Composition for forming resist underlayer film

Abstract

A composition for forming a resist underlayer film, the composition containing: a compound or a polymer (A) that has a polymerizable multiple bond; an onium salt (B) that is at least one among an aromatic sulfonium salt, an aromatic iodonium salt, and an ammonium salt; and a solvent (C).

Description

Composition for forming a resist underlayer film

[0001] The present invention relates to a composition for forming a resist underlayer film, a resist underlayer film, a laminate, a method for manufacturing a semiconductor device, and a method for forming a pattern.

[0002] Conventionally, microfabrication using lithography with resist compositions has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with an active light such as ultraviolet light through a mask pattern on which the device pattern is drawn, developing the film, and then etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern. In recent years, semiconductor devices have become more highly integrated, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. Consequently, poor resist pattern formation has become a major problem. Therefore, in order to solve this problem, methods of providing a resist underlayer film between the resist and the semiconductor substrate are being widely investigated.

[0003] A composition for forming a resist underlayer has been proposed, comprising a polymer (A) having one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds in its side chain, and a solvent (see Patent Document 1).

[0004] International Publication No. 2024 / 029548 brochure

[0005] One of the properties required of a resist underlayer film is good curability. The present invention has been made in view of the above circumstances, and aims to provide a resist underlayer film forming composition capable of forming a resist underlayer film with good curability, and a method for manufacturing a resist underlayer film, a laminate, a semiconductor device, and a pattern formation method using the resist underlayer film forming composition.

[0006] The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved, and have completed the present invention having the following gist.

[0007] That is, the present invention includes the following embodiments. [1] A composition for forming a resist underlayer film, comprising a compound or polymer (A) having a polymerizable multiple bond, an onium salt (B) which is at least one of an aromatic sulfonium salt, an aromatic iodonium salt, and an ammonium salt, and a solvent (C). [2] The composition for forming a resist underlayer film according to [1], wherein the onium salt (B) is an onium salt represented by the following formula (B1) or an inner salt represented by the following formula (B2). (In formula (B1), Y １ｃ ＋ represents a monovalent aromatic sulfonium cation or a monovalent aromatic iodonium cation. In formula (B1), Y １ａ － represents a monovalent anion. In formula (B2), X ＋ is S ＋ or I ＋ represents, and each R １１１ is bonded to X ＋ , each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted polycyclic or monocyclic cycloalkyl group having 3 to 30 carbon atoms, an optionally substituted polycyclic or monocyclic aryl group having 6 to 30 carbon atoms, or a combination comprising at least one of the foregoing, n1 represents 1 or 2, when X ＋ is I ＋ , n1 represents 1, when X ＋ is S ＋ , n1 represents 2, when X ＋ is S ＋ , the two R １１１ may together form a ring, Ar １１１ represents an optionally substituted divalent aromatic group having 6 to 30 carbon atoms, L １１１ and L １１２Each of these independently represents a divalent linking group having 1 to 30 carbon atoms, which may contain a heteroatom comprising O, S, N, F, or a combination of at least one of these. １１１ R represents a divalent monocyclic, polycyclic, or fused polycyclic alicyclic group having 5 to 30 carbon atoms, which may contain a heteroatom including O, S, N, F, or a combination of at least one of these, and may have substituents. １１１ and Ar １１１ They may also form a ring together, Z － represents an oxygen-containing anionic group, n2, n3, and n4 each independently represent 0 or 1, and n represents 0 or 1.) [3] Y in formula (B1) １ｃ ＋ The resist underlayer film forming composition according to [2], wherein the underlayer film forming composition is a monovalent aromatic sulfonium cation represented by the following formula (B1-1) or a monovalent aromatic iodonium cation represented by the following formula (B1-2). (In formula (B1-1), R １０１ , R １０２ , and R １０３ Each of these independently represents one of the following (i) to (iv), R １０１ and R １０２ , R １０２ and R １０３ , or R １０１ and R １０３ They may be bonded to each other to form a ring. However, R １０１ , R １０２ , and R １０３ At least one of the following formulas (ii) to (iv): (i) A linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, which may be substituted and may contain a halogen atom, a carbonyl group, an ester group, an ether group, a thioether group, an amide group, a lactone ring, or an aryl group (ii) An aromatic hydrocarbon group which may be substituted and may contain -S- (iii) An aralkyl group having 7 to 20 carbon atoms which may be substituted (iv) A thiophenyl group which may be substituted In formula (B1-2), R １０４ and R１０５ Each independently represents an aryl group having 6 to 20 carbon atoms, which may have substituents, and R １０４ and R １０５ (These may be bonded to each other to form a ring.) [4] Y in the onium salt represented by formula (B1) １ａ － However, halogen anions, cyanide anions, bicarbonate anions, nitrate anions, nitrite anions, R １０１ SO ３ － or R １０１ CO ２ － (R １０１ A resist underlayer film forming composition according to [2] or [3], wherein the onium salt (B) is an intramolecular salt represented by the following formula (B2-1) or an intramolecular salt represented by the following formula (B2-2). (In formulas (B2-1) and (B2-2), R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , and R ｂ５ Each independently represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, which may contain heteroatoms. Each independently represents an integer from 0 to 5. Each independently represents 0 or 1, except that at least one of m11, m12, and m13 is 1. Each independently represents 0 or 1, except that at least one of m14 and m15 is 1. However, the sum of m1 and m11 is 5 or less. However, the sum of m2 and m12 is 5 or less. However, the sum of m3 and m13 is 5 or less. However, the sum of m4 and m14 is 5 or less. However, the sum of m5 and m15 is 5 or less. If m1 is 2 to 5, two adjacent R ｂ１ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m2 is 2 to 5, two adjacent R ｂ２These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m3 is 2 to 5, two adjacent R ｂ３ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m4 is 2 to 5, two adjacent R ｂ４ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m5 is 2 to 5, two adjacent R ｂ５ These may bond with each other to form a ring with the carbon atoms to which they are bonded. n represents 0 or 1.) [6] The resist underlayer film forming composition according to [1], wherein the onium salt (B) is an ammonium salt represented by the following formula (B3). (In formula (B3), R Ｂ３１ Each of these independently represents a hydrogen atom, or an alkyl group, alkenyl group, alkynyl group, aryl group, or aralkyl group which may be substituted with a heteroatom or which may have a heteroatom interposed. Ｂ３１ They may also form a ring structure together. ３ａ － represents a monovalent anion.) [7] Y in the ammonium salt represented by the above formula (B3) ３ａ －The resist underlayer film forming composition according to [6], wherein the compound or polymer (A) is one of the polymers (A-1) to (A-6) listed below, or one of the compounds (A-7) listed below. Polymer (A-1): A polymer obtained by polymerizing the polymerizable unsaturated bonds of a compound having a group having polymerizable unsaturated bonds (however, the polymer has polymerizable multiple bonds). Polymer (A-2): A polymer having a structural unit represented by the following formula (A2). Polymer (A-3): A polymer having a hydroxyl group bonded to a carbon atom in the main chain and a polymerizable multiple bond. Polymer (A-4): A polydiene polymer having polymerizable multiple bonds, which may be modified. Polymer (A-5): A polymer having a structural unit represented by the following formula (A5). Polymer (A-6): The following resin (G): A resin (G) having a composite unit structure, wherein the composite unit structure comprises: a unit structure (A) having an aromatic ring, and a unit structure (B) having one or more carbon atoms, and is obtained by a reaction that generates a covalent bond between the carbon atoms constituting the aromatic ring of the unit structure (A) and the carbon atoms in the unit structure (B) (however, the resin (G) has polymerizable multiple bonds). Compound (A-7): A compound having three or more polymerizable multiple bonds. (In formula (A2), L ２１ L represents a single bond or a linking group. ２２ (This represents a monovalent group having polymerizable multiple bonds.) (In formula (A5), Ar represents a group having a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, or fluorene ring.) ５１R represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether-bond-containing group. ５２ L represents a divalent group which may have substituents. ５１ L represents a single bond or a linking group. ５２ represents a group having polymerizable multiple bonds. m represents an integer from 0 to 4. n represents an integer from 0 to 3. However, m + n is 4 or less. However, when m is 0, R ５２ (It has polymerizable multiple bonds.) [9] The resist underlayer film forming composition according to any one of [1] to [8], which has poor film-forming properties when it does not contain the onium salt (B).

[10] The rate of film thickness reduction (A) relative to the resist solvent when a resist underlayer film with a thickness of 5 nm is formed at a heating temperature of 150°C or 220°C. １ [%]) and the film thickness reduction rate (A) when the onium salt (B) is not included. ２ A resist underlayer film forming composition according to any one of [1] to [9], wherein [%]) satisfies the relationship of the following formula (F1). ２ [%]-A １[%] (F1)

[11] The resist underlayer film forming composition according to any one of [1] to

[10] , wherein the solvent comprises at least one selected from the group consisting of carboxylic acids having a hydroxyl group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers.

[12] The resist underlayer film forming composition according to any one of [1] to

[11] , further comprising a crosslinking agent.

[13] The resist underlayer film forming composition according to

[12] , wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

[14] The resist underlayer film forming composition according to

[12] or

[13] , wherein the content of the crosslinking agent is 1% to 60% by mass with respect to the compound or polymer (A).

[15] The resist underlayer film forming composition according to any one of [1] to

[11] , which does not contain a crosslinking agent.

[16] A resist underlayer film forming composition according to any one of [1] to

[15] , further comprising a curing catalyst.

[17] A resist underlayer film forming composition according to any one of [1] to

[16] , further comprising a surfactant.

[18] A resist underlayer film forming composition according to any one of [1] to

[17] , used in EB or EUV lithography.

[19] A resist underlayer film forming composition according to any one of [1] to

[18] , used for forming an underlayer film of a metal-containing resist.

[20] A resist underlayer film, which is a cured product of a resist underlayer film forming composition according to any one of [1] to

[19] .

[21] A laminate comprising a semiconductor substrate and the resist underlayer film according to

[20] .

[22] A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of [1] to

[19] ; ​​and forming a resist film on the resist underlayer film.

[23] A pattern formation method comprising: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of [1] to

[19] ; ​​forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern; and etching the resist underlayer film using the resist pattern as a mask.

[0008] According to the present invention, it is possible to provide a resist underlayer film formation composition capable of forming a resist underlayer film with good curability, as well as a method for manufacturing a resist underlayer film, a laminate, a semiconductor device, and a pattern formation method using the resist underlayer film formation composition.

[0009] (Composition for forming a resist underlayer film) The resist underlayer film composition of the present invention comprises a compound or polymer (A), an onium salt (B), and a solvent (C).

[0010] A resist underlayer film formation composition containing a compound or polymer (A) having polymerizable multiple bonds can form a resist underlayer film with good curability by containing an onium salt (B).

[0011] <Compound or Polymer (A)> Compound or polymer (A) has polymerizable multiple bonds. In the present invention, the polymerizable multiple bonds are, for example, one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds.

[0012] Examples of groups having polymerizable multiple bonds include (meth)acryloyl groups, optionally substituted vinylaryl groups (e.g., styryl groups, α-methylstyryl groups), vinyloxy groups, vinylamino groups, allyl groups, alkynyl groups, alkynyloxy groups, and alkynylamino groups.

[0013] The compound or polymer (A) may have two or more polymerizable multiple bonds in one molecule, or it may have three or more polymerizable multiple bonds.

[0014] The molecular weight of compound or polymer (A) is not particularly limited, but for example, the weight-average molecular weight of compound or polymer (A) is 300 or more. For example, the weight-average molecular weight of compound or polymer (A) is 3,500 or more.

[0015] The compound or polymer (A) may or may not have, for example, a phenolic hydroxyl group. If the compound or polymer (A) has a phenolic hydroxyl group, the weight-average molecular weight of the compound or polymer (A) is, for example, 3,500 or more.

[0016] Furthermore, there is no clear boundary between the compound and the polymer. Also, in this specification, there is no clear boundary between the polymer and the resin.

[0017] The following are examples of compounds or polymers (A).

[0018] <<Polymer (A-1)>> Polymer (A-1) is a polymer formed by the polymerization of polymerizable unsaturated bonds in a compound having a group with polymerizable unsaturated bonds. Polymer (A-1) may be a homopolymer or a copolymer. Examples of groups having polymerizable unsaturated bonds include (meth)acryloyl groups, optionally substituted vinylaryl groups (e.g., styryl groups, α-methylstyryl groups), vinyloxy groups, vinylamino groups, allyl groups, alkynyl groups, alkynyloxy groups, and alkynylamino groups.

[0019] For example, in polymer (A-1), polymerizable multiple bonds are attached to the main chain of polymer (A-1) via linking groups having a structure obtained by the reaction of an epoxy group and a nucleophilic functional group. Examples of nucleophilic functional groups include one or more selected from the group consisting of carboxyl groups, hydroxyl groups, amino groups, and thiol groups. The hydroxyl group may or may not be a phenolic hydroxyl group. When the epoxy group and the carboxyl group react, they react as follows to form the following structure (S1). (In the formula, * represents a bond.)

[0020] Furthermore, for example, in polymer (A-1), polymerizable multiple bonds are attached to the main chain of polymer (A-1) via linking groups having a structure obtained by the reaction of an isocyanate group and a nucleophilic functional group. In this case, the nucleophilic functional group may be one or more selected from the group consisting of a hydroxyl group, an amino group, and a thiol group. The hydroxyl group may or may not be a phenolic hydroxyl group.

[0021] The polymer (A-1) preferably has a structural unit represented by the following formula (1). (In formula (1), R １ L represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. １ L represents a single bond or a linking group. ２ (This represents a monovalent group having the polymerizable multiple bond.)

[0022] R １ Examples of halogen atoms in this context include fluorine, chlorine, bromine, and iodine atoms. １ Examples of monovalent organic groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. １The monovalent organic group having 1 to 20 carbon atoms in the formula may be substituted with a hydroxyl group, or may be interrupted at one or more locations by a heteroatom. Examples of heteroatoms include oxygen, nitrogen, and sulfur atoms. Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-icosyl groups. These alkyl groups may be linear, branched, or cyclic. Examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 1-dodecenyl, 1-tetradecenyl, 1-hexadecenyl, 1-octadecenyl, and 1-icocenyl. These alkenyl groups may be linear, branched, or cyclic. Examples of alkynyl groups having 2 to 20 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-pentynyl, 1-hexynyl, 1-heptynyl, 1-octinyl, 1-noninyl, 1-decynyl, 1-dodecynyl, 1-tetradecynyl, 1-hexadecinyl, 1-octadecynyl, and 1-icosinyl groups. These alkynyl groups may be linear, branched, or cyclic. Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, allyloxy, cyclohexyloxy, phenoxy, benzyloxy, and 1-naphthyloxy groups. Examples of aryl groups having 6 to 20 carbon atoms include phenyl, tolyl, o-xylyl, biphenyl, naphthyl, anthracenyl, phenantrenyl, chrysenyl, triphenylenyl, and pyrenyl groups.

[0023] L １ When L is a linking group, the number of carbon atoms in the linking group is not particularly limited, and examples thereof include 1 to 30. L １ may contain a heteroatom. Examples of the heteroatom include a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom. L １ When L is a linking group, examples of the linking group include a linking group having a structure obtained by reacting an epoxy group with a nucleophilic functional group, and a linking group having a structure obtained by reacting an isocyanate group with a nucleophilic functional group.

[0024] L １ Examples of L include the following linking groups (L1-1) to (L1-23). (In the formula, *1 represents a bonding site. *2 represents a bonding site. R Ｌ１ each independently represent an optionally substituted alkyl group or an optionally substituted aryl group. Z is a direct bond, a linear, branched or alicyclic alkylene group having 1 to 30 carbon atoms, or an arylene group, and may contain a heteroatom on a carbon or between carbon-carbon bonds. The heteroatoms are a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom, and a structure in which any of these are combined may also be used.) When *1 is a bonding site bonded to a carbon atom bonded to R in formula (1), *2 is a bonding site bonded to L in formula (1). １ When *2 is a bonding site bonded to a carbon atom bonded to R in formula (1), *1 is a bonding site bonded to L in formula (1). ２ When *2 is a bonding site bonded to a carbon atom bonded to R in formula (1), *1 is a bonding site bonded to L in formula (1). １ When *2 is a bonding site bonded to a carbon atom bonded to R in formula (1), *1 is a bonding site bonded to L in formula (1). ２ It is a bonding site bonded to.

[0025] R Ｌ１ The alkyl group in R may be linear, branched, or cyclic. R Ｌ１ The substituent in the optionally substituted alkyl group of R may be a substituent that replaces a hydrogen atom, or may be inserted between carbons in an alkyl chain. R Ｌ１Examples of the substituent in include those containing a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. When the substituent is an oxygen atom or a sulfur atom, the oxygen atom or the sulfur atom is, for example, inserted between carbons in an alkyl chain.

[0026] L ２ is a monovalent group having a polymerizable multiple bond. The monovalent group may be the polymerizable multiple bond itself. The number of carbon atoms of the monovalent group is not particularly limited, and may be, for example, 1 to 40, or 1 to 30.

[0027] L ２ includes, for example, monovalent groups shown in the following Group (L2). Group (L2) (wherein * represents a binding site.)

[0028] In addition, L in the structural unit represented by Formula (1) １ -L ２ preferably has a structure represented by any one of the following Formulas (1a) to (1f). (In Formulas (1a) to (1f), R ２ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. X represents a single bond, an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a naphthylene group. n represents 0 or 1. *a and *b represent binding sites, *a is on the main chain side of polymer (A-1), and *b is on the terminal side of the side chain of polymer (A-1).) In addition, *b may be a binding site to a hydrogen atom or an alkyl group.

[0029] Examples of the structural unit represented by Formula (1) include the following structural units.

[0030] Examples of the monomer that provides the structural unit represented by formula (1) include the following monomers. R ０ represents a hydrogen atom or a methyl group. R １ represents =CH ２ .

[0031] An example of the polymer (A-1) containing a structural unit represented by formula (1) can be obtained by, for example, reacting a glycidyl (meth)acrylate-based polymer with a compound (C1) having a polymerizable multiple bond and a carboxy group as described below. The glycidyl (meth)acrylate-based polymer may be a homopolymer or a copolymer. Examples of the copolymer include a copolymer of glycidyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, and a copolymer of glycidyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0032] (In the formula, R １ , and L ２ each have the same definitions as R １ , and L ２ in formula (1).)

[0033] The reaction can be carried out, for example, in the presence of a catalyst such as tetrabutylphosphonium bromide.

[0034] Examples of the compound (C1) having a polymerizable multiple bond and a carboxy group include acrylic acid, methacrylic acid, 4-vinylbenzoic acid, sorbic acid, tetrolic acid, tiglic acid, 1-cyclohexene-1-carboxylic acid, 2-benzylacrylic acid, trans-cinnamic acid, trans-4-methoxycinnamic acid, α-phenylcinnamic acid, monomethyl fumarate, α-cyanocinnamic acid, 4-nitrocinnamic acid, and 3-nitrocinnamic acid.

[0035] Another example of a polymer (A-1) containing the structural unit represented by formula (1) can be obtained, for example, by reacting a (meth)acrylate polymer having a hydroxyl group with a compound (C2) having polymerizable multiple bonds and isocyanate groups, as shown below. The (meth)acrylate polymer having a hydroxyl group may be a homopolymer or a copolymer. (In the formula, R １ , and L ２ These are R in equation (1), respectively. １ , and L ２ This is synonymous with R. １１ R represents a divalent organic group. １２ (This represents a single bond or a divalent organic group.) １１ For example, an alkylene group has 1 to 4 carbon atoms. １２ These are, for example, single bonds or alkylene groups having 1 to 4 carbon atoms.

[0036] Another example of a polymer (A-1) containing the structural unit represented by formula (1) can be obtained, for example, by reacting a styrene-based polymer having a hydroxyl group or an amino group with a compound (C2) having polymerizable multiple bonds and an isocyanate group, as shown below. The styrene-based polymer having a hydroxyl group or an amino group may be a homopolymer or a copolymer. (In the formula, R １ , and L ２ These are R in equation (1), respectively. １ , and L ２ This is synonymous with R. １２ (This represents a single bond or a divalent organic group.) １２ These are, for example, single bonds or alkylene groups having 1 to 4 carbon atoms.

[0037] Examples of compounds (C2) having polymerizable multiple bonds and isocyanate groups include the following compounds.

[0038] Polymer (A-1) may have at least one of the following structural units other than the structural unit represented by formula (1): the structural unit represented by formula (A-1a), the structural unit represented by formula (A-1b), the structural unit represented by formula (A-1c), and the structural unit derived from maleimide.

[0039] (In formula (A-1a), R １ Ar represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. １ L represents a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or pyrene ring. １ L represents a hydroxyl group, cyano group, nitro group, amino group, alkylamino group, carboxyl group, formyl group, acyl group, sulfonyl-containing group, ether-bonded group, thiol group, or ester group. ２ m1 represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms. The hydrogen atoms of these aryl groups may be substituted with alkyl groups, alkenyl groups, or alkynyl groups, and the carbon-carbon bonds of these substituted alkyl groups, alkenyl groups, or alkynyl groups may be broken by oxygen atoms. m1 represents an integer from 0 to 3. m2 represents an integer from 0 to 5. However, the sum of m1 and m2 is from 0 to 5. If m1 is 2 or 3, multiple L １ They may be the same or different. If m2 is 2 to 5, multiple L ２ R may be the same or different. In equation (A-1b), １ L represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. ３ R represents a hydrogen atom or a monovalent group. In formula (A-1c), R １ L represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. ４ L represents a hydrogen atom or a monovalent group. ５ L represents a hydrogen atom or a monovalent group. ４ and L ５ (They may also form a ring structure together.)

[0040] L １ The alkylamino group in this case is -NHR or -NR ２ A group represented by is an example. Here, R may be interrupted once or more by an oxygen atom in the middle of the hydrocarbon chain, and may be substituted with a hydroxyl group or a halogen atom, a saturated or unsaturated linear, branched or cyclic hydrocarbon group (-R ａ ) represents R ａ Examples include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms. -NR ２ In this case, the two Rs may be the same or different. １ Examples of acyl groups in this context include groups represented by -COR, where R is the hydrocarbon group -R ａ Or it represents a halogen atom. L １ The sulfonyl-containing group in this is -SO ２ A group represented by R is an example. Here, R is the hydrocarbon group -R which may be substituted with a hydroxyl group or a halogen atom. ａ , represents an alkylamino group or a hydroxyl group. L １ As for the ether bond-containing group in R, １１ -O-R １１ Examples include residues of ether compounds containing an ether bond represented by . Here, R １１ Each of these independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, anthranyl group, or a pyrenyl group. The ether bond-containing group may be an organic group containing an ether bond, such as a methoxy group, an ethoxy group, or a phenoxy group, or an organic group containing an epoxy group or an oxetane group. １ The ester group in this is -CO ２ Examples of groups represented by R or -OCOR include the hydrocarbon group -R, where R may be substituted with a hydroxyl group or a halogen atom. ａ It represents.

[0041] L ２In this context, the halogen atom, alkyl group, alkenyl group, and alkynyl group are R １ Examples include halogen atoms, alkyl groups, alkenyl groups, and atoms or groups similar to alkynyl groups in L. ２ Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, allyloxy, cyclohexyloxy, phenoxy, benzyloxy, and 1-naphthyloxy groups. m1 represents an integer from 0 to 3, and may be 0, 1, 2, or 3. m2 represents an integer from 0 to 5, and may be 0, 1, 2, 3, 4, or 5.

[0042] L in equation (A-1b) ３ Examples of monovalent groups include hydrogen atoms, halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, alkylamino groups, isocyanate groups, alkylisocyanate groups, carboxyl groups, formyl groups, acyl groups, sulfonyl-containing groups, ether-bond-containing groups, thiol groups, ester groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms. ３ One or more hydrogen atoms in the monovalent group may be substituted with substituents. Examples of such substituents include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, alkylamino groups, isocyanate groups, alkylisocyanate groups, carboxyl groups, formyl groups, acyl groups, sulfonyl-containing groups, ether-bond-containing groups, thiol groups, ester groups, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms. ３The monovalent group may be separated by one or more atoms or groups selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and carbonyl groups, or it may form a ring structure bonded by one or more atoms or groups selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and carbonyl groups.

[0043] L ３ Examples of alkyl isocyanate groups in the monovalent group include the group represented by -RNCO, where R may be substituted with a hydroxyl group or a halogen atom, the hydrocarbon group -R ａ This represents a divalent group, which is formed by removing one hydrogen atom from a given atom.

[0044] L in equation (A-1c) ４ and L ５ These are, independently, L in equation (A-1b). ３ It is similar to that.

[0045] Also, L ３ Examples include the group represented by the following formula (A-1b-1), the group represented by the following formula (A-1b-2), the group represented by the following formula (A-1b-3), and the group represented by the following formula (A-1b-4).

[0046]

[0047] (In formulas (A-1b-1) to (A-1b-4), X １０ L represents a single bond or a carbonyl group. ３ａ Each of these independently represents a hydrogen atom or a monovalent group. * represents a bond.

[0048] L ３ａ As a monovalent group in the above formula (A-1b), L ３ A similar monovalent group can be cited.

[0049] Examples of monomers used to derive formula (A-1a) include the following compounds. In the formula, R ０ R represents a hydrogen atom or a methyl group. １ is, =CH ２ It represents.

[0050]

[0051] Examples of monomers used for deriving formula (A-1b) include the following compounds. In the formula, R ０ represents a hydrogen atom or a methyl group. R １ represents =CH ２ .

[0052]

[0053] Examples of monomers used for deriving formula (A-1c) include the following compounds. R ０ represents a hydrogen atom or a methyl group. R １ represents =CH ２ .

[0054]

[0055] The proportion of the structural unit represented by formula (1) in the polymer (A-1) is not particularly limited, but the molar ratio of the structural unit represented by formula (1) relative to all structural units of the polymer (A-1) may be, for example, more than 0 mol% and 100 mol% or less, more than 0 mol% and 90 mol% or less, or more than 0 mol% and 60 mol% or less.

[0056] The proportions of the structural units represented by formula (A-1a), formula (A-1b), formula (A-1c), and maleimide-derived structural units in polymer (A-1) are not particularly limited. However, the molar ratios of the structural units represented by formula (A-1a), formula (A-1b), formula (A-1c), and maleimide-derived structural units to the total structural units of polymer (A-1) may, for example, be 0 mol% or more and less than 100 mol%, 0 mol% or more and 90 mol%, or 0 mol% or more and 60 mol%.

[0057] The molecular weight of polymer (A-1) is not particularly limited. The lower limit of the weight-average molecular weight of polymer (A-1) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight-average molecular weight of polymer (A-1) is, for example, 100,000, 50,000, 30,000, 20,000, or 10,000.

[0058] <<Polymer (A-2)>> Polymer (A-2) is a polymer having a structural unit represented by the following formula (A2). (In formula (A2), L ２１ L represents a single bond or a linking group. ２２ (This represents a monovalent group having polymerizable multiple bonds.)

[0059] L in the structural unit represented by formula (A2) ２１ -L ２２ For example, it has a structure represented by any of the above formulas (1a) to (1f).

[0060] L ２１ When it is a linking group, there are no particular restrictions on the number of carbon atoms in the linking group, but for example, 1 to 30 are possible. ２１ Examples include linking groups having a structure obtained by the reaction of an epoxy group and a nucleophilic functional group. Examples of nucleophilic functional groups include one or more selected from the group consisting of hydroxyl groups, amino groups, and thiol groups. The hydroxyl group may or may not be a phenolic hydroxyl group.

[0061] L ２１ Examples include the following linking groups (L21-1) to (L21-4). (*1 represents the bond with the cyclohexane ring. *2 represents L) ２２ (This represents a combination of two elements.)

[0062] L ２２ This is a monovalent group having a polymerizable multiple bond. This monovalent group may be the polymerizable multiple bond itself. The number of carbon atoms in this monovalent group is not particularly limited, but for example, it may be 1 to 40 or 1 to 30. ２２ Examples include the monovalent group shown in Group (L2) above.

[0063] Examples of structural units represented by formula (A2) include the structural unit represented by the following formula (A2-1). (In formula (A2-1), L ２２ (This represents a monovalent group having polymerizable multiple bonds.)

[0064] Polymer (A-2) is, for example, a polymer having a structural unit represented by formula (A-E) as shown below, to which a carboxylic acid (L ２２ It can be obtained by reacting with -COOH. (In the formula, L ２２ (This represents a monovalent group having polymerizable multiple bonds.)

[0065] The polymer having the structural unit represented by formula (A-E) may be a commercially available product. An example of a commercially available product is EHPE3150 (trade name, manufactured by Daicel Corporation).

[0066] The molecular weight of polymer (A-2) is not particularly limited. The lower limit of the weight-average molecular weight of polymer (A-2) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight-average molecular weight of polymer (A-2) is, for example, 100,000, 50,000, 30,000, 20,000, or 10,000.

[0067] <<Polymer (A-3)>> Polymer (A-3) is a polymer having hydroxyl groups bonded to carbon atoms in the main chain and polymerizable multiple bonds. The carbon atoms to which these hydroxyl groups are bonded are, for example, secondary carbon atoms and tertiary carbon atoms. Polymer (A-3) may have, for example, an ether group (-O-), an ester group (-COO-), a nitrogen atom, and a sulfur atom in its main chain.

[0068] The polymer (A-3) has, for example, a structural unit represented by the following formula (A3). (In formula (A3), A independently represents a hydrogen atom, a methyl group, or an ethyl group. Q １ and Q ２ Each of these independently represents a divalent group. However, Q １ and Q ２ At least one of them has polymerizable multiple bonds.

[0069] <<<Q １ and Q ２ >>> Q １ and Q ２ Q is a divalent group, １ and Q ２ It is not particularly limited as long as at least one of them has polymerizable multiple bonds. １ and Q ２ The number of carbon atoms in each atom can be independently, for example, 1 to 50, 1 to 40, 2 to 40, 3 to 40, 3 to 30, or 3 to 20. １ and Q ２ Each of these may independently have at least one of an ether group (-O-), an ester group (-COO-), a nitrogen atom, and a sulfur atom.

[0070] Q １ and Q ２ Examples include the divalent group represented by the following formula (A3-1-1), the divalent group represented by the following formula (A3-1-2), and the divalent group represented by the following formula (A3-1-3). (In formula (A3-1-1), X １X represents a divalent organic group having 1 to 50 carbon atoms. n1 and n2 each independently represent 0 or 1. In formula (A3-1-2), X ２ This represents a group represented by one of the following formulas (A3-1-2-1) to (A3-1-2-3). １ and Z ２ Each of these independently represents a single bond or a group represented by the following formula (A3-1-2-4). In formula (A3-1-3), X １ * represents a divalent organic group with 1 to 50 carbon atoms. n1 and n2 independently represent 0 or 1. * represents a bond. (In formula (A3-1-2-1) to formula (A3-1-2-3), R １ and R ２ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, and each of the alkyl groups having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may independently be substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups having 2 to 6 carbon atoms, alkoxyalkoxy groups having 2 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms, and R １ and R ２ These may be bonded to each other to form a ring with 3 to 6 carbon atoms. ３represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group. The alkyl group having 1 to 6 carbon atoms, the benzyl group, and the phenyl group may each be independently substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, alkoxyalkyl groups having 2 to 6 carbon atoms, alkoxyalkoxy groups having 2 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. * represents a bond. *1 represents a bond that bonds to a carbon atom in formula (A3-1-2). *2 represents a bond that bonds to a nitrogen atom in formula (A3-1-2). (In formula (A3-1-2-4), m represents an integer from 1 to 4. n represents an integer from 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents a bond with the nitrogen atom in formula (A3-1-2). *4 represents a bond.)

[0071] X in equations (A3-1-1) and (A3-1-3) １ X represents a divalent organic group with 1 to 30 carbon atoms. １ The number of carbon atoms may be 1 to 25 or 1 to 20. １ It may or may not have an aromatic ring. An example of an aromatic ring is an aromatic hydrocarbon ring. １ For example, the group may represent an alkylene group, a phenylene group, a naphthylene group, anthrylene group, a group represented by the following formula (A3-1-1-1), or a group represented by the following formula (A3-1-1-2), and the phenylene group, the naphthylene group, and the anthrylene group may each be independently substituted with a group or atom selected from the group consisting of alkyl groups having 1 to 30 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, cyano groups, hydroxyl groups, ester groups, amide groups, amino groups, thiol groups, and alkylthio groups having 1 to 10 carbon atoms. (In formulas (A3-1-1-1) and (A3-1-1-2), Rａ Each of these independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. W represents a single bond, -CH ２ -, -C(CH ３ ) ２ -, -C (CF ３ ) ２ -, -CO-, -O-, -S-, or SO ２ - Represents a divalent group containing a fluorene ring. m independently represents 0 or 1. n independently represents an integer from 0 to 4.

[0072] Examples of divalent groups containing a fluorene ring include the following divalent groups: (* indicates a bond. The ring may be substituted with a substituent.)

[0073] Examples of divalent groups represented by formula (A3-1-1) that have polymerizable multiple bonds include the following divalent groups: (* indicates a link.)

[0074] Examples of divalent groups represented by formula (A3-1-2) that have polymerizable multiple bonds include the following divalent groups: (* indicates a link.)

[0075] Examples of divalent groups represented by formula (A3-1-1) that do not have polymerizable multiple bonds include the following divalent groups: (* indicates a link.)

[0076] Examples of divalent groups represented by formula (A3-1-3) that do not have polymerizable multiple bonds include the following divalent groups: (* indicates a link.)

[0077] X in a divalent group represented by formula (A3-1-1) that does not have polymerizable multiple bonds １For example, the following structures can be cited. (* indicates a link.)

[0078] Examples of divalent groups represented by formula (A3-1-2) that do not have polymerizable multiple bonds include the following divalent groups: (* indicates a link.)

[0079] The molecular weight of polymer (A-3) is not particularly limited. The lower limit of the weight-average molecular weight of polymer (A-3) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight-average molecular weight of polymer (A-3) is, for example, 100,000, 50,000, 30,000, 20,000, or 10,000.

[0080] <<Polymer (A-4)>> Polymer (A-4) is a polydiene having polymerizable multiple bonds, which may be modified.

[0081] The polymer (A-4) may be an unmodified polydiene or a modified polydiene insofar as it has polymerizable multiple bonds.

[0082] Examples of polydienes include polybutadiene, polyisoprene, and polyhexadiene.

[0083] The polymer (A-4) has, for example, at least one selected from the structural units represented by the following formula (A4-1-1) and the structural units represented by the following formula (A4-1-2). The structural unit represented by formula (A4-1-2) may be either a cis or trans isomer.

[0084] The molar ratio (X:Y) of structural units (X) represented by formula (A4-1) and structural units (Y) represented by formula (A41-2) in polymer (A-4) is not particularly limited, but may be 100:0 to 10:90, 95:5 to 10:90, 90:10 to 20:80, 90:10 to 50:50, or 90:10 to 80:20.

[0085] Examples of unmodified polydienes include polybutadienes whose terminals are not modified and which have at least one structural unit selected from the structural units represented by formula (A4-1-1) and the structural unit represented by formula (A4-2-1). Unmodified polybutadienes may be commercially available products. Examples of commercially available products include NISSO-PB B-1000, B-2000, and B-3000 (manufactured by Nippon Soda Co., Ltd.).

[0086] Examples of modified polybutadiene include polybutadiene with hydroxyl groups at both ends and epoxidized polybutadiene. Polybutadiene with hydroxyl groups at both ends may be commercially available. Examples of commercially available products include NISSO-PB G-1000, G-2000, G-3000 (manufactured by Nippon Soda Co., Ltd.) and Poly bd R-45HT, R-15HT (manufactured by Idemitsu Kosan Co., Ltd.). Epoxidized polybutadiene may also be commercially available. Examples of commercially available products include NISSO-PB JP-100, JP-200 (manufactured by Nippon Soda Co., Ltd.) and Epolid PB3600 (manufactured by Daicel Corporation).

[0087] The polymer (A-4) preferably has at least one selected from the structural units represented by the following formula (A4-2-1) and the structural units represented by the following formula (A4-2-2). (In formulas (A4-2-1) and (A4-2-2), L ４１ Each of these independently represents a monovalent group having polymerizable multiple bonds.

[0088] L ４１ The number of carbon atoms is not particularly limited, but for example, it may be 1 to 30 or 1 to 20.

[0089] L ４１ A monovalent group represented by the following formula (A4-3) is preferred. (In formula (A4-3), X represents an ether bond (-O-), a thioether bond (-S-), a -NH-, an ester bond, or an amide bond.) ４２ (This represents a monovalent group having polymerizable multiple bonds.)

[0090] L ４２ The number of carbon atoms is not particularly limited, but for example, it may be 1 to 30 or 1 to 10. ４１ If the number of carbon atoms is between 1 and 30, for example, L ４２ The number of carbon atoms in L is between 1 and 29. ４１ If the number of carbon atoms is between 1 and 20, for example, L ４２ The number of carbon atoms is between 1 and 19.

[0091] L ４１ and L ４２ Polymerizable multiple bonds in this context include carbon-carbon double bonds, carbon-carbon triple bonds, carbon-nitrogen double bonds, and carbon-nitrogen triple bonds.

[0092] L in formula (A4-3) ４２ Examples include the monovalent group shown in Group (L2) above.

[0093] An example of a structural unit represented by formula (A4-2-1) can be obtained, for example, by the following reaction using epoxidized polybutadiene. (wherein X and L) ４２ X and L in equation (A4-3) are... ４２ These are the same as above.

[0094] An example of a structural unit represented by formula (A4-2-2) can be obtained, for example, by the following reaction using epoxidized polybutadiene. (wherein X and L) ４２ X and L in equation (A4-3) are... ４２ These are the same as above.

[0095] The above reaction can be carried out in the presence of a catalyst, for example, tetrabutylphosphonium bromide.

[0096] During the above reaction, polymerization inhibitors may be used to suppress the polymerization of polymerizable multiple bonds. Examples of polymerization inhibitors include hydroquinone, methoquinone, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical.

[0097] The lower limit of the weight-average molecular weight of polymer (A-4) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight-average molecular weight of polymer (A-4) is, for example, 30,000, 20,000, or 10,000.

[0098] <<Polymer (A-5)>> Polymer (A-5) is a polymer having a structural unit represented by the following formula (A5). (In formula (A5), Ar represents a group having a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, or fluorene ring.) ５１ R represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether-bond-containing group. ５２ L represents a divalent group which may have substituents. ５１ L represents a single bond or a linking group. ５２ represents a group having polymerizable multiple bonds. m represents an integer from 0 to 4. n represents an integer from 0 to 3. However, m + n is 4 or less. However, when m is 0, R ５２ It has polymerizable multiple bonds.

[0099] As Ar, benzene rings and naphthalene rings are preferred.

[0100] R ５１ Preferably, the group is an alkyl or alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group.

[0101] R ５２ R represents a divalent group which may have substituents. ５２ The number of carbon atoms can range from 1 to 30, for example. ５２ The compound may or may not have a ring structure. Examples of ring structures include aromatic hydrocarbon rings and aliphatic hydrocarbon rings. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and fluorene rings. An example of an aliphatic hydrocarbon ring is a dicyclopentadiene ring. ５２ R may have a group having a polymerizable multiple bond, or it may not have a group having a polymerizable multiple bond. ５２ If R has a group having polymerizable multiple bonds, ５２ For example, a divalent group represented by the following formula (A52a) can be cited. (In formula (A52a), R ５２ａ L represents a hydrocarbon group having an aromatic ring and containing 6 to 30 carbon atoms. ５１ and L ５２ These are L in formula (A5), respectively. ５１ and L ５２ This is synonymous with L. ５１ R ５２ａ It bonds to the aromatic ring inside. p represents an integer from 0 to 3. * represents a bond.

[0102] R ５２ａ Examples of aromatic rings in this context include benzene rings and naphthalene rings. ５２ａ Examples include the following groups (trivalent to pentavalent groups). (In the formula, * represents a bond. *1 is L) ５１ (This represents a bonding operation that connects to [another element].)

[0103] R ５２ Examples include the following divalent groups. (In the formula, L ５１ and L５２ These are L in formula (A5), respectively. ５１ and L ５２ This is synonymous with [the above]. (* represents a binding action.)

[0104] L ５１ When it is a linking group, there are no particular restrictions on the number of carbon atoms in the linking group, but for example, 1 to 20 can be cited. ５１ Examples include linking groups having a structure obtained by the reaction of an epoxy group and a nucleophilic functional group. Examples of nucleophilic functional groups include one or more selected from the group consisting of hydroxyl groups, amino groups, thiol groups, and amide groups. The hydroxyl group may or may not be a phenolic hydroxyl group.

[0105] L ５１ Examples include the following linking groups (L51-1) to (L51-4). (*1 represents a bond with Ar. *2 represents L) ５２ (This represents a combination of two elements.)

[0106] L ５２ This is a monovalent group having a polymerizable multiple bond. This monovalent group may be the polymerizable multiple bond itself. The number of carbon atoms in this monovalent group is not particularly limited, but for example, it may be 1 to 40, 1 to 30, or 1 to 20. ５２ Examples include the monovalent group shown in Group (L2) above.

[0107] Polymer (A-5) can be obtained, for example, by reacting a polymer having a structural unit represented by the following formula (A5m) or formula (A5n) with a compound represented by any of the following formulas (L52-1) to (L52-4). (In formulas (A5m) and (A5n), Ar, R ５１ , R ５２ , m, and n are Ar, R in formula (A5), respectively. ５１ , R ５２ , m, and n are synonymous. In equation (A5n), R ５２ａ R in equation (A52a) ５２ａThis is synonymous. p represents an integer from 0 to 3. In equations (L52-1) to (L52-4), L ５２ L in formula (A5) ５２ (This is synonymous.) The hydroxyl group in formula (L52-2) is usually a phenolic hydroxyl group.

[0108] Examples of structural units represented by formula (A5m) or formula (A5n) include the following structural units.

[0109]

[0110] Polymers having structural units represented by formula (A5m) or formula (A5n) may be commercially available products. Examples of commercially available products include EPPN-201, EOCN-104S, EOCN-103S, EOCN-102S, EOCN-1020-70, EOCN-1020-55, NC-2000-L, NC-3000-L, NC-3000-H, NC-3100, NC-7000L, NC-7000H, NC-3500, XD-1000, EPPN-502H, EPPN-502HY, EPPN-501H, FAE-2500 (all manufactured by Nippon Kayaku Co., Ltd.), EPICLON® HP-5000, EPICLON® HP-7200 (manufactured by DIC Corporation), and others.

[0111] Examples of polymers (A-5) include polymers having structural units represented by the following formula. (In the formula, L ５１ , and L ５２ These are L in formula (A5), respectively. ５１ , and L ５２ (This is synonymous with...)

[0112] L ５１ For example, L51-1 is a linking group. ５２ This is, for example, a monovalent group as shown in Group (L2) above.

[0113] The molecular weight of polymer (A-5) is not particularly limited. The lower limit of the weight-average molecular weight of polymer (A-5) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight-average molecular weight of polymer (A-5) is, for example, 100,000, 50,000, 30,000, 20,000, or 10,000.

[0114] <<Polymer (A-6)>> Polymer (A-6) is a resin (G) having a composite unit structure. The composite unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms. Resin (G) is a resin obtained by a reaction that generates a covalent bond between the carbon atoms constituting the aromatic ring of unit structure (A) and the carbon atoms in unit structure (B). In this specification, resin (G) may be referred to as "novolac resin".

[0115] Resin (G) has polymerizable multiple bonds. Examples of groups having polymerizable unsaturated bonds in resin (G) include the monovalent groups shown in Group (L2) above. Examples of groups having polymerizable unsaturated bonds include the monovalent groups represented below. Note that the group having polymerizable multiple bonds may be the polymerizable multiple bond itself. (* indicates a link.)

[0116] In resin (G), for example, the composite unit structure has polymerizable multiple bonds. In resin (G), the unit structure (A) may have polymerizable multiple bonds, or the unit structure (B) may have polymerizable multiple bonds.

[0117] The unit structure (A) has, for example, at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring. The unit structure (A) does not have heteroatoms as atoms constituting an aromatic ring or atoms bonded to an aromatic ring.

[0118] The unit structure (A) has, for example, a group having a polymerizable multiple bond. In this case, for example, the group having a polymerizable multiple bond is bonded to an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, or a nitrogen atom bonded to an aromatic ring in the unit structure (A). The unit structure (A) has, for example, a group having a polymerizable multiple bond as a substituent (S) described later.

[0119] Unit structure (B) is, for example, a unit structure derived from an aldehyde compound or an aldehyde equivalent. An aldehyde equivalent is an organic compound that enables covalent bonding with an aromatic ring and is an organic compound having a ketone group; an acetal group; a ketal group; a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl group, alkoxy group or halo group bonded to the α-carbon atom of an alkylaryl group; or a carbon-carbon unsaturated bond.

[0120] The unit structure (B) has, for example, a group having a polymerizable multiple bond. The unit structure (B) has, for example, a substituent (S) having a polymerizable multiple bond, as described later.

[0121] [I. Definitions of Terms] In this specification, the definitions of the main terms relating to novolac resin, which is one aspect of the present invention, are described below. Unless otherwise specified, the following definitions of terms apply to novolac resin.

[0122] (I-1) "Novolac Resin" The term "novolac resin" is used in a broad sense to broadly encompass resins formed by the covalent bonding (substitution reaction, addition reaction, condensation reaction, or addition-condensation reaction, etc.) between an organic compound having a functional group that enables covalent bonding with an aromatic ring [for example, an aldehyde group; a ketone group; an acetal group; a ketal group; a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl group, alkoxy group or halo group bonded to the α-carbon atom (benzyl carbon atom, etc.) of an alkylaryl group; a carbon-carbon unsaturated bond such as that found in divinylbenzene or dicyclopentadiene] and an aromatic ring in a compound having an aromatic ring (preferably having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as atoms constituting the aromatic ring or atoms bonded to the aromatic ring).

[0123] Therefore, the novolac resin referred to in this specification is formed by linking multiple compounds having aromatic rings, through which an organic compound containing carbon atoms derived from the functional group (sometimes called a "linked carbon atom") forms a covalent bond with the aromatic ring in a compound having an aromatic ring via the linked carbon atoms, thereby forming a resin.

[0124] In this specification, the terms unit structure (A) and unit structure (B) are used to refer to the unit structures constituting "novolac resin". Unit structure (A) is a unit structure derived from a compound having an aromatic ring. Unit structure (B) is a unit structure derived from a compound having a functional group that enables covalent bonding with the aromatic ring of unit structure (A).

[0125] (I-2) "Residue" A "residue" refers to an organic group in which a hydrogen atom bonded to a carbon atom or heteroatom (such as a nitrogen atom, oxygen atom, or sulfur atom) is replaced by a bonding position. It may be a monovalent or polyvalent group. For example, replacing one hydrogen atom with one bonding position results in a monovalent organic group, while replacing two hydrogen atoms with bonding positions results in a divalent organic group.

[0126] (I-3) "Aromatic Ring" (Aromatic Group, Aryl Group, Arylene Group) The term "aromatic ring" is a concept that encompasses aromatic hydrocarbon rings, aromatic heterocycles, and their residues [sometimes called "aromatic group," "aryl group" (in the case of a monovalent group), or "arylene group" (in the case of a divalent group)], and includes not only monocyclic (aromatic monocyclic) but also polycyclic (aromatic polycyclic). In the case of a polycyclic, at least one monocycle is an aromatic monocycle, but the remaining monocycles that form a fused ring with the aromatic monocycle may be monocyclic heterocycles (heteromonocycles) or monocyclic alicyclic hydrocarbons (alicyclic monocycles). In this specification, heteroaryl groups are included in aryl groups. Heteroarylene groups are included in arylene groups.

[0127] Aromatic rings include aromatic hydrocarbon rings such as benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, cumene, anthracene, phenanthrene, triphenylene, benzoanthracene, pyrene, chrysene, fluorene, biphenyl, corannellene, perylene, fluorantene, benzo[k]fluorantene, benzo[b]fluorantene, benzo[gh]perylene, coronene, dibenzo[g,p]chrysene, acenaphthylene, acenaphthene, naphthacene, pentacene, cyclooctatetraene, and more typically aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and pyrene; and furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, pyro Aromatic heterocyclic compounds such as furan, thiophene, pyrrole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindolefluorene, bisindolebenzofluorene, bisindoledibenzofluorene, purine, quinoline, isoquinoline, chromene, thiantrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, and indolocarbazole are examples, but are not limited to these.

[0128] Aromatic rings (e.g., benzene rings, naphthalene rings, etc.) may optionally have substituents, but examples of such substituents include the following atoms and groups: • Halogen atoms • Saturated or unsaturated linear, branched or cyclic hydrocarbon groups (-R) which may be interrupted once or more by oxygen atoms in the hydrocarbon chain. ａ ) (including alkyl groups, alkenyl groups, and alkynyl groups (e.g., propargyl groups), and aryl groups, which may be interrupted once or more by oxygen atoms in the middle of the hydrocarbon chain.), -OR (where R is the hydrocarbon group -R) ａ (Represents:) ・Aryloxy group・-NH ２ , -NHR or -NR ２ (The two Rs may be the same or different from each other), where R is the hydrocarbon group -R ａ Represents: hydroxyl group, hydroxyalkyl group, carboxyl group, formyl group, cyano group, nitro group, ester group (for example, -CO ２ R or -OCOR, where R is the hydrocarbon group -R ａ (This represents...) ・Amide group [for example, -NHCOR, -CONHR, -NRCOR (the two Rs may be the same or different) or -CONR ２ (The two Rs may be the same or different from each other), where R is the hydrocarbon group -R ａ This represents: 】 ・Sulfonyl-containing group (e.g., -SO ２ R, where R is the hydrocarbon group -R ａ ) Or it represents a hydroxyl group -OH. ) ・Thiol group (-SH) ・Sulfide-containing group (-SR, where R is the hydrocarbon group -R) ａ (This represents...) ・Organic group containing an ether bond [R １１ -O-R １１ (R １１ Each of these independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, anthranyl group, or a pyrenyl group. ) Residues of ether compounds represented by ; for example, organic groups containing ether bonds, including methoxy, ethoxy, and phenoxy groups.

[0129] The term "aromatic ring" further includes organic groups having a fused ring of one or more aromatic rings (such as benzene, naphthalene, anthracene, and pyrene) and one or more aliphatic or heterocyclic rings. Examples of aliphatic rings include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene, while examples of heterocyclic rings include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0130] An "aromatic ring" may also be an organic group having a structure in which two or more aromatic rings are linked by a divalent linking group. Examples of divalent linking groups include alkylene groups, arylene groups, -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２ - are some examples. In addition, the divalent linking group may be a divalent group obtained by removing one hydrogen atom from any substituent of the aromatic ring mentioned above.

[0131] (I-4) "Heterocycle" The term "heterocycle" encompasses both aliphatic heterocycles and aromatic heterocycles, and includes not only monocyclic (heteromonocyclic) but also polycyclic (heteropolycyclic) compounds. In the case of polycyclic compounds, at least one monocycle is a heteromonocycle, but the remaining monocycles may be aromatic hydrocarbon monocycles or alicyclic monocycles. Examples of aromatic heterocycles can be found in (I-3) above. Similar to the aromatic rings in (I-3) above, they may have substituents.

[0132] (I-5) "Non-aromatic ring" (aliphatic ring) When the "non-aromatic ring" is a monocyclic ring, the "non-aromatic monocyclic ring" refers to a monocyclic hydrocarbon that does not belong to the aromatic group, and is typically a monocyclic alicyclic compound. It may also be called an aliphatic monocyclic ring (which may include aliphatic heterocyclic rings, and may contain unsaturated bonds as long as it does not belong to the aromatic compound). Similar to the aromatic ring in (I-3) above, it may have substituents.

[0133] Examples of non-aromatic monocyclic compounds (aliphatic rings, aliphatic monocyclic compounds) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0134] When the "non-aromatic ring" is polycyclic, "non-aromatic polycyclic" refers to a polycyclic hydrocarbon that does not belong to the aromatic group, and is typically a polycyclic alicyclic compound. It may also be called an aliphatic polycyclic [which may include aliphatic heterocyclics (where at least one of the monocyclic rings is an aliphatic heterocyclic ring), or it may contain unsaturated bonds as long as it does not belong to the aromatic compound]. It includes non-aromatic dicyclic, non-aromatic tricyclic, and non-aromatic tetracyclic compounds.

[0135] When "non-aromatic ring" refers to a bicyclic non-aromatic ring, it is a fused ring composed of two monocyclic hydrocarbons that do not belong to the aromatic group, and is typically a fused ring of two alicyclic compounds. In this specification, it may also be called an aliphatic bicyclic ring (which may include aliphatic heterocyclic rings, and may contain unsaturated bonds as long as they do not belong to the aromatic group). Examples of non-aromatic bicyclic rings include bicyclopentane, bicyclooctane, and bicycloheptene.

[0136] When "non-aromatic ring" refers to a tricyclic compound, it is a fused ring composed of three monocyclic hydrocarbons that do not belong to the aromatic group. Typically, it is a fused ring of three alicyclic compounds (each of which may be a heterocyclic compound, and may contain unsaturated bonds as long as they do not belong to the aromatic group). Examples of non-aromatic tricyclic compounds include tricyclooctane, tricyclononane, and tricyclodecane.

[0137] When "non-aromatic ring" refers to a tetracyclic compound, it is a fused ring composed of four monocyclic hydrocarbons that do not belong to the aromatic group. Typically, it is a fused ring of four alicyclic compounds (each of which may be a heterocyclic compound, and may contain unsaturated bonds as long as they do not belong to the aromatic group). Examples of non-aromatic tetracyclic compounds include hexadecahydropyrene.

[0138] (I-6) "Carbon atoms constituting a ring (part)" means carbon atoms constituting a hydrocarbon ring (which may be an aromatic ring, an aliphatic ring, or a heterocycle) in an unsubstituted state.

[0139] (I-7) A "hydrocarbon group" is a group formed by removing one or more hydrogen atoms from a hydrocarbon, and such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0140] (I-8) In the chemical structural formulas showing the unit structure of novolac resin in this specification, bonds (indicated by *) may be shown for convenience, but unless otherwise specified, such bonds can take any bondable position in the unit structure and do not limit the bondable position in the unit structure in any way.

[0141] <<<Resin (G)>>> Resin (G) has a composite unit structure. The composite unit structure has a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms.

[0142] The composite unit structure of resin (G) can be represented, for example, by the following formula (AB). (In equation (AB), A represents unit structure (A), and B represents unit structure (B).)

[0143] <<<<<A-1: Unit Structure (A)>>>>> Unit structure (A) has an aromatic ring. Unit structure (A) may have, for example, at least one of the following: an oxygen atom constituting the aromatic ring, a sulfur atom constituting the aromatic ring, an oxygen atom bonded to the aromatic ring, a nitrogen atom constituting the aromatic ring, and a nitrogen atom directly bonded to the aromatic ring. Unit structure (A) does not have to have heteroatoms as, for example, atoms constituting the aromatic ring and atoms bonded to the aromatic ring.

[0144] The number of carbon atoms in the unit structure (A) is not particularly limited, but for example, it is 4 to 100, and preferably 4 to 50.

[0145] Preferably, such aromatic ring has 4 to 30 carbon atoms, more preferably 4 to 24 carbon atoms.

[0146] Preferably, such aromatic rings are one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings; or fused rings of a benzene ring, naphthalene ring, anthracene ring, pyrene ring and a heterocycle or aliphatic ring (such as a fluorene ring, benzofluorene ring, dibenzofluorene ring, indole ring, carbazole ring, indrocarbazole ring, etc.).

[0147] The aromatic ring may optionally have substituents, but from the viewpoint of polymerization reactivity, the substituent may contain the minimum necessary amount of heteroatoms. Furthermore, two or more aromatic rings may be linked by a linking group, and the linking group may contain the minimum necessary amount of heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and the like.

[0148] The "aromatic ring" may contain at least one heteroatom selected from N, S, and O on, within, or between the rings.

[0149] Examples of heteroatoms that may be contained on the ring include nitrogen atoms in amino groups (e.g., propargylamino group) and cyano groups; oxygen atoms in oxygen-containing substituents such as formyl group, hydroxyl group, carboxyl group, alkoxy group, alkenyloxy group, alkynyloxy group (e.g., propargyloxy group), and aryloxy group; and nitrogen and oxygen atoms in oxygen-containing substituents and nitrogen-containing substituents such as nitro group. Examples of heteroatoms that may be contained within the ring include oxygen atoms in furan and xanthene, nitrogen atoms in carbazole and pyrrole, and sulfur atoms in phenothiazine. Examples of heteroatoms that may be contained in the linking group of two or more aromatic rings include -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO ２Examples of atoms contained in the compound include nitrogen atoms, oxygen atoms, and sulfur atoms. In this specification, "atoms constituting an aromatic ring" is synonymous with "atoms contained within the ring." "Atoms bonded to an aromatic ring" refers, for example, to "atoms or groups contained on the ring that are directly bonded to the ring" and "atoms contained between rings that are directly bonded to the ring." For example, the atoms constituting a benzene ring are carbon atoms. For example, the atoms constituting a pyrrole ring are carbon atoms and nitrogen atoms. For example, the oxygen atom of the hydroxyl group in phenol is not an atom constituting an aromatic ring. For example, the oxygen atom of the hydroxyl group in phenol is an atom bonded to a benzene ring and is an atom of a group contained on a benzene ring that is directly bonded to the benzene ring.

[0150] <<<<<A-2: Examples of skeletons constituting unit structure (A)>>>>> Unit structure (A) has, for example, a skeleton having aromatic rings.

[0151] Preferred aromatic ring skeletons include aromatic amine skeletons, nitrogen-containing aromatic heterocyclic skeletons, and phenol skeletons.

[0152] The unit structure (A) is, for example, a residue obtained by removing two hydrogen atoms from a skeleton having an aromatic ring. The skeleton having an aromatic ring is derived, for example, from a compound having an aromatic ring used in the synthesis of resin (G). The skeleton having an aromatic ring is, for example, a residue obtained by removing two hydrogen atoms from a compound having an aromatic ring used in the synthesis of resin (G).

[0153] The aromatic ring skeleton may have substituents. Examples of substituents include halo groups (halogen atoms), alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, hydroxyalkyl groups, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, ether-bond-containing groups, etc. Examples of alkyl groups include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. Examples of alkenyl groups include linear, branched, or cyclic alkenyl groups having 2 to 10 carbon atoms. Examples of alkoxy groups include groups represented by -OR, where R is a saturated or unsaturated linear, branched, or cyclic hydrocarbon group (-R) which may be interrupted once or more times by an oxygen atom in the hydrocarbon chain. ａ ) represents. Examples of the number of carbon atoms in an alkoxy group include 1 to 20. Examples of aryl groups include aryl groups with 6 to 30 carbon atoms. Examples of aryloxy groups include aryloxy groups with 6 to 30 carbon atoms. Examples of amino groups include -NH ２ , -NHR or -NR ２ A group represented by the hydrocarbon group -R is an example. Here, R is the hydrocarbon group -R ａ Represents -NR ２ In this, the two Rs may be the same or different. Examples of hydroxyalkyl groups include linear, branched, or cyclic hydroxyalkyl groups having 1 to 20 carbon atoms. Examples of ester groups include -CO ２ A group represented by R or -OCOR is an example. Here, R is the hydrocarbon group -R ａ This represents the amide group, which can be -NHCOR, -CONHR, -NRCOR, or -CONR. ２ A group represented by the hydrocarbon group -R is an example. Here, R is the hydrocarbon group -R ａ This represents a group, and if there are two Rs, the two Rs may be the same or different. Examples of sulfonyl-containing groups include -SO ２A group represented by R is an example. Here, R is the hydrocarbon group -R ａ Alternatively, it represents a hydroxyl group -OH. Examples of sulfide-containing groups include groups represented by -SR, where R is the hydrocarbon group -R. ａ This represents the ether bond-containing group, R １１ -O-R １１ Examples include residues of ether compounds containing an ether bond represented by . Here, R １１ Each of these independently represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group or an ethyl group, or an aryl group, such as a phenyl group, a naphthyl group, anthranyl group, or a pyrenyl group. The ether bond-containing group may be an organic group containing an ether bond, such as a methoxy group, an ethoxy group, or a phenoxy group.

[0154] <<<<<<A-2-1: Aromatic Amine Skeleton>>>>>> An aromatic amine skeleton refers to a skeleton having an aromatic ring and a nitrogen atom bonded to the aromatic ring but not constituting a ring. Examples of aromatic amine skeletons include those represented by the following formulas (A-1a) to (A-1c). As will be described later, in unit structure (A), the hydrogen atom of the NH group may be replaced by a substituent. Examples of substituents include those described in (I-3) "Aromatic Ring" above, those described in (A-2) "Examples of Skeletons Constituting Unit Structure (A)" above, and substituents (S) represented by the following formulas (S1) to (S7). (In formulas (A-1a) to (A-1c), Ar １１ Each of these independently represents a residue of an aromatic ring. １１ Each of these independently represents a hydrogen atom or an aromatic ring residue.

[0155] Ar １１ and R １１ Examples of aromatic rings in the residues of the aromatic ring include aromatic rings represented by the following formula (G1). These aromatic rings may have substituents.

[0156] <<<<<<A-2-2: Nitrogen-containing aromatic heterocyclic skeleton>>>>>> A nitrogen-containing aromatic heterocyclic skeleton refers to a skeleton having an aromatic heterocyclic ring in which nitrogen atoms are present as atoms constituting the heterocyclic ring. Examples of nitrogen-containing aromatic heterocyclic rings include pyrrole rings, indole rings, carbazole rings, pyridine rings, acridine rings, phenoxazine rings, and phenothiazine rings. These nitrogen-containing aromatic heterocyclic rings may have substituents. Examples of nitrogen-containing aromatic heterocyclic skeletons include skeletons represented by the following formulas (A-2a), (A-2b-1), (A-2b-2), (A-2c-1), (A-2c-2), (A-2c-3), (A-2c-4), (A-2d), (A-2e), (A-3a), or (A-3b). As will be described later, in unit structure (A), the hydrogen atoms of the NH group may be replaced by substituents. Examples of substituents include those described in (I-3) "Aromatic Ring" above, those described in (A-2) "Examples of Skeletons Constituting Unit Structure (A)" above, and substituents (S) represented by formulas (S1) to (S7) described later. (In the formula, Ar ２１ Each of these independently represents a residue of an aromatic ring. ２１ Each of these independently represents a hydrogen atom or an aromatic ring residue. ２２ Each of these independently represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or an aromatic ring residue. Two adjacent R ２２ These may together form an unsaturated aliphatic ring. Note that one of the unsaturated bonds in an unsaturated aliphatic ring refers to the unsaturated bond constituting the pyrrole ring. Each R independently represents a hydrogen atom, an aromatic ring residue, or a bond with L. L represents a single bond or a linking group. n1 represents 1, and n2 represents 1 or 2. In formulas (A-2b-2) and (A-2c-4), when L is a single bond, the substructures (In1) and (In2), and the substructures (Ca1) and (Ca2), are bonded by two nitrogen atoms or two Ar ２１ They are bonded together by bonding with each other, or by bonding between nitrogen atoms and Ar２１ The bond is formed by the combination of and . In formulas (A-2b-2) and (A-2c-4), when L is a linking group, L is N or Ar ２１ (It is connected to this.)

[0157] Ar ２１ , R ２１ , R ２２ Examples of aromatic rings in the residues of the aromatic ring of R include aromatic rings represented by the following formula (G2). These aromatic rings may have substituents.

[0158] Two adjacent R ２２ Examples of unsaturated aliphatic rings formed by these elements together include the following rings. These aliphatic rings may have substituents.

[0159] Examples of linking groups in L include saturated hydrocarbon groups with 1 to 5 carbon atoms and an (n1 + n2) valency, and residues obtained by removing (n1 + n2) hydrogen atoms from an aromatic ring.

[0160] <Formula (A-2d)> (In formula (A-2d), R １１ Each of these independently represents a hydrogen atom or an aromatic group, and Ar is an aromatic ring portion, each independently representing a benzene ring, a fused ring composed of two to three benzene rings, or a structure represented by the following formula (Ar01), X ０ These are single bonds, -O-, -S-, -NR １２ - or -CR １３ R １４ - represents R １２ R １１ Same as or different from R １１ It is the same as the definition of R １３ and R １４ Each of the following represents a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms, where n is 1 or 2. When n is 1, Z represents a monovalent organic group, and when n is 2, Z represents a divalent organic group.

[0161] Furthermore, in the unit structure (A), R in formula (A-2d) １１R may be a substituent. １１ If R is a substituent or aromatic group, １１ For example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) are further substituted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, an aryl group, or a halo group, or (iii) may have its hydrocarbon chain further interrupted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, or an arylene group.

[0162] An example of a skeleton represented by formula (A-2d) is the skeleton represented by the following formula (A-2d-1). (R in equation (A-2d-1)) １１ , Ar, and X ０ These are R in equation (A-2d), respectively. １１ , Ar, and X ０ This is synonymous with R. ２１ (These are aryl groups having 6 to 30 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, or alkynyl groups having 2 to 10 carbon atoms.)

[0163] In formulas (A-2d) and (A-2d-1), Ar is, for example, a benzene ring or a naphthalene ring. The Ar in formulas (A-2d) and (A-2d-1) may also be a structure represented by the following formula (Ar01). (R in equation (Ar01)) １１ａ R in equation (A-2d-1) １１ It is synonymous with R ２１ａ R in equation (A-2d-1) ２１ It is synonymous with Ar ａ This is equivalent to Ar in equation (A-2d-1), and X ０ａ X in equation (A-2d-1) ０ This is equivalent to: In formula (Ar01), two carbon atoms a and b, b and c, or c and d, X in formula (A-2d) or formula (A-2d-1) ０(It forms a fused ring with a monocyclic portion containing the element.)

[0164] Here, X ０ The monocyclic portion containing refers to the monocyclic portion represented by the following formula (AP011) in formula (A-2d).

[0165] The skeleton represented by formula (A-2d) is preferably the skeleton represented by formula (A-2d-1) above, the skeleton represented by formula (A-2d-2) below, or the skeleton represented by formula (A-2d-3) below. (In equations (A-2d-2) and (A-2d-3), R １１ , Ar, and X ０ These are R in equation (A-2d), respectively. １１ , Ar, and X ０ This is synonymous with L. L represents a single bond or a divalent linking group, and examples of divalent linking groups include -O-, -S-, and -SO. ２ -, -CO-, -CONH-, -COO-, -NR １０１ -, - (CR １０２ R １０３ )m １ -, - (Ar １０１ )m ２ -ien-CH ２ - (Ar １０１ )m ２ -CH ２ R represents - or - (cyclo-R). １０１ , R １０２ , and R １０３ Each of these independently represents a hydrogen atom; a hydrocarbon group having 1 to 5 carbon atoms; or an aryl group having 6 to 30 carbon atoms; m １ represents integers from 1 to 10. And Ar １０１ Each of these independently represents an arylene group having 6 to 30 carbon atoms; m ２ R represents an integer from 1 to 3, which is the number of aromatic rings that are bonded to each other by single bonds. "cyclo-R" represents a divalent alicyclic hydrocarbon group of 5 to 8 members, preferably 6 to 8 members, which may form a fused ring with one or two benzene rings or naphthalene rings. ２２Each of these independently represents an arylene group having 6 to 30 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, or an alkynylene group having 2 to 10 carbon atoms, which may be substituted.

[0166] <Formula (A-2e)> (In formula (A-2e), L represents a single bond or a divalent linking group between any two carbon atoms constituting each azaaryl condensed ring, R １１ and R ２１ Each of these independently represents a hydrogen atom or an aromatic ring residue, and R １２ and R ２２ Each of these independently represents a substituent, and n1 and n2 independently represent R １２ and R ２２ This represents the number of substituents, and may be 0. １ and Ar ２ Each of these is a benzene ring or a fused ring composed of two or three benzene rings, each independently forming a fused ring with the pyrrole ring portion in formula (A-2e).

[0167] Furthermore, in the unit structure (A), R in formula (A-2e) １１ and R ２１ R may be a substituent. １１ and R ２１ If R is a substituent or an aromatic group residue, １１ and R ２１ For example, (i) a methylol group, (ii) an aryl group having 6 to 30 carbon atoms, or (iii) a linear, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms, provided that (ii) and (iii) are further substituted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, an aryl group, or a halo group, or (iii) may have its hydrocarbon chain further interrupted with an oxygen atom-containing substituent, a sulfur atom-containing substituent, a nitrogen atom-containing substituent, or an arylene group.

[0168] In formula (A-2e), L is a single bond or a divalent linking group. L may be bonded to any carbon atom constituting each azaaryl fused ring, and Ar １ Ar ２ That is, in the azaaryl condensed ring and It may be bonded to aromatic carbon atoms that make up the ring, but it is preferable that it is bonded to carbon atoms that make up the pyrrole ring portion in the azaaryl condensed ring.

[0169] Preferred linking groups (L) include -O-, -S-, and -SO ２ -, -CO-, -CONH-, -COO-, -NH-, -(CR １０２ R １０３ )m １ -, - (Ar １０１ )m ２ -ien-CH ２ - (Ar １０１ )m ２ -CH ２ Selected from the group consisting of - and - (cyclo-R) -. １０２ and R １０３ Each of these independently represents a hydrogen atom; a hydrocarbon group with 1 to 5 carbon atoms; or an aryl group with 6 to 30 carbon atoms; m １ represents integers from 1 to 10. And Ar １０１ Each of these represents an arylene group with 6 to 30 carbon atoms; m ２ is an integer from 1 to 3, which is the number of aromatic rings that are bonded to each other by single bonds. "cyclo-R" represents a divalent alicyclic hydrocarbon group of 5 to 8 members, preferably 6 to 8 members, which may form a fused ring with one or two benzene rings or naphthalene rings.

[0170] <Formulas (A-3a) and (A-3b)> (In the formula, Ar ３１ and Ar ３２ Each of these independently represents a residue in an aromatic ring, or together with the carbon atoms bonded to them, they represent a residue in an aromatic ring. X represents -O, -S-, -NH-, -CH ２ -ien-CH ２ -CH ２ (This represents -, or -CH=CH-.)

[0171] Ar ３１ and Ar ３２ Examples of aromatic rings in the residues of the aromatic ring include the aromatic ring represented by the aforementioned formula (G1). ３１ and Ar ３２ Examples of aromatic rings formed by these rings together with the carbon atoms bonded to them include fluorene rings, benzofluorene rings, and dibenzofluorene rings.

[0172] Examples of skeletons represented by formula (A-2a) include the following. The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the NH group may be replaced by substituents. The same applies to the following skeletons.

[0173] Other examples of nitrogen-containing aromatic heterocyclic skeletons include the following:

[0174] <<<<<<A-2-3: Phenol Skeleton>>>>> The phenol skeleton refers to a skeleton having an aromatic ring and a hydroxyl group bonded to the aromatic ring. There is no particular limit to the number of hydroxyl groups bonded to the aromatic ring of the phenol skeleton; there may be one or more. If there are more, there may be 2 to 10 or 2 to 8. If there are more, the hydroxyl groups may be bonded to the same aromatic ring (e.g., a benzene ring) or to different aromatic rings. As will be described later, in the unit structure (A), the hydrogen atoms of the hydroxyl groups bonded to the aromatic ring may be replaced by substituents. Examples of substituents include the substituents described in (I-3) "Aromatic Ring" above, the substituents described in (A-2) "Examples of Skeletons Constituting the Unit Structure (A)" above, and substituents (S) represented by formulas (S1) to (S7) described later.

[0175] Examples of phenol skeletons include those represented by the following formula (A-4). The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the hydroxyl group may be replaced by substituents. The same applies to the following skeletons. (In the formula, n1, n2, n4, n5, n6, and n9 each independently represent an integer between 1 and 4. n3a, n3b, n7a, n7b, n8a, and n8b each independently represent an integer between 0 and 4. However, the sum of n3a and n3b ​​is 1 or greater, the sum of n7a and n7b is 1 or greater, and the sum of n8a and n8b is 1 or greater.)

[0176] Furthermore, examples of phenol skeletons include those represented by the following formulas (A-5a), (A-5b), (A-5c), or (A-5d). (In the formula, Ar ４１ Each of these independently represents a residue of an aromatic ring. k1 and k2 each independently represent an integer of 1 or 2. １ is -O-, -CO-, -S-, -SO ２ - Represents an alkylene group which may be substituted with a halogen atom. When k1 is 1, X ２１ These are single bonds, -O-, -CO-, -S-, -SO ２ - Represents an alkylene group which may be substituted with a halogen atom. When k2 is 1, X ２２ These are single bonds, -O-, -CO-, -S-, -SO ２ - Represents an alkylene group which may be substituted with a halogen atom. When k1 is 2, X ２１ This represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom. When k2 is 2, X ２２ This represents a trivalent saturated hydrocarbon group which may be substituted with a halogen atom. １ This represents a trivalent saturated hydrocarbon group. ２represents a tetravalent saturated hydrocarbon group. m1 and m2 each independently represent integers from 0 to 3, provided that the sum of m1 and m2 is 1 or greater. m3 to m5 each independently represent integers from 0 to 3, provided that the sum of m3 to m5 is 1 or greater. m6 to m8 each independently represent integers from 0 to 3, provided that the sum of m6 to m8 is 1 or greater. m9 to m12 each independently represent integers from 0 to 3, provided that the sum of m9 to m12 is 1 or greater.

[0177] Ar ４１ Examples of aromatic rings in the aromatic ring residues include aromatic rings represented by the following formula (G3). These aromatic rings may have substituents.

[0178] X １ , and X ２ Examples of the number of carbon atoms in the alkylene group, which may be substituted with halogen atoms, include 1 to 20. Examples of the structure of the alkylene group include linear, branched, and cyclic structures, as well as combinations of two or more of these. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0179] Y １ , and Y ２ Examples of the number of carbon atoms in a saturated hydrocarbon group include 1 to 20. Examples of the structure of a saturated hydrocarbon group include linear, branched, and cyclic structures, as well as combinations of two or more of these.

[0180] Furthermore, examples of phenol skeletons include those represented by the following formulas (A-6a), (A-6b-1), (A-6b-2), (A-6c), or (A-6d). (In formulas (A-6a), (A-6b-1), (A-6b-2), (A-6c), and (A-6d), Ar ５１Each of the following independently represents a residue in an aromatic ring. Each of n11 independently represents an integer from 1 to 4. Each of the following independently represents either 0 or 1. When p is 1, the oxygen atom forms a bridging structure between aromatic rings as an ether bond; when p is 0, there is no ether bond that forms a bridging structure between aromatic rings. L represents a single bond or a divalent linking group.

[0181] Ar ５１ Examples of aromatic rings in include those represented by the above formula (G1), with benzene rings and naphthalene rings being preferred. Examples of L include a divalent group obtained by removing two hydrogen atoms from the following structure.

[0182] n11, for example, can each independently represent either 1 or 2.

[0183] Furthermore, examples of phenol skeletons include those represented by the following formulas (A-7a), (A-7b), or (A-7c). (In formula (A-7a), formula (A-7b), and formula (A-7c), Ar ６１ Each of these independently represents a residue in an aromatic ring. n21 independently represents an integer from 1 to 4.

[0184] Ar ６１ Examples of aromatic rings in this formula include those represented by formula (G1) above, with benzene rings and naphthalene rings being preferred. n21 independently represents, for example, 1 or 2.

[0185] Furthermore, examples of phenol skeletons include those represented by the following formulas: (A-8a-1), (A-8a-2), (A-8b), (A-8c), (A-8d), (A-8e), (A-8f), (A-8g-1), or (A-8g-2). (In equations (A-8a-1), (A-8b), (A-8c), (A-8e), (A-8f), (A-8g-1), and (A-8g-2), n31 independently represents an integer from 1 to 4. In equation (A-8a-2), n32 and n33 independently represent integers from 0 to 4, provided that the sum of n32 and n33 is 1 or greater. In equation (A-8d), n32 and n33 independently represent integers from 0 to 4, provided that the sum of n32 and n33 is 1 or greater. In equation (A-8b), X １ X represents -O- or -NH-. In formula (A-8d), X ２ These are -O-, -S-, or -CH ２ It represents -. In equation (A-8e), X ３ is -S-, -CH ２ It represents - or -NH-. In formula (A-8f), X ４ represents -CO- or -O-, X ５ is, -CH ２ (Represents - or -O-.)

[0186] n31, for example, independently represents 1 or 2. n32 and n33, for example, independently represent 0, 1, or 2.

[0187] Examples of skeletons represented by formula (A-4) include the following. The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the hydroxyl group may be replaced by substituents. The same applies to the following skeletons.

[0188] Other skeletons of the phenol skeleton include, for example, the following:

[0189] Furthermore, the hydrogen atoms of NH in the aromatic ring skeleton, the hydrogen atoms of the hydroxyl group bonded to the aromatic ring in the aromatic ring skeleton, and the hydrogen atoms bonded to the aromatic ring in the aromatic ring skeleton may be replaced with substituents. Examples of such substituents include substituents (S) represented by the following formulas (S1) to (S7).

[0190] (In formulas (S1) to (S7), R ｓａ R represents a monovalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms. ｓｂ Each of these independently represents a single bond or a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｃ Each of these independently represents a divalent non-aromatic hydrocarbon group having 1 to 10 carbon atoms. ｓｄ ａｌｋｙｎｙｌ Each of these independently represents an alkynyl group with 2 to 4 carbon atoms. ｓａ Each of these independently represents a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms. ｓｂ Each of these independently represents a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms. ｓａ and X ｓｂ Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or X ｓａ and X ｓｂ The carbon atom bonded to the hydroxyl group, together with the carbon atom, forms a carbonyl group. n represents an integer from 0 to 5. * represents a bond.

[0191] <R ｓａ > R ｓａ Examples of monovalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms and monovalent unsaturated hydrocarbon groups having 2 to 10 carbon atoms. Monovalent unsaturated hydrocarbon groups having 2 to 10 carbon atoms have one or more carbon-carbon multiple bonds. When a monovalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, or all be carbon-carbon triple bonds, or a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated.

[0192] <R ｓｂ , and R ｓｃ > R ｓｂ , and R ｓｃExamples of divalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms include alkylene groups having 1 to 10 carbon atoms and divalent unsaturated hydrocarbon groups having 2 to 10 carbon atoms. Divalent unsaturated hydrocarbon groups having 2 to 10 carbon atoms have one or more carbon-carbon multiple bonds. When a divalent unsaturated hydrocarbon group having 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, the two or more carbon-carbon multiple bonds may all be carbon-carbon double bonds, or all be carbon-carbon triple bonds, or a mixture of carbon-carbon double bonds and carbon-carbon triple bonds. The two or more carbon-carbon multiple bonds may or may not be conjugated. ｓｂ , and R ｓｃ Examples include the following groups: (* indicates a link.)

[0193] <R ｓｄ ａｌｋｙｎｙｌ > R ｓｄ ａｌｋｙｎｙｌ This represents an alkynyl group having 2 to 4 carbon atoms. Examples of alkynyl groups having 2 to 4 carbon atoms include the ethynyl group, the 1-propynyl group, and the propargyl group (2-propynyl group).

[0194] <Ar ｓａ > Ar ｓａ In this context, a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon with 6 to 20 carbon atoms. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0195] <Ar ｓｂ > Ar ｓｂ In this context, a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue obtained by removing two hydrogen atoms from an aromatic hydrocarbon with 6 to 20 carbon atoms. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, and biphenyl.

[0196] < X ｓａ and Xｓｂ > X ｓａ and X ｓｂ Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include monovalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms and monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms. Examples of monovalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms. Monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms are residues obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6 to 20 carbon atoms. Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, perinaphthane, pyrene, fluorene, and biphenyl.

[0197] Examples of substituents represented by formula (S1) include the following groups. (* indicates a link.)

[0198] Examples of substituents represented by formula (S2) include the following groups. (* indicates a link.)

[0199] Examples of substituents represented by formula (S3) include the following groups. (* indicates a link.)

[0200] Examples of substituents represented by formula (S4) include the following groups. (* indicates a link.)

[0201] Examples of substituents represented by formula (S5) include the following groups. (* indicates a link.)

[0202] Examples of substituents represented by formula (S6) include the following groups. (* indicates a link.)

[0203] Examples of substituents represented by formula (S7) include the following groups. (* indicates a link.)

[0204] Other substituents include, for example, the following groups: (* indicates a link.)

[0205] The unit structure (A) is preferably at least one selected from the following. Note that the positions of the two bonds shown in each unit structure described below are for convenience only and can extend from any possible carbon atom, and do not limit their positions.

[0206] (Example of a unit structure composed of an aromatic amine skeleton) -NH- can also take the form of a structure in which the hydrogen atom on N is substituted.

[0207]

[0208] (Examples of unit structures composed of nitrogen-containing aromatic heterocyclic skeletons)

[0209] (Examples of unit structures composed of a phenol skeleton)

[0210] <<<B-1: Unit Structure (B)>>> Unit structure (B) has one or more carbon atoms. Unit structure (B) is a unit structure derived, for example, from an aldehyde compound or an aldehyde equivalent. Unit structure (B) is one or more unit structures that include a linked carbon atom [see (I-1) above] bonded to the aromatic ring in unit structure (A), and includes, for example, structures represented by formulas (B1), (B2), or (B3) shown below. Unit structure (B) can link two unit structures (A) by covalent bonding with unit structure (A).

[0211] <<<<<B-2: Formula (B1)>>>>> The unit structure (B) includes, for example, the structure represented by the following formula (B1). The unit structure (B) may also be the structure represented by the following formula (B1). In formula (B1), R and R' each independently represent a hydrogen atom, an aromatic ring having 6 to 30 carbon atoms which may have substituents, a heterocycle having 3 to 30 carbon atoms which may have substituents, or a linear, branched, or cyclic alkyl group having 10 or fewer carbon atoms which may have substituents. R and R' may together with the carbon atoms they bond to to form a ring structure. * represents a bond.

[0212] Examples of substituents include hydroxyl groups, carboxyl groups, formyl groups, nitro groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, cyano groups, groups in which the H of a hydroxyl group is replaced by the above substituent (S), and halo groups.

[0213] Furthermore, the two bonds in formula (B1) can each be covalently bonded to the respective aromatic rings in the two unit structures (A).

[0214] In the definitions of R and R' in formula (B1), refer to (I-3) and (I-4) above for "aromatic ring" and "heterocyclic ring."

[0215] In the definitions of R and R' in formula (B1), "alkyl group" refers to, for example, methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1- Ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group Tyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2Examples include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group.

[0216] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenantrenyl, naphthalenyl, and pyrenyl.

[0217] Examples of structures having a ring structure formed by R and R' together with the carbon atoms to which they are bonded include the structure represented by the following formula. (In the formula, Ar represents each residue of an aromatic ring independently. The carbon atoms indicated by * are the carbon atoms bonded to R and R' in formula (B1).)

[0218] Examples of Ar aromatic rings include the aromatic ring represented by formula (G1).

[0219] The unit structure (B) containing the structure represented by formula (B1) is derived, for example, from an aldehyde compound or a ketone compound. Examples of aldehyde compounds include the compound represented by the following formula (B-1a). Examples of ketone compounds include the compound represented by the following formula (B-1b). (In formulas (B-1a) and (B-1b), R and R' are equivalent to R and R' in formula (B1), respectively, except that R is an atom other than a hydrogen atom. In formula (B-1b), R and R' may, together with the carbon atom to which they are bonded, form a ring structure.)

[0220] For example, when obtaining resin (G), the carbonyl groups in formulas (B-1a) and (B-1b) are converted to *-C-* in formula (B1).

[0221] A few specific examples of unit structures (B) that include the structure represented by formula (B1) are given below. * basically indicates the bonding site with unit structure (A). Needless to say, it is also acceptable for the example structure to be included as part of the whole.

[0222]

[0223] <<<<<B-3: Formula (B2)>>>>> The unit structure (B) includes, for example, the structure represented by the following formula (B2). The unit structure (B) may also be the structure represented by the following formula (B2).

[0224] In formula (B2), Z ０ This represents an aromatic ring residue, an aliphatic ring residue, or an organic group consisting of two or more aromatic or aliphatic rings linked by a single bond, which may have substituents and have 6 to 30 carbon atoms. Examples of organic groups consisting of two or more aromatic or aliphatic rings linked by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and bicyclohexyl.

[0225] Examples of substituents include hydroxyl groups, carboxyl groups, formyl groups, nitro groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, cyano groups, groups in which the H of a hydroxyl group is replaced by the above substituent (S), and halo groups.

[0226] J １ and J ２ Each of these independently represents a divalent organic group which may have direct bonds or substituents. Preferably, the divalent organic group is a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an aryl group (such as a phenyl group or a substituted phenyl group), or a halo group (for example, fluorine). Examples of linear alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0227] The unit structure (B) containing the structure represented by formula (B2) is derived, for example, from compounds having a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom, compounds having a hydroxyl group, alkoxy group, or halo group bonded to the α-carbon (benzyl carbon atom, etc.) of an alkylaryl group, or compounds having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0228] Examples of compounds having a hydroxyl group or alkoxy group bonded to a secondary or tertiary carbon atom include the compound represented by the following formula (B-2a). Examples of compounds having a hydroxyl group, alkoxy group, or halo group bonded to the α-carbon atom (benzyl carbon atom, etc.) of an alkylaryl group include the compound represented by the following formula (B-2b). Examples of compounds having two carbon-carbon double bonds include the compound represented by the following formula (B-2c) or (B-2d). (In formula (B-2a), formula (B-2b), and formula (B-2b), J １ J ２ , and Z ０ J in equation (B2) １ J ２ , and Z ０ These are synonymous. In equation (B-2a), X ａ , and X ｂ Each of these independently represents a hydroxyl group or an alkoxy group bonded to a secondary or tertiary carbon atom. In formula (B-2b), Y ａ , and Y ｂ Each of these independently represents a hydroxyl group, alkoxy group, or halo group bonded to the α-carbon (benzyl carbon atom, etc.) of the alkylaryl group. In formula (B-2d), n represents an integer from 0 to 4.

[0229] For example, when obtaining resin (G), X in formula (B-2a) ａ -J １ However, in formula (B2) *-J １ It is converted to J. ２ -X ｂ However, J in formula (B2) ２-* is converted to For example, when obtaining resin (G), Y in formula (B-2b) ａ -J １ However, in formula (B2) *-J １ It is converted to J. ２ -Y ｂ However, J in formula (B2) ２ -It will be converted to *.

[0230] An example of formula (B-2a) is the following compound.

[0231] An example of formula (B-2b) is the following compound.

[0232] An example of formula (B-2c) is the following compound.

[0233] A few specific examples of unit structures containing the structure represented by formula (B2) are given below. * indicates the bonding site with unit structure (A). Needless to say, any unit structure may include the example structure as part of the whole.

[0234]

[0235] <<<<B-4: Formula (B3)>>>> In formula (B3), Z is a monocyclic or dicyclic, tricyclic, or tetracyclic fused ring having 4 to 25 carbon atoms, which may have substituents. The number of carbon atoms referred to herein means only the number of carbon atoms constituting the ring skeleton of the monocyclic or dicyclic, tricyclic, or tetracyclic fused ring, excluding substituents, and does not include the number of heteroatoms constituting the heterocyclic ring if the monocyclic or fused ring is a heterocyclic ring.

[0236] The monoring described above is a monoring whose number of π electrons does not satisfy 4n+2 (where n is a non-negative integer) (hereinafter sometimes referred to as a "non-Hückel monoring"); at least one of the monorings constituting the diring, triring, and tetraring described above is a monoring whose number of π electrons does not satisfy 4n+2 (where n is a non-negative integer), and the remaining monorings may be monorings whose number of π electrons satisfies 4n+2 (where n is a non-negative integer) or monorings whose number of π electrons does not satisfy 4n+2 (where n is a non-negative integer).

[0237] The monocyclic, or bicyclic, tricyclic, or tetracyclic fused ring, may further form fused rings with one or more aromatic rings to form a quintuple or higher fused ring, wherein the number of carbon atoms in the quintuple or higher fused ring is preferably 40 or less. The number of carbon atoms referred to herein means only the number of carbon atoms constituting the ring skeleton of the quintuple or higher fused ring, excluding substituents, and does not include the number of heteroatoms constituting the heterocycle when the quintuple or higher fused ring is a heterocycle.

[0238] X and Y are the same or different, -CR ３１ R ３２ - Represents the base, R ３１ and R ３２ Each of these terms may be the same or different, representing a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0239] x and y represent the numbers X and Y, respectively, and each can independently represent either 0 or 1.

[0240] In formula (B3) And in formula (B3) At least one of these is bonded to any of the carbon atoms constituting the non-Hückel monoring of Z (referred to as "carbon Z") (when x=1, y=1) or extends from carbon Z (when x=0, y=0).

[0241] For example, in formula (B3) It is bonded to any of the carbon atoms constituting the non-Hückel monoring of Z (referred to as "carbon atom 1") (when x=1) or extends from carbon atom 1 (when x=0),

[0242] In formula (B3) It is bonded to any of the carbon atoms constituting the non-Hückel monoring of Z (referred to as "carbon atom 2") (when y=1) or extends from carbon atom 2 (when y=0), and carbon atom 1 and carbon atom 2 may be the same or different. If they are different, they may belong to the same non-Hückel monoring or to different non-Hückel monorings.

[0243] Furthermore, formula (B3) may optionally include linked carbon atoms other than carbon atoms 1 and 2. Note that if Z is a tricyclic or multicyclic fused ring, the permutational positional relationship between carbon atoms 1 and 2 in formula (B3) and one or two non-Hückel monorings to which they belong, and the remaining monoring, is arbitrary. Similarly, if carbon atoms 1 and 2 belong to different non-Hückel monorings (referred to as "non-Hückel monoring 1" and "non-Hückel monoring 2," respectively), the permutational positional relationship between non-Hückel monoring 1 and non-Hückel monoring 2 in the fused ring is also arbitrary. Some specific examples of organic groups containing the structure represented by formula (B3) are given below. The bonding site with unit structure A is not particularly limited. Needless to say, the structure may include the example structure as part of the whole.

[0244] Although examples with more than two bonding sites (*) are included, these surplus bonding sites can be used for bonding to aromatic rings in other polymer chains, crosslinking, etc., or they may be hydrogen bonds.

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251] In formula (B3) below, And in formula (B3) We will now describe the case where only one of the atoms is bonded to any of the carbon atoms constituting the non-Hückel monoring of Z (referred to as "carbon atom Z") (when x=1, y=1) or extends from carbon atom Z (when x=0, y=0). As a more specific structure of equation (B3) in this case, for example, in the following equation (C31), p and k can be bonding hands. １ and k ２ Of these, p and k １ , or p and k ２ This can result in the unit structure (B) represented by formula (B3). The remaining bonds are connected to hydrogen atoms.

[0252] Furthermore, in the following equation (C32), p and k can be bonding points. １ , k ２ And of m, p and k １ , p and k ２ Alternatively, p and m can form a unit structure (B) represented by formula (B3). The remaining bonds are bonded to hydrogen atoms.

[0253] A few more specific examples of formula (B3) corresponding to formula (C31) or formula (C32) are given below. * indicates the bonding site with the unit structure (A).

[0254] In equation (B3), bonds extend from the aromatic rings in these structures to other unit structures (for example, unit structure (A)), but these bonds are omitted in the specific examples below. Needless to say, any unit structure may include the example structure as part of the whole. Furthermore, in the above specific example, if there are no bonds from the aromatic ring, it can be considered a specific example of a polymer end.

[0255] Novolac resins having the structure represented by formula (AB) can be prepared by known methods. For example, ring-containing compounds represented by H-A-H and OHC-B, O=C-B, RO-B-OR, RO-CH ２ -B-CH ２It can be prepared by condensing oxygen-containing compounds represented by -OR, etc. Here, A and B are the same as above. R represents a hydrogen atom, a halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0256] The ring-containing compound and the oxygen-containing compound may be used individually, or two or more may be used in combination. In this condensation reaction, the oxygen-containing compound can be used in a ratio of 0.1 to 10 moles, preferably 0.1 to 2 moles, per mole of the ring-containing compound.

[0257] Examples of catalysts used in the condensation reaction include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoromethanesulfonic acid; and carboxylic acids such as formic acid and oxalic acid. The amount of catalyst used varies depending on the type of catalyst used, but is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass, per 100 parts by mass of the cyclic compound (total of multiple types).

[0258] The condensation reaction can be carried out without a solvent, but it is usually carried out using a solvent. The solvent is not particularly limited as long as it can dissolve the reaction substrate and does not inhibit the reaction. Examples include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, tetrahydropyran, dioxane, 1,2-dichloromethane, 1,2-dichloroethane, toluene, N-methylpyrrolidone, and dimethylformamide. The condensation reaction temperature is usually 40°C to 200°C, preferably 100°C to 180°C. The reaction time varies depending on the reaction temperature, but is usually 5 minutes to 50 hours, preferably 5 minutes to 24 hours.

[0259] The weight-average molecular weight of polymer (A-6) (novolac resin according to one embodiment of the present invention) is usually 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0260] <<Compound (A-7)>> Compound (A-7) is a compound having three or more polymerizable multiple bonds. Compound (A-7) is different from polymers (A-1) to (A-6) described above. An example of compound (A-7) is the compound represented by the following formula (A7-1). (In equation (A7-1), n ​​represents an integer from 3 to 6. X represents an n-valence base. L ７１ L represents a single bond or a divalent group. ７２ (This represents a monovalent group having polymerizable multiple bonds.)

[0261] <<<n and X>>> In formula (A7-1), n ​​may be 3, 4, 5, or 6. In formula (A7-1), X represents an n-valent group. The number of carbon atoms in X is not particularly limited and may be, for example, 1 to 60, 1 to 40, or 1 to 30. In formula (A7-1), X may or may not have a ring structure. Examples of ring structures include aromatic rings and aliphatic rings. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings. Another example of a ring structure is an isocyanurate ring.

[0262] When n is between 3 and 4, X can be a structure represented by any of the following equations (A7-2-1) to (A7-2-9). (* represents a bond. a, b, c, and d represent 0 or 1, and a + b + c + d = 1.)

[0263] <<<L ７１ >>> L in formula (A7-1) ７１ For example, a divalent group represented by the following formula (L71-1) can be cited. (In formula (L71-1), X ａ This represents an oxygen atom or a sulfur atom. ａ * represents a single bond or a carbonyl group. n represents 0 or 1. *1 represents the bond with X in formula (A7-1). *2 represents L ７２ (This represents a combination of two elements.)

[0264] <<<L ７２ >>> L in formula (A7-1) ７２ Examples include the monovalent group shown in Group (L2) above.

[0265] The compound represented by formula (A7-1) can be obtained, for example, by the reaction of an epoxy compound having three or more epoxy groups with a compound represented by any of the following formulas (L72-1) to (L72-3). (In formulas (L72-1) to (L72-3), L ７２ L in equation (A7-1) ７２ (This is synonymous.) The hydroxyl group in formula (L72-2) is usually a phenolic hydroxyl group.

[0266] Examples of epoxy compounds include the following: (* represents a bond. a, b, c, and d represent 0 or 1, and a + b + c + d = 1.)

[0267] Examples of compound (A-7) include the following compounds. (In the formula, R ａ represents a hydrogen atom, a methyl group, or a benzyl group. * represents a bond. a, b, c, and d represent 0 or 1, and a + b + c + d = 1.

[0268] The content of the compound or polymer (A) of the present invention in the resist underlayer film forming composition is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of suitably obtaining the effects of the present invention, 50% to 99.9% by mass is preferred, 60% to 99.5% by mass is more preferred, and 80% to 99% by mass is particularly preferred, relative to the film constituent components. Film constituent components refer to components other than the solvent in the resist underlayer film forming composition.

[0269] <Onium Salt (B)> The onium salt is at least one of aromatic sulfonium salts, aromatic iodonium salts, and ammonium salts. In this invention, pyridinium salts are not included in ammonium salts. As the onium salt, for example, an onium salt used in resist compositions in the field of photolithography, which is called a photoacid generator or photodegradable quencher, can be used. The onium salt (B) may also be an intramolecular salt.

[0270] As the onium salt (B), from the viewpoint of suitably obtaining the effects of the present invention, an onium salt represented by the following formula (B1) and an intramolecular salt represented by the following formula (B2) are preferred. (In formula (B1), Y １ｃ ＋ represents a monovalent aromatic sulfonium cation or a monovalent aromatic iodonium cation. In formula (B1), Y １ａ － X represents a monovalent anion. In formula (B2), X ＋ is, S ＋ Or I ＋ This represents each R １１１ is, X ＋ Bonded to each other, each independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted polycyclic or monocyclic cycloalkyl group having 3 to 30 carbon atoms, an optionally substituted polycyclic or monocyclic aryl group having 6 to 30 carbon atoms, or a combination containing at least one of the above, where n1 represents 1 or 2, X ＋ I ＋ When representing, n1 represents 1, X ＋ is S ＋ When representing, n1 represents 2, X ＋ is S ＋ When representing two R １１１ They may be together forming a ring, Ar １１１ L represents a divalent aromatic group having 6 to 30 carbon atoms, which may have substituents. １１１ and L １１２Each of these independently represents a divalent linking group having 1 to 30 carbon atoms, which may contain a heteroatom comprising O, S, N, F, or a combination of at least one of these. １１１ R represents a divalent monocyclic, polycyclic, or fused polycyclic alicyclic group having 5 to 30 carbon atoms, which may contain a heteroatom including O, S, N, F, or a combination of at least one of these, and may have substituents. １１１ and Ar １１１ They may also form a ring together, Z － (where n represents an oxygen-containing anionic group, n2, n3, and n4 each independently represent 0 or 1, and n represents 0 or 1.)

[0271] Aromatic sulfonium cations and aromatic iodonium cations may have substituents at any position. Furthermore, the number of substituents is not particularly limited.

[0272] <<Y １ｃ ＋ >> Y in equations (B1) and (B2) １ｃ ＋ Examples include a monovalent aromatic sulfonium cation represented by the following formula (B1-1) or a monovalent aromatic iodonium cation represented by the following formula (B1-2). (In formula (B1-1), R １０１ , R １０２ , and R １０３ Each of these independently represents one of the following (i) to (iv), R １０１ and R １０２ , R １０２ and R １０３ , or R １０１ and R １０３ They may be bonded to each other to form a ring. However, R １０１ , R １０２ , and R １０３At least one of the following formulas (ii) to (iv): (i) A linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, which may be substituted and may contain a halogen atom, a carbonyl group, an ester group, an ether group, a thioether group, an amide group, a lactone ring, or an aryl group (ii) An aromatic hydrocarbon group which may be substituted and may contain -S- (iii) An aralkyl group having 7 to 20 carbon atoms which may be substituted (iv) A thiophenyl group which may be substituted In formula (B1-2), R １０４ and R １０５ Each independently represents an aryl group having 6 to 20 carbon atoms, which may have substituents, and R １０４ and R １０５ (They may be joined to each other to form a ring.)

[0273] Examples of aromatic hydrocarbon rings in aromatic hydrocarbon groups and aralkyl groups include benzene rings and naphthalene rings. Examples of the number of carbon atoms in the aromatic hydrocarbon group in (ii) above include 6 to 30.

[0274] Examples of substituents (X) in (i) to (iv) above include halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, allyl groups, vinyl groups, alkenyl groups, alkynyl groups, amide groups, alkoxy groups, carboxyl groups, ester groups, acetyl groups, aldehyde groups, epoxy groups, carbonyl groups, thiol groups, thioether groups, sulfonyl groups, sulfide groups, sulfo groups, ether groups, linear, branched, or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 20 carbon atoms, monohalogenated methylene groups (-CHX-), dihalogenated methylene groups (-CX-) ２ -), monohalogenated methyl group (-CH ２ X), dihalogenated methyl group (-CHX ２ ), trihalogenated methyl group (-CX ３ Examples include substituents such as halogen atoms (where X represents a halogen atom) or combinations thereof.

[0275] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1) include the monovalent aromatic sulfonium cation represented by the following formula (B1-1-1). (In formula (B1-1-1), each Ar independently represents an aromatic hydrocarbon group which may have substituents.)

[0276] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0277] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1-1) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0278] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1) include the monovalent aromatic sulfonium cation represented by the following formula (B1-1-2). (In formula (B1-1-2), Ar independently represents an aromatic hydrocarbon group which may have substituents.)

[0279] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0280] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1-2) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0281] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1) include monovalent aromatic sulfonium cations represented by the following formula (B1-1-3). (In formula (B1-1-3), Ar independently represents an optionally substituted aromatic hydrocarbon group. Z represents -O-, -S-, -SO ２ -, -CR ２ - (R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may have substituents), or -NH-.)

[0282] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include a benzene ring and a naphthalene ring. A hydrocarbon group having 1 to 20 carbon atoms may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include a benzene ring and a naphthalene ring.

[0283] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1-3) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0284] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1) include monovalent aromatic sulfonium cations represented by the following formula (B1-1-4). (In formula (B1-1-4), Ar represents an aromatic hydrocarbon group which may have substituents. ａ Each of these independently represents a hydrogen atom or a substituent.

[0285] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0286] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1-4) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0287] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1) include the monovalent aromatic sulfonium cation represented by the following formula (B1-1-5). (In formula (B1-1-5), Ar independently represents an aromatic hydrocarbon group which may have substituents. ａ Each of these independently represents a hydrogen atom or a substituent.

[0288] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0289] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1-5) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0290] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1) include the monovalent aromatic sulfonium cation represented by the following formula (B1-1-6). (In formula (B1-1-6), Ar represents an aromatic hydrocarbon group which may have substituents. ｂ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may have substituents. ｂ (It may also form a ring together with -S-.)

[0291] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include a benzene ring and a naphthalene ring. Two R ｂ Examples of rings formed by the combination of -S- include five-membered rings and six-membered rings. The ring may contain atoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. The ring may also have the above substituent (X).

[0292] Examples of monovalent aromatic sulfonium cations represented by formula (B1-1-6) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0293] Examples of monovalent aromatic iodonium cations represented by formula (B1-2) include the monovalent aromatic iodonium cation represented by the following formula (B1-2-1). (In formula (B1-2-1), each Ar independently represents an optionally substituted aromatic hydrocarbon group.)

[0294] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0295] Examples of monovalent aromatic iodonium cations represented by formula (B1-2-1) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0296] Examples of monovalent aromatic iodonium cations represented by formula (B1-2) include the monovalent aromatic iodonium cation represented by the following formula (B1-2-2). (In formula (B1-2-2), each Ar independently represents an optionally substituted aromatic hydrocarbon group.)

[0297] Examples of substituents include the substituent (X) mentioned above. When an aromatic hydrocarbon group has substituents, the number of substituents is not particularly limited. Examples of aromatic hydrocarbon rings in an aromatic hydrocarbon group include benzene rings and naphthalene rings.

[0298] Examples of monovalent aromatic iodonium cations represented by formula (B1-2-2) include the following monovalent cations. (In the formula, X represents each substituent (X) independently.)

[0299] <<Y １ａ － >> Y １ａ － These include halogen anions, cyanide anions, bicarbonate anions, nitrate anions, nitrite anions, and R １０１ SO ３ － or R １０１ CO ２ － (R １０１ R represents a monovalent organic group having 1 to 40 carbon atoms. １０１ The monovalent organic group having 1 to 40 carbon atoms in this compound may or may not have a heteroatom. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms.

[0300] Y １ａ － For example, a monovalent anion represented by the following formula can be cited.

[0301]

[0302]

[0303]

[0304]

[0305]

[0306] <<Intramolecular salt represented by formula (B2)>> X in formula (B2) ＋ is, S ＋ (Sulfur cation) or I ＋ This represents an iodine cation. Note that intramolecular salts are also called zwitterions.

[0307] R in equation (B2) １１１ is, X ＋ Each atom is bonded to a molecule and independently represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted polycyclic or monocyclic cycloalkyl group having 3 to 30 carbon atoms, an optionally substituted polycyclic or monocyclic aryl group having 6 to 30 carbon atoms, or a combination containing at least one of the above. Examples of substituents include the substituent (X) mentioned above.

[0308] In equation (B2), n1 represents either 1 or 2. ＋ I ＋ When representing, n1 represents 1. ＋ is S＋ When representing , n1 represents 2. ＋ is S ＋ When representing two R １１１ They may come together to form a ring. In this case, the two R １１１ These atoms may be directly bonded to form a ring, or they may be bonded via an oxygen atom or a sulfur atom to form a ring.

[0309] Ar in equation (B2) １１１ This represents a divalent aromatic group having 6 to 30 carbon atoms, which may have substituents. Examples of substituents include the substituent (X) mentioned above. Examples of aromatic rings in the aromatic group include aromatic hydrocarbon rings. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings. １１１ and Ar １１１ They may also form a ring together.

[0310] L in equation (B2) １１１ and L １１２ Each of these independently represents a divalent linking group having 1 to 30 carbon atoms. This linking group may contain at least one combination of O, S, N, F, or heteroatoms thereof. １１１ and L １１２ For example, a divalent linking group having 1 to 30 carbon atoms, including -O-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NR-, or -O-C(=O)-NR-. R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may have substituents. Also, L １１２ For example, these may be alkylene groups having 1 to 30 carbon atoms that may have substituents, arylene groups having 6 to 30 carbon atoms that may have substituents, aralkylene groups having 7 to 30 carbon atoms that may have substituents, or combinations containing at least one of these groups.

[0311] M in equation (B2) １１１This represents a divalent monocyclic, polycyclic, or fused polycyclic alicyclic group having 5 to 30 carbon atoms. The divalent group may contain a heteroatom including O, S, N, F, or a combination of at least one of these, and may have substituents. Examples of substituents include the substituent (X) mentioned above. １１１ Examples of such groups include adamantyl groups having 19 or fewer carbon atoms, norbornanyl groups having 19 or fewer carbon atoms, lactone-containing groups having 7 to 20 carbon atoms, steroidal groups having 20 carbon atoms, and nonsteroidal organic groups having 20 or more carbon atoms.

[0312] Also, Z in equation (B2) － This represents an oxygen-containing anionic group. － For example, -C(=O)O － , -SO ２ NH － , -SO ３ － These are some examples.

[0313] Examples of intramolecular salts include the intramolecular salt represented by the following formula (B2-1) and the intramolecular salt represented by the following formula (B2-2). (In formulas (B2-1) and (B2-2), R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , and R ｂ５ Each independently represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, which may contain heteroatoms. Each independently represents an integer from 0 to 5. Each independently represents 0 or 1, except that at least one of m11, m12, and m13 is 1. Each independently represents 0 or 1, except that at least one of m14 and m15 is 1. However, the sum of m1 and m11 is 5 or less. However, the sum of m2 and m12 is 5 or less. However, the sum of m3 and m13 is 5 or less. However, the sum of m4 and m14 is 5 or less. However, the sum of m5 and m15 is 5 or less. If m1 is 2 to 5, two adjacent Rｂ１ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m2 is 2 to 5, two adjacent R ｂ２ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m3 is 2 to 5, two adjacent R ｂ３ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m4 is 2 to 5, two adjacent R ｂ４ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m5 is 2 to 5, two adjacent R ｂ５ These atoms may bond to each other, forming a ring with the carbon atoms to which they are bonded. (n represents 0 or 1.)

[0314] Examples of intramolecular salts represented by formula (B2) include the following compounds:

[0315] As the onium salt (B), an ammonium salt represented by the following formula (B3) is preferred from the viewpoint of suitably obtaining the effects of the present invention. (In formula (B3), R Ｂ３１ Each of these independently represents a hydrogen atom, or an alkyl group, alkenyl group, alkynyl group, aryl group, or aralkyl group which may be substituted with a heteroatom or which may have a heteroatom interposed. Ｂ３１ They may also form a ring structure together. ３ａ － (This represents a monovalent anion.)

[0316] R Ｂ３１ The number of carbon atoms can range from 1 to 20, for example. Ｂ３１ However, in the case of alkyl groups that may be substituted with heteroatoms or may have heteroatoms interposed, the number of carbon atoms in the alkyl group can be, for example, 1 to 10. Ｂ３１ However, in the case of an alkenyl group that may be substituted with a heteroatom or may have a heteroatom interposed, the number of carbon atoms in the alkenyl group can be, for example, 2 to 10. Ｂ３１However, in the case of an alkynyl group that may be substituted with a heteroatom or may have a heteroatom interposed, the number of carbon atoms in the alkynyl group can be, for example, 2 to 10. Ｂ３１ However, in the case of an aryl group that may be substituted with a heteroatom or may have a heteroatom interposed, the number of carbon atoms in the aryl group can be, for example, 6 to 10. Ｂ３１ However, in the case of an aralkyl group that may be substituted with a heteroatom or may have a heteroatom interposed, the number of carbon atoms in the aralkyl group can be, for example, 7 to 10.

[0317] R Ｂ３１ Preferably, the alkyl group has 1 to 3 carbon atoms, or the aralkyl group has 7 to 8 carbon atoms.

[0318] Examples of cations in the ammonium salt represented by formula (B3) include the following cations.

[0319] The monovalent anion (Y) in the ammonium salt represented by formula (B3) ３ａ － For example, Y １ａ － An example of anion is given in the explanation. Also, Y ３ａ － Examples of such anions include the following:

[0320] Y ３ａ － Preferred anions include halogen-containing anions, hydroxide anions, carboxylic acid anions, sulfonate anions, phenol anions, sulfonamide anions, and boron-containing anions.

[0321] The content of the onium salt (B) in the resist underlayer film forming composition is not particularly limited, but is, for example, 0.1% to 30% by mass, preferably 1% to 20% by mass, relative to the compound or polymer (A).

[0322] <Solvent (C)> Solvent (C) is not particularly limited and may be water or an organic solvent. Examples of organic solvents include carboxylic acids having a hydroxyl group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, alkylene glycol monoalkyl ether carboxylic acid esters (monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers).

[0323] Examples of carboxylic acids having a hydroxyl group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, and methyl 2-hydroxy-3-methylbutyrate.

[0324] Examples of linear or cyclic alkyl ketones include methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0325] An example of a cyclic lactone is γ-butyrolactone.

[0326] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutylcarbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether.

[0327] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene glycol monoalkyl ether acetates. Examples of alkylene glycol monoalkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate. Examples of alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0328] These solvents can be used individually or in combination of two or more.

[0329] The mass percentage of the organic solvent in solvent (C) is not particularly limited, but 50% to 100% by mass is preferred.

[0330] The solvent (C) content in the resist underlayer film forming composition is not particularly limited, but is preferably 50% to 99.99% by mass, more preferably 75% to 99.95% by mass, and particularly preferably 90% to 99.9% by mass.

[0331] <Crosslinking Agent> The composition for forming the resist underlayer film may or may not contain a crosslinking agent. The crosslinking agent is not particularly limited. The crosslinking agent has a structure different from the compound or polymer (A) of the present invention.

[0332] As crosslinking agents, aminoplast crosslinking agents and phenoplast crosslinking agents are preferred. Aminoplast crosslinking agents are addition condensates of compounds having amino groups, such as melamine and guanamine, with formaldehyde. Phenoplast crosslinking agents are addition condensates of compounds having phenolic hydroxyl groups with formaldehyde.

[0333] Examples of crosslinking agents include compounds having two or more of the following structures. (In the structure, R １０１ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * represents a bond. The bond is, for example, attached to a nitrogen atom or a carbon atom constituting an aromatic hydrocarbon ring.

[0334] R １０１ Preferably, the group is a hydrogen atom, a methyl group, an ethyl group, or a group represented by the following structure. (In the structure, R １０２ represents a hydrogen atom, a methyl group, or an ethyl group. * represents a bonding bond.

[0335] Preferred crosslinking agents include melamine compounds, guanamine compounds, glycoluryl compounds, urea compounds, and compounds having a phenolic hydroxyl group. These can be used individually or in combination of two or more.

[0336] Examples of melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are methoxymethylated or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are acyloxymethylated or mixtures thereof.

[0337] Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are methoxymethylated or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated or mixtures thereof.

[0338] Examples of glycoluryl compounds include tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof.

[0339] Furthermore, the glycoluryl compound may also be, for example, a glycoluryl derivative represented by the following formula (1E). (In equation (1E), four R １ Each of these independently represents either a methyl group or an ethyl group, R ２ and R ３ Each of these independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group.

[0340] Examples of glycoluryl derivatives represented by formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0341] A glycoluryl derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0342] (In formula (2E), R ２ and R ３ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, R ４ Each of these independently represents an alkyl group having 1 to 4 carbon atoms.

[0343] (In formula (3d), R １ (This represents a methyl group or an ethyl group.)

[0344] Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0345] Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which one to four methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, and tetramethoxyethylurea.

[0346] Examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-1) or (G-2). (In equations (G-1) and (G-2), Q １ R indicates a single bond or an m1-valent organic group. １ and R ４ Each of these represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms. ２ and R ５ Each represents either a hydrogen atom or a methyl group. ３ and R ６ Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. １ is 1 ≤ n １ n is an integer ≤ 3. ２ is 2 ≤ n ２ An integer n ≤ 5 ３ is 0 ≤ n ３ n is an integer ≤ 3. ４ is 0 ≤ n ４ integers ≤ 3, 3 ≤ (n １ +n ２ +n ３ +n ４ This shows integers n ≤ 6. ５ is 1 ≤ n５ n is an integer ≤ 3. ６ is 1 ≤ n ６ An integer n ≤ 4 ７ is 0 ≤ n ７ n is an integer ≤ 3. ８ is 0 ≤ n ８ integers ≤ 3, 2 ≤ (n ５ +n ６ +n ７ +n ８ (This represents an integer between 5 and 2. m1 represents an integer between 2 and 10.)

[0347] Furthermore, examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-3) or (G-4). Compounds represented by formulas (G-1) or (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In equations (G-3) and (G-4), Q ２ R indicates a single bond or an m2 valent organic group. ８ , R ９ , R １１ and R １２ Each represents either a hydrogen atom or a methyl group. ７ and R １０ Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. ９ is 1 ≤ n ９ n is an integer ≤ 3. １０ is 2 ≤ n １０ An integer n ≤ 5 １１ is 0 ≤ n １１ n is an integer ≤ 3. １２ is 0 ≤ n １２ integers ≤ 3, 3 ≤ (n ９ +n １０ +n １１ +n １２ This shows integers n ≤ 6. １３ is 1 ≤ n １３ n is an integer ≤ 3. １４ is 1 ≤ n １４ An integer n ≤ 4 １５ is 0 ≤ n １５ n is an integer ≤ 3. １６ is 0 ≤ n １６integers ≤ 3, 2 ≤ (n １３ +n １４ +n １５ +n １６ ) indicates an integer ≤ 5. m² indicates an integer between 2 and 10. ) Q ２ Examples of m2 valent organic groups in this context include m2 valent organic groups having 1 to 4 carbon atoms.

[0348] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0349] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds. The above compound can be obtained as a product of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. An example of such a product is TMOM-BP, a trade name of Asahi Organic Chemicals Co., Ltd.

[0350] Among these, glycoluryl compounds are preferred, specifically tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof, and tetramethoxymethyl glycoluryl is more preferred.

[0351] The molecular weight of the crosslinking agent is not particularly limited, but it is preferably 1,000 or less.

[0352] The content of the crosslinking agent in the resist underlayer film forming composition is not particularly limited, but is, for example, 1% to 60% by mass, preferably 10% to 50% by mass, relative to the compound or polymer (A) of the present invention.

[0353] <Curing Catalyst> The curing catalyst included as an optional component in the resist underlayer film formation composition is preferably an acid and / or its salt and / or a thermal acid generator. Examples of acids include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 4-hydroxybenzenesulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, etc. Salts of the above-mentioned acids can also be used. The salts are not limited to those mentioned above, but ammonia derivative salts such as trimethylamine salt and triethylamine salt, pyridine derivative salts, morpholine derivative salts, etc. can be suitably used. Examples of such salts include pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium-phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium salt of p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid. Examples of thermal acid generators include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE® CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), and other alkyl organic sulfonates.

[0354] Only one type of curing catalyst may be used, or two or more types may be used in combination.

[0355] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% to 50% by mass relative to the crosslinking agent, preferably 1% to 30% by mass.

[0356] <Surfactants> Surfactants are used, for example, to prevent the occurrence of pinholes and striations, and to further improve the applicability to uneven surfaces. Examples of surfactants include linear or branched alkylbenzene sulfonic acid (e.g., dodecylbenzenesulfonic acid), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is usually 2.0% by mass or less, preferably 1.0% by mass or less, relative to the film components of the resist underlayer film forming composition. These surfactants may be added individually or in combination of two or more types.

[0357] The film constituent components contained in the resist underlayer film forming composition of the present invention, i.e., the components excluding the solvent, are, for example, 0.01% to 10% by mass, and preferably 0.01% to 2% by mass.

[0358] The resist underlayer formation composition is preferably used in EB or EUV lithography. The resist underlayer formation composition is preferably used to form an underlayer of a metal-containing resist.

[0359] A resist underlayer film formation composition, for example, has poor film formation properties if it does not contain onium salt (B). A resist underlayer film formation composition has better film formation properties compared to one that does not contain onium salt (B). Poor film formation properties refer to the inability to obtain a film due to coating defects during spin coating. More specifically, poor film formation properties include the following: - Poor uniformity of film thickness within the silicon wafer surface - Poor surface roughness within the silicon wafer surface - The film is repelled from the coating substrate - Holes or depressions called pinholes are formed in the film - Convex foreign matter is generated in the film - Sea island shapes are formed in the film - The film becomes sharkskin-like and a film without gloss is obtained These can be judged by film thickness measurement using an optical system, observation with an optical microscope or cross-sectional SEM, and observation with AFM. Good film formation properties include the following: - When the uniformity of the film thickness within the silicon wafer is good during spin coating. - When the surface roughness on the silicon wafer surface is good. - When the film is not repelled from the coated substrate. - When no holes or indentations called pinholes are formed in the film. - When no convex foreign matter is generated in the film. - When no sea island shapes are formed in the film. - When a glossy film is obtained without a sharkskin-like texture. These can be judged using the same method as described above.

[0360] When a resist underlayer film is formed in the resist underlayer film with a thickness of 5 nm at a heating temperature of 150°C or 220°C, the film thickness reduction rate (A) relative to the resist solvent is the same when an onium salt (B) is included. １ [%]) and the film thickness reduction rate (A) when onium salt (B) is not included. ２ [%]) preferably satisfies the following relationship (F1): 5% ≤ A２ [%]-A １ [%] (F1) A １ : The rate of reduction in film thickness of the resist underlayer formed from the resist underlayer formation composition (FA1) containing onium salt (B) A ２ : The rate of reduction in the thickness of the resist underlayer film formed from a resist underlayer film forming composition (FA2) having the same composition as resist underlayer film forming composition (FA1) which contains onium salt (B) except for not containing onium salt (B). The conditions for forming the resist underlayer film and the conditions for immersion in the resist solvent include, for example, the conditions described in the [Resist Solvent Dissolution Test] in the examples described later. The resist solvent is a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 7 / 3 (mass ratio). A ２ [%]-A １ [%] is preferably 5% or more, and more preferably 10% or more. A ２ [%]-A １ There is no particular upper limit on [%], for example, A ２ [%]-A １ As a percentage, a value of 50% or less is given. The film thickness reduction rate can be calculated using the following formula: Film thickness reduction rate [%] = [(F ｔ０ -F ｔ１ ) / F ｔ０ )] × 100 F ｔ０ : Film thickness before immersion F ｔ１ : Film thickness after immersion

[0361] (Resist Underlayer Film) The resist underlayer film of the present invention is a cured product of the resist underlayer film forming composition described above. The resist underlayer film can be manufactured, for example, by coating the resist underlayer film forming composition described above onto a semiconductor substrate and firing it.

[0362] Examples of semiconductor substrates to which the resist underlayer film formation composition is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0363] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon films and silicon oxide films (e.g., SiO2). ２ Examples include substrates, silicon nitride films (e.g., SiN substrates), silicon oxide nitride films (e.g., SiON substrates), BPSG (Boro-Phosphoric Acid Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0364] The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate coating method such as a spinner or coater. Then, the resist underlayer film is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes, more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes. Baking may be performed in an atmospheric environment, or N ２ It's fine to do it in a relaxed atmosphere.

[0365] The thickness of the resist underlayer film can be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm ( The wavelengths are 5 nm to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.03 μm (30 nm), 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), or 0.005 μm (5 nm).

[0366] The method for measuring the film thickness of the resist underlayer in this specification is as follows: • Measurement device name: Ellipsometer-type film thickness measuring device RE-3100 (SCREEN Corporation) • SWE (single-wavelength ellipsometer) mode • Arithmetic mean of 8 points (for example, 8 points measured at 1 cm intervals in the wafer X direction)

[0367] (Laminate) The laminate of the present invention comprises a semiconductor substrate and a resist underlayer film of the present invention. Examples of the semiconductor substrate include the semiconductor substrate described above. The resist underlayer film is disposed on top of the semiconductor substrate, for example.

[0368] (Method for manufacturing semiconductor devices, method for forming patterns) The method for manufacturing semiconductor devices of the present invention includes at least the following steps: - A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition of the present invention; and - A step of forming a resist film on the resist underlayer film.

[0369] The pattern formation method of the present invention includes at least the following steps: • A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition of the present invention; • A step of forming a resist film on the resist underlayer film; • A step of irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern; and • A step of etching the resist underlayer film using the resist pattern as a mask.

[0370] Typically, a resist film is formed on top of a resist underlayer. The thickness of the resist film can be, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, or 1,000 nm or less. The lower limits are 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, and 10 nm.

[0371] The resist film formed on the resist underlayer by a known method (e.g., coating and firing of a resist composition) is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation. Both negative-type and positive-type photoresists can be used. In this specification, resists that respond to EB are also referred to as photoresists. Examples of photoresists include positive-type photoresists consisting of a novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator, and resists containing metal elements. Examples include V146G (manufactured by JSR Corporation), APEX-E (manufactured by Cyprey Corporation), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), and AR2772 and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Additionally, examples include fluorine-containing polymer photoresists, such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0372] Also, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 While so-called resist compositions and metal-containing resist compositions such as resist compositions, radiation-sensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions described in JP 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., can be used, they are not limited to these.

[0373] Examples of resist compositions include the following compositions.

[0374] A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protecting groups that are removed by the action of an acid, and a compound represented by the following general formula (121).

[0375] In general formula (121), m represents an integer from 1 to 6. １ and R ２ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. １ is -O-, -S-, -COO-, -SO ２ -, or -SO ３ Represents -. L ２ W represents an alkylene group or single bond which may have substituents. １ This represents a cyclic organic group which may have substituents. ＋ This represents a cation.

[0376] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to the third to seventh period of groups 3 to 15 of the periodic table.

[0377] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) that includes an acid-dissociable group, and an acid generator.

[0378] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. １ R is a hydroxyl group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. If n is 2 or greater, multiple R １ They are the same or different. R ２ R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), ３ R is a monovalent group having 1 to 20 carbon atoms and containing the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. ４(These are a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0379] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by the following formula, and structural units having an acid-unstable group, and an acid generator.

[0380] [In the formula, R ２ X represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom, which may have a halogen atom. １ These are single bonds, -CO-O-* or -CO-NR ４ - represents *, where * represents a bond with -Ar, R ４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have one or more groups selected from the group consisting of hydroxyl groups and carboxyl groups.

[0381] Examples of resist films include the following:

[0382] A resist film comprising a base resin containing repeating units represented by the following formula (a1) and / or repeating units represented by the following formula (a2), and repeating units that generate acid bonded to the polymer main chain upon exposure.

[0383] (In equations (a1) and (a2), R Ａ Each of these is independently either a hydrogen atom or a methyl group. １ and R ２ These are each independently tertiary alkyl groups having 4 to 6 carbon atoms. ３ Each of these is independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. １ X is a linking group having 1 to 12 carbon atoms, containing a single bond, a phenylene group or a naphthylene group, or at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. ２ (These are single bonds, ester bonds, or amide bonds.)

[0384] Examples of resist materials include the following:

[0385] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0386] (In equations (b1) and (b2), R Ａ X is a hydrogen atom or a methyl group. １ X is a single bond or an ester group. ２ X is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a portion of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and X ２ At least one hydrogen atom in is replaced by a bromine atom. ３ Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. １ ~Rf ４ Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf １ and Rf ２ These may combine to form a carbonyl group. １ ~R ５ Each of these is independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonic acid ester group. １ and R ２These may combine to form a ring with the sulfur atom to which they are bonded.

[0387] A resist material comprising a base resin containing a polymer having repeating units represented by the following formula (a).

[0388] (In formula (a), R Ａ R is a hydrogen atom or a methyl group. １ R is a hydrogen atom or an acid-unstable group. ２ This is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. １ This is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond or a phenylene group, or an ester group or a lactone ring. ２ is -O-, -O-CH ２ It is - or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. However, m + u is an integer from 1 to 4.

[0389] A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, comprising a base component (A) whose solubility in a developer changes due to the action of the acid and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the fluorine additive component (F) contains a fluororesin component (F1) having a constituent unit (f1) containing a base-dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1), the resist composition.

[0390] [In formula (f2-r-1), Rf ２１ Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group. n'' is an integer from 0 to 2. * represents a bond.

[0391] The aforementioned constituent unit (f1) includes a constituent unit represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0392] [In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group that does not have an acid-dissociable site. A ａｒｙｌ X is a divalent aromatic cyclic group which may have substituents. ０１ R is a single bond or a divalent linking group. ２ These are, independently, organic groups that contain a fluorine atom.

[0393] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MORs), and a typical example is a tin oxide-based resist. Examples of metal oxide resist materials include a coating composition containing a metal oxo-hydroxo network having an organic ligand via a metal-carbon bond and / or metal-carboxylate bond, as described in Japanese Patent Application Publication No. 2019-113855. An example of a metal-containing resist uses a peroxo ligand as a radiosensitizing stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described in the patent document described in paragraph

[0011] of Publication No. 2019-532489, for example. Examples of such patent documents include U.S. Patent No. 9,176,377B2, U.S. Patent Application Publication No. 2013 / 0224652A1, U.S. Patent No. 9,310,684B2, U.S. Patent Application Publication No. 2016 / 0116839A1, and U.S. Patent Application Publication No. 15 / 291738.

[0394] A coating comprising a metal oxo-hydroxo network having organic ligands via metal-carbon bonds and / or metal-carboxylate bonds.

[0395] Inorganic oxo / hydroxo-based compositions.

[0396] A coating solution comprising an organic solvent; a first organometallic composition comprising formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (Here, 0 < z ≤ 2 and 0 < (z + x) ≤ 4), equation R'ｎ SnX ４－ｎ A first organometallic composition represented by (where n = 1 or 2), or a mixture thereof, where R and R' are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand or a combination thereof having a hydrolyzable bond to Sn; and a hydrolyzable metal compound of the formula MX' ｖ A coating solution comprising a hydrolyzable metal compound represented by (where M is a metal selected from groups 2 to 16 of the periodic table, v is a number from 2 to 6, and X' is a ligand or combination thereof having a hydrolyzable M-X bond).

[0397] Organic solvent and formula RSnO （３／２－ｘ／２） (OH) ｘ A coating solution comprising a first organometallic compound represented by the formula (wherein 0 < x < 3), wherein the solution contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl group or cycloalkyl group having 3 to 31 carbon atoms, wherein the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0398] An aqueous solution of an inorganic pattern-forming precursor comprising a mixture of water, a metal oxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0399] Other examples of metal-containing resists include the compositions described in Japanese Patent Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Publication No. 2020-122959, Japanese Patent Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229. These contents are incorporated into this specification to the same extent as if they were all explicitly stated.

[0400] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and includes a method of applying a coating-type resist material (a composition for forming a metal-containing resist film), which is a metal-containing resist, and firing it.

[0401] Furthermore, the metal-containing resist film may be formed by vapor deposition. An example of a method for forming a metal-containing resist film by vapor deposition is the method described in Japanese Patent Application Publication No. 2017-116923. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein to the same extent as if they were fully disclosed. In Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film in the present invention is referred to as a metal oxide-containing film.

[0402] Irradiation with light or an electron beam is performed, for example, through a mask (reticle) for forming a predetermined pattern. For example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet) or EB (electron beams) are used. The resist underlayer film forming composition of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably for EUV (extreme ultraviolet) exposure. The electron beam irradiation energy and the amount of light exposure are not particularly limited.

[0403] A bake (PEB: Post Exposure Bake) may be performed after irradiation with light or electron beam and before development. The bake temperature is not particularly limited, but is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C. The bake time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and particularly preferably 30 seconds to 3 minutes.

[0404] The film can be developed using either a wet process or a dry process.

[0405] For wet development, for example, alkaline developers, acidic developers, and organic solvents are used. The wet development temperature can range from 5°C to 50°C. The wet development time can range from 10 seconds to 300 seconds.

[0406] As alkaline developers, for example, aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine can be used. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, and more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Instead of an alkaline developer, a method can be used in which development is performed with an organic solvent such as butyl acetate, and the parts of the photoresist whose alkali dissolution rate has not improved are developed.

[0407] Acidic developers and organic solvents can be used as developers for metal-containing resists, and development is performed with the developer after irradiation with light or electron beam. As a result, for example, when a negative-type metal-containing resist film is used, the unexposed areas of the metal-containing resist film are removed, and a pattern of the metal-containing resist film is formed.

[0408] Examples of acidic developers include acidic developers containing halides (e.g., HCl or HBr), organic acids (e.g., formic acid, acetic acid, or citric acid), or organofluorine compounds (e.g., trifluoroacetic acid) (e.g., aqueous acidic developers or acidic developers in organic solvents).

[0409] Examples of developers (organic solvents) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, lactic acid Tyl, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, 2-heptanone,Examples include cyclohexanone, acetone, γ-butyrolactone, isopropyl alcohol, propylene glycol methyl ether, and propylene glycol methyl ether acetate. Furthermore, surfactants can be added to these developing solutions.

[0410] Development processes, including dry development, can remove exposed or unexposed regions by any useful development process. In one embodiment using a metal-containing resist, the exposed region may have activated reaction centers, such as metal dangling bonds, M-H groups (where M is a metal atom), or dimerized M-M bonds (where M is a metal atom). In certain embodiments, M-H groups may be selectively removed using one or more dry development processes (e.g., halide chemistry). In other embodiments, M-M bonds may be selectively removed using wet development processes (e.g., using high-temperature ethanol and water to provide soluble M(OH)n groups). In yet another embodiment, the exposed region is removed using wet development (e.g., using a positive-tone developer). In some embodiments, the unexposed region is removed using dry development.

[0411] Dry developing processes may include the use of halides, such as HCl-based or HBr-based processes. While this disclosure is not limited to any particular theory or mechanism of operation, approaches may involve using vapor or plasma to form volatile products with cleaning agents (e.g., HCl, HBr, and BCl). ３ This is understood to utilize the chemical reactivity of the dry-deposited photoresist film with (). The dry-deposited photoresist film can be removed at etching rates of up to 1 nm / second. Rapid removal of the dry-deposited photoresist film by these chemical reactions is applicable to chamber cleaning, back cleaning, bevel cleaning, and PR development. The film can be removed by vapor at various temperatures (e.g., HCl or HBr at temperatures above -10°C, or BCl at temperatures above 80°C). ３ This can be removed using ), but plasma may be used to further accelerate or enhance the reactivity.

[0412] Next, the resist underlayer film is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred. If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. After that, the semiconductor substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device.

[0413] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0414] The weight-average molecular weights of the compounds and polymers shown in the synthesis examples below were obtained by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows: Column temperature: 40°C Flow rate: 0.35 ml / min Eluent: Tetrahydrofuran (THF) Standard sample: Polystyrene (Tosoh Corporation)

[0415] The polymers used in the polymer synthesis composition for forming the resist underlayer film were synthesized using the compounds or polymer groups A to C, catalyst group D, solvent group E, separatory solvent group F, and reprecipitation solvent group G shown below.

[0416] ○ Compound or polymer groups A to C

[0417] ○Catalyst Group D Tetrabutylphosphonium bromide: D1 4-hydroxy-TEMPO free radical (1 wt% PGME solution): D2 Benzyltriethylammonium chloride: D3 Hydroquinone: D4 Methanesulfonic acid: D5 Tetrabutylammonium iodide: D6 Paratoluenesulfonic acid (10 wt% isopropanol solution): D7

[0418] ○ Solvent Group E Propylene glycol monomethyl ether (=PGME): E1 Propylene glycol monomethyl ether acetate (=PGMEA): E2 Tetrahydrofuran: E3 25 wt% sodium hydroxide aqueous solution: E4 Isopropanol: E5

[0419] ○Separatory solvent group F: Butyl acetate / water: F1, Methyltetrahydropyran / water: F2

[0420] ○Reprecipitation solvent group G: Methanol: G1, Methanol / Water: G2

[0421] [Synthesis Examples 1 to 22] The reaction materials shown in Table 1-1 or Table 1-2 below were placed in a flask, nitrogen purging was performed, and the reaction was carried out for the specified time and temperature shown in Table 1-1 or Table 1-2. After the reaction was completed, the polymer solution was cooled, and an ion exchange treatment was performed using a cation exchange resin and anion exchange resin as needed to obtain the polymer solution (Tables 1-1 and 1-2).

[0422] [Synthesis Examples 23 to 26] The reaction materials shown in Table 1-3 were placed in a flask, nitrogen purging was performed, and the reaction was carried out for the specified time and temperature shown in Table 1-3. After the reaction was complete, the compound solution or polymer solution was cooled, and reprecipitation was performed using the specified solvent. The recovered compound or polymer was then dried overnight at 40°C. In addition, for Synthesis Example 26 only, reprecipitation purification was not performed, and liquid-liquid extraction was carried out three times using the specified solvent, and the organic layer was recovered and used in the next reaction (Table 1-3).

[0423] [Synthesis Examples 27-30] The reaction materials shown in Table 1-4 were placed in a flask, nitrogen purging was performed, and the reaction was carried out at the specified time and temperature shown in Table 1-4. After the reaction was complete, the polymer solution was cooled, and liquid-liquid extraction was performed three times using the specified solvent. After the organic layer was recovered, it was concentrated to a solid content of 30% using an evaporator, reprecipitation was performed using the specified solvent, and the recovered resin was dried overnight at 40°C. Subsequently, the polymer solution was obtained by dissolving it in PGMEA solution and performing ion exchange treatment using cation exchange resin and anion exchange resin as needed (Table 1-4).

[0424]

[0425]

[0426]

[0427]

[0428] The structures and weight-average molecular weights (Mw) of polymers S1 to S11 are shown below.

[0429] The structures and weight-average molecular weights (Mw) of compounds S12 to S14 are shown below.

[0430] The structures and weight-average molecular weights (Mw) of polymers S13 to S30 are shown below.

[0431] Preparation of resist underlayer film formation compositions: Polymers (S1) to (S22), (S27) to (S30), additives (Ad1 to Ad13 below), and solvents (PGMEA, PGME) were mixed in the mass ratios shown in Tables 2-1 to 2-6 below, and then filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare resist underlayer film formation compositions (M1 to M46, comparative M1 to comparative M32, reference M1 to reference M2). The values ​​listed in Tables 2-1 to 2-6 represent parts by mass.

[0432]

[0433]

[0434]

[0435]

[0436]

[0437]

[0438]

[0439] [Elution Test in Resist Solvent] Each of the resist underlayer formation compositions (M1 to M46, comparative M1 to comparative M32, reference M1, M2) was applied onto a silicon wafer using a spin coater, and fired in air at the predetermined temperature and time described in Tables 3-1 to 3-4 to form a resist underlayer with a thickness of approximately 5 nm. The formed resist underlayer was immersed in a general-purpose thinner, PGME / PGMEA = 7 / 3 (mass ratio), for 60 seconds, spin-dried, and then fired at 100°C for 30 seconds. The resistance to the solvent was confirmed by comparing the film thickness before and after immersion in the thinner. The film thickness reduction rate was calculated using the following formula: Film thickness reduction rate [%] = [(F ｔ０ -F ｔ１ ) / F ｔ０ )] × 100 F ｔ０ : Film thickness before immersion F ｔ１ : A "○" was given if the rate of decrease in film thickness before and after thinner immersion was 5-10% lower than the corresponding comparative example, and a "◎" was given if it was less than 10% lower. A "×" was given if there was no change in the rate of decrease in film thickness or if no film was obtained due to poor coating. The results are shown in Tables 3-1 to 3-4. The corresponding comparative example is listed next to the example.

[0440]

[0441]

[0442]

[0443] In addition to Comparative Example 1, Comparative Example 32 also corresponds to Comparative Example 32 in Examples 1 and 38-41. Even in that case, the degree of curing improvement in the examples remains unchanged and is rated "◎".

[0444] The results from Examples 1 to 46 and Comparative Examples 1 to 32 show that when a compound or polymer having polymerizable multiple bonds is used in combination with a predetermined additive, an improvement in curability can be confirmed. The results from Reference Examples 1 and 2 show that when a compound or polymer without polymerizable multiple bonds is used, no improvement in curability can be confirmed.

[0445] [Evaluation of Coating Film Uniformity] The resist underlayer film formation compositions of the comparative examples and examples listed in Table 4 were applied onto silicon wafers using a 12-inch coater manufactured by Tokyo Electron Limited, and fired in air at the predetermined temperature and time listed in Table 4 to form a resist underlayer film of approximately 5 nm. Subsequently, the uniformity of the film thickness within the wafer surface was evaluated by measuring the film thickness at 85 points along the circumference of the entire wafer. The indicators of film thickness uniformity were the variation in film thickness (maximum film thickness - minimum film thickness) and 3σ of the film thickness, and those with a smaller variation in film thickness and 3σ of the film thickness than the corresponding comparative example were judged as "○" (Table 4).

[0446] [Surface Roughness Evaluation] Silicon wafers with a resist underlayer formed, prepared for the coating film uniformity evaluation, were cut. Surface roughness was evaluated using AFM on the cut samples. Surface roughness was judged using RMS (= Sq. root mean square height) as the index. An RMS value of 0.5 nm or less was judged as "○", and a value higher than that was judged as "×" (Table 4).

[0447]

[0448] By using additives, it is possible to reduce the uniformity of film thickness and surface roughness of the coated film, regardless of the type and position (main chain or side chain) of polymerizable multiple bonds in the resin or low molecular weight compound, thereby forming a higher quality resist underlayer film than conventional methods.

[0449] [Process Margin Evaluation] The resist underlayer formation compositions of Examples 3-4, Comparative Example 2, and Comparative Example 33 were applied to silicon wafers by spin coating. These were fired for 60 seconds at the temperatures listed in Table 5 to obtain a resist underlayer with a thickness of 5 nm. An EUV-compatible positive resist solution was spin-coated and fired onto this resist underlayer to obtain an EUV resist film. Exposure was performed using an EUV exposure apparatus under predetermined conditions, and PEB treatment was carried out. Subsequently, development was performed using a 2.38% tetramethylammonium hydroxide solution to obtain a resist pattern with a line size of approximately 15 nm. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) was used to measure the length of the resist pattern. The process margin (difference between the minimum line size and the maximum line size) in the defect-free area of ​​the obtained resist pattern was compared. A "○" was used to indicate that the process margin was larger than that of the comparative example. The results are shown in Table 5.

[0450]

[0451] From the above, it was found that process margins can be expanded by using additives.

Claims

1. A composition for forming a resist underlayer film, comprising a compound or polymer (A) having polymerizable multiple bonds, an onium salt (B) which is at least one of an aromatic sulfonium salt, an aromatic iodonium salt, and an ammonium salt, and a solvent (C).

2. The composition for forming a resist underlayer film according to claim 1, wherein the onium salt (B) is an onium salt represented by the following formula (B1) or an intramolecular salt represented by the following formula (B2). (In formula (B1), Y １ｃ ＋ represents a monovalent aromatic sulfonium cation or a monovalent aromatic iodonium cation. In formula (B1), Y １ａ － represents a monovalent anion. In formula (B2), X ＋ is S ＋ or I ＋ represents, and each R １１１ is bonded to X ＋ and each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms which may have a substituent, a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms which may have a substituent, or a combination comprising at least one of the foregoing, n1 represents 1 or 2, when X ＋ represents I ＋ , n1 represents 1, when X ＋ represents S ＋ , n1 represents 2, when X ＋ represents S ＋ , the two R １１１ may together form a ring, Ar １１１ represents a divalent aromatic group having 6 to 30 carbon atoms which may have a substituent, L １１１ and L １１２ each independently represents a divalent linking group having 1 to 30 carbon atoms that may contain a heteroatom including O, S, N, F, or a combination containing at least one of these, M １１１ represents a divalent monocyclic, polycyclic, or fused polycyclic alicyclic group having 5 to 30 carbon atoms that may contain a heteroatom including O, S, N, F, or a combination containing at least one of these, and may have a substituent, R １１１ and Ar １１１ may together form a ring, Z － (where n represents an oxygen-containing anionic group, n2, n3, and n4 each independently represent 0 or 1, and n represents 0 or 1.) 3. Y in formula (B1) １ｃ ＋ The resist underlayer film forming composition according to claim 2, wherein the underlayer is a monovalent aromatic sulfonium cation represented by the following formula (B1-1) or a monovalent aromatic iodonium cation represented by the following formula (B1-2). (In formula (B1-1), R １０１ , R １０２ , and R １０３ Each of these independently represents one of the following (i) to (iv), R １０１ and R １０２ , R １０２ and R １０３ , or R １０１ and R １０３ They may be bonded to each other to form a ring. However, R １０１ , R １０２ , and R １０３ At least one of the following formulas (ii) to (iv): (i) A linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, which may be substituted and may contain a halogen atom, a carbonyl group, an ester group, an ether group, a thioether group, an amide group, a lactone ring, or an aryl group (ii) An aromatic hydrocarbon group which may be substituted and may contain -S- (iii) An aralkyl group having 7 to 20 carbon atoms which may be substituted (iv) A thiophenyl group which may be substituted In formula (B1-2), R １０４ and R １０５ Each independently represents an aryl group having 6 to 20 carbon atoms, which may have substituents, and R １０４ and R １０５ (They may be joined to each other to form a ring.) 4. Y in the onium salt represented by the above formula (B1) １ａ － However, halogen anions, cyanide anions, bicarbonate anions, nitrate anions, nitrite anions, R １０１ SO ３ － or R １０１ CO ２ － (R １０１ The resist underlayer film forming composition according to claim 2, wherein represents a monovalent organic group having 1 to 40 carbon atoms.

5. The resist underlayer film forming composition according to claim 1, wherein the onium salt (B) is an intramolecular salt represented by the following formula (B2-1) or an intramolecular salt represented by the following formula (B2-2). (In formulas (B2-1) and (B2-2), R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , and R ｂ５ Each independently represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, which may contain heteroatoms. Each independently represents an integer from 0 to 5. Each independently represents 0 or 1, except that at least one of m11, m12, and m13 is 1. Each independently represents 0 or 1, except that at least one of m14 and m15 is 1. However, the sum of m1 and m11 is 5 or less. However, the sum of m2 and m12 is 5 or less. However, the sum of m3 and m13 is 5 or less. However, the sum of m4 and m14 is 5 or less. However, the sum of m5 and m15 is 5 or less. If m1 is 2 to 5, two adjacent R ｂ１ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m2 is 2 to 5, two adjacent R ｂ２ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m3 is 2 to 5, two adjacent R ｂ３ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m4 is 2 to 5, two adjacent R ｂ４ These may bond with each other to form a ring with the carbon atoms to which they are bonded. When m5 is 2 to 5, two adjacent R ｂ５ These atoms may bond to each other, forming a ring with the carbon atoms to which they are bonded. (n represents 0 or 1.) 6. The resist underlayer film forming composition according to claim 1, wherein the onium salt (B) is an ammonium salt represented by the following formula (B3). (In formula (B3), R Ｂ３１ Each of these independently represents a hydrogen atom, or an alkyl group, alkenyl group, alkynyl group, aryl group, or aralkyl group which may be substituted with a heteroatom or which may have a heteroatom interposed. Ｂ３１ They may also form a ring structure together. ３ａ － (This represents a monovalent anion.) 7. Y in the ammonium salt represented by formula (B3) above ３ａ － The resist underlayer film forming composition according to claim 6, wherein the underlayer film is represented by a halogen-containing anion, a hydroxide anion, a carboxylic acid anion, a sulfonate anion, a phenol anion, a sulfonamide anion, or a boron-containing anion.

8. The resist underlayer film forming composition according to claim 1, wherein the compound or polymer (A) is one of the following polymers (A-1) to (A-6), or one of the following compounds (A-7). Polymer (A-1): A polymer obtained by polymerizing the polymerizable unsaturated bonds of a compound having a group having polymerizable unsaturated bonds (however, the polymer has polymerizable multiple bonds). Polymer (A-2): A polymer having a structural unit represented by the following formula (A2). Polymer (A-3): A polymer having a hydroxyl group bonded to a carbon atom in the main chain and a polymerizable multiple bond. Polymer (A-4): A polydiene polymer having polymerizable multiple bonds, which may be modified. Polymer (A-5): A polymer having a structural unit represented by the following formula (A5). Polymer (A-6): The following resin (G): A resin (G) having a composite unit structure, wherein the composite unit structure comprises: a unit structure (A) having an aromatic ring, and a unit structure (B) having one or more carbon atoms, and is obtained by a reaction that generates a covalent bond between the carbon atoms constituting the aromatic ring of the unit structure (A) and the carbon atoms in the unit structure (B) (however, the resin (G) has polymerizable multiple bonds). Compound (A-7): A compound having three or more polymerizable multiple bonds. (In formula (A2), L ２１ L represents a single bond or a linking group. ２２ (This represents a monovalent group having polymerizable multiple bonds.) (In formula (A5), Ar represents a group having a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, or fluorene ring.) ５１ R represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an amino group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a formyl group, a cyano group, a nitro group, an ester group, an amide group, a sulfonyl-containing group, a thiol group, a sulfide-containing group, or an ether-bond-containing group. ５２ L represents a divalent group which may have substituents. ５１ L represents a single bond or a linking group. ５２ represents a group having polymerizable multiple bonds. m represents an integer from 0 to 4. n represents an integer from 0 to 3. However, m + n is 4 or less. However, when m is 0, R ５２ It has polymerizable multiple bonds.

9. The resist underlayer film forming composition according to claim 1, wherein the film-forming properties are poor when the onium salt (B) is not contained.

10. When a resist underlayer film with a thickness of 5 nm is formed at a heating temperature of 150°C or 220°C, the rate of film thickness reduction relative to the resist solvent (A １ [%]) and the film thickness reduction rate (A) when the onium salt (B) is not included. ２ The resist underlayer film forming composition according to claim 1, wherein [%]) satisfies the relationship of the following formula (F1). 5% ≤ A ２ [%]-A １ [%] (F1) 11. The resist underlayer film forming composition according to claim 1, wherein the solvent comprises at least one selected from the group consisting of a carboxylic acid having a hydroxyl group, a linear or cyclic alkyl ketone, a cyclic lactone, an alkylene glycol monoalkyl ether, a monocarboxylic acid ester of an alkylene glycol monoalkyl ether, and an alkoxycarboxylic acid ester of an alkylene glycol monoalkyl ether.

12. The resist underlayer film forming composition according to claim 1, further comprising a crosslinking agent.

13. The resist underlayer film forming composition according to claim 12, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

14. The resist underlayer film forming composition according to claim 12, wherein the content of the crosslinking agent is 1% by mass to 60% by mass relative to the compound or polymer (A).

15. A composition for forming a resist underlayer film according to claim 1, which does not contain a crosslinking agent.

16. The resist underlayer film forming composition according to claim 1, further comprising a curing catalyst.

17. The resist underlayer film forming composition according to claim 1, further comprising a surfactant.

18. The resist underlayer film forming composition according to claim 1, used in EB or EUV lithography.

19. The resist underlayer film forming composition according to claim 1, used for forming an underlayer film of a metal-containing resist.

20. A resist underlayer film, which is a cured product of a resist underlayer film forming composition according to any one of claims 1 to 19.

21. A laminate comprising a semiconductor substrate and a resist underlayer film according to claim 20.

22. A method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 19; and forming a resist film on the resist underlayer film.

23. A pattern formation method comprising: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition according to any one of claims 1 to 19; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern; and etching the resist underlayer film using the resist pattern as a mask.

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