compounds include 1,3-butadiene and isoprene; Examples of nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; Examples of unsaturated dicarboxylate dialkyl ester compounds include diethyl itaconate, etc. In addition to the above, other monomers constituting structural unit (1) include, for example, vinyl chloride, vinylidene chloride, vinyl acetate, etc.

[0049] From the viewpoint of adjusting the glass transition temperature of the polymer components to suppress melt flow during thermal curing, it is preferable that the polymer (a1-1) contains structural units (1) other than structural units (II-1) and structural units (III-1), which are structural units (1) derived from at least one monomer selected from the group consisting of alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, and (meth)acrylates having an aromatic ring structure.

[0050] From the viewpoint of appropriately raising the glass transition temperature of polymer (a1-1), the content of structural units other than structural unit (II-1) and structural unit (III-1) (1) is preferably 5% by mass or more, and more preferably 10% by mass or more, relative to the total structural units constituting polymer (a1-1). Furthermore, the content of these structural units is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total structural units constituting polymer (a1-1).

[0051] Polymer (a1-1) 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. Examples of polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyric acid)dimethyl. The amount of polymerization initiator used is preferably 0.01 to 30 parts by mass per 100 parts by mass of the total amount of monomers used in the reaction. Examples of polymerization solvents include alcohols, ethers, ketones, esters, hydrocarbons, etc. The amount of polymerization solvent used is preferably such that the total amount of monomers used in the reaction is 0.1 to 60% by mass of the total amount of reaction solution.

[0052] In polymerization, the reaction temperature is typically 30°C to 180°C. The reaction time varies depending on the type of polymerization initiator and monomer and the reaction temperature, but is usually 0.5 to 10 hours. The polymer obtained by the polymerization reaction may be used in the preparation of the radiation-sensitive composition while still dissolved in the reaction solution, or it may be isolated from the reaction solution before being used in the preparation of the radiation-sensitive composition. The polymer can be isolated by known isolation methods, such as pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator.

[0053] [A] When polymer component [A] contains polymer (a1-1), [A] polymer component may consist only of polymer (a1-1) having structural unit (I-1), as long as it contains structural unit (I-1), or it may further contain polymers that do not have structural unit (I-1) together with polymer (a1-1). For example, when polymer component [A] contains structural unit (I-1), structural unit (II-1), and structural unit (III-1), the same polymer may have all of structural unit (I-1), structural unit (II-1), and structural unit (III-1), or a polymer different from the polymer having structural unit (I-1) may have at least one selected from the group consisting of structural unit (II-1) and structural unit (III-1). When structural unit (I-1), structural unit (II-1), and structural unit (III-1) are contained in two or more different polymers in polymer component [A], it is preferable that the content ratio of each structural unit contained in polymer component [A] satisfies the above range. In order to reduce the number of components constituting the radiation-sensitive composition while improving developability and chemical resistance, it is preferable that the polymer component [A] contains a polymer having structural units (I-1), (II-1), and (III-1). Each polymer constituting the polymer component [A] is preferably an alkali-soluble resin.

[0054] For polymer (a1-1), the weight-average molecular weight (Mw) in polystyrene terms, determined by gel permeation chromatography (GPC), is preferably 2,000 or more. An Mw of 2,000 or more is preferable because it allows for the production of a cured film with sufficiently high heat resistance and chemical resistance, as well as good developability. The Mw of polymer (a1-1) 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 formation, 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.

[0055] Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight Mw to number-average molecular weight Mn, is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. Note that if the polymer component [A] consists of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above range.

[0056] [Regarding polymerization (a1-2)] Polymer (a1-2) is a polymer containing structural unit (I-2) having an acid-dissociable group. The acid-dissociable group is a hydrogen atom-substituting group found in acidic groups such as carboxyl groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, and sulfonic acid groups, and is a group that dissociates upon the action of an acid. In this composition containing polymer (a1-2), the acid-dissociable group is removed by the acid generated when the composition is irradiated with radiation, resulting in the formation of an acidic group. This makes it possible to change the solubility of the polymer component in the developer and obtain a cured film with a pattern formed on it.

[0057] In particular, structural unit (I-2) is preferably a structural unit in which an acid-dissociable group is removed by the action of an acid to produce a carboxyl group (hereinafter also referred to as "structural unit (I-2-1)"), or a structural unit in which an acid-dissociable group is removed by the action of an acid to produce a phenolic hydroxyl group (hereinafter also referred to as "structural unit (I-2-2)").

[0058] • Regarding structural units (I-2-1) Structural units (I-2-1) include structural units derived from protected unsaturated carboxylic acids. The unsaturated carboxylic acids used are not particularly limited and include, for example, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated acid anhydrides, and unsaturated polycarboxylic acids.

[0059] Specific examples of these include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, (meth)acrylic acid-2-carboxyethyl ester, and 4-vinylbenzoic acid. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, and citraconic acid. Examples of unsaturated anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of unsaturated polycarboxylic acids include ω-carboxypolycaprolactone mono(meth)acrylate.

[0060] Examples of acid-dissociable groups included in structural unit (I-2-1) include acetal functional groups, tertiary alkyl groups, and tertiary alkyl carbonate groups. Of these, acetal functional groups are preferred because they are easily dissociated by acid.

[0061] When the acid-dissociable group is an acetal functional group, the structural unit (I-2-1) preferably has a protected carboxyl group, specifically a carboxylic acid acetal ester structure, and more preferably has a group represented by the following formula (X-1). [ka] (In formula (X-1), R 31 , R 32 and R 33 (1) R 31 R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. 32 and R 33 Each of these is independently an alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. (2)R 31 R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. 32 and R 33is mutually aligned and R 32 and OR 33 represents a cyclic ether structure formed together with the carbon atom to which they are bonded. "*" represents a bond.)

[0062] R 31 、R 32 and R 33 The alkyl group having 1 to 12 carbon atoms represented by is linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 4. R 31 、R 32 and R 33 Specific examples of the alkyl group having 1 to 12 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 and the like.

[0063] R 31 、R 32 and R 33 Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group and the like. R 32 and R 33 Examples of the aralkyl group having 7 to 20 carbon atoms represented by include phenylmethyl group, phenylethyl group, methylphenylmethyl group and the like.

[0064] R 32 and R 33 The cyclic ether structure formed by being mutually aligned is preferably 5 or more members. Specifically, for example, a tetrahydrofuran ring structure, a tetrahydropyran ring structure and the like can be mentioned.

[0065] In terms of being easily dissociated by an acid, R 31 is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

[0066] Specific examples of the acetal ester structure of the carboxylic acid represented by the above formula (X-1) include 1-methoxyethoxycarbonyl group, 1-ethoxyethoxycarbonyl group, 1-propoxyethoxycarbonyl group, 1-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 2-tetrahydrofuranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group, and 1-phenylmethoxyethoxycarbonyl group.

[0067] Among the above, the structural units (I-2-1) are preferably the structural units represented by formula (Y-1) and formula (Y-2). [ka] (In formula (Y-1), R 30 X is a hydrogen atom or a methyl group. 30 R is a single bond or an arylene group. 40 R is a hydrogen atom or an alkyl group. 41 and R 42 Each of these is independently an alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. [ka] (In formula (Y-2), R 30 X is a hydrogen atom or a methyl group. 31 R is a single bond or an arylene group. 43 ~R 49 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. k is either 1 or 2.

[0068] A preferred example of a structural unit (I-2-1) is the structural unit represented by the following formula. In the formula, R 30 This is either a hydrogen atom or a methyl group. [ka]

[0069] • Regarding structural units (I-2-2) Structural unit (I-2-2) is not particularly limited, as long as it has a protected phenolic hydroxyl group. From the viewpoint of the sensitivity of this composition, structural unit (I-2-2) is preferably at least one selected from the group consisting of structural units derived from hydroxystyrene or its derivatives and structural units derived from (meth)acrylic compounds having a hydroxybenzene structure.

[0070] The acid-dissociable group possessed by structural unit (I-2-2) is not particularly limited. From the viewpoint of the sensitivity, pattern shape, and storage stability of this composition, the acid-dissociable group possessed by structural unit (I-2-2) is preferably an acetal-based functional group. Examples of acetal-based functional groups that can be used in structural unit (I-2-2) are the same groups as those that can be used in structural unit (I-2-1). Among them, "-OC(R 31 )(R 32 )(OR 33 )" (However, R 31 , R 32 and R 33 It is preferable that the group is a phenolic hydroxyl group protected by a group represented by formula (X-1), which is synonymous with formula (X-1). In this case, the protected phenolic hydroxyl group contained in structural unit (I-2-2) can be represented by the following formula (Z-1). [ka] (In formula (Z-1), Ar 1 R is an arylene group. 31 , R 32 and R 33 This is equivalent to equation (X-1). "*" represents a bond.

[0071] The structural unit (I-2-2) contains "-C(R 31 )(R 32 )(OR 33Preferred specific examples of the group represented by ) include 1-alkoxyalkyl groups and 1-arylalkoxyalkyl groups. Specifically, examples include 1-ethoxyethyl group, 1-methoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-(2-cyclohexylethoxy)ethyl group, and 1-benzyloxyethyl group.

[0072] A preferred example of a structural unit (I-2-2) is the structural unit represented by the following formula. In the formula, R 30 This is either a hydrogen atom or a methyl group. [ka]

[0073] The content of structural unit (I-2) in polymer (a1-2) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total structural units constituting polymer (a1-2). Furthermore, the content of structural unit (I-2) is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less, relative to the total structural units constituting polymer (a1-2). Setting the content of structural unit (I-2) within the above range is preferable in that it is possible to increase the sensitivity of the first composition and the coating film exhibits better resolution.

[0074] If the first composition contains polymer (a1-2), the polymer component [A] may further contain structural units other than structural unit (I-2) (hereinafter also referred to as "other structural units (2)"). Examples of other structural units (2) include structural units having crosslinkable groups (II-2) and structural units having acidic groups (III-2). Other structural units (2) may be introduced into polymer (a1-2), introduced as structural units of a polymer different from polymer (a1-2), or introduced into both a polymer different from polymer (a1-2) and polymer (a1-2). It is preferable that polymer (a1-2) further contains structural units (II-2) and structural units (III-2) together with structural unit (I-2) in order to obtain the effect of improving developability and curing adhesion while minimizing the number of components constituting the first composition.

[0075] • Structural units (II-2) The crosslinkable group of structural unit (II-2) is not particularly limited, as long as it is a group that undergoes a hardening reaction by heat treatment. In terms of high thermosetting properties, the crosslinkable group is preferably one or both of an oxyranyl group and an oxetanyl group. Specific examples and preferred examples of structural unit (II-2) are the same as those shown in the description of structural unit (II-1).

[0076] When polymer (a1-2) contains structural unit (II-2), the content of structural unit (II-2) 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 (a1-2). Furthermore, the content of structural unit (II-2) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer (a1-2).

[0077] • Structural units (III-2) It is preferable that the polymer (a1-2) further contains a structural unit (III-2) having an acidic group, as this can improve solubility in alkaline developers and enhance curing reactivity. Specific and preferred examples of structural unit (III-2) are the same as those shown in the description of structural unit (III-1).

[0078] When polymer (a1-2) contains structural unit (III-2), the content of structural unit (III-2) 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 (a1-2), from the viewpoint of providing good solubility in alkaline developer. Furthermore, the content of structural unit (III-2) is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, relative to the total structural units constituting polymer (a1-2).

[0079] When the first composition contains polymer (a1-2), other structural units (2) that the polymer component may contain include the structural units exemplified in other structural units (1). When polymer (a1-2) contains structural units other than structural units (II-2) and structural units (III-2) as other structural units (2), the content of such structural units is preferably 50% by mass or less, and more preferably 40% by mass or less, relative to the total structural units constituting polymer (a1-2).

[0080] Polymers (a1-2) can be produced, for example, by using unsaturated monomers to 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 known methods such as radical polymerization. The details of the polymerization method are the same as for polymer (a1-1).

[0081] For polymer (a1-2), the weight-average molecular weight (Mw) in polystyrene equivalent by GPC is preferably 1,000 or more. The Mw of polymer (a1-2) is more preferably 2,000 or more, and even more preferably 5,000 or more. Furthermore, from the viewpoint of improving film-forming properties, the Mw of polymer (a1-2) is preferably 200,000 or less, and more preferably 50,000 or less. In addition, for polymer (a1-2), the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), is preferably 5.0 or less, and more preferably 3.0 or less.

[0082] [About siloxane polymers] The siloxane polymer is not particularly limited as long as it can form a cured film by hydrolysis condensation. Preferably, the siloxane polymer is a polymer obtained by hydrolyzing a hydrolyzable silane compound represented by the following formula (6). (R 21 ) r Si(OR 22 ) 4-r …(6) (In formula (6), R 21 It is a non-hydrolyzable monovalent group. 22 is an alkyl group having 1 to 4 carbon atoms. r is an integer from 0 to 3. However, if r is 2 or 3, multiple R in the formula. 21 These are either identical or different from each other. When r is between 0 and 2, there are multiple R in the formula. 22 They are either identical or different from one another.

[0083] R 21 Examples include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, groups having a (meth)acryloyl group, and groups having an epoxy group. R 22 Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, etc. Among these, R is chosen because of its high hydrolysis properties. 22 A methyl group or an ethyl group is preferred. r is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0084] Specific examples of monomers constituting siloxane polymers include silane compounds having four hydrolyzable groups, such as tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabendyloxysilane, and tetra-n-propoxysilane; Examples of silane compounds having three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, etc. Examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane; Examples of silane compounds having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane, respectively.

[0085] Siloxane polymers can be obtained by hydrolyzing and condensing one or more of the above hydrolyzable silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis and condensation reaction, the proportion of water used depends on the hydrolyzable group (-OR) of the hydrolyzable silane compound. 22 The amount of water is preferably 0.1 to 3 moles, more preferably 0.2 to 2 moles, and even more preferably 0.5 to 1.5 moles, per 1 mole of the total amount of ). By using such an amount of water, the reaction rate of hydrolysis condensation can be optimized.

[0086] Examples of catalysts used in hydrolysis-condensation reactions include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and is set appropriately, but is preferably 0.0001 to 0.2 moles, and more preferably 0.0005 to 0.1 moles, per mole of hydrolyzable silane compound. Examples of organic solvents used in the above hydrolysis-condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Of these, it is preferable to use an organic solvent that is water-insoluble or poorly water-soluble. Examples include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid ester compounds. The proportion of organic solvent used is preferably 10 to 10,000 parts by mass, and more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the total hydrolyzable silane compounds used in the reaction.

[0087] During the hydrolysis-condensation reaction, the reaction temperature is preferably 130°C or lower, and more preferably 40-100°C. The reaction time is preferably 0.5-24 hours, and more preferably 1-12 hours. During the reaction, the mixture may be stirred or kept under reflux. After the hydrolysis-condensation reaction, a dehydrating agent may be added to the reaction solution, and then water and the resulting alcohol may be removed from the reaction system by evaporation.

[0088] For siloxane polymers, the weight-average molecular weight (Mw) in polystyrene equivalent, calculated by GPC, is preferably 500 or higher. An Mw of 500 or higher is preferable because it allows for the production of a cured film with sufficiently high heat resistance and solvent resistance, as well as good developability. More preferably, Mw is 1000 or higher. Furthermore, from the viewpoint of improving film formation and suppressing a decrease in radiation sensitivity, Mw is preferably 10000 or less, and more preferably 5000 or less. In addition, the molecular weight distribution (Mw / Mn) is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less.

[0089] The content of (A-1) polymer is preferably 20% 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 (i.e., the total mass of components other than solvents in the radiation-sensitive composition). Furthermore, the content of (A-1) polymer is preferably 99% by mass or less, and more preferably 95% by mass or less, based on the total amount of solids contained in the radiation-sensitive composition. By setting the content of (A-1) polymer within the above range, a cured film can be obtained that has sufficiently high heat resistance and chemical resistance, as well as good developability and transparency.

[0090] <[B]Silanol compounds> [B]Silanol compounds are compounds having a substructure in which a hydrophobic group and a hydroxyl group are bonded to the same silicon atom. However, [B]silanol compounds do not have an alkoxy group. By including such [B]silanol compounds together with (A-1) polymers in a radiation-sensitive composition, a cured film with a low dielectric constant and excellent developability can be obtained. Furthermore, [B]silanol compounds are preferred because they are stable and hydrophobic in alkaline developers and have little effect on unexposed areas (e.g., on sensitivity).

[0091] Examples of hydrophobic groups that can be found in a [B]silanol compound include hydrocarbon groups and fluorinated hydrocarbon groups. Among these, hydrocarbon groups are preferred as the hydrophobic group of a [B]silanol compound, such as monovalent linear hydrocarbon groups having 1 to 12 carbon atoms, monovalent alicyclic hydrocarbon groups having 3 to 12 carbon atoms, and monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms. Of these, monovalent linear hydrocarbon groups and monovalent aromatic hydrocarbon groups are preferred as the hydrophobic group of a [B]silanol compound, with alkyl groups having 1 to 10 carbon atoms and aryl groups having 6 to 12 carbon atoms being more preferred.

[0092] C1-C10 alkyl groups may be linear or branched. Specific examples of C1-C10 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, 3-pentyl, and tert-pentyl groups. Among these, linear or branched alkyl groups with C1-C5 are preferred, linear or branched alkyl groups with C1-C3 are more preferred, and methyl or ethyl groups are even more preferred.

[0093] Examples of aryl groups having 6 to 12 carbon atoms include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, trimethylphenyl, and naphthyl groups. Among these, phenyl, methylphenyl, or ethylphenyl groups are preferred, and phenyl or methylphenyl groups are more preferred.

[0094] [B] Specifically, as the silanol compound, the compound represented by the following formula (2) can be preferably used. (R 4 ) m Si(OH) 4-m …(2) (In formula (2), R 4 (where m is an integer between 1 and 3)

[0095] In equation (2) above, R 4The monovalent hydrocarbon group represented by is preferably a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Of these, a monovalent chain hydrocarbon group or an aromatic hydrocarbon group is more preferred, and an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 12 carbon atoms are even more preferred.

[0096] In formula (2) above, m is preferably 1 or 2, as this can further enhance the development adhesion and low dielectric constant effects of the cured film.

[0097] [B]Specific examples of silanol compounds include, for example, trimethylsilanol, ethyldimethylsilanol, diethylmethylsilanol, triethylsilanol, methylsilanetriol, diphenylsilanediol, phenylsilanetriol, triphenylsilanol, bis(4-tolyl)silanediol, tris(4-tolyl)silanol, and the like.

[0098] When forming a film, the coating film made of a radiation-sensitive composition is usually heated (pre-baked) to remove solvent components contained in the radiation-sensitive composition. From the viewpoint of suppressing the volatilization of the [B]silanol compound during this pre-baking process and leaving a large amount of the [B]silanol compound in the film after pre-baking, a compound with a sufficiently high boiling point can preferably be used as the [B]silanol compound. Specifically, the boiling point of the [B]silanol compound is preferably 80°C or higher, more preferably 95°C or higher, even more preferably 120°C or higher, even more preferably 150°C or higher, and most preferably 180°C or higher. In this specification, the boiling point of the compound is the value at 1 atmosphere.

[0099] [B]Silanol compound is preferably used with a boiling point higher than the pre-bake temperature. By using a silanol compound with a boiling point higher than the pre-bake temperature, the amount of [B]silanol compound remaining in the film after pre-bake can be increased, further enhancing the improvement effect of developing adhesion and low dielectric constant of the cured film. Specifically, the boiling point of the [B]silanol compound is preferably 5°C or more higher than the pre-bake temperature, more preferably 10°C or more higher, even more preferably 20°C or more higher, even more preferably 30°C or more higher, and even more preferably 50°C or more higher.

[0100] [B] Among the silanol compounds mentioned above, compounds having aromatic rings are particularly preferred because they have a high boiling point and high hydrophobicity, and can significantly improve the development adhesion and dielectric constant of the cured film. Specific examples of such [B]silanol compounds include diphenylsilanediol, phenylsilanetriol, triphenylsilanol, bis(4-tolyl)silanediol, and tris(4-tolyl)silanol. Of these, compounds having two or more aromatic rings are preferred, and compounds having three or more aromatic rings are more preferred, as they offer a higher improvement in the development adhesion and dielectric constant of the cured film.

[0101] [B] The molecular weight of the silanol compound is preferably 90 or more, more preferably 100 or more, and even more preferably 150 or more. Furthermore, the molecular weight of the [B] silanol compound is preferably 500 or less, more preferably 450 or less, and even more preferably 400 or less. When the [B] silanol compound is within the above range, it is preferable in that it is possible to improve the developability adhesion of the cured film and achieve a low dielectric constant while suppressing a decrease in the sensitivity and developability solubility of the radiation-sensitive composition.

[0102] In the first composition, the content of the [B]silanol compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more, per 100 parts by mass of the (A-1) polymer. Furthermore, the content of the [B]silanol compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the (A-1) polymer. When the content of the [B]silanol compound is 0.5 parts by mass or more, it is preferable in that the improvement effect of developing adhesion and low dielectric constant of the coating film by having the [B]silanol compound in the film can be sufficiently obtained. Furthermore, when the content of the [B]silanol compound is 25 parts by mass or less, it is preferable in that the decrease in sensitivity caused by the [B]silanol compound can be suppressed.

[0103] <[C] Photoacid Generator> The photoacid generator can be any compound that generates acid upon irradiation, and is not particularly limited. Examples of photoacid generators include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinone diazide compounds.

[0104] Specific examples of oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds include the compounds described in paragraphs 0078 to 0106 of Japanese Patent Publication No. 2014-157252 and the compounds described in International Publication No. 2016 / 124493. From the viewpoint of radiation sensitivity, it is preferable to use at least one selected from the group consisting of oxime sulfonate compounds and sulfonimide compounds as the photoacid generator.

[0105] The oxime sulfonate compound is preferably a compound having a sulfonate group represented by the following formula (7). [ka] (In formula (7), R 23 This refers to a monovalent hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group are replaced by substituents. (* indicates a bond.)

[0106] In equation (7) above, R 23 Examples of monovalent hydrocarbon groups include C1-C20 alkyl groups, C4-C12 cycloalkyl groups, and C6-C20 aryl groups. Examples of substituents include C1-C5 alkyl groups, C1-C5 alkoxy groups, oxo groups, and halogen atoms.

[0107] Examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, {2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene}-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in International Publication No. 2016 / 124493. Examples of commercially available oximesulfonate compounds include Irgacure PAG121 from BASF.

[0108] Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphasulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphasulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphasulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenylmaleimide, and trifluoromethanesulfonic acid-1,8-naphthalimide.

[0109] As a photoacid generator, one or more of the following may be used in combination with a quinone diazide compound: an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, and a carboxylic acid ester compound. Alternatively, a quinone diazide compound may be used alone.

[0110] Quinone diazide compounds are radiation-sensitive acid generators that produce carboxylic acids upon irradiation with radiation. Examples of quinone diazide compounds include condensates of phenolic compounds or alcoholic compounds (hereinafter also referred to as "parent compounds") and orthonaphthoquinone diazide compounds. Of these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the parent compound and an orthonaphthoquinone diazide compound. Specific examples of parent compounds include, for example, the compounds described in paragraphs 0065 to 0070 of Japanese Patent Publication No. 2014-186300. The orthonaphthoquinone diazide compound is preferably 1,2-naphthoquinone diazidesulfonic acid halide.

[0111] As the quinone diazide compound, a condensate of a phenolic compound or alcoholic compound as the parent compound and 1,2-naphthoquinone diazidosulfonic acid halide can be preferably used, and a condensate of a phenolic compound and 1,2-naphthoquinone diazidosulfonic acid halide can be more preferably used.

[0112] Specific examples of quinone diazide compounds include 4,4'-dihydroxydiphenylmethane, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, and 1,4 Examples include ester compounds of a phenolic hydroxyl group-containing compound selected from -bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol with 1,2-naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride.

[0113] 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.

[0114] In the first composition, the content of the [C] photoacid generator is preferably 0.05 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the (A-1) polymer. Furthermore, the content of the [C] photoacid generator is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, per 100 parts by mass of the (A-1) polymer. When the content of the [C] photoacid generator is 0.05 parts by mass or more, sufficient acid is generated by irradiation with radiation, and the difference in solubility between the irradiated and unirradiated parts in the alkaline solution can be sufficiently large. This allows for good patterning. In addition, the amount of acid involved in the reaction with the [A] polymer component can be increased, and sufficient heat resistance and solvent resistance can be ensured. On the other hand, when the content of the [C] photoacid generator is 20 parts by mass or less, the amount of unreacted photoacid generator after exposure can be sufficiently reduced, which is preferable in that it can suppress the decrease in developability due to the residual [C] photoacid generator.

[0115] Here, if water absorption occurs at the edges of the unexposed areas during development, the alkoxy groups present at the edges of the unexposed areas may become silanol groups, increasing the hydrophilicity of the edges of the unexposed areas and potentially reducing the development adhesion of the coating film. To suppress this decrease in development adhesion, it is conceivable to increase the hydrophobicity of the film by incorporating hydrophobic additives into the radiation-sensitive composition or by introducing structural units derived from hydrophobic monomers into the polymer components. However, increasing the hydrophobicity of the film tends to lead to a decrease in the sensitivity of the radiation-sensitive composition. In contrast, in this disclosure, by incorporating a [B] silanol compound into a radiation-sensitive composition using the (A-1) polymer, it is possible to improve the development adhesion of the cured film formed by the radiation-sensitive composition while maintaining high sensitivity of the radiation-sensitive composition.

[0116] Furthermore, if water absorption occurs at the edges of the unexposed areas during development, and the alkoxy groups in the unexposed areas are converted to silanol groups, the presence of hydroxyl groups in the polymer side chains may increase the dielectric constant of the cured film. In contrast, in this disclosure, the dielectric constant of the cured film can be reduced by incorporating a [B] silanol compound into a radiation-sensitive composition using the (A-1) polymer.

[0117] It is presumed that the above-mentioned effects of this disclosure are due to the hydrophobicization of the substrate surface by the hydrophobic groups of the [B]silanol compound, and that the silanol groups present at the edges of the unexposed areas are capped by the [B]silanol compound. However, this presumption does not limit the content of this disclosure in any way.

[0118] <Other ingredients> The first composition may further contain, in addition to the above-mentioned [A] polymer component, [B] silanol compound, and [C] photoacid generator, other components (hereinafter also referred to as "other components").

[0119] (solvent) The first composition is a liquid composition in which [A] a polymer component, [B] a silanol compound, [C] a photoacid generator, and optionally other components are preferably dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each component of the first composition and does not react with each component.

[0120] Specific examples of solvents include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethyl glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Of these, the solvent preferably includes at least one selected from the group consisting of ethers and esters, and more preferably at least one selected from the group consisting of ethylene glycol alkyl ether acetate, diethylene glycols, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether acetate.

[0121] (Adhesion enhancer) Adhesion enhancers are components that improve the adhesion between the cured film formed using a radiation-sensitive composition and the substrate. Functional silane coupling agents having reactive functional groups are preferably used as adhesion enhancers. Examples of reactive functional groups in functional silane coupling agents include carboxyl groups, (meth)acryloyl groups, epoxy groups, vinyl groups, and isocyanate groups.

[0122] Specific examples of functional coupling agents include, for example, trimethoxysilyl benzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

[0123] When an adhesion aid is added to the first composition, its content is preferably 0.01 parts by mass or more and 30 parts by mass or less, and more preferably 0.1 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of the (A-1) polymer.

[0124] (Acid diffusion control agent) The acid diffusion control agent is a component that controls the diffusion length of the acid generated from the [C] photoacid generator upon exposure. By incorporating the acid diffusion control agent into the first composition, the diffusion length of the acid can be appropriately controlled, resulting in improved pattern developability. Furthermore, by incorporating the acid diffusion control agent, chemical resistance can be enhanced while improving developability.

[0125] As the acid diffusion control agent, any basic compound used as an acid diffusion control agent in chemically amplified resists can be arbitrarily selected and used. Examples of such basic compounds include aliphatic amines, aromatic amines, heterocyclic aromatic amines, quaternary ammonium hydroxides, and quaternary ammonium carboxylic acid salts. Specific examples of basic compounds used as acid diffusion control agents in chemically amplified resists include the compounds described in paragraphs 0128 to 0147 of Japanese Patent Application Publication No. 2011-232632. Preferably, at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines can be used as the acid diffusion control agent incorporated into the first composition.

[0126] As the aromatic amine and heterocyclic aromatic amine, at least one selected from the group consisting of aniline derivatives, imidazole derivatives, and pyrrole derivatives can preferably be used. Specific examples of aromatic amines and heterocyclic aromatic amines include, for example, aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine; imidazole derivatives such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, and N-(tert-butoxycarbonyl)-2-phenylbenzimidazole; and pyrrole, 2H-pyrrole, and 1-methyl Examples include pyrrole derivatives such as tylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, and N-methylpyrrole; pyridine derivatives such as pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl-4-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, and nicotine, as well as compounds described in Japanese Patent Application Publication No. 2011-232632.

[0127] When an acid diffusion control agent is incorporated into the first composition, its content is preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more, per 100 parts by mass of the (A-1) polymer, from the viewpoint of sufficiently obtaining the effect of improving chemical resistance due to the incorporation of the acid diffusion control agent. Furthermore, the content of the acid diffusion control agent is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the (A-1) polymer.

[0128] (Basic compounds) The first composition may contain a basic compound (excluding an acid diffusion control agent; hereinafter also referred to as "[E] basic compound"). By using [B] silanol compound and [E] basic compound in combination, the developability of the cured film can be further improved. Furthermore, according to the first composition further containing [E] basic compound, a cured film with a lower dielectric constant can be obtained.

[0129] [E] The basic compound may be an inorganic base (such as sodium carbonate), an organic base, or both. An organic base is preferred as the basic compound because it has a high effect in improving development adhesion.

[0130] The basic compound is preferably an organic base with an acid dissociation constant (pKa) of 8 or higher. Examples of such organic bases include primary chain amines, secondary chain amines, tertiary chain amines, alicyclic amines, aromatic amines, amidines, guanidines, and organic phosphazenes. In order to sufficiently improve development adhesion while suppressing a decrease in sensitivity, the basic compound is preferably at least one selected from the group consisting of amidines, guanidines, and organic phosphazenes.

[0131] Specific examples of these include cyclic amidines such as diazabicyclononene (1,5-diazabicyclo[4.3.0]nona-5-ene, DBN), diazabicycloundecene (1,8-diazabicyclo[5.4.0]undeca-7-ene, DBU), and 6-dibutylamino-1,8-diazabicyclo[5.4.0]undeca-7-ene (DBA-DBU).

[0132] Examples of guanidines include chain-like or cyclic guanidines such as guanidine, tetramethylguanidine (TMG), butylguanidine, diphenylguanidine (DPG), 7-methyl-1,5,7-triazabicyclodeca-5-ene (7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, MTBD), and 1,5,7-triazabicyclodeca-5-ene (1,5,7-triazabicyclo[4.4.0]deca-5-ene, TBD).

[0133] Examples of organic phosphazenes include 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorin (BEMP).

[0134] [E] Among the basic compounds, organic bases with an acid dissociation constant (pKa) of 9 or higher are preferred. Particularly preferred are at least one compound selected from the group consisting of amidines, guanidines, and organic phosphazenes, with an acid dissociation constant (pKa) of 9 to 14, and more preferably at least one compound selected from the group consisting of cyclic amidines, linear guanidines, and cyclic guanidines, with an acid dissociation constant (pKa) of 10 to 14.

[0135] In this specification, the acid dissociation constant refers to the acid dissociation constant (pKa) in water at 25°C. The acid dissociation constant (pKa) is given by pKa = -log 10 It is represented by Ka. If two or more dissociation steps are possible, the first dissociation is considered. For inorganic bases, one hydrogen ion H is released from an electrically neutral molecule (HA). + It dissociates to form a monovalent anion (A -This is the acid dissociation constant (pKa) at the stage where ) occurs. For organic bases, the electrically neutral molecule (B) is a single hydrogen ion H + It accepts a monovalent cation (BH + This is the acid dissociation constant (pKa) at the stage where [E]basic compounds become [E]basic compounds. More specifically, the acid dissociation constant (pKa) of the conjugate acid (BH) of the [E]basic compound is [E]basic compound. + ) dissociates as an acid (BH + →B+H + This refers to the acid dissociation constant (pKa) of ).

[0136] When a radiation-sensitive composition contains an [E] basic compound, the content of the [E] basic compound is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more, per 100 parts by mass of the (A-1) polymer, from the viewpoint of obtaining sufficient improvement in development adhesion. Furthermore, the content of the [E] basic compound is preferably 5 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the (A-1) polymer.

[0137] Other components, in addition to those mentioned above, include, for example, polyfunctional polymerizable compounds (such as polyfunctional (meth)acrylates), surfactants (such as fluorinated surfactants, silicone surfactants, and nonionic surfactants), polymerization inhibitors, antioxidants, chain transfer agents, and orthoesters. The proportions of these components are appropriately selected according to each component, within a range that does not impair the effects of this disclosure.

[0138] The solid content concentration of the first composition (the ratio of the total mass of components other than the solvent in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) is appropriately selected considering viscosity, volatility, etc. The solid content concentration of the first composition is preferably in the range of 5 to 60% by mass. If the solid content concentration is 5% by mass or more, a sufficient film thickness can be ensured when the radiation-sensitive composition is applied to a substrate. If the solid content concentration is 60% by mass or less, the film thickness will not become excessively large, and the viscosity of the radiation-sensitive composition can be made appropriately high, ensuring good applicability. The solid content concentration of the first composition is more preferably 10 to 55% by mass, and even more preferably 12 to 50% by mass.

[0139] [Second composition] Next, a second composition will be described. The second composition is a resin composition containing [A] a polymer component, [B] a silanol compound, [Dq] a quinone diazide compound, [E] a basic compound, and a solvent. The second composition is suitable as a positive-type resin composition.

[0140] <[A] Polymer component> The second composition includes, as the [A] polymer component, a polymer that is at least one selected from the group consisting of polymers containing structural units having acidic groups (hereinafter also referred to as "polymer (a2)") and siloxane polymers (hereinafter also referred to as "(A-2) polymer").

[0141] [Regarding polymer (a2)] Polymer (a2) is a polymer containing a structural unit having an acidic group (hereinafter also referred to as "structural unit (III-3)"). Specific examples and preferred examples of structural unit (III-3) are the same as those shown in the description of structural unit (III-1) that polymer (a1-1) may contain.

[0142] In polymer (a2), the content of structural unit (III-3) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, relative to the total structural units constituting polymer (a2), from the viewpoint of providing good solubility in alkaline developer. Furthermore, the content of structural unit (III-3) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total structural units constituting polymer (a2).

[0143] When polymer (a2) is included, the polymer component [A] may further include structural units other than structural unit (III-3) (hereinafter also referred to as "other structural units (3)"). A preferred specific example of other structural units (3) is structural unit (II-3) having a crosslinkable group. Other structural units (3) may be introduced into polymer (a2), introduced as structural units of a polymer different from polymer (a2), or introduced into both polymers. It is preferable that polymer (a2) further includes structural unit (II-3) in order to obtain the effect of improving developability while minimizing the number of components constituting the second composition.

[0144] • Structural units (II-3) The crosslinkable group of structural unit (II-3) is not particularly limited, as long as it is a group that undergoes a hardening reaction by heat treatment. In terms of high thermosetting properties, it is preferable that it be one or more selected from the group consisting of oxyranyl groups and oxetanyl groups. Specific examples and preferred examples of structural unit (II-3) are the same as those shown in the description of structural unit (II-1).

[0145] When polymer (a2) contains structural unit (II-3), the content of structural unit (II-3) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to the total structural units constituting polymer (a2). Furthermore, the content of structural unit (II-3) is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to the total structural units constituting polymer (a2). Setting the content of structural unit (II-3) within the above range is preferable because it allows the coating film to exhibit better resolution and the resulting cured film to have sufficiently high heat resistance and chemical resistance.

[0146] When the second composition contains polymer (a2), other structural units (3) that the polymer component may contain include the structural units exemplified in other structural units (1). When polymer (a2) contains structural units other than structural unit (II-3) as other structural units (3), the content of such structural units is preferably 80% by mass or less, and more preferably 70% by mass or less, relative to the total structural units constituting polymer (a2).

[0147] Polymer (a2) 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 known methods such as radical polymerization. The details of the polymerization method are the same as for polymer (a1-1).

[0148] For polymer (a2), the weight-average molecular weight (Mw) in polystyrene terms, calculated by GPC, is preferably 1,000 or more. More preferably, the Mw of polymer (a2) is 2,000 or more, and even more preferably 5,000 or more. Furthermore, from the viewpoint of improving film-forming properties, the Mw of polymer (a2) is preferably 200,000 or less, and more preferably 50,000 or less.

[0149] For polymer (a2), the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), is preferably 5.0 or less, and more preferably 3.0 or less.

[0150] [About siloxane polymers] The siloxane polymer included in the second composition is the same as the specific and preferred examples of the siloxane polymer that may be included in the first composition.

[0151] <Quinone diazide compounds> The second composition contains a [Dq]quinone diazide compound as a radiation-sensitive compound that generates a carboxylic acid upon irradiation with radiation. Examples of the [Dq]quinone diazide compound are the same compounds as the specific and preferred examples of the quinone diazide compound exemplified as the [C]photoacid generator in the description of the first composition.

[0152] In the second composition, the content of the quinone diazide compound 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 the (A-2) polymer contained in the second composition. Furthermore, the content of the quinone diazide compound is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of the (A-2) polymer contained in the second composition.

[0153] If the quinone diazide compound content is 2 parts by mass or more, sufficient acid is generated by irradiation with active light, and the difference in solubility in the alkaline solution between the irradiated and unirradiated areas can be sufficiently large. This allows for good patterning. In addition, the amount of acid involved in the reaction with the (A-2) polymer can be increased, ensuring sufficient heat resistance and chemical resistance. On the other hand, if the quinone diazide compound content is 60 parts by mass or less, the amount of unreacted quinone diazide compound can be sufficiently reduced, which is preferable in that it suppresses the decrease in developability and transparency caused by the residual quinone diazide compound.

[0154] <Silanol compounds> The second composition contains the above-described [B]silanol compound. Specific and preferred examples of the [B]silanol compound included in the second composition are the same as those for the first composition.

[0155] In the second composition, the content of the [B]silanol compound 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, based on 100 parts by mass of the (A-2) polymer contained in the second composition. Furthermore, the content of the [B]silanol compound 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, based on 100 parts by mass of the (A-2) polymer contained in the second composition.

[0156] <Basic compounds> The second composition contains an [E] basic compound. Specific and preferred examples of the [E] basic compound included in the second composition are the same as those in the first composition.

[0157] In the second composition, the content of the [E] basic compound is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more, per 100 parts by mass of the (A-2) polymer contained in the second composition, from the viewpoint of sufficiently obtaining the effect of improving development adhesion. Furthermore, the content of the [E] basic compound is preferably 5 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the (A-2) polymer.

[0158] <Solvent> The second composition contains a solvent. Preferably, the second composition is a liquid composition in which [A] polymer component, [Dq] quinone diazide compound, [B] silanol compound, [E] basic compound, and optionally added components are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each component in the second composition and does not react with each component. Specific examples of the solvent included in the second composition are the same as those included in the first composition.

[0159] In the second composition, the solvent content (total amount if two or more solvents are included) is preferably 50 to 95 parts by mass, and more preferably 60 to 90 parts by mass, per 100 parts by mass of all components of the second composition.

[0160] <Other ingredients> The second composition may further contain other components (other components) in addition to the polymer component [A], the quinone diazide compound, the silanol compound, the basic compound [E], and the solvent described above. Specific and preferred examples of other components that may be included in the second composition are the same as those for the first composition.

[0161] The solid content concentration of the second composition can be appropriately selected considering viscosity, volatility, etc. The solid content concentration of the second composition is preferably in the range of 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 12 to 50% by mass.

[0162] [Third composition] Next, a third composition will be described. The third composition is a resin composition containing [A] a polymer component, [B] a silanol compound, [Di] a photopolymerization initiator, [M] a polymerizable monomer, [E] a basic compound, and a solvent. The third composition is suitable as a negative-type resin composition.

[0163] <[A] Polymer component> The third composition includes, as [A] polymer component, a polymer containing a structural unit having an acidic group (hereinafter also referred to as "polymer (a3)").

[0164] [Regarding polymers (a3)] Polymer (a3) ​​is a polymer containing a structural unit having an acidic group (hereinafter also referred to as "structural unit (III-4)"). Specific examples and preferred examples of structural unit (III-4) are the same as those shown in the description of structural unit (III-1) that polymer (a1-1) may contain. In polymer (a3), the content of structural unit (III-4) is preferably 1% by mass or more, and more preferably 2% by mass or more, relative to the total structural units constituting polymer (a3), from the viewpoint of providing good solubility in alkaline developer to the unexposed areas. Furthermore, the content of structural unit (III-4) is preferably 35% by mass or less, and more preferably 30% by mass or less, relative to the total structural units constituting polymer (a3).

[0165] [A] The polymer component may further contain structural units other than structural unit (III-4) (hereinafter also referred to as "other structural units (4)"). A preferred specific example of other structural units (4) is structural unit (II-4) having a crosslinkable group. Other structural units (4) may be introduced into polymer (a3), introduced as structural units of a polymer different from polymer (a3), or introduced into both of those polymers. It is preferable that polymer (a3) ​​further contains structural units (II-4) in order to obtain the effect of improving developability while minimizing the number of components constituting the third composition.

[0166] • Structural units (II-4) The crosslinkable group of structural unit (II-4) is not particularly limited, as long as it is a group that undergoes a hardening reaction by heat treatment. In terms of high thermosetting properties, it is preferable that it be one or more selected from the group consisting of oxyranyl groups and oxetanyl groups. Specific examples and preferred examples of structural unit (II-4) are the same as those shown in the description of structural unit (II-1).

[0167] When polymer (a3) ​​contains structural unit (II-4), the content of structural unit (II-4) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, relative to the total structural units constituting polymer (a3). Furthermore, the content of structural unit (II-4) is preferably 65% ​​by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less, relative to the total structural units constituting polymer (a3).

[0168] [A] Other structural units (4) that the polymer component may contain include those similar to the structural units exemplified as other structural units (1).

[0169] Polymer (a3) ​​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 known methods such as radical polymerization. The details of the polymerization method are the same as for polymer (a1-1).

[0170] For polymer (a3), the weight-average molecular weight (Mw) in polystyrene terms, calculated by GPC, is preferably 1,000 or more. More preferably, the Mw of polymer (a3) ​​is 2,000 or more, and even more preferably 5,000 or more. Furthermore, from the viewpoint of improving film-forming properties, the Mw of polymer (a3) ​​is preferably 200,000 or less, and more preferably 50,000 or less.

[0171] For polymer (a3), the molecular weight distribution (Mw / Mn), expressed as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), is preferably 5.0 or less, and more preferably 3.0 or less.

[0172] <polymerizable monomers> The third composition contains a [M] polymerizable monomer. The [M] polymerizable monomer contained in the third composition is a compound having one or more polymerizable groups, preferably two or more. Examples of polymerizable groups include ethylenically unsaturated groups, oxyranyl groups, oxetanyl groups, and N-alkoxymethylamino groups. Of these, ethylenically unsaturated groups and N-alkoxymethylamino groups are preferred in terms of high polymerizability, and vinyl group-containing groups such as (meth)acryloyl groups, vinyl groups, and vinylphenyl groups are preferred.

[0173] Specifically, as the [M] polymerizable monomer, compounds having two or more (meth)acryloyl groups or compounds having two or more N-alkoxymethylamino groups are preferred, and compounds having two or more (meth)acryloyl groups are particularly preferred. The number of polymerizable groups in one molecule of the [M] polymerizable monomer is preferably 2 to 10, and more preferably 2 to 8.

[0174] [M]Specific examples of polymerizable monomers include compounds having two or more (meth)acryloyl groups, such as polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates obtained by reacting a hydroxyl-containing (meth)acrylate with a polyfunctional isocyanate, and polyfunctional (meth)acrylates having carboxyl groups obtained by reacting a hydroxyl-containing (meth)acrylate with an acid anhydride.

[0175] Examples of compounds having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, or a urea structure. The melamine structure and benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as the basic skeleton, and the concept includes melamine, benzoguanamine, or their condensates. Specific examples of compounds having two or more N-alkoxymethylamino groups include N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, N,N,N',N'-tetra(alkoxymethyl)benzoguanamine, and N,N,N',N'-tetra(alkoxymethyl)glycoluryl.

[0176] [M] Among the polymerizable monomers, polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates having carboxyl groups, N,N,N',N',N'',N''-hexa(alkoxymethyl)melamine, and N,N,N',N'-tetra(alkoxymethyl)benzoguanamine are preferred, polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, polyfunctional urethane (meth)acrylates, and polyfunctional (meth)acrylates having carboxyl groups are more preferred, and polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid are even more preferred.

[0177] Specific examples of polyfunctional (meth)acrylates obtained by reacting aliphatic polyhydroxy compounds with trivalent or higher nucleotides with (meth)acrylic acid include, for example, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, trimethylolpropanedi(meth)acrylate, and dipentaerythritol polyacrylate. Of these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferred because they increase the intermolecular or intramolecular crosslinking density and further improve the curability of the film even by low-temperature firing.

[0178] The content of the [M] polymerizable monomer in the third composition is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, per 100 parts by mass of polymer (a3) ​​contained in the third composition. Furthermore, the content of the [M] polymerizable monomer is preferably 1,000 parts by mass or less, and more preferably 500 parts by mass or less, per 100 parts by mass of polymer (a3). When the content of the [M] polymerizable monomer is within the above range, it is preferable in that sufficient curability and alkali developability can be ensured as a cured film, and the occurrence of background staining, film residue, etc. on the unexposed parts of the substrate or light-shielding layer can be sufficiently suppressed.

[0179] <Photopolymerization initiator> The third composition contains a [Di] photopolymerization initiator as a radiation-sensitive compound. The [Di] photopolymerization initiator included in the third composition (hereinafter also simply referred to as "photopolymerization initiator") is preferably a compound that is sensitive to active light with a wavelength of 300 nm or higher (preferably 300-450 nm) and initiates and promotes the polymerization of [M] polymerizable monomers. When using a photopolymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or higher, it may be used in combination with a sensitizer to enable it to be sensitive to active light with a wavelength of 300 nm or higher and initiate and promote the polymerization of [M] polymerizable monomers.

[0180] Known compounds can be used as photopolymerization initiators. Specific examples include oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organoboric acid compounds, disulfonic acid compounds, α-aminoketone compounds, onium salt compounds, and acylphosphine (oxide) compounds. Among these, at least one selected from the group consisting of oxime ester compounds, α-aminoketone compounds, and hexaarylbiimidazole compounds is preferred, with oxime ester compounds or α-aminoketone compounds being more preferred, in order to increase the sensitivity of the third composition. Commercially available photopolymerization initiators may also be used, such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF).

[0181] In the third composition, the content of the photopolymerization initiator is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more, based on 100 parts by mass of polymer (a3) ​​contained in the third composition. Furthermore, the content of the photopolymerization initiator is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, based on 100 parts by mass of polymer (a3) ​​contained in the third composition.

[0182] <Silanol compounds> The third composition contains a [B]silanol compound. Specific and preferred examples of the [B]silanol compound included in the third composition are the same as those for the first composition.

[0183] In the third composition, the content of the [B]silanol compound 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, based on 100 parts by mass of polymer (a3) ​​contained in the third composition. Furthermore, the content of the [B]silanol compound 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, based on 100 parts by mass of polymer (a3) ​​contained in the third composition.

[0184] <Basic compounds> The third composition contains an [E] basic compound. Specific and preferred examples of the [E] basic compound included in the third composition are the same as those for the first composition.

[0185] In the third composition, the content of the [E] basic compound is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more, per 100 parts by mass of polymer (a3) ​​contained in the third composition, from the viewpoint of sufficiently obtaining the effect of improving development adhesion. Furthermore, the content of the [E] basic compound is preferably 5 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of polymer (a3).

[0186] <Solvent> The third composition contains a solvent. The third composition is preferably a liquid composition in which [A] polymer component, [M] polymerizable monomer, [Di] photopolymerization initiator, [B] silanol compound, [E] basic compound, and optionally added components are dissolved or dispersed in a solvent. The solvent used is preferably an organic solvent that dissolves each component of the third composition and does not react with each component. Specific examples of the solvent included in the third composition are the same as those included in the first composition.

[0187] In the third composition, the solvent content (total amount if two or more solvents are included) is preferably 50 to 95 parts by mass, and more preferably 60 to 90 parts by mass, per 100 parts by mass of all components of the third composition.

[0188] <Other components> In addition to the above-described [A] polymer component, [M] polymerizable monomer, [Di] photoinitiator, [B] silanol compound, [E] basic compound, and solvent, the third composition may further contain components other than these (other components). Specific examples and preferred examples of the other components that may be included in the third composition are the same as those of the first composition.

[0189] The solid content concentration of the third composition is appropriately selected in consideration of viscosity, volatility, etc., but is preferably in the range of 5 to 60% by mass, more preferably 10 to 55% by mass, and still more preferably 12 to 50% by mass.

[0190] According to the present disclosure described above, the following radiation-sensitive compositions are provided. [1] At least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the above formula (1) or an acid dissociable group and a siloxane polymer, A photoacid generator, A silanol compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom and having no alkoxy group, A radiation-sensitive composition containing.

[0191] [2] The radiation-sensitive composition according to [1], wherein the silanol compound has a boiling point of 80°C or higher. [3] The radiation-sensitive composition according to [1] or [2], wherein the silanol compound is a compound represented by the following formula (2). (R 4 ) m Si(OH) 4-m …(2) (In formula (2), R 4 is a monovalent hydrocarbon group. m is an integer of 1 to 3.) [4] The radiation-sensitive composition according to any one of [1] to [3], wherein the silanol compound has an aromatic ring. [5] The radiation-sensitive composition according to any one of [1] to [4], wherein the group represented by formula (1) above is bonded to an aromatic ring group or a chain hydrocarbon group. [6] The radiation-sensitive composition according to any one of [1] to [5], wherein the structural unit (I) has at least one selected from the group consisting of a group represented by formula (3-1), a group represented by formula (3-2), and a group represented by formula (3-3). [7] The radiation-sensitive composition according to any one of [1] to [6], wherein the photoacid generator comprises at least one selected from the group consisting of oximesulfonate compounds and sulfonimide compounds. [8] A radiation-sensitive composition according to any one of [1] to [7], further comprising an acid diffusion control agent. [9] The radiation-sensitive composition according to [8], wherein the acid diffusion control agent is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines.

[10] A radiation-sensitive composition according to any one of [1] to [9], further containing a basic compound (excluding an acid diffusion control agent).

[11] The radiation-sensitive composition according to

[10] , wherein the basic compound is an organic base.

[12] The radiation-sensitive composition according to

[11] , wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.

[13] The radiation-sensitive composition according to

[11] or

[12] , wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphazenes.

[14] The radiation-sensitive composition according to any one of [1] to

[13] , wherein the polymer containing the structural unit (I) further comprises a structural unit having one or more selected from the group consisting of an oxyranyl group and an oxetanyl group.

[15] The radiation-sensitive composition according to any one of [1] to

[14] , wherein the polymer containing the structural unit (I) further contains a structural unit having an acidic group.

[0192]

[16] Polymers containing structural units having acidic groups (excluding polymers having structural units represented by the above formula (1)), Quinone diazide compounds and A silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and which does not have an alkoxy group, Basic compounds and, Solvents and, A radiation-sensitive composition containing the following:

[0193]

[17] The radiation-sensitive composition according to

[16] , wherein the polymer containing the acidic group structural unit further contains a crosslinkable group structural unit.

[18] The radiation-sensitive composition according to

[17] , wherein the crosslinkable group is one or more selected from the group consisting of an oxyranyl group and an oxetanyl group.

[19] The radiation-sensitive composition according to any one of

[16] to

[18] , wherein the quinone diazide compound is a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinone diazidosulfonic acid halide.

[20] The silanol compound is a radiation-sensitive composition according to any one of

[16] to

[19] , wherein the silanol compound has a boiling point of 80°C or higher.

[21] The silanol compound is a compound represented by the following formula (2), the radiation-sensitive composition according to any one of

[16] to

[20] . (R 4 ) m Si(OH) 4-m …(2) (In formula (2), R 4 (where m is an integer between 1 and 3)

[22] The silanol compound is a radioactive composition according to any one of

[16] to

[21] , wherein the silanol compound has an aromatic ring.

[23] The radiation-sensitive composition according to any one of

[16] to

[22] , wherein the basic compound is an organic base.

[24] The radiation-sensitive composition according to

[23] , wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.

[25] The radiation-sensitive composition according to

[23] or

[24] , wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphazenes.

[0194]

[26] A polymer containing a structural unit having an acidic group, Polymerizable monomers, Photopolymerization initiator and A silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and which does not have an alkoxy group, Basic compounds and, Solvents and, A radiation-sensitive composition containing the following:

[0195]

[27] The radiation-sensitive composition according to

[26] , wherein the polymer containing the acidic group structural unit further contains a crosslinkable group structural unit.

[28] The radiation-sensitive composition according to

[27] , wherein the crosslinkable group is one or more selected from the group consisting of an oxyranyl group and an oxetanyl group.

[29] The silanol compound is a radiation-sensitive composition according to any one of

[26] to

[28] , wherein the silanol compound has a boiling point of 80°C or higher.

[30] The silanol compound is a compound represented by the following formula (2), the radiation-sensitive composition according to any one of

[26] to

[29] . (R 4 ) m Si(OH) 4-m …(2) (In formula (2), R 4 (where m is an integer between 1 and 3)

[31] The radioactive composition according to any one of

[26] to

[30] , wherein the silanol compound has an aromatic ring.

[32] The radiation-sensitive composition according to any one of

[26] to

[31] , wherein the basic compound is an organic base.

[33] The radiation-sensitive composition according to

[32] , wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more. 〔34〕The basic compound is at least one selected from the group consisting of amidines, guanidines, and organic phosphazenes, and the radiation-sensitive composition according to 〔32〕or〔33〕.

[0196] <Hardened film and method for producing the same> The hardened film of the present disclosure is formed by the radiation-sensitive composition prepared as described above. The radiation-sensitive composition has high radiation sensitivity and excellent storage stability. Further, by using the radiation-sensitive composition, a pattern film having high adhesion to the substrate even after development, a low dielectric constant, and excellent chemical resistance can be formed. Therefore, the radiation-sensitive composition can be preferably used as a forming material for, for example, an interlayer insulating film, a planarizing film, a spacer, a protective film, a colored pattern film for a color filter, a partition wall, a bank, and the like.

[0197] In the production of the hardened film, a positive-type hardened film can be formed according to the type of the photosensitizer by using the radiation-sensitive composition described above. The hardened film can be produced by a method including, for example, the following steps 1 to 4 using the radiation-sensitive composition. (Step 1) A step of forming a coating film using the radiation-sensitive composition. (Step 2) A step of exposing at least a part of the coating film. (Step 3) A step of developing the exposed coating film. (Step 4) A step of heating the developed coating film. Hereinafter, each step will be described in detail.

[0198] [Step 1: Coating step] In this process, the radiation-sensitive composition is applied to the surface on which the film is to be formed (hereinafter also referred to as the "film-forming surface"), and preferably the solvent is removed by 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 forming an interlayer insulating film, the radiation-sensitive composition is applied to a substrate on which switching elements such as TFTs are provided, and a coating film is formed. Examples of substrates include glass substrates, silicon substrates, and resin substrates. The surface of the substrate on which the coating film is formed may have a thin metal film formed thereon depending on the application, and various surface treatments such as HMDS (hexamethyldisilazane) treatment may be applied.

[0199] 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, or bar coating are preferred. Pre-baking conditions vary depending on the type and proportion of each component in the radiation-sensitive composition, but are typically 60 to 130°C for 0.5 to 10 minutes. The thickness of the resulting coating film (i.e., the film thickness after pre-baking) is preferably 0.1 to 12 μm. Vacuum-coated drying (VCD) may be performed on the radiation-sensitive composition applied to the film-forming surface before pre-baking.

[0200] [Step 2: Pixelation Step] In this step, at least a portion of the coating film formed in step 1 is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured film with a pattern 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 / m². 2 It is preferable.

[0201] [Process 3: Development process] In this step, the coating film irradiated with radiation in step 2 is developed. Specifically, the coating film irradiated with radiation in step 2 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% 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.

[0202] [Process 4: Heating process] In this step, the coating developed in step 3 above is subjected to a heating process (post-bake). Post-bake can be performed using a heating device such as an oven or a hot plate. Regarding the post-bake conditions, the heating temperature is, for example, 120 to 250°C. The heating time is, for example, 5 to 40 minutes when performing the heating treatment on a hot plate, and 10 to 80 minutes when performing the heating treatment in an oven. In this way, a cured film having the desired pattern can be formed on the substrate. The shape of the pattern on the cured film is not particularly limited and examples include line-and-space patterns, dot patterns, hole patterns, and grid patterns.

[0203] <Semiconductor elements> The semiconductor device of this disclosure comprises a cured film formed using the above-mentioned radiation-sensitive composition. The cured film is preferably an interlayer insulating film that insulates the wiring within the semiconductor device. The semiconductor device of this disclosure can be manufactured using known methods.

[0204] <Display element> The display element of this disclosure comprises a cured film formed using the above-mentioned radiation-sensitive composition. Alternatively, the display element of this disclosure may also comprise a semiconductor element of this disclosure, thereby comprising a cured film formed using the above-mentioned radiation-sensitive composition. Furthermore, the display element of this disclosure may also comprise a planarization film formed on a TFT substrate as the cured film formed using the above-mentioned radiation-sensitive composition. Examples of display elements include liquid crystal display elements and organic electroluminescent (EL) display elements. [Examples]

[0205] 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 "%" refer to mass unless otherwise specified. In these examples, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were measured by the following method.

[0206] [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: Showa Denko's GPC-101 • GPC columns: Shimadzu GLC's GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804 were joined. • 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

[0207] [monomer] The abbreviations for the monomers used in the synthesis of the polymer are as follows: Monomers that provide structural units (I) • Monomer having a group represented by the above formula (1) MPTMS: 3-Methacryloxypropyltrimethoxysilane MPTES:3-Methacryloxypropyltriethoxysilane STMS: p-Styryltrimethoxysilane SDMS: p-Styryldimethoxyhydroxysilane STES:p-Styryltriethoxysilane • Monomers having acid-dissociating groups MATHF: 2-tetrahydrofuranyl methacrylate

[0208] Other monomers AA: Acrylic acid MA: Methacrylic acid MI: Maleimide OXMA:OXE-30 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (3-ethyloxetan-3-yl)methyl methacrylate GMA: Glycidyl methacrylate ECHMA:3,4-Epoxycyclohexylmethyl methacrylate EDCPMA: Methacrylic acid [3,4-Epoxytricyclo(5.2.1.0 2,6 ) Decan-9-il] MMA: Methyl methacrylate ST: Styrene

[0209] <Synthesis of polymer (A)> [Synthesis Example 1] Synthesis of Polymer (A-1) In a flask equipped with a condenser and stirrer, 24 parts of propylene glycol monomethyl ether were charged, followed by 39 parts of methyltrimethoxysilane and 18 parts of 3-methacryloxypropyltrimethoxysilane. The solution was heated until it reached 60°C. After reaching 60°C, 0.1 parts of formic acid and 19 parts of water were added, and the solution temperature was raised to 75°C while gently stirring, and this temperature was maintained for 2 hours. After cooling to 45°C, 28 parts by mass of trimethyl orthoformate was added as a dehydrating agent, and the mixture was stirred for 1 hour. The solution temperature was then reduced to 40°C, and the mixture was evaporated while maintaining the temperature to remove water and methanol generated by hydrolysis condensation, thereby obtaining a polymer solution containing polymer (A-1). The solid content concentration of this polymer solution was 35% by mass, the weight-average molecular weight (Mw) of polymer (A-1) was 1,800, and the molecular weight distribution (Mw / Mn) was 2.2.

[0210] [Synthesis Example 2] Synthesis of Polymer (A-2) Except for changing the monomers used to 39 parts phenyltrimethoxysilane and 18 parts 3-methacryloxypropyltrimethoxysilane, polymer (A-2) having the same solid content concentration, weight-average molecular weight, and molecular weight distribution as polymer (A-1) was obtained using the same method as in Synthesis Example 1.

[0211] [Synthesis Example 3] Synthesis of Polymer (A-3) Ten parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methyl ethyl ether were charged into a flask equipped with a condenser and a stirrer. Subsequently, 15 parts of 3-methacryloxypropyltrimethoxysilane, 10 parts of methacrylic acid, 20 parts of (3-ethyloxetan-3-yl)methyl methacrylate, 30 parts of glycidyl methacrylate, and 25 parts of methyl methacrylate were charged. After purging with nitrogen, the temperature of the solution was raised to 70°C while gently stirring, and this temperature was maintained for 5 hours to obtain a polymer solution containing polymer (A-3). The solid content concentration of this polymer solution was 34.0% by mass, the Mw of polymer (A-3) was 10,500, and the molecular weight distribution (Mw / Mn) was 2.2.

[0212] [Synthesis Examples 4-12, 19, 20] Synthesis of polymers (A-4)-(A-12), (CA-1), (CA-2) Polymer solutions containing polymers (A-4) to (A-12), (CA-1), and (CA-2), respectively, having the same solid content concentration, weight-average molecular weight, and molecular weight distribution as polymer (A-3), were obtained using the same method as in Synthesis Example 3, except that the components used were of the types and amounts (parts by mass) shown in Table 1.

[0213] [Synthesis Examples 13-18] Synthesis of polymers (A-13)-(A-18) Polymer solutions containing polymers (A-13) to (A-18), each having the same solid content concentration, weight-average molecular weight, and molecular weight distribution as polymer (A-3), were obtained using the same method as in Synthesis Example 3, except that the components used were of the types and amounts (parts by mass) shown in Table 1.

[0214] [Table 1]

[0215] <Preparation of radiation-sensitive composition (1)> The polymer (A), silanol compound (B), photoacid generator (C), additive (X), and solvent (G) used in the preparation of the radiation-sensitive composition are shown below.

[0216] 《Polymerization (A)》 A-1~A-12: Polymers synthesized in synthesis examples 1~12 (A-1)~(A-12) CA-1~CA-2: Polymers (CA-1) and (CA-2) synthesized in synthesis examples 19 and 20.

[0217] Silanol compounds (B) B-1: Trimethylsilanol B-2: Triethylsilanol B-3: Methylsilanetriol B-4: Diphenylsilanediol B-5: Phenylsilanetriol B-6: Triphenylsilanol B-7: Tris(4-trill)silanol

[0218] 《Photoacid Generator (C)》 C-1: Irgacure PAG121 (BASF) C-2: OS-17 as described in International Publication No. 2016 / 124493 C-3: OS-25 as described in International Publication No. 2016 / 124493

[0219] Additive (X) • Adhesion enhancer X-1:3-Glycidyloxypropyltrimethoxysilane X-2:2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane • Acid diffusion control agent X-3:2-phenylbenzimidazole X-4:N-(tert-butoxycarbonyl)-2-phenylbenzimidazole X-5: 4-methyl-2-phenylbenzimidazole

[0220] Solvent (G) G-1: Diethylene glycol ethyl methyl ether G-2: Propylene glycol monomethyl ether G-3: Propylene glycol monomethyl ether acetate

[0221] [Reference example 1] To the polymer solution containing polymer (A-1) obtained in Synthesis Example 1 above, 5 parts of silanol compound (B-1), 1 part of photoacid generator (C-2), and 5 parts of additive (X-1) were mixed in an amount equivalent to 100 parts (solids) of polymer (A-1). Diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether were added in a 1:1 mass ratio so that the final solids concentration was 20% by mass. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0222] [Reference Examples 2-20, Comparative Examples 1-5] The radiation-sensitive compositions of Reference Examples 2-20 and Comparative Examples 1-5 were prepared using the same method as in Reference Example 1, except that the types and amounts (parts by mass) of each component shown in Table 2 were used. In Table 2, for solvent (G), in the examples using two types of organic solvents (Reference Examples 1, 2, 4-14, 18-20, Comparative Example 5), solvent 1 and solvent 2 were mixed and used in a mass ratio of solvent 1:solvent 2 = 1:1. In the examples using three types of organic solvents (Reference Examples 3, 15-17, Comparative Examples 1-4), solvent 1, solvent 2, and solvent 3 were mixed and used in a mass ratio of solvent 1:solvent 2:solvent 3 = 5:4:1.

[0223] [Table 2]

[0224] <Rating> The following items were evaluated using the radiation-sensitive compositions of Reference Examples 1-20 and Comparative Examples 1-5, according to the method described below. The evaluation results are shown in Table 3.

[0225] [Radiation sensitivity] A radiation-sensitive composition was applied to a silicon substrate that had been HMDS-treated at 60°C for 60 seconds using a spinner. The substrate 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 irradiated with a predetermined amount of ultraviolet light from a mercury lamp through a pattern mask having a 10 μm wide line-and-space pattern. Next, development was performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer at 25°C for 60 seconds, followed by rinsing with ultrapure water for 1 minute. At this time, the minimum exposure required to form a 10 μm wide line-and-space pattern was measured. The measured minimum exposure was 300 J / m². 2 When the value is less than 300 J / m³, the radiation sensitivity is good. 2 In the above cases, the radiation sensitivity can be evaluated as poor.

[0226] [Evaluation of chemical resistance of cured films] The chemical resistance of the cured film was evaluated by the degree of swelling caused by the stripping solution. A radiation-sensitive composition was applied to a silicon substrate using a spinner, and 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. Subsequently, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to expose the film at 3000 J / m². 2 After irradiating the entire substrate with light, the substrate was baked (post-bake) for 30 minutes in an oven heated to 230°C to form a cured film. The resulting cured film was immersed in an N-methyl-2-pyrrolidone solvent heated to 40°C for 6 minutes, and the percentage change in film thickness before and after immersion was determined. This percentage change in film thickness was used as an indicator of chemical resistance and evaluated according to the following criteria. AA: Film thickness change rate is less than 2% A: Film thickness change rate is 2% or more but less than 5% B: Film thickness change rate is 5% or more but less than 10% C: Film thickness change rate is 10% or more but less than 15% D: Film thickness change rate of 15% or more Chemical resistance can be evaluated as good if the result is AA, A, or B, and as poor if the result is C or D. Film thickness was measured at 25°C using an optical interference film thickness analyzer (Lambda Ace VM-1010).

[0227] [Evaluation of storage stability] The prepared radiation-sensitive composition was sealed in a light-shielding, airtight container. After 7 days at 25°C, the container was opened, and measurements were taken according to the above evaluation of [radiation sensitivity]. The percentage increase in radiation sensitivity (minimum exposure) before and after 7 days of storage was calculated. A value of less than 5% was judged as "AA", 5% or more but less than 10% as "A", 10% or more but less than 20% as "B", 20% or more but less than 30% as "C", and 30% or more as "D". Storage stability can be evaluated as good in the case of AA, A, or B, and as poor in the case of C or D.

[0228] [Evaluation of substrate adhesion (developer 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. At this time, the minimum width of the line-and-space pattern that remained on the substrate without peeling off was measured. If the measured minimum width was 2 μm or less, it was judged as "AA"; if it was greater than 2 μm and 5 μm or less, it was judged as "A"; if it was greater than 5 μm and 10 μm or less, it was judged as "B"; if it was greater than 10 μm and 30 μm or less, it was judged as "C"; and if it was greater than 30 μm, it was judged as "D". In the case of AA, A, or B, the development adhesion was evaluated as good, and in the case of C or D, the development adhesion was evaluated as poor.

[0229] [Evaluation of relative permittivity] Using a spinner, a radiation-sensitive composition was applied to a glass substrate, and 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. Subsequently, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to expose the material at 3000 J / m². 2 After irradiating the entire substrate surface with light, the material was baked (post-bake) for 30 minutes in an oven heated to 230°C to form a cured film. The relative permittivity of the obtained cured film at a frequency of 10 kHz was measured. The rate of decrease in relative permittivity was calculated using the relative permittivity of Reference Example 5 as a reference, and this rate of decrease was evaluated according to the following criteria. AA: Permittivity decrease rate of 20% or more A: The rate of decrease in relative permittivity is 15% or more but less than 20%. B: The rate of decrease in relative permittivity is 10% or more but less than 15%. C: The rate of decrease in relative permittivity is 5% or more but less than 10%. D: The rate of decrease in relative permittivity is less than 5%. The relative permittivity can be evaluated as good if it is AA, A, or B, acceptable if it is C, and poor if it is D.

[0230] [Table 3]

[0231] In Table 3, "-" indicates that the sensor could not be evaluated because it was not resolved during the sensitivity evaluation.

[0232] As shown in Table 3, each of the radiation-sensitive compositions in Reference Examples 1 to 20 exhibited good practical characteristics in terms of radiation sensitivity, chemical resistance, storage stability, development adhesion, and dielectric constant, demonstrating a good balance of various properties. In contrast, Comparative Examples 1 to 3 did not resolve upon exposure, and exhibited low chemical resistance and dielectric constant. Furthermore, while the radiation-sensitive compositions of Comparative Examples 4 and 5 were evaluated similarly to Reference Examples 1 to 20 in terms of radiation sensitivity, chemical resistance, and storage stability, their development adhesion and dielectric constant were lower than those of Reference Examples 1 to 20.

[0233] <Preparation of radiation-sensitive composition (2)> The compounds used in the preparation of the radiation-sensitive composition are listed below. Note that the polymer (A), silanol compound (B), photoacid generator (C), additive (X), and solvent (G) are the same as those used in the preparation of the radiation-sensitive composition (1), and therefore their descriptions are omitted. Basic compounds (E) E-1:1,8-Diazabicyclo[5.4.0]-7-Undecene E-2:1,5,7-Triazabicyclo[4.4.0]deca-5-en

[0234] [Example 21, Reference Examples 22-29] The radiation-sensitive compositions of Example 21 and Reference Examples 22-29 were prepared using the same method as in Reference Example 1, except that the components used were of the types and amounts (parts by mass) shown in Table 4. In Table 4, for solvent (G), in the example using two organic solvents, solvent 1 and solvent 2 were mixed in a mass ratio of solvent 1:solvent 2 = 1:1. In the example using three organic solvents, solvent 1, solvent 2, and solvent 3 were mixed in a mass ratio of solvent 1:solvent 2:solvent 3 = 5:4:1 (the same applies to Table 6).

[0235] [Table 4]

[0236] <Rating> Each item was evaluated using the radiation-sensitive compositions of Example 21 and Reference Examples 22-29 in the same manner as in Reference Example 1. The evaluation results are shown in Table 5. Note that the radiation-sensitive compositions of Example 21 and Reference Examples 22-29 have the same composition as the radiation-sensitive compositions of Reference Examples 2, 5, 7, 8, 10, 13, 14, 16, and 19, except that they contain a basic compound (E).

[0237] [Table 5]

[0238] As shown in Table 5, the radiation-sensitive compositions in Example 21 and Reference Examples 22-29, compared to Reference Examples 2, 5, 7, 8, 10, 13, 14, 16, and 19, which have the same composition except for the absence of basic compound (E), showed improved developability while maintaining high levels of radiation sensitivity, chemical resistance, and storage stability. Furthermore, it was confirmed that the dielectric constant of the cured film improved by incorporating basic compound (E).

[0239] <Preparation of radiation-sensitive composition (3)> The compounds used in the preparation of the radiation-sensitive composition are listed below. Note that the polymer (A), silanol compound (B), photoacid generator (C), additive (X), and solvent (G) are the same compounds used in the preparation of the radiation-sensitive composition (1), as well as the basic compound (E), as described above and are therefore omitted from this description. 《Polymerization (A)》 A-13~A-18: Polymers synthesized in synthesis examples 13~18 (A-13)~(A-18) 《Radiation sensitive compound (D)》 D-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) D-2: 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 (1.0 mol) D-3: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol) D-4: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid chloride (1.0 mol) D-5: Irgacure OXE02 (BASF) Polymerizable monomer (M) M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[0240] [Examples 30-35 and Comparative Examples 6-14] Except for using the types and amounts (parts by mass) of components shown in Table 6, the radiation-sensitive compositions of Reference Examples 30, 31, Examples 32-35, and Comparative Examples 6-14 were prepared using the same method as in Reference Example 1. The radiation-sensitive compositions of Reference Examples 30 and 31 correspond to the first composition, the radiation-sensitive compositions of Examples 32-34 correspond to the second composition, and Example 35 corresponds to the third composition.

[0241] [Table 6]

[0242] <Rating> Each item was evaluated using the same method as in Reference Example 1, with respect to the radiation-sensitive compositions of Reference Examples 30, 31, Examples 32-35, and Comparative Examples 6-14. The evaluation results are shown in Table 7.

[0243] [Table 7]

[0244] The first compositions, Reference Examples 30 and 31, each of the radiation-sensitive compositions, exhibited good practical properties in terms of radiation sensitivity, chemical resistance, storage stability, development adhesion, and dielectric constant, demonstrating a good balance of various properties. In particular, the radiation-sensitive composition of Reference Example 31, which contains a basic compound (E), was able to improve development adhesion while maintaining high levels of radiation sensitivity, chemical resistance, storage stability, and dielectric constant. The second compositions, the radiation-sensitive compositions of Examples 32 to 34, were able to improve developability while maintaining high levels of radiation sensitivity, chemical resistance, and storage stability, compared to Comparative Examples 6, 9, and 12, which had almost the same composition except for the absence of basic compound (E). The third composition, the radiation-sensitive composition of Example 35, improved chemical resistance and developability compared to Comparative Example 14, which did not contain the basic compound (E), while maintaining high levels of radiation sensitivity, storage stability, and dielectric constant.

Claims

1. Polymers containing structural units having acidic groups (excluding polymers having structural units represented by the following formula (1)), Quinone diazide compounds and A silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and which does not have an alkoxy group, Basic compounds and, Solvents and, A radiation-sensitive composition containing the following: 【Chemistry 1】 (In formula (1), R １ , R ２ and R ３ 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 １ , R ２ and R ３ One or more of these are alkoxy groups having 1 to 6 carbon atoms. (* indicates a bonding bond.)

2. The radiation-sensitive composition according to claim 1, wherein the quinone diazide compound is a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinone diazidosulfonic acid halide.

3. A polymer containing structural units having acidic groups, Polymerizable monomers, Photopolymerization initiator and A silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and which does not have an alkoxy group, Basic compounds and, Solvents and, A radiation-sensitive composition containing [a specific substance].

4. The radiation-sensitive composition according to claim 1 or 3, wherein the polymer containing the acidic group structural unit further comprises a crosslinkable group structural unit.

5. The radiation-sensitive composition according to claim 4, wherein the crosslinkable group is one or more selected from the group consisting of oxyranyl groups and oxetanyl groups.

6. Siloxane polymer and, Photoacid generator, A silanol compound having a substructure in which a hydrophobic group and a hydroxyl group are bonded to a silicon atom, and which does not have an alkoxy group, Basic compounds and, A radiation-sensitive composition containing [a specific substance].

7. The radiation-sensitive composition according to claim 6, wherein the photoacid generator comprises at least one selected from the group consisting of oximesulfonate compounds and sulfonimide compounds.

8. The radiation-sensitive composition according to claim 1, 3, or 6, wherein the silanol compound has a boiling point of 80°C or higher.

9. The radiation-sensitive composition according to claim 1, 3, or 6, wherein the silanol compound is a compound represented by the following formula (2). (R) ４ ) ｍ Si (O) ４－ｍ …(2) (In formula (2), R ４ (where m is an integer between 1 and 3.)

10. The radiation-sensitive composition according to claim 1, 3, or 6, wherein the silanol compound has an aromatic ring.

11. The radiation-sensitive composition according to claim 1, 3, or 6, wherein the basic compound is at least one selected from the group consisting of inorganic bases and organic bases having an acid dissociation constant (pKa) of 8 or more.

12. The radiation-sensitive composition according to claim 1, 3, or 6, wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.

13. The radiation-sensitive composition according to claim 1, 3, or 6, wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organophosphazenes.

14. A step of forming a coating film using the radiation-sensitive composition described in claim 1, 3, or 6, A step of irradiating at least a portion of the coating film with radiation, A step of developing the coating film that has been irradiated with radiation, A step of heating the developed coating film, A method for manufacturing a cured film, including [the specified element].

15. A cured film formed using the radiation-sensitive composition according to claim 1, 3, or 6.

16. A semiconductor element comprising the cured film described in claim 15.

17. A display element comprising the cured film described in claim 15.

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