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

Abstract

To provide a radiation-sensitive composition that can form a cured film having excellent development adhesion.SOLUTION: A radiation-sensitive composition is a radiation-sensitive composition comprising: at least one polymer selected from the group consisting of a polymer that contains a structural unit (I) having a group represented by formula (1) or an acid-dissociable group, and a siloxane polymer; a photoacid generator; and 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. In formula (1), R1, R2 and R3 are each 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, where at least one of R1, R2 and R3 is an alkoxy group having 1 to 6 carbon atoms and "*" represents a bond.SELECTED DRAWING: None

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 device, and a display device. [Background technology]

[0002] Cured films (e.g., interlayer insulating films, spacers, protective films, etc.) of semiconductor elements and display elements are generally formed using a radiation-sensitive composition containing a polymer component and a radiation-sensitive compound (e.g., a photoacid generator, a photopolymerization initiator, etc.). For example, a coating film formed from the radiation-sensitive composition is irradiated with radiation and subjected to a development treatment to form a pattern, and then the resulting film is thermally cured by a heat treatment, thereby obtaining a cured film having a pattern shape.

[0003] As a material for forming a cured film in a semiconductor element or a display element, Patent Documents 1 and 2 propose a radiation-sensitive composition containing a silicon-containing polymer, such as a polymer having a silicon-containing functional group such as an alkoxysilyl group or a siloxane polymer, and a photoacid generator.

[0004] When a coating film is formed using the radiation-sensitive composition of Patent Document 1, an acid is generated from the photoacid generator upon exposure during pattern formation, and the generated acid decomposes the alkoxy groups, making the exposed areas soluble in a developer. The unexposed areas are alkali-insoluble, and after development, they are heated to undergo dehydration condensation and hardening, forming a cured film. Furthermore, with the radiation-sensitive composition of Patent Document 2, the acid generated from the photoacid generator upon exposure promotes self-crosslinking of the siloxane polymer, forming a cured film.

[0005] Furthermore, as a material for forming a cured film in a semiconductor element or a display element, Patent Document 3 proposes a radiation-sensitive composition containing a polymer containing a structural unit having an acidic group, a polymerizable monomer, and a photopolymerization initiator. Patent Document 4 proposes a chemically amplified radiation-sensitive composition containing a polymer containing a structural unit having an acid-dissociable group and a photoacid generator. Patent Document 5 proposes a radiation-sensitive composition containing a polymer containing a structural unit having an acidic group and a quinone diazide compound. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2017-107024 [Patent Document 2] International Publication No. 2011 / 065215 [Patent Document 3] Japanese Patent Application Laid-Open No. 2003-5357 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-232632 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-186300 Summary of the Invention [Problem to be solved by the invention]

[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 development, causing peeling of the film pattern. In particular, in recent years, there has been a demand for even higher quality display devices, and as patterns become thinner due to the demand for even higher quality display devices, peeling of the film pattern tends to occur more easily during development. From the perspective of suppressing a decrease in production yield, it is required that the radiation-sensitive composition is less likely to peel between the film and the substrate during development (i.e., has good development adhesion).

[0008] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a radiation-sensitive composition that can form a cured film having excellent development adhesion. [Means for solving the problem]

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

[0010] [1] A radiation-sensitive composition comprising at least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) or an acid-dissociable group, and a siloxane polymer; a photoacid generator; and 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: [ka] (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, provided that R 1 , R 2 and R 3 At least one of the groups is an alkoxy group having 1 to 6 carbon atoms. "*" represents a 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 the above formula (1)), a quinone diazide compound, 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 basic compound, and a solvent.

[0012] [3] A radiation-sensitive composition comprising: a polymer including a structural unit having an acidic group; a polymerizable monomer; a photopolymerization initiator; 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 basic compound; and a solvent.

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

[0014] The radiation-sensitive composition of the present disclosure can form a cured film with excellent development adhesion. DETAILED DESCRIPTION OF THE INVENTION

[0015] Matters related to the embodiments will be explained in detail below. In this specification, a numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure.

[0016] As used herein, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed solely of a chain structure. However, the group may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and it also includes groups that have a chain structure as part of it. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, it does not necessarily have to be composed solely of an aromatic ring structure, and it may also contain a chain structure or an alicyclic hydrocarbon structure as part of it. The ring structures of the alicyclic hydrocarbon group and aromatic hydrocarbon group may have a substituent composed of a hydrocarbon structure. The term "cyclic hydrocarbon group" refers to both alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0017] 《Radiation sensitive composition》 The radiation-sensitive composition of the present disclosure (hereinafter also referred to as "the composition") is used, for example, to form a cured film for a display device. The composition is a resin composition containing a polymer component [A] and a silanol compound [B]. Below, the components contained in the first composition, second composition, and third composition, which are specific embodiments of the composition, as well as other components that may be blended as necessary, are described. Note that, 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 resin composition containing [A] a polymer component, [B] a silanol compound, and [C] a photoacid generator.

[0019] <[A] Polymer component> The polymer component [A] contains at least one polymer selected from the group consisting of a polymer containing a structural unit (I) having a group represented by the following formula (1) or an acid-dissociable group, and a siloxane polymer (hereinafter also referred to as "polymer (A-1)"): [ka] (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, provided that R 1 , R 2 and R 3 At least one of the groups is an alkoxy group 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, it is thought that in the cured film formed using the radiation-sensitive compositions of Patent Documents 1 and 2, water absorption occurs from the edges of the unexposed areas during development, converting the alkoxy groups in the unexposed areas into silanol groups, thereby increasing the hydrophilicity of the unexposed areas. In this case, there is a concern that the adhesion of the unexposed areas to the substrate (development adhesion) will decrease, making the pattern more 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, if water absorption occurs from the edges of the unexposed areas during development, and the alkoxy groups in the unexposed areas are converted to silanol groups, there is a concern that the dielectric constant of the cured film will increase due to the presence of hydroxyl groups in the polymer side chains. Therefore, an object of the present disclosure is to provide a radiation-sensitive composition that, when containing a silicon-containing polymer as a polymer component, can form a cured film that has excellent development adhesion and a low dielectric constant.

[0023] In this regard, a radiation-sensitive composition containing a silicon-containing polymer, which is 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, a photoacid generator, and the above silanol compound, can form a cured film that has excellent development adhesion and a low dielectric constant.

[0024] [Regarding polymer (a1-1)] Structural unit (I-1) In the above formula (1), R 1 ~R 3 Examples of the alkoxy group having 1 to 6 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group. 1 ~R 3 The alkoxy group represented by the formula (1) preferably has 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group. In particular, when the group represented by the formula (1) is bonded to an aromatic ring group, R 1 ~R 3 The alkoxy group represented by the formula (1) is preferably a methoxy group. When the group represented by the formula (1) is bonded to a chain hydrocarbon group, R 1 ~R 3 The alkoxy group represented by the formula (I) is preferably an ethoxy group.

[0025] R 1 ~R 3 The alkyl group having 1 to 10 carbon atoms represented by the formula (R) may be linear or branched. 1 ~R 3Examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. 1 ~R 3 The alkyl group represented by the formula (I) is preferably a methyl group, an ethyl group or a propyl group.

[0026] R 1 ~R 3 One of the groups represented by the formula (I) is an alkoxy group having 1 to 6 carbon atoms. The remaining group is preferably a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, more preferably a hydroxy 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 crosslinked structure, R 1 ~R 3 Among these, it is preferred that two or more are alkoxy groups having 1 to 6 carbon atoms, and it is particularly preferred that all of them are alkoxy groups having 1 to 6 carbon atoms.

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

[0029] The group represented by the formula (1) is preferably bonded to a benzene ring, a naphthalene ring, or an alkyl chain. Specifically, the structural unit (I-1) preferably has at least one selected from the group consisting of a group represented by the following formula (3-1), a group represented by the following formula (3-2), and a group represented by the following formula (3-3). [ka] (In formula (3-1), formula (3-2) and formula (3-3), A 1 and A 2 are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. n1 is an integer of 0 to 4. n2 is an integer of 0 to 6. However, when n1 is 2 or more, multiple A 1 are the same or different. When n2 is 2 or more, multiple A 2 are the same or different. R 6 is an alkanediyl group. 1 , R 2 and R 3 is the same as the above formula (1). "*" represents a bond.

[0030] In the above formula (3-1) and formula (3-2), A 1 and A 2 Examples of the alkoxy group having 1 to 6 carbon atoms and the alkyl group having 1 to 6 carbon atoms represented by the formula (1) are 1 ~R 3 The group bonded to the aromatic ring, "-SiR 1 R 2 R 3 " is located at A 1 and A 2 For example, in the case of the above formula (3-1), "-SiR 1 R 2 R 3The position of " may be any of the ortho, meta, and para positions relative to the position of the bond represented by "*". The para position is preferred. n1 is preferably 0 or 1, and more preferably 0. n2 is preferably 0 to 2, and more preferably 0. In the above formula (3-3), R 6 From the viewpoint of increasing the heat resistance of the resulting cured film, R 6 The carbon number is preferably 1 to 6, and more preferably 1 to 4.

[0031] In terms of increasing 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 the formula (3-1) and the group represented by the formula (3-2) among the formulas (3-1) to (3-3). 1 R 2 R 3 When " is directly bonded, it is possible to stabilize the silanol groups generated in the presence of water. This is preferable in that the solubility of the exposed area in an alkaline developer can be increased, and a good pattern can be formed. Among these, the structural unit (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 specifically, it is preferably at least one selected from the group consisting of structural units represented by the following formula (4-1) and structural units represented by the following formula (4-2). [ka] (In formula (4-1) and formula (4-2), R A is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. 7 and R 8 R are each independently a divalent aromatic ring group or a chain hydrocarbon group. 1 , R2 and R 3 is the same as the above formula (1).

[0033] In the above formula (4-1) and formula (4-2), R 7 , R 8 The divalent aromatic ring group represented by the formula (I) is preferably a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalenediyl group. Examples of the substituent include one or more selected from the group consisting of a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The divalent chain hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.

[0034] R is advantageous in that it can produce a cured film with higher heat resistance, chemical resistance, and hardness, and can increase the solubility of exposed areas in alkaline developing solutions. 7 , R 8 Among the above, is preferably a divalent aromatic ring group, and particularly preferably a substituted or unsubstituted phenylene group.

[0035] Specific examples of the structural unit represented by the formula (4-1) include structural units represented by the following formulas (4-1-1) and (4-1-2): Specific examples of the structural unit represented by the formula (4-2) include structural units represented by the following formulas (4-2-1) and (4-2-2): [ka] (In formula (4-1-1), formula (4-1-2), formula (4-2-1) and formula (4-2-2), R 11 and R 12 are each independently an alkyl group having 1 to 4 carbon atoms. 13 is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. n3 is an integer of 1 to 4. A 1 , A 2 , n1 and n2 have the same meanings as in the formulas (3-1) and (3-2). Ahas the same meaning as the above formula (4-1) and formula (4-2).

[0036] Specific examples of the monomer constituting the structural unit (I-1) include compounds having a group represented by the above formula (3-1), such as styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, styryldiethoxyhydroxysilane, (meth)acryloxyphenyltrimethoxysilane, (meth)acryloxyphenyltriethoxysilane, (meth)acryloxyphenylmethoxydimethoxysilane, and (meth)acryloxyphenylethyldiethoxysilane; Examples of compounds having a 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, and (meth)acryloxynaphthyltrimethoxysilane; Examples of compounds having a group represented by the above formula (3-3) include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, etc. In this specification, "(meth)acryl" includes both "acrylic" and "methacrylic".

[0037] The content of the structural unit (I-1) in the 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, based on all structural units constituting the polymer (a1-1). The content of the 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, based on all structural units constituting the polymer (a1-1). By setting the content of the structural unit (I-1) within the above range, the heat resistance and chemical resistance of the resulting cured film can be sufficiently improved, sensitivity can be increased, and the coating film exhibits better resolution.

[0038] Other structural units The polymer (a1-1) may further contain structural units other than the structural unit (I-1) (hereinafter also referred to as "other structural units (1)"). Examples of the 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 (III-1) having an acidic group. In this specification, the term "epoxy group" also refers to oxiranyl groups and oxetanyl groups.

[0039] Structural Unit (II-1) The polymer (a1-1) preferably contains the structural unit (II-1) in that it can further improve the resolution and adhesion of the film. Furthermore, the epoxy group functions as a crosslinkable group, which is preferable in that it can form a cured film with high chemical resistance and long-term suppression of deterioration. The structural unit (II-1) is preferably a structural unit derived from an unsaturated monomer having an epoxy group, and specifically, 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 formula (5-1) and formula (5-2), R 20 is a monovalent group having an oxiranyl group or an oxetanyl group. Ais a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. 1 is a single bond or a divalent linking group.

[0040] In the above formula (5-1) and formula (5-2), R 20 Examples include oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl group, 3-ethyloxetanyl group, and the like. X 1 The divalent linking group is preferably an alkanediyl group such as a methylene group, an ethylene group, or a 1,3-propanediyl group; or a divalent group in which any methylene group of an alkanediyl group has been replaced with an oxygen atom.

[0041] Specific examples of the monomer having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

[0042] The content of the structural unit (II-1) in the 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, based on all structural units constituting the polymer (a1-1). The content of the 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, based on all structural units constituting the polymer (a1-1). By setting the content of the structural unit (II-1) within the above range, the coating film exhibits better resolution, and the resulting cured film can be made to have sufficiently high heat resistance and chemical resistance. This is preferable.

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

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

[0045] The structural unit (III-1) is preferably a structural unit derived from an unsaturated monomer having an acidic group. Specific examples of unsaturated monomers having an acidic group include monomers constituting structural units having a carboxyl group, such as unsaturated monocarboxylic acids (e.g., (meth)acrylic acid, crotonic acid, 4-vinylbenzoic acid); unsaturated dicarboxylic acids (e.g., maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid); monomers constituting structural units having a sulfonic acid group, such as vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acryloxyethylsulfonic acid; and monomers constituting structural units having a phenolic hydroxyl group, such as 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acrylate. Furthermore, maleimide can also be used as a monomer constituting the structural unit (III-1).

[0046] The content of the structural unit (III-1) in the 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, based on the total structural units constituting the polymer (a1-1), from the viewpoint of imparting good solubility in an alkaline developer. On the other hand, if the content of the structural unit (III-1) is too high, the difference in solubility in an alkaline developer between the exposed and unexposed areas becomes small, which may make it difficult to obtain a good pattern shape. From this viewpoint, the content of the 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, based on the total structural units constituting the polymer (a1-1).

[0047] Further examples of the other structural unit (1) include structural units derived from at least one monomer selected from the group consisting of (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, aromatic vinyl compounds, N-substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, and unsaturated dicarboxylic acid dialkyl ester compounds. By introducing these structural units into the polymer, the glass transition temperature of the polymer component can be adjusted, and the pattern shape and chemical resistance of the resulting cured film can be improved.

[0048] Specific examples of the above-mentioned monomers include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate; Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, and methylcyclohexyl (meth)acrylate. 2,6 ] decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 2,5 ] decan-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, and N-naphthylmaleimide. 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, (meth)acrylic acid glycerin carbonate, (γ-lactam-2-yl) (meth)acrylate, and N-(meth)acryloxyethylhexahydrophthalimide; Conjugated diene compounds include 1,3-butadiene and isoprene; Nitrogen-containing vinyl compounds include (meth)acrylonitrile and (meth)acrylamide; Examples of the unsaturated dicarboxylic acid dialkyl ester compound include diethyl itaconate, etc. In addition to the above, examples of the monomer constituting the other structural unit (1) include, for example, monomers such as vinyl chloride, vinylidene chloride, and vinyl acetate.

[0049] From the viewpoint of adjusting the glass transition temperature of the polymer component and suppressing the melt flow during thermal curing, the polymer (a1-1) preferably contains, as the structural unit (1) other than the structural unit (II-1) and the structural unit (III-1), a structural unit derived from at least one monomer selected from the group consisting of a (meth)acrylic acid alkyl ester, a (meth)acrylic acid ester having an alicyclic structure, and a (meth)acrylic acid ester having an aromatic ring structure.

[0050] The content of the structural units (1) other than the structural units (II-1) and (III-1) is preferably 5% by mass or more, more preferably 10% by mass or more, based on all structural units constituting the polymer (a1-1), from the viewpoint of appropriately increasing the glass transition temperature of the polymer (a1-1). The content of the structural units is preferably 50% by mass or less, more preferably 40% by mass or less, based on all structural units constituting the polymer (a1-1).

[0051] Polymer (a1-1) can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in an appropriate solvent in the presence of a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(isobutyrate) dimethyl. The proportion of the 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 the polymerization solvent include alcohols, ethers, ketones, esters, and hydrocarbons. The amount of the polymerization solvent used is preferably such that the total amount of the monomers used in the reaction is 0.1 to 60% by mass relative to the total amount of the reaction solution.

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

[0053] When the polymer component [A] contains a polymer (a1-1), the polymer component [A] may be composed solely of the polymer (a1-1) having the structural unit (I-1), as long as it contains the structural unit (I-1), or it may further contain a polymer not having the structural unit (I-1) in addition to the polymer (a1-1). For example, when the polymer component [A] contains the structural unit (I-1), the structural unit (II-1), and the structural unit (III-1), the same polymer may contain all of the structural units (I-1), (II-1), and (III-1), or a polymer other than the polymer having the structural unit (I-1) may contain at least one selected from the group consisting of the structural unit (II-1) and the structural unit (III-1). Note that when two or more different polymers in the polymer component [A] contain the structural unit (I-1), the structural unit (II-1), and the structural unit (III-1), it is preferable that the content ratio of each structural unit contained in the polymer component [A] satisfy the above range. The polymer component [A] preferably contains a polymer having the structural unit (I-1), the structural unit (II-1), and the structural unit (III-1), in order to obtain improved adhesion and chemical resistance while reducing the number of components constituting the radiation-sensitive composition. Each polymer constituting the polymer component [A] is preferably an alkali-soluble resin.

[0054] The weight average molecular weight (Mw) of polymer (a1-1) in terms of polystyrene as determined by gel permeation chromatography (GPC) is preferably 2,000 or more. An Mw of 2,000 or more is preferred because it allows for the formation of a cured film having sufficiently high heat resistance and chemical resistance and 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-forming properties, the Mw is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 15,000 or less.

[0055] The molecular weight distribution (Mw / Mn), which is the ratio of the weight-average molecular weight Mw to the number-average molecular weight Mn, is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.5 or less. When the polymer component [A] is composed of two or more polymers, it is preferable that the Mw and Mw / Mn of each polymer satisfy the above-mentioned ranges.

[0056] [Regarding polymer (a1-2)] The polymer (a1-2) is a polymer containing a structural unit (I-2) having an acid-dissociable group. The acid-dissociable group is a group that substitutes a hydrogen atom of an acidic group such as a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, or a sulfonic acid group, and is a group that dissociates under the action of an acid. When the composition containing the polymer (a1-2) is irradiated with radiation, the acid-dissociable group is eliminated by the acid generated, resulting in the formation of an acidic group. This allows the solubility of the polymer component in a developer to be changed, and a cured film having a pattern formed thereon can be obtained.

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

[0058] About structural units (I-2-1) The structural unit (I-2-1) may be a structural unit derived from a protected unsaturated carboxylic acid. The unsaturated carboxylic acid to be used is not particularly limited, and examples thereof include 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 acid anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of unsaturated polycarboxylic acids include ω-carboxypolycaprolactone mono(meth)acrylate.

[0060] Examples of the acid-dissociable group contained in the structural unit (I-2-1) include an acetal functional group, a tertiary alkyl group, a tertiary alkyl carbonate group, etc. Among these, an acetal functional group is preferred because it is easily dissociated by an acid.

[0061] When the acid-dissociable group is an acetal functional group, the structural unit (I-2-1) preferably has an acetal ester structure of a carboxylic acid as the protected carboxy group, and specifically, preferably has a group represented by the following formula (X-1): [ka] (In formula (X-1), R 31 , R 32 and R 33 is either (1) or (2) below. (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 are each 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 33are aligned with each other. 32 and OR 33 represents a cyclic ether structure formed together with the carbon atom to which it is bonded. "*" represents a bond.)

[0062] R 31 , R 32 and R 33 The alkyl group having 1 to 12 carbon atoms represented by the formula (I) may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 6, and 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 the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

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

[0064] R 32 and R 33 The cyclic ether structure formed by combining these rings preferably has 5 or more ring members. Specific examples include a tetrahydrofuran ring structure and a tetrahydropyran ring structure.

[0065] R 31 Among these, a hydrogen atom, a methyl group, or an ethyl group is preferred, and a hydrogen atom is more preferred.

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

[0067] Of the above, the structural unit (I-2-1) is preferably a structural unit represented by the following formula (Y-1) or a structural unit represented by the following formula (Y-2). [ka] (In formula (Y-1), R 30 is a hydrogen atom or a methyl group. 30 is a single bond or an arylene group. 40 is a hydrogen atom or an alkyl group. 41 and R 42 are each 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 is a hydrogen atom or a methyl group. 31 is a single bond or an arylene group. 43 ~R 49 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and k is 1 or 2.

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

[0069] About structural units (I-2-2) The 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 the present composition, the structural unit (I-2-2) is preferably at least one selected from the group consisting of a structural unit derived from hydroxystyrene or a derivative thereof and a structural unit derived from a (meth)acrylic compound having a hydroxybenzene structure.

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

[0071] -C(R 31 )(R 32 )(OR 33)" can include, for example, a 1-alkoxyalkyl group and a 1-arylalkoxyalkyl group. Specific examples include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, a 1-(2-ethylhexyloxy)ethyl group, a 1-propoxyethyl group, a 1-cyclohexyloxyethyl group, a 1-(2-cyclohexylethoxy)ethyl group, and a 1-benzyloxyethyl group.

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

[0073] The content of the structural unit (I-2) in the 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, based on all structural units constituting the polymer (a1-2). The content of the 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, based on all structural units constituting the polymer (a1-2). By setting the content of the structural unit (I-2) within the above range, the sensitivity of the first composition can be increased, and the coating film exhibits better resolution, which is preferable.

[0074] When the first composition contains a polymer (a1-2), the polymer component [A] may further contain a structural unit other than the structural unit (I-2) (hereinafter also referred to as "other structural unit (2)"). Examples of the other structural unit (2) include a structural unit (II-2) having a crosslinkable group and a structural unit (III-2) having an acidic group. The other structural unit (2) may be introduced into the polymer (a1-2), or may be introduced as a structural unit of a polymer different from the polymer (a1-2), or may be introduced into both the polymer (a1-2) and a polymer different from the polymer (a1-2). In terms of achieving improved adhesion upon development and curing while minimizing the number of components constituting the first composition, it is preferable that the polymer (a1-2) further contain the structural unit (II-2) and the structural unit (III-2) in addition to the structural unit (I-2).

[0075] Structural Unit (II-2) The crosslinkable group of the structural unit (II-2) is not particularly limited as long as it is a group that undergoes a curing reaction by heat treatment. In terms of high thermosetting properties, the crosslinkable group is preferably one or both of an oxiranyl group and an oxetanyl group. Specific examples and preferred examples of the structural unit (II-2) include the same examples as those described in the explanation of the structural unit (II-1).

[0076] When the polymer (a1-2) contains the structural unit (II-2), the content of the 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, based on all structural units constituting the polymer (a1-2). The content of the 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, based on all structural units constituting the polymer (a1-2).

[0077] Structural Unit (III-2) The polymer (a1-2) preferably further comprises a structural unit (III-2) having an acidic group, which can improve the solubility in an alkaline developer and the curing reactivity. Specific and preferred examples of the structural unit (III-2) include the same examples as those described in the description of the structural unit (III-1).

[0078] When the polymer (a1-2) contains the structural unit (III-2), the content of the 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, based on all structural units constituting the polymer (a1-2), from the viewpoint of imparting good solubility in an alkaline developer. The content of the 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, based on all structural units constituting the polymer (a1-2).

[0079] When the first composition contains a polymer (a1-2), examples of the other structural units (2) that may be contained in the polymer component [A] include the structural units exemplified for the other structural units (1). When the polymer (a1-2) contains a structural unit other than the structural unit (II-2) and the structural unit (III-2) as the other structural unit (2), the content of the structural unit is preferably 50% by mass or less, and more preferably 40% by mass or less, of all structural units constituting the polymer (a1-2).

[0080] The polymer (a1-2) can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in a suitable solvent in the presence of a polymerization initiator, etc. The details of the polymerization method are the same as those for the polymer (a1-1).

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

[0082] [Regarding siloxane polymers] The siloxane polymer is not particularly limited as long as it can form a cured film by hydrolysis and condensation. The siloxane polymer is preferably 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 is a non-hydrolyzable monovalent group. 22 is an alkyl group having 1 to 4 carbon atoms. r is an integer of 0 to 3. However, when r is 2 or 3, multiple R 21 are the same or different. When r is 0 to 2, multiple R 22 are the same or different from each other.)

[0083] R 21 Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a group having a (meth)acryloyl group, and a group having an epoxy group. R 22 Examples of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. 22 is preferably a methyl group or an ethyl group. r is preferably 0 to 2, more preferably 0 or 1, and even more preferably 1.

[0084] Specific examples of the monomer constituting the siloxane polymer include silane compounds having four hydrolyzable groups, such as tetramethoxysilane, tetraethoxysilane, triethoxymethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, 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, and 3-(meth)acryloxypropyltriethoxysilane; Examples of silane compounds having two hydrolyzable groups include dimethyldimethoxysilane and diphenyldimethoxysilane; Examples of silane compounds having one hydrolyzable group include trimethylmethoxysilane and trimethylethoxysilane.

[0085] The siloxane polymer 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 an organic solvent. The proportion of water used in the hydrolysis and condensation reaction depends on the hydrolyzable group (-OR) possessed by the hydrolyzable silane compound. 22 The amount of water is preferably 0.1 to 3 mol, more preferably 0.2 to 2 mol, and even more preferably 0.5 to 1.5 mol, relative to 1 mol of the total amount of (a) and (b). By using such an amount of water, the reaction rate of the hydrolysis and condensation can be optimized.

[0086] Examples of catalysts used in the hydrolysis and condensation reaction include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, etc. 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 mol, more preferably 0.0005 to 0.1 mol, per 1 mol of the hydrolyzable silane compound. Examples of organic solvents used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use water-insoluble or slightly water-soluble organic solvents, such as 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 the 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 and condensation reaction, the reaction temperature is preferably 130°C or lower, more preferably 40 to 100°C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. During the reaction, the mixture may be stirred or may be placed under reflux. After the hydrolysis and condensation reaction, a dehydrating agent may be added to the reaction solution, followed by evaporation to remove water and the produced alcohol from the reaction system.

[0088] The weight average molecular weight (Mw) of the siloxane polymer, as calculated using polystyrene standards by GPC, is preferably 500 or more. An Mw of 500 or more is preferred in that a cured film having sufficiently high heat resistance and solvent resistance and good developability can be obtained. Mw is more preferably 1,000 or more. From the viewpoints of improving film-forming properties and suppressing a decrease in radiation sensitivity, Mw is preferably 10,000 or less, more preferably 5,000 or less. 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 the (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 the solvent in the radiation-sensitive composition). The content of the (A-1) polymer is preferably 99% by mass or less, 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 the (A-1) polymer within the above ranges, a cured film having sufficiently high heat resistance and chemical resistance, as well as good developability and transparency, can be obtained.

[0090] <[B]Silanol Compound> The silanol compound [B] is a compound having a partial structure in which a hydrophobic group and a hydroxyl group are bonded to the same silicon atom. However, the silanol compound [B] does not have an alkoxy group. By incorporating such a silanol compound [B] together with the polymer (A-1) in the radiation-sensitive composition, a cured film having a low dielectric constant and excellent development adhesion can be obtained. Furthermore, the silanol compound [B] is preferred because it is stable and hydrophobic in alkaline developers and has little effect on unexposed areas (for example, on sensitivity).

[0091] Examples of the hydrophobic group contained in the silanol compound [B] include hydrocarbon groups and fluorinated hydrocarbon groups. Among these, the hydrophobic group contained in the silanol compound [B] is preferably a hydrocarbon group, such as a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. Among these, the hydrophobic group contained in the silanol compound [B] is preferably a monovalent chain hydrocarbon group or a monovalent aromatic hydrocarbon group, and more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0092] The alkyl group having 1 to 10 carbon atoms may be linear or branched. Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, and a tert-pentyl group. Among these, a linear or branched alkyl group having 1 to 5 carbon atoms is preferred, a linear or branched alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group or an ethyl group is even more preferred.

[0093] Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a trimethylphenyl group, a naphthyl group, etc. Among these, a phenyl group, a methylphenyl group, or an ethylphenyl group is preferred, and a phenyl group or a methylphenyl group is more preferred.

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

[0095] In the above formula (2), R 4The monovalent hydrocarbon group represented by the formula (I) 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 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 the above formula (2), m is preferably 1 or 2, since this can further enhance the effects of developing adhesion and lowering the dielectric constant of the cured film.

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

[0098] When forming a film, a coating film made of a radiation-sensitive composition is usually heated (prebaked) to remove the solvent component contained in the radiation-sensitive composition. To suppress the volatilization of the [B] silanol compound during this prebaking and to ensure that a large amount of the [B] silanol compound remains in the film after prebaking, a compound with a sufficiently high boiling point is preferably 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 even more preferably 180°C or higher. In this specification, the boiling point of the compound is measured at 1 atmosphere.

[0099] The boiling point of the silanol compound [B] is preferably higher than the prebake temperature. By using a silanol compound with a boiling point higher than the prebake temperature, the amount of the silanol compound [B] remaining in the film after prebake can be increased, and the effects of improving the development adhesion and low dielectric constant of the cured film can be further enhanced. Specifically, the boiling point of the silanol compound [B] is preferably 5°C or higher than the prebake temperature, more preferably 10°C or higher, even more preferably 20°C or higher, even more preferably 30°C or higher, and even more preferably 50°C or higher.

[0100] Among the above-mentioned silanol compounds, compounds having an aromatic ring are particularly preferred for use as the silanol compound [B], since they have a high boiling point and are highly hydrophobic, and can enhance the effect of improving the development adhesion and reducing the dielectric constant of the cured film. Specific examples of such silanol compounds [B] include diphenylsilanediol, phenylsilanetriol, triphenylsilanol, bis(4-tolyl)silanediol, and tris(4-tolyl)silanol. Among these, compounds having two or more aromatic rings are preferred, and compounds having three or more aromatic rings are more preferred, since they can enhance the effect of improving the development adhesion and reducing the dielectric constant of the cured film.

[0101] The molecular weight of the silanol compound [B] is preferably at least 90, more preferably at least 100, and even more preferably at least 150. The molecular weight of the silanol compound [B] is preferably at most 500, more preferably at most 450, and even more preferably at most 400. When the silanol compound [B] is in the above range, it is possible to increase the development adhesion of the cured film while suppressing a decrease in the sensitivity and development solubility of the radiation-sensitive composition, and it is also advantageous in that a low dielectric constant can be achieved.

[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, relative to 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, relative to 100 parts by mass of the (A-1) polymer. A content of the [B] silanol compound of 0.5 parts by mass or more is preferred because the presence of the [B] silanol compound in the film can sufficiently improve the development adhesion and reduce the dielectric constant of the coating film. A content of the [B] silanol compound of 25 parts by mass or less is preferred because it can suppress a decrease in sensitivity due to the [B] silanol compound.

[0103] <[C] Photoacid generator> The photoacid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation, and examples of the photoacid generator 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, sulfonate ester compounds, and carboxylate ester compounds include the compounds described in paragraphs 0078 to 0106 of JP 2014-157252 A and the compounds described in WO 2016 / 124493 A. 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 is a monovalent hydrocarbon group or a monovalent group in which some or all of the hydrogen atoms of the hydrocarbon group have been substituted with substituents. "*" represents a bond.

[0106] In the above formula (7), R 23 Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an oxo group, and a halogen atom.

[0107] Examples of oxime sulfonate compounds include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, {2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene}-2-(2-methylphenyl)acetonitrile), 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, and compounds described in WO 2016 / 124493. Commercially available oxime sulfonate compounds include Irgacure PAG121 manufactured by BASF.

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

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

[0110] The quinone diazide compound is a radiation-sensitive acid generator that generates a carboxylic acid upon irradiation with radiation. Examples of the quinone diazide compound include condensates of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother nucleus") with an orthonaphthoquinone diazide compound. Of these, the quinone diazide compound used is preferably a condensate of a compound having a phenolic hydroxyl group as the mother nucleus with an orthonaphthoquinone diazide compound. Specific examples of the mother nucleus include the compounds described in paragraphs 0065 to 0070 of JP-A No. 2014-186300. The orthonaphthoquinone diazide compound is preferably 1,2-naphthoquinone diazide sulfonic acid halide.

[0111] As the quinone diazide compound, a condensation product of a phenolic compound or alcoholic compound as the mother nucleus with 1,2-naphthoquinone diazide sulfonic acid halide can be preferably used, and a condensation product of a phenolic compound with 1,2-naphthoquinone diazide sulfonic 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, 1,4 and ester compounds of a phenolic hydroxyl group-containing compound selected from 4,6-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-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

[0113] In the condensation reaction to obtain the above condensation product, the ratio of the mother nucleus to the 1,2-naphthoquinone diazide sulfonic acid halide is such that the amount of 1,2-naphthoquinone diazide sulfonic acid halide used is preferably 30 to 85 mol %, more preferably 50 to 70 mol %, based on the number of OH groups in the mother nucleus. The above condensation reaction can be carried out according to a known method.

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

[0115] Here, if water absorption occurs at the edge of the unexposed area during development, the alkoxy groups present at the edge of the unexposed area may convert to silanol groups, increasing the hydrophilicity of the edge of the unexposed area and potentially reducing the development adhesion of the coating film. To prevent this reduction in development adhesion, it is conceivable to increase the hydrophobicity of the film by incorporating a hydrophobic additive into the radiation-sensitive composition or by introducing a structural unit derived from a hydrophobic monomer into the polymer component. However, increasing the hydrophobicity of the film is likely to result in a decrease in the sensitivity of the radiation-sensitive composition. In contrast, in the present disclosure, by incorporating a silanol compound [B] into a radiation-sensitive composition using the (A-1) polymer, it is possible to improve the development adhesion of a cured film formed from the radiation-sensitive composition while maintaining high sensitivity of the radiation-sensitive composition.

[0116] Furthermore, if water absorption occurs at the end of the unexposed area during development and the alkoxy groups in the unexposed area are converted to silanol groups, the presence of hydroxyl groups in the polymer side chains is thought to increase the dielectric constant of the cured film. In response to this, in the present disclosure, by blending a silanol compound [B] with a radiation-sensitive composition using the polymer (A-1), it is possible to reduce the dielectric constant of the cured film.

[0117] The above-described effects of the present disclosure are presumably due to the hydrophobicity of the substrate surface caused by the hydrophobic groups of the silanol compound [B] and the capping of silanol groups present at the edges of unexposed areas by the silanol compound [B], although this presumption does not limit the content of the present disclosure in any way.

[0118] <Other ingredients> The first composition may further contain components other than the above-mentioned [A] polymer component, [B] silanol compound, and [C] photoacid generator (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 other components added as needed are dissolved or dispersed, preferably in a solvent. The solvent used is preferably an organic solvent that dissolves each of the components added to the first composition but does not react with each of the components.

[0120] Specific examples of the solvent include 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, dimethylene 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 contains 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 aid) The adhesion aid is a component that improves the adhesion between a cured film formed using the radiation-sensitive composition and a substrate. A functional silane coupling agent having a reactive functional group can be preferably used as the adhesion aid. Examples of the reactive functional group possessed by the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

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

[0123] When an adhesion aid is blended into the first composition, the content ratio thereof 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, relative to 100 parts by mass of the (A-1) polymer.

[0124] (acid diffusion control agent) The acid diffusion controller is a component that controls the diffusion length of the acid generated from the photoacid generator [C] upon exposure. By incorporating an acid diffusion controller into the first composition, the diffusion length of the acid can be appropriately controlled, thereby improving pattern developability. In addition, by incorporating an acid diffusion controller, chemical resistance can be enhanced while improving development adhesion.

[0125] The acid diffusion controller can be arbitrarily selected from basic compounds used as acid diffusion controllers in chemically amplified resists. Examples of such basic compounds include aliphatic amines, aromatic amines, heterocyclic aromatic amines, quaternary ammonium hydroxides, and quaternary ammonium carboxylates. Specific examples of basic compounds used as acid diffusion controllers in chemically amplified resists include the compounds described in paragraphs

[0128] to

[0147] of JP 2011-232632 A. The acid diffusion controller blended in the first composition is preferably at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines.

[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 be preferably used. Specific examples of aromatic amines and heterocyclic aromatic amines include 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; pyrrole, 2H-pyrrole, 1-methyl-2-phenylbenzimidazole, and the like. Examples of the compound include pyrrole derivatives such as ethylpyrrole, 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 JP 2011-232632 A.

[0127] When an acid diffusion controller is incorporated into the first composition, the content thereof is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, per 100 parts by mass of the (A-1) polymer, from the viewpoint of fully obtaining the effect of improving chemical resistance due to the incorporation of the acid diffusion controller. The content of the acid diffusion controller is preferably 10 parts by mass or less, 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 acid diffusion controllers; hereinafter, also referred to as "basic compound [E]"). By using the silanol compound [B] and the basic compound [E] in combination, the development adhesion of the cured film can be further improved. Furthermore, a cured film with a lower dielectric constant can be obtained by using the first composition further containing the basic compound [E].

[0129] The basic compound [E] may be an inorganic base (such as sodium carbonate), an organic base, or both. In terms of a high effect of improving development adhesion, the basic compound [E] is preferably an organic base.

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

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

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

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

[0134] Among the above, the basic compound [E] is preferably an organic base having an acid dissociation constant (pKa) of at least 9. In particular, at least one compound selected from the group consisting of amidines, guanidines, and organic phosphazenes, having an acid dissociation constant (pKa) of 9 to 14, is preferred, and at least one compound selected from the group consisting of cyclic amidines, chain guanidines, and cyclic guanidines, having an acid dissociation constant (pKa) of 10 to 14, is more preferred.

[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 expressed as pKa = -log 10 It is expressed by Ka. If two or more steps of dissociation are considered, the first step is considered. For inorganic bases, one hydrogen ion H is released from an electrically neutral molecule (HA). + dissociates to form monovalent anions (A -) is the acid dissociation constant (pKa). For organic bases, the electrically neutral molecule (B) dissociates into one hydrogen ion, H + accepts monovalent cations (BH + The acid dissociation constant (pKa) of the [E] basic compound is the acid dissociation constant (pKa) of the [E] basic compound at the stage where the ... + ) dissociates as an acid (BH + →B+H + ) refers to the acid dissociation constant (pKa) of

[0136] When the radiation-sensitive composition contains a basic compound [E], the content of the basic compound [E] is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, relative to 100 parts by mass of the polymer (A-1), from the viewpoint of sufficiently improving the adhesion after development. The content of the basic compound [E] is preferably 5 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the polymer (A-1), from the viewpoint of sufficiently improving the adhesion after development.

[0137] In addition to the above, other components include, for example, polyfunctional polymerizable compounds (polyfunctional (meth)acrylates, etc.), surfactants (fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc.), polymerization inhibitors, antioxidants, chain transfer agents, orthoesters, etc. The blending ratio of these components is appropriately selected depending on each component within a range that does not impair the effects of the present disclosure.

[0138] The solids 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 taking into consideration viscosity, volatility, and the like. The solids concentration of the first composition is preferably in the range of 5 to 60 mass%. A solids concentration of 5 mass% or more ensures a sufficient coating thickness when the radiation-sensitive composition is applied to a substrate. On the other hand, a solids concentration of 60 mass% or less prevents the coating thickness from becoming too large, and further allows the viscosity of the radiation-sensitive composition to be appropriately increased, ensuring good coatability. The solids concentration of the first composition is more preferably 10 to 55 mass%, and even more preferably 12 to 50 mass%.

[0139] [Second Composition] Next, the 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 resin composition.

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

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

[0142] In order to provide good solubility in an alkaline developer, the content of the structural unit (III-3) in the polymer (a2) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more, based on the total structural units constituting the polymer (a2). The content of the 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, based on the total structural units constituting the polymer (a2).

[0143] When the polymer (a2) is contained, the polymer component [A] may further contain a structural unit other than the structural unit (III-3) (hereinafter also referred to as "other structural unit (3)"). A preferred example of the other structural unit (3) is the structural unit (II-3) having a crosslinkable group. The other structural unit (3) may be introduced into the polymer (a2), or may be introduced as a structural unit of a polymer different from the polymer (a2), or may be introduced into both of these polymers. From the viewpoint of obtaining an effect of improving development adhesion while minimizing the number of components constituting the second composition, it is preferred that the polymer (a2) further contains the structural unit (II-3).

[0144] Structural Unit (II-3) The crosslinkable group of the structural unit (II-3) is not particularly limited as long as it is a group that undergoes a curing reaction by heat treatment. In terms of high thermosetting properties, it is preferable that it is one or more selected from the group consisting of an oxiranyl group and an oxetanyl group. Specific examples and preferred examples of the structural unit (II-3) are the same as those shown in the explanation of the 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, based on all 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, based on all structural units constituting polymer (a2). By setting the content of structural unit (II-3) within the above range, the coating film exhibits better resolution, and the resulting cured film can be made to have sufficiently high heat resistance and chemical resistance. This is preferable.

[0146] When the second composition contains a polymer (a2), examples of the other structural units (3) that may be contained in the polymer component [A] include the structural units exemplified in the other structural units (1). When the polymer (a2) contains a structural unit other than the structural unit (II-3) as the other structural unit (3), the content of the structural unit is preferably 80 mass% or less, and more preferably 70 mass% or less, of all structural units constituting the polymer (a2).

[0147] The polymer (a2) can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in a suitable solvent in the presence of a polymerization initiator, etc. The details of the polymerization method are the same as those for the polymer (a1-1).

[0148] The weight average molecular weight (Mw) of polymer (a2) in terms of polystyrene measured by GPC is preferably 1,000 or more. The Mw of polymer (a2) is more preferably 2,000 or more, and even more preferably 5,000 or more. 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] The molecular weight distribution (Mw / Mn) of the polymer (a2), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably 5.0 or less, more preferably 3.0 or less.

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

[0151] <Quinone diazide compounds> The second composition contains a quinone diazide compound [Dq] as a radiation-sensitive compound that generates a carboxylic acid upon irradiation. Examples of the quinone diazide compound [Dq] include the same specific and preferred examples of the quinone diazide compound exemplified as the photoacid generator [C] 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 polymer (A-2) contained in the second composition. 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 polymer (A-2) contained in the second composition.

[0153] When the content of the quinone diazide compound is 2 parts by mass or more, sufficient acid is generated by irradiation with actinic rays, and the difference in solubility in alkaline solution between the irradiated and unirradiated areas can be sufficiently increased. This allows for good patterning. Furthermore, 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, when the content of the quinone diazide compound is 60 parts by mass or less, the amount of unreacted quinone diazide compound can be sufficiently reduced, which is advantageous in that it can suppress deterioration in developability and transparency due to residual quinone diazide compound.

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

[0155] In the second composition, the content of the silanol compound [B] is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the polymer (A-2) contained in the second composition. The content of the silanol compound [B] is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the polymer (A-2) contained in the second composition.

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

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

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

[0159] In the second composition, the content of the solvent (the total amount when two or more solvents are contained) 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 components other than the above-mentioned [A] polymer component, [Dq] quinone diazide compound, [B] silanol compound, [E] basic compound, and solvent. Specific and preferred examples of the other components that may be contained 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 taking into consideration viscosity, volatility, etc. The solid content concentration of the second composition is preferably in the range of 5 to 60 mass %, more preferably 10 to 55 mass %, and even more preferably 12 to 50 mass %.

[0162] [Third Composition] Next, the 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 resin composition.

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

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

[0165] The polymer component [A] may further contain a structural unit other than the structural unit (III-4) (hereinafter also referred to as "other structural unit (4)"). A preferred example of the other structural unit (4) is the structural unit (II-4) having a crosslinkable group. The other structural unit (4) may be introduced into the polymer (a3), or may be introduced as a structural unit of a polymer different from the polymer (a3), or may be introduced into both of these polymers. From the viewpoint of obtaining an effect of improving development adhesion while minimizing the number of components constituting the third composition, it is preferred that the polymer (a3) ​​further contains the structural unit (II-4).

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

[0167] When the polymer (a3) ​​contains the structural unit (II-4), the content of the 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, based on all structural units constituting the polymer (a3). The content of the 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, based on all structural units constituting the polymer (a3).

[0168] Examples of the other structural unit (4) that may be contained in the polymer component [A] include the same structural units as those exemplified as the other structural unit (1).

[0169] The polymer (a3) ​​can be produced, for example, by a known method such as radical polymerization using an unsaturated monomer capable of introducing each of the structural units described above in a suitable solvent in the presence of a polymerization initiator, etc. The details of the polymerization method are the same as those for the polymer (a1-1).

[0170] The weight average molecular weight (Mw) of the polymer (a3) ​​as calculated on a polystyrene basis by GPC is preferably 1,000 or more. The Mw of the polymer (a3) ​​is more preferably 2,000 or more, and even more preferably 5,000 or more. From the viewpoint of improving film-forming properties, the Mw of the polymer (a3) ​​is preferably 200,000 or less, and more preferably 50,000 or less.

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

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

[0173] Specifically, the polymerizable monomer [M] is preferably a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups, and particularly preferably a compound having two or more (meth)acryloyl groups. The number of polymerizable groups per molecule of the polymerizable monomer [M] is preferably 2 to 10, more preferably 2 to 8.

[0174] Specific examples of the polymerizable monomer [M] 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 (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional (meth)acrylates having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride.

[0175] Examples of compounds having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The terms "melamine structure" and "benzoguanamine structure" refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and include melamine, benzoguanamine, and condensates thereof. 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)glycoluril.

[0176] Among the polymerizable monomers [M], 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 a carboxy group, 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 a carboxy group 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 a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, trimethylolpropane di(meth)acrylate, dipentaerythritol polyacrylate, etc. Among these, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol polyacrylate are particularly preferred, since they increase the inter- or intramolecular crosslinking density and can further improve the curability of the film even by low-temperature baking.

[0178] The content of the polymerizable monomer [M] 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 the polymer (a3) ​​contained in the third composition. Furthermore, the content of the polymerizable monomer [M] is preferably 1,000 parts by mass or less, and more preferably 500 parts by mass or less, per 100 parts by mass of the polymer (a3). A content of the polymerizable monomer [M] within the above range is preferable in that it ensures sufficient curability and alkaline developability as a cured film, and also sufficiently suppresses the occurrence of background smears and film residues on the substrate or light-shielding layer in unexposed areas.

[0179] <Photopolymerization initiator> The third composition contains a [Di] photopolymerization initiator as a radiation-sensitive compound. The [Di] photopolymerization initiator (hereinafter also referred to simply as "photopolymerization initiator") contained in the third composition is preferably a compound that responds to actinic rays with a wavelength of 300 nm or more (preferably 300 to 450 nm) and initiates and promotes polymerization of the [M] polymerizable monomer. When using a photopolymerization initiator that is not directly sensitive to actinic rays with a wavelength of 300 nm or more, it may be used in combination with a sensitizer so that it responds to actinic rays with a wavelength of 300 nm or more and initiates and promotes polymerization of the [M] polymerizable monomer.

[0180] Known compounds can be used as the photopolymerization initiator. Specific examples include oxime ester compounds, organic halogenated compounds, oxidiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric 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, as they can further 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, per 100 parts by mass of the polymer (a3) ​​contained in the third composition. 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, per 100 parts by mass of the polymer (a3) ​​contained in the third composition.

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

[0183] In the third composition, the content of the silanol compound [B] is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the polymer (a3) ​​contained in the third composition. The content of the silanol compound [B] is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the polymer (a3) ​​contained in the third composition.

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

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

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

[0187] In the third composition, the content of the solvent (the total amount when two or more solvents are contained) 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 ingredients> The third composition may further contain components other than the above-mentioned [A] polymer component, [M] polymerizable monomer, [Di] photopolymerization initiator, [B] silanol compound, [E] basic compound, and solvent (other components). Specific examples and preferred examples of the other components that may be contained in the third composition are the same as those for the first composition.

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

[0190] According to the present disclosure described above, the following radiation-sensitive composition is 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 comprising:

[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, and 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 the formula (1) 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 the above formula (3-1), a group represented by the above formula (3-2), and a group represented by the above formula (3-3). [7] The radiation-sensitive composition according to any one of [1] to [6], wherein the photoacid generator includes at least one compound selected from the group consisting of an oxime sulfonate compound and a sulfonimide compound. [8] The radiation-sensitive composition according to any one of [1] to [7], further comprising an acid diffusion controller. [9] The radiation-sensitive composition according to [8], wherein the acid diffusion controller is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines.

[10] The radiation-sensitive composition according to any one of [1] to [9], further comprising a basic compound (excluding an acid diffusion controller).

[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 organic phosphazenes.

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

[13] , wherein the polymer containing the structural unit (I) further contains a structural unit having one or more selected from the group consisting of an oxiranyl 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] A polymer containing a structural unit having an acidic group (excluding a polymer having a structural unit represented by the above formula (1)), a quinone diazide compound; 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 basic compound; A solvent, A radiation-sensitive composition comprising:

[0193]

[17] The radiation-sensitive composition according to

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

[18] The radiation-sensitive composition according to

[17] , wherein the crosslinkable group is at least one selected from the group consisting of an oxiranyl 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 condensation product of a phenolic compound or an alcoholic compound with 1,2-naphthoquinone diazide sulfonic acid halide.

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

[16] to

[20] , 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, and m is an integer of 1 to 3.

[22] The radiation-sensitive 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 organic phosphazenes.

[0194]

[26] A polymer including a structural unit having an acidic group; a polymerizable monomer; a photopolymerization initiator; 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 basic compound; A solvent, A radiation-sensitive composition comprising:

[0195]

[27] The radiation-sensitive composition according to

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

[28] The radiation-sensitive composition according to

[27] , wherein the crosslinkable group is at least one selected from the group consisting of an oxiranyl group and an oxetanyl group.

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

[26] to

[29] , 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, and m is an integer of 1 to 3.

[31] The radiation-sensitive 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 radiation-sensitive composition according to

[32] or

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

[0196] <Cured film and method for producing same> The cured film of the present disclosure is formed from the radiation-sensitive composition prepared as described above. The radiation-sensitive composition has high radiation sensitivity and excellent storage stability. Furthermore, by using the radiation-sensitive composition, it is possible to form a pattern film that exhibits high adhesion to the substrate even after development, has a low dielectric constant, and is excellent in chemical resistance. Therefore, the radiation-sensitive composition can be preferably used as a material for forming, 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, etc.

[0197] When producing a cured film, by using the above-mentioned radiation-sensitive composition, a positive cured film can be formed depending on the type of photosensitizer. The cured film can be produced using the above-mentioned radiation-sensitive composition by a method including, for example, the following steps 1 to 4. (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 to light. (Step 3) A step of developing the coating film after exposure. (Step 4) A step of heating the developed coating film. Each step will be described in detail below.

[0198] [Process 1: Coating process] In this step, the radiation-sensitive composition is applied to a surface on which a film is to be formed (hereinafter also referred to as "film-forming surface"), and the solvent is preferably removed by a heat treatment (pre-bake) to form a coating film on the film-forming surface. The material of the film-forming surface is not particularly limited. For example, when forming an interlayer insulating film, the radiation-sensitive composition is applied to a substrate provided with switching elements such as TFTs to form a coating film. Examples of the substrate that can be used include a glass substrate, a silicon substrate, and a resin substrate. The surface of the substrate on which the coating film is to be formed may have a metal thin film formed thereon depending on the application, or may have been subjected to various surface treatments such as HMDS (hexamethyldisilazane) treatment.

[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, and bar coating are preferred. Prebaking conditions vary depending on the types and content ratios of each component in the radiation-sensitive composition, but are, for example, 60 to 130°C for 0.5 to 10 minutes. The thickness of the coating film formed (i.e., the film thickness after prebaking) is preferably 0.1 to 12 μm. The radiation-sensitive composition applied to the surface to be coated may be subjected to reduced pressure drying (VCD) before prebaking.

[0200] [Step 2: Exposure step] In this step, at least a portion of the coating film formed in step 1 above is irradiated with radiation. At this time, by irradiating the coating film with radiation through a mask having a predetermined pattern, a cured film having a pattern can be formed. Examples of radiation include charged particle beams such as ultraviolet light, far ultraviolet light, visible light, X-rays, and electron beams. Among these, ultraviolet light is preferred, and examples thereof include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). The radiation exposure dose is 0.1 to 20,000 J / m 2 is preferred.

[0201] [Process 3: Development process] In this step, the coating film irradiated in step 2 is developed. Specifically, the coating film irradiated in step 2 is developed using a developer to remove the irradiated portions, resulting in positive development. Examples of the developer include an aqueous solution of an alkali (basic compound). Examples of alkali include sodium hydroxide, tetramethylammonium hydroxide, and the alkalis exemplified in paragraph

[0127] of JP 2016-145913 A. The alkali concentration in the aqueous alkali solution is preferably 0.1 to 5% by mass in order to obtain adequate developability. Examples of the development method include a puddle method, a dipping method, a swinging immersion method, and a shower method. The development time varies depending on the composition of the composition, but is, for example, 30 to 120 seconds. After the development step, the patterned coating film is preferably rinsed with running water.

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

[0203] <Semiconductor element> The semiconductor device of the present disclosure includes a cured film formed using the radiation-sensitive composition. The cured film is preferably an interlayer insulating film that insulates wiring in the semiconductor device. The semiconductor device of the present disclosure can be manufactured using a known method.

[0204] <Display element> The display element of the present disclosure includes a cured film formed using the radiation-sensitive composition. Furthermore, the display element of the present disclosure may include a semiconductor element of the present disclosure, thereby including a cured film formed using the radiation-sensitive composition. Furthermore, the display element of the present disclosure may include a planarizing film formed on a TFT substrate as a cured film formed using the radiation-sensitive composition. Examples of display elements include liquid crystal display elements and organic electroluminescence (EL) display elements. [Example]

[0205] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified. In these examples, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were measured by the following methods.

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

[0207] [Monomer] The abbreviations of the monomers used in the synthesis of the polymers are as follows: <<Monomer that provides structural unit (I)>> A 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 with acid-labile groups MATHF: 2-Tetrahydrofuranyl methacrylate

[0208] Other Monomers AA: acrylic acid MA: methacrylic acid MI: Maleimide OXMA: OXE-30 (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-yl] MMA: methyl methacrylate ST: styrene

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

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

[0211] [Synthesis Example 3] Synthesis of polymer (A-3) A flask equipped with a condenser and a stirrer was charged with 10 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methyl ethyl ether. 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 and purged with nitrogen. The temperature of the solution was raised to 70°C with gentle stirring and maintained at this temperature for 5 hours, yielding a polymer solution containing polymer (A-3). The solids concentration of this polymer solution was 34.0% by mass, and the Mw of polymer (A-3) was 10,500, with a molecular weight distribution (Mw / Mn) of 2.2.

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

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

[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] Polymer (A) A-1 to A-12: Polymers (A-1) to (A-12) synthesized in Synthesis Examples 1 to 12 CA-1 to CA-2: Polymers (CA-1) and (CA-2) synthesized in Synthesis Examples 19 and 20

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

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

[0219] Additive (X) Adhesion aid 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] [Example 1] To the polymer solution containing the polymer (A-1) obtained in Synthesis Example 1, 5 parts of a silanol compound (B-1), 1 part of a photoacid generator (C-2), and 5 parts of an additive (X-1) were mixed in amounts corresponding to 100 parts (solids) of the polymer (A-1), and diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether were added in a mass ratio of 1:1 so that the final solids concentration was 20 mass%. The mixture was then filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

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

[0223] [Table 2]

[0224] <Evaluation> The radiation-sensitive compositions of Examples 1 to 20 and Comparative Examples 1 to 5 were evaluated for the following items by the methods described below. The evaluation results are shown in Table 3.

[0225] [Radiation sensitivity] Using a spinner, the radiation-sensitive composition was applied to a silicon substrate that had been treated with HMDS at 60°C for 60 seconds, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was irradiated with a predetermined amount of ultraviolet light from a mercury lamp through a pattern mask with a 10 μm-wide line-and-space pattern. Next, a development process was carried out at 25°C for 60 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide as the developer, followed by rinsing with running ultrapure water for 1 minute. The minimum exposure dose required to form a 10 μm-wide line-and-space pattern was measured. The measured minimum exposure dose was 300 J / m. 2 The radiation sensitivity is good when the radiation level is less than 300 J / m 2 In the above cases, the radiation sensitivity can be evaluated as poor.

[0226] [Evaluation of chemical resistance of cured film] The chemical resistance of the cured film was evaluated based on the degree of swelling caused by the stripping solution. The radiation-sensitive composition was applied to a silicon substrate using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. Subsequently, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to expose the film to 3000 J / m 2 After irradiating the entire substrate with light, the substrate was post-baked for 30 minutes in an oven heated to 230°C to form a cured film. The resulting cured film was immersed in N-methyl-2-pyrrolidone solvent heated to 40°C for 6 minutes, and the change in film thickness (%) before and after immersion was determined. This change in film thickness was used as an index of chemical resistance and was evaluated according to the following criteria. AA: Film thickness change rate is less than 2% A: Film thickness change rate is 2% or more and less than 5% B: Film thickness change rate is 5% or more and less than 10% C: Film thickness change rate is 10% or more and less than 15% D: Film thickness change rate is 15% or more The chemical resistance can be evaluated as good in the cases of AA, A, or B, and as poor in the case of C or D. The film thickness was measured at 25°C using an optical interference film thickness measuring device (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 made according to the above-mentioned [Radiation Sensitivity] evaluation, and the rate of increase in radiation sensitivity (minimum exposure dose) before and after 7 days of storage was calculated. A value of less than 5% was rated as "AA," a value of 5% or more but less than 10% was rated as "A," a value of 10% or more but less than 20% was rated as "B," a value of 20% or more but less than 30% was rated as "C," and a value of 30% or more was rated as "D." A value of AA, A, or B indicates good storage stability, while a value of C or D indicates poor storage stability.

[0228] [Evaluation of substrate adhesion (development adhesion)] The radiation-sensitive composition was applied to a silicon substrate that had not been subjected to HMDS treatment using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 μm. This coating film was exposed to light from 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 sample was then exposed to ultraviolet light. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide was used as the developer, and the sample was then developed for 60 seconds at 25°C, followed by rinsing with running ultrapure water for 1 minute. The minimum width of the line-and-space pattern remaining on the substrate was measured. A minimum width measurement of 2 μm or less was rated as "AA," greater than 2 μm and less than 5 μm as "A," greater than 5 μm and less than 10 μm as "B," greater than 10 μm and less than 30 μm as "C," and greater than 30 μm as "D." AA, A, or B indicates good developer adhesion, while C or D indicates poor developer adhesion.

[0229] [Evaluation of relative permittivity] The radiation-sensitive composition was applied to a glass substrate using a spinner, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with an average thickness of 3.0 µm. Subsequently, a proximity exposure machine (Canon's "MA-1200" (ghi-ray mixed)) was used to expose the coating film to 3000 J / m 2 After irradiating the entire substrate surface with light, the substrate was baked (post-baked) for 30 minutes in an oven heated to 230°C to form a cured film. The dielectric constant of the resulting cured film was measured at a frequency of 10 kHz. The reduction rate of the dielectric constant was calculated based on the dielectric constant of Example 5, and this reduction rate was evaluated according to the following criteria. AA: Dielectric constant reduction rate is 20% or more A: The reduction in the dielectric constant is 15% or more but less than 20% B: The reduction in the relative dielectric constant is 10% or more but less than 15% C: The reduction in the relative dielectric constant is 5% or more but less than 10% D: The reduction in the dielectric constant is less than 5% In the case of AA, A or B, the relative dielectric constant is evaluated as good, in the case of C, the relative dielectric constant is fair, and in the case of D, the relative dielectric constant is poor.

[0230] [Table 3]

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

[0232] As shown in Table 3, the radiation-sensitive compositions of Examples 1 to 20 were all good in terms of practical properties, such as radiation sensitivity, chemical resistance, storage stability, development adhesion, and dielectric constant, and were well-balanced in terms of various properties. In contrast, the compositions of Comparative Examples 1 to 3 did not resolve upon exposure, and the chemical resistance and dielectric constant were also low. Furthermore, the radiation-sensitive compositions of Comparative Examples 4 and 5 were evaluated to be equivalent to those of Examples 1 to 20 in terms of radiation sensitivity, chemical resistance, and storage stability, but were lower in development adhesion and dielectric constant than those of Examples 1 to 20.

[0233] <Preparation of Radiation-Sensitive Composition (2)> The compounds used in the preparation of the radiation-sensitive composition are shown below. Note that the polymer (A), silanol compound (B), photoacid generator (C), additive (X), and solvent (G) are the same as those in the preparation of the radiation-sensitive composition (1), and therefore descriptions thereof are omitted. Basic Compounds (E) E-1: 1,8-diazabicyclo[5.4.0]-7-undecene E-2: 1,5,7-triazabicyclo[4.4.0]dec-5-ene

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

[0235] [Table 4]

[0236] <Evaluation> The radiation-sensitive compositions of Examples 21 to 29 were evaluated for each item in the same manner as in Example 1. The evaluation results are shown in Table 5. The radiation-sensitive compositions of Examples 21 to 29 each had the same composition as the radiation-sensitive compositions of Examples 2, 5, 7, 8, 10, 13, 14, 16, and 19, except that a basic compound (E) was added.

[0237] [Table 5]

[0238] As shown in Table 5, the radiation-sensitive compositions of Examples 21 to 29 were able to further improve development adhesion while maintaining high levels of radiation sensitivity, chemical resistance, and storage stability, compared with Examples 2, 5, 7, 8, 10, 13, 14, 16, and 19, which had the same composition but did not contain the basic compound (E). It was also confirmed that the incorporation of the basic compound (E) improved the relative dielectric constant of the cured film.

[0239] <Preparation of Radiation-Sensitive Composition (3)> The compounds used in the preparation of the radiation-sensitive composition are shown below. Details of the polymer (A), silanol compound (B), photoacid generator (C), additive (X), and solvent (G) that are the same as those in the preparation of the radiation-sensitive composition (1), as well as the basic compound (E), are as described above, and will not be repeated here. Polymer (A) A-13 to A-18: Polymers (A-13) to (A-18) synthesized in Synthesis Examples 13 to 18 《Radiation sensitive compound (D)》 D-1: Condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) D-2: Condensation product of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol) D-3: Condensation product of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) D-4: Condensation product of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol) D-5: Irgacure OXE02 (BASF) <Polymerizable monomer (M)> M-1: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

[0240] [Examples 30 to 35 and Comparative Examples 6 to 14] The radiation-sensitive compositions of Examples 30 to 35 and Comparative Examples 6 to 14 were prepared in the same manner as in Example 1, except that the types and amounts (parts by mass) of each component were used as shown in Table 6. The radiation-sensitive compositions of Examples 30 and 31 correspond to the first composition, the radiation-sensitive compositions of Examples 32 to 34 correspond to the second composition, and Example 35 corresponds to the third composition.

[0241] [Table 6]

[0242] <Evaluation> The radiation-sensitive compositions of Examples 30 to 35 and Comparative Examples 6 to 14 were evaluated for each item in the same manner as in Example 1. Table 7 shows the evaluation results.

[0243] [Table 7]

[0244] The radiation-sensitive compositions of Examples 30 and 31, which are the first compositions, were all good in terms of practical properties such as radiation sensitivity, chemical resistance, storage stability, development adhesion, and dielectric constant, and were well-balanced in terms of various properties. In particular, the radiation-sensitive composition of Example 31, which contained 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 radiation-sensitive compositions of Examples 32 to 34, which are the second compositions, were able to improve development adhesion 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 compositions except for not containing the basic compound (E). The radiation-sensitive composition of Example 35, which is the third composition, was able to improve the chemical resistance and development adhesion while maintaining high levels of radiation sensitivity, storage stability, and relative dielectric constant, as compared to Comparative Example 14, which did not contain the basic compound (E).

Claims

1. a polymer containing a structural unit (I) having a group represented by the following formula (1); 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 comprising: 【Chemistry 1】 (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. １ , R ２ and R ３ At least one of the groups is an alkoxy group having 1 to 6 carbon atoms. "*" indicates a bond.

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

3. The radiation-sensitive composition according to claim 1 , 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 is a monovalent hydrocarbon group, and m is an integer of 1 to 3.

4. The radiation-sensitive composition according to claim 1 , wherein the silanol compound has an aromatic ring.

5. 2. The radiation-sensitive composition according to claim 1, wherein the group represented by formula (1) is bonded to an aromatic ring group or a chain hydrocarbon group.

6. The radiation-sensitive composition according to claim 1, wherein the structural unit (I) has at least one selected from the group consisting of a group represented by the following formula (3-1), a group represented by the following formula (3-2), and a group represented by the following formula (3-3): 【Chemistry 2】 (In formula (3-1), formula (3-2) and formula (3-3), A １ and A ２ are each independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. n1 is an integer of 0 to 4. n2 is an integer of 0 to 6. However, when n1 is 2 or more, multiple A １ are the same or different from each other. When n2 is 2 or more, multiple A ２ are the same or different. ６ is an alkanediyl group. １ , R ２ and R ３ is the same as in formula (1). "*" represents a bond.

7. The radiation-sensitive composition according to claim 1 , wherein the photoacid generator comprises at least one selected from the group consisting of an oxime sulfonate compound and a sulfonimide compound.

8. The radiation-sensitive composition according to claim 1 , further comprising an acid diffusion controller.

9. 9. The radiation-sensitive composition according to claim 8, wherein the acid diffusion controller is at least one selected from the group consisting of aromatic amines and heterocyclic aromatic amines.

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

11. 11. The radiation-sensitive composition according to claim 10, wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 8 or more.

12. 12. The radiation-sensitive composition according to claim 11, wherein the basic compound is an organic base having an acid dissociation constant (pKa) of 9 or more.

13. 12. The radiation-sensitive composition according to claim 11, wherein the basic compound is at least one selected from the group consisting of amidines, guanidines, and organic phosphazenes.

14. 2. The radiation-sensitive composition according to claim 1, wherein the polymer containing the structural unit (I) further contains a structural unit having at least one selected from the group consisting of an oxiranyl group and an oxetanyl group.

15. The radiation-sensitive composition according to claim 1 , wherein the polymer containing the structural unit (I) further contains a structural unit having an acidic group.

16. forming a coating film using the radiation-sensitive composition according to any one of claims 1 to 15; irradiating at least a portion of the coating with radiation; developing the radiation-irradiated coating film; heating the developed coating; A method for producing a cured film, comprising:

17. A cured film formed using the radiation-sensitive composition according to any one of claims 1 to 15.

18. A semiconductor device comprising the cured film according to claim 17.

19. A display device comprising the cured film according to claim 17.

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