Composition for forming resist underlayer film

Abstract

A composition for forming a resist underlayer film, the composition containing a resin (A), a photoacid generator (B), and a solvent (C), wherein the photoacid generator (B) has a cation moiety and an anion moiety, and the cation moiety is an aromatic onium cation having a halogen atom bonded to an aromatic ring.

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] As a resist underlayer film forming composition, for example, a resist underlayer film forming composition has been proposed that contains a polymer having a substructure represented by a specific formula and a solvent (see claim 9 of Patent Document 1).

[0004] International Publication No. 2023 / 068075 brochure

[0005] The required properties of a resist underlayer include, for example, that it does not intermix with the resist film formed on the upper layer (i.e., it is insoluble in the resist solvent) and that it can form a fine resist pattern. 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 that can form a fine resist pattern, 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 forming composition.

[0006] The inventors of the present invention conducted diligent research to solve the above problems and, as a result, found that they could solve the above problems, and completed the present invention having the following gist.

[0007] In other words, the present invention encompasses the following embodiments: [1] A resist underlayer film forming composition comprising a resin (A), a photoacid generator (B), and a solvent (C), wherein the photoacid generator (B) has a cationic portion and an anionic portion, and the cationic portion is an aromatic onium cation having a halogen atom bonded to an aromatic ring. [2] The resist underlayer film forming composition according to [1], wherein the resin (A) is a resin other than a vinyl resin. [3] The resist underlayer film forming composition according to [1] or [2], wherein the anionic portion is a sulfonic acid anion, and the sulfonic acid anion does not contain a substructure represented by the following formula (An-1). (In formula (An-1), R ａ and R ｂ Each independently represents a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. * represents a bond.) [4] The resist underlayer film forming composition according to any one of [1] to [3], wherein the aromatic onium cation is an aromatic sulfonium cation or an aromatic iodonium cation. [5] The resist underlayer film forming composition according to [4], wherein the aromatic sulfonium cation is represented by the following formula (C1-1), and the aromatic iodonium cation is represented by the following formula (C1-2). (In formula (C1-1), R １０１, R １０２ and R １０３ each independently represent any one of the following (i) to (iv), and R １０１ and R １０２ , R １０２ and R １０３ or R １０１ and R １０３ may be bonded to each other to form a ring. Provided that at least one of R １０１ , R １０２ and R １０３ is any one of the following formulas (ii) to (iv), and at least one of R １０１ , R １０２ and R １０３ has a halogen atom bonded to an aromatic ring. (i) a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, which may have a substituent 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 have a substituent and may contain -S- (iii) an aralkyl group having 7 to 20 carbon atoms which may have a substituent (iv) an optionally substituted thiophenyl group In formula (C1-2), R １０４ and R １０５ each independently represent an optionally substituted aryl group having 6 to 20 carbon atoms, and R １０４ and R １０５ may be bonded to each other to form a ring. Provided that R １０４ and R １０５(At least one of the members has a halogen atom bonded to an aromatic ring.) [6] The resist underlayer film forming composition according to any one of [1] to [5], wherein the anion portion is a sulfonic acid anion, and the pKa of the sulfonic acid anion at 25°C is -6.0 to -1.0. [7] The resist underlayer film forming composition according to any one of [1] to [6], wherein the resin (A) is at least one of a polyester resin, a polyether resin, a novolac resin, a resin having an ether bond, a thioether bond, an amide bond, or an ester bond in its side chain, a polyimide resin, and a polyamide resin. [8] The resist underlayer film forming composition according to any one of [1] and [3] to [6], wherein the resin (A) includes a vinyl resin, and the vinyl resin includes a resin having at least one structural unit represented by the following formula (A-1). (In formula (A-1), R １ X represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. ０ represents a single bond, -COO- or -CONH-, L ０ (wherein represents a monovalent organic group.) [9] The resist underlayer film forming composition according to any one of [1] to [6], wherein the resin (A) comprises a resin having at least one of a resin having a structural unit represented by the following formula (A-2) and a resin having a structural unit represented by the following formula (A-3). (In formula (A-2), A independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q １ and Q ２ Each of these independently represents a divalent organic group, X １ ~X ４ These terms independently represent a single bond, an ether bond, a thioether bond, an amide bond, or an ester bond. (In formula (A-3), T ３ Q represents a group having a monocyclic aliphatic ring that constitutes the main chain. ３ represents a divalent linking group, Ar ３(wherein represents a monovalent organic group.)

[10] The resist underlayer film forming composition according to any one of [1] to [6], wherein the resin (A) comprises a reaction product of a reaction raw material comprising a compound having two or more epoxy groups and a compound having at least two groups that can react with epoxy groups.

[11] The resist underlayer film forming composition according to [7], wherein the resin (A) comprises a resin having an ether bond, a thioether bond, an amide bond, or an ester bond in its side chain, and the resin having an ether bond, a thioether bond, an amide bond, or an ester bond in its side chain comprises a resin having at least one structural unit represented by the following formula (A-4). (In formula (A-4), Ar ４ L represents a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or pyrene ring, which may have substituents. ５ m5 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, and m5 represents an integer from 0 to 5. When m5 is 2 to 5, multiple L ５ They may be the same or they may be different. ４ Q represents a divalent organic group that makes up the main chain. ４ Q represents a divalent linking group having an ether bond, thioether bond, amide bond, or ester bond. ５ (wherein is a monovalent organic group which may have substituents. k is an integer from 1 to 3.)

[12] The resist underlayer film forming composition according to [7], wherein the resin comprises the novolac resin, and the novolac resin comprises a resin having a composite structural unit represented by the following formula (A-6). (In formula (A-6), A represents a structure having an aromatic ring, and B represents a structure having one or more carbon atoms.)

[13] The resist underlayer film forming composition according to

[12] , wherein A in formula (A-6) has a skeleton having an aromatic ring, and the skeleton is at least one of an aromatic amine skeleton, a nitrogen-containing aromatic heterocyclic skeleton, and a phenol skeleton.

[14] The resist underlayer film forming composition according to

[12] , wherein A in formula (A-6) has a skeleton having an aromatic ring, and the skeleton is at least one of the following skeletons represented by formula (A-1a), formula (A-1b), formula (A-1c), formula (A-2a), formula (A-2b-1), formula (A-2b-2), formula (A-2c-1), formula (A-2c-2), formula (A-2c-3), and formula (A-2c-4), wherein at least one hydrogen atom in the skeleton may be replaced by a substituent. (In formulas (A-1a) to (A-1c), Ar １１ Each of these independently represents a residue of an aromatic ring. １１ These are, independently, hydrogen, O, S, and NR. ｂ , NR ｂ CO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group or aromatic ring residue having 2 to 15 carbon atoms, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ (This represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.) (In the formula, Ar ２１ Each of these independently represents a residue of an aromatic ring. ２１ These are, independently, hydrogen, O, S, and NR. ｂ , NR ｂCO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group or aromatic ring residue having 2 to 15 carbon atoms, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ R represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 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. R is independently a hydrogen atom, O, S, and NR. ｂ , NR ｂ CO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group, aromatic ring residue, or bond with L, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ n1 represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 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 ２１They are bonded by bonding with each other, or by bonding between nitrogen atoms and Ar ２１ 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 bonded with.)

[15] The resist underlayer film forming composition according to

[12] , wherein A in formula (A-6) has a skeleton having an aromatic ring, and the skeleton is at least one of the following formulas (A-4a), (A-5a), (A-5b), (A-5c), (A-5d), and (A-6a), and in the skeleton, at least one hydrogen atom may be replaced with a substituent. (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.) (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. (In the formula, Ar ５１ Each of the above independently represents a residue of an aromatic ring. Each of the above independently represents an integer from 1 to 4.)

[16] The resist underlayer film forming composition according to

[14] , wherein the substituent in the skeleton, which may replace at least one hydrogen atom, is one or more groups selected from 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, and ether bond-containing groups.

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

[13] to

[16] , wherein A in formula (A-6) has a skeleton having an aromatic ring, and in the skeleton, at least one hydrogen atom may be replaced by a group represented by the following formula (A-10). (In formula (A-10), R １ R represents a single bond or a divalent organic group with 1 to 20 carbon atoms. ２) represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and * represents a bond. )

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

[17] , 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.

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

[18] , further comprising a crosslinking agent.

[20] The resist underlayer film forming composition according to

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

[21] The resist underlayer film forming composition according to

[19] or

[20] , wherein the content of the crosslinking agent is 1% to 60% by mass with respect to the resin (A).

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

[21] , further comprising a curing catalyst.

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

[22] , further comprising a surfactant.

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

[23] , used in EB or EUV lithography.

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

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

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

[25] .

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

[26] .

[28] 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

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

[29] 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

[25] ; 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 capable of forming a fine resist pattern, 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 resin (A), a photoacid generator (B), and a solvent (C). The photoacid generator (B) has a cationic portion and an anionic portion. The cationic portion is an aromatic onium cation having a halogen atom bonded to an aromatic ring.

[0010] A resist underlayer film formation composition can form a resist underlayer film on which a fine resist pattern can be formed, by including a photoacid generator having an aromatic onium cation having a halogen atom bonded to an aromatic ring.

[0011] <Resin (A)> Resin (A) is, for example, at least one of vinyl resins, polyester resins, polyether resins, novolac resins, resins having ether bonds, thioether bonds, amide bonds, or ester bonds in their side chains, polyimide resins, and polyamide resins. Examples of vinyl resins include polystyrene resins, polyacrylic resins, polymethacrylic resins, and polyacrylamide resins. Examples of polyamide resins include polyamides and polyamic acids. Resin (A) is preferably polyester resins, polyether resins, novolac resins, or resins having ether bonds, thioether bonds, amide bonds, or ester bonds in their side chains. Resin (A) may be a resin other than a vinyl resin. Resin (A) is preferably resin (A-1) to resin (A-6) described later, and more preferably resin (A-2) to resin (A-6). These resins may be used individually or in combination of two or more. The resin may be a polymer, oligomer, or low molecular weight compound.

[0012] Resin (A) may or may not have an aromatic ring, but it is preferable that it has an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include 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, and cyclooctatetraene. Examples of aromatic heterocycles include furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, pyrrole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindolefluorene, bisindolebenzofluorene, bisindoledibenzofluorene, purine, quinoline, isoquinoline, chromene, thianthlene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, and indolocarbazole.

[0013] The resin (A) may or may not have an aliphatic hydrocarbon ring. The aliphatic hydrocarbon ring may be a monoring or a fused ring.

[0014] The resin (A) may or may not have a heterocycle. Examples of heteroatoms in the heterocycle include oxygen atoms, nitrogen atoms, and sulfur atoms. Examples of heterocycles include heterocycles containing nitrogen atoms. Examples of structures containing heterocycles containing nitrogen atoms include the following structure. (In the formula, * represents a bond.)

[0015] An example of resin (A) is shown below.

[0016] <<Resin (A-1)>> Resin (A) preferably contains at least a resin having a structural unit represented by the following formula (A-1) (hereinafter also referred to as "Resin (A-1)"). Resin (A-1) corresponds to a vinyl resin. As described later, Resin (A-1) may be a homopolymer having one type of structural unit, or a copolymer having two or more types of structural units.

[0017]

[0018] (In formula (A-1), R １ X represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. ０ represents a single bond, -COO- or -CONH-, L ０ (This represents a monovalent organic group.)

[0019] R １ Examples of halogen atoms in this context include fluorine, chlorine, bromine, and iodine atoms. １Examples 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. Examples of alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, and n-icosyl group. 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.

[0020] L ０ Examples of the monovalent organic group in include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a group formed from a combination of any of the foregoing with one or more selected from a carbonyl group, an ether group, a thioether group, and an amino group. L ０ The monovalent organic group in has, for example, an aromatic hydrocarbon ring. That is, at least one hydrogen atom of the monovalent organic group of L ０ is substituted with a group having an aromatic hydrocarbon ring. Examples of such a group having an aromatic hydrocarbon ring include a phenyl group, a tolyl group, an o-xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a chrysenyl group, a triphenylenyl group, and a pyrenyl group.

[0021] Resin (A-1) preferably comprises a resin having at least any one of a structural unit represented by formula (A-1a) below, a structural unit represented by formula (A-1b) below, a structural unit represented by formula (A-1c) below, and a structural unit derived from maleimide. Resin (A-1) may be a homopolymer of these structural units, or may be a copolymer. Further, resin (A-1) only needs to contain at least these structural units, and may be a copolymer of these structural units with other structural units.

[0022] (In formula (A-1a), R １ represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms, and Ar １ represents a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or a pyrene ring, and L １ represents a hydroxy group, a cyano group, a nitro group, an amino group, an alkylamino group, a carboxy group, a formyl group, an acyl group, a sulfonyl-containing group, an ether bond-containing group, a thiol group, or an ester group, and L ２represents 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 atom of these aryl groups may be substituted with an alkyl group, an alkenyl group, or an alkynyl group, and the carbon-carbon bond of these substituted alkyl groups, alkenyl groups, or alkynyl groups may be interrupted by an oxygen atom. m1 represents an integer of 0 to 3. m2 represents an integer of 0 to 5; provided that the sum of m1 and m2 is 0 to 5. When m1 is 2 or 3, a plurality of L １ may be the same or different. When m2 is 2 to 5, a plurality of L ２ may be the same or different. In formula (A-1b), R １ represents a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms, and L ３ represents a hydrogen atom or a monovalent group. In formula (A-1c), R １ represents a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 20 carbon atoms, L ４ represents a hydrogen atom or a monovalent group, and L ５ represents a hydrogen atom or a monovalent group. L ４ and L ５ may together form a ring structure.)

[0023] As the alkylamino group for L １ , groups represented by -NHR or -NR ２ can be mentioned. Here, R represents a saturated or unsaturated linear, branched or cyclic hydrocarbon group (-R ａ ) which may be interrupted one or more times by an oxygen atom in the middle of the hydrocarbon chain, and may be substituted with a hydroxy group or a halogen atom. As R ａ , for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and the like can be mentioned. In -NR ２ , the two R groups may be the same as or different from each other. As the acyl group for L １ , groups represented by -COR can be mentioned. Here, R is the aforementioned hydrocarbon group -Rａ 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.

[0024] L ２ In 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.

[0025] 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. ３ The 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.

[0026] 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 It represents.

[0027] L in equation (A-1c) ４ and L ５ These are, independently, L in equation (A-1b). ３ It is similar to that.

[0028] Also, L ３ For example, a group represented by the following formula (A-1b-1) can be cited.

[0029]

[0030] (In formula (A-1b-1), X １０ is -O-, -S-, -COO-, -N(L ３ｂ ) CO- or -N(L ３ｂ ) represents L ３ａ L represents a monovalent group. ３ｂ X represents a hydrogen atom or a monovalent group. １０ However, -N(L ３ｂ )- When L ３ａ and L ３ｂ These may form a ring structure together. (* represents a bonding hand.)

[0031] L ３ａ As a monovalent group in the above formula (A-1b), L ３ A similar monovalent group can be cited. ３ｂ As a monovalent group in the above formula (A-1b), L ３ A similar monovalent group can be cited.

[0032] 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.

[0033]

[0034] Examples of monomers used to derive formula (A-1b) include the following compounds. In the formula, R ０ R represents a hydrogen atom or a methyl group. １ is, =CH ２ It represents.

[0035]

[0036] Examples of monomers used to derive formula (A-1c) include the following compounds. In the formula, R ０ R represents a hydrogen atom or a methyl group. １ is, =CH ２ It represents.

[0037]

[0038] The resin (A-1) may be a homopolymer having one type of structural unit, or a copolymer having two or more types of structural units.

[0039] The proportion of structural units represented by formula (A-1a), formula (A-1b), or formula (A-1c) in resin (A-1) is not particularly limited. However, the molar ratio of structural units represented by formula (A-1a), formula (A-1b), or formula (A-1c) to the total structural units of resin (A-1) may be, for example, 5 mol% or more and 100 mol% or less, or 5 mol% or more and less than 100 mol%.

[0040] The resin (A-1) may contain structural units other than those represented by formula (A-1a), formula (A-1b), or formula (A-1c). In this case, the molar ratio of the other structural units to the total structural units of the resin (A-1) is preferably, for example, greater than 0 mol% and 90 mol% or less, greater than 0 mol% and 80 mol% or less, greater than 0 mol% and 70 mol% or less, greater than 0 mol% and 60 mol% or less, greater than 0 mol% and 50 mol% or less, greater than 0 mol% and 40 mol% or less, greater than 0 mol% and 30 mol% or less, greater than 0 mol% and 20 mol% or less, greater than 0 mol% and 10 mol% or less, greater than 0 mol% and 5 mol% or less, or greater than 0 mol% and 1 mol% or less.

[0041] Examples of resin (A-1) include the polymers described in International Publication No. 2015 / 178235. The contents of International Publication No. 2015 / 178235 are incorporated herein to the same extent as if they were fully expressed.

[0042] The molecular weight of resin (A-1) is not particularly limited. The lower limit of the weight-average molecular weight of resin (A-1) is, for example, 500, 1,000, 2,000, or 3,000. The upper limit of the weight-average molecular weight of resin (A-1) is, for example, 100,000, 50,000, 30,000, 20,000, or 10,000.

[0043] <<Resin (A-2)>> Resin (A) preferably contains a resin having a structural unit represented by the following formula (A-2) (hereinafter also referred to as "Resin (A-2)"). An example of Resin (A-2) is a polyester resin or a polyether resin.

[0044] (In formula (A-2), A independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q １ and Q ２ Each of these independently represents a divalent organic group, X １ ~X ４ These terms independently represent a single bond, an ether bond, a thioether bond, an amide bond, or an ester bond.

[0045] Q １ and Q ２ The number of carbon atoms is not particularly limited; for example, it may be 1 to 50, 3 to 40, or 6 to 30. １ ~X ４ If it is an ester bond, X １ and X ３ -OCO- is preferred, X ２ and X ４ -COO- is preferred.

[0046] Q １ and Q ２Examples of divalent organic groups include alkylene groups having 1 to 20 carbon atoms, alkenylene groups having 2 to 20 carbon atoms, alkylylene groups having 2 to 20 carbon atoms, and aryl groups having 6 to 50 carbon atoms. At least one hydrogen atom in these organic groups may be substituted with a substituent. Examples of 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, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms. Also, Q １ and Q ２ The divalent organic group may be fragmented by one or more atoms or groups selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and carbonyl groups, may be in a branched chain form, or 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.

[0047] From the viewpoint of favorably obtaining the effects of the present invention, Q in formula (A-2) １ Preferably, it is represented by the following formula (A-2-1). From the viewpoint of suitably obtaining the effects of the present invention, Q in formula (A-2) ２ Preferably, it is represented by any of the following formulas (A-2-2a), (A-2-2b), and (A-2-2c).

[0048] (In equations (A-2-1) and (A-2-2a) to (A-2-2c), R ａEach of these independently 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. W represents a single bond, -CH ２ -, -C(CH ３ ) ２ -, -C (CF ３ ) ２ -, -CO-, -O-, -S-, or SO ２ (This represents a negative value. Each 'm' independently represents an integer from 0 to 2. Each 'n' independently represents an integer from 0 to 4.)

[0049] Examples of alkyl groups having 1 to 20 carbon atoms include the alkyl groups described in the section on "Vinyl Resins".

[0050] Examples of alkenyl groups having 2 to 10 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, and 1-methyl-3-butenyl group. Nyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group Xenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl Examples include the nyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0051] Examples of alkynyl groups having 2 to 10 carbon atoms include those in which the carbon-carbon double bond of the aforementioned alkenyl group is replaced with a carbon-carbon triple bond.

[0052] Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, and 4-methyl-n Examples include pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group, cyclopentyloxy group, cyclohexyloxy group, norbornioxy group, adamantyloxy group, etc.

[0053] Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, o-xylyl, biphenyl, naphthyl, anthracenyl, phenantrenyl, crisenyl, triphenylenyl, and pyrenyl groups. Examples of aryloxy groups having 6 to 30 carbon atoms include phenoxy, benzyloxy, and 1-naphthyloxy groups. Examples of hydroxyalkyl groups having 1 to 20 carbon atoms include groups in which at least one hydrogen atom of an alkyl group having 1 to 20 carbon atoms is substituted with a hydroxyl group. Examples of ester groups include -CO ２ Examples include groups represented by R or -OCOR. Here, R may be substituted with a hydroxyl group or a halogen atom, or the hydrocarbon group -R ａ This represents the amide group, which can be -NHCOR, -CONHR, -NRCOR, or -CONR. ２examples include a group represented by. Here, R is the hydrocarbon group-R which may be substituted with a hydroxy group or a halogen atom ａ , and when there are two R groups, the two R groups may be the same or different from each other. Examples of the sulfonyl-containing group include -SO ２ a group represented by R. Here, R is the hydrocarbon group-R which may be substituted with a hydroxy group or a halogen atom ａ represents an alkylamino group or a hydroxy group. Examples of the sulfide-containing group include a group represented by -SR. Here, R is the hydrocarbon group-R which may be substituted with a hydroxy group or a halogen atom ａ represents. Examples of the ether bond-containing group include R １１ -O-R １１ includes a residue of an ether compound containing an ether bond represented by. Here, R １１ each 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, an anthranyl group, or a pyrenyl group. The ether bond-containing group may be, for example, an organic group containing an ether bond including a methoxy group, an ethoxy group, or a phenoxy group, or may be an organic group containing an epoxy group or an oxetane group.

[0054] From the viewpoint of more suitably obtaining the effects of the present invention, m in formula (A-2-1) is preferably 0 or 1. From the viewpoint of more suitably obtaining the effects of the present invention, m in formula (A-2-2a) is preferably 0 or 1, and more preferably 0.

[0055] From the viewpoint of more suitably obtaining the effects of the present invention, n in formula (A-2-1) and formulas (A-2-2a) to (A-2-2c) is each independently preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0056] R ａ is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

[0057] Q in formula (A-2) １ and Q ２ may have a structure represented by the following formula (A-2-3).

[0058] (In formula (A-2-3), X １１ represents a divalent group represented by any one of the following formulas (A-2-3a) to (A-2-3d). * represents a bond.)

[0059] (In formulas (A-2-3a) to (A-2-3d), R １ to R ７ each independently represent an alkyl group having 1 to 10 carbon atoms which may be interrupted by a hydrogen atom, an oxygen atom or a sulfur atom, an alkenyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, an alkynyl group having 2 to 10 carbon atoms which may be interrupted by an oxygen atom or a sulfur atom, a benzyl group or a phenyl group, wherein at least one hydrogen atom of the benzyl group or the phenyl group is selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups and alkylthio groups having 1 to 6 carbon atoms. It may be substituted with at least one monovalent group. R １ and R ２ may be bonded to each other to form a ring having 3 to 6 carbon atoms. R ３ and R ４ may be bonded to each other to form a ring having 3 to 6 carbon atoms. * represents a bond. *1 represents a bond bonded to a carbon atom in formula (A-2-3). *2 represents a bond bonded to a nitrogen atom in formula (A-2-3).)

[0060] The structure represented by formula (A-2-3) is, for example, a structure derived from cyanuric acid, a structure derived from hydantoin, or a structure derived from uracil.

[0061] In formula (A-2), Q １ or Q ２ includes, for example, the structures exemplified below. In the formulas, * represents a bond.

[0062]

[0063] The resin (A-2) may further have a monovalent group represented by the following formula (E). The monovalent group represented by formula (E) is located, for example, at the end of the resin (A-2).

[0064] (In formula (E), L represents an oxygen atom, a sulfur atom, or an ester group. Z represents a monovalent group with 1 to 30 carbon atoms. * represents a bond.)

[0065] For Z, for example, R in formula (A-1) of the above-mentioned <<Resin (A-1)>>. １ Similar monovalent organic groups having 1 to 20 carbon atoms can be cited. The number of carbon atoms in Z is preferably 6 to 30. Z may have, for example, an aromatic hydrocarbon ring, an aliphatic ring, or an acyclic hydrocarbon group. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, etc. The aliphatic ring may have its carbon-carbon bond interrupted by a heteroatom and may also be substituted with substituents.

[0066] Examples of monovalent groups represented by formula (E) include the group represented by the following formula (E-1), the group represented by the following formula (E-2), the group represented by the following formula (E-3), and the group represented by the following formula (E-4). (In formulas (E-1) and (E-2), A Ｅ２ Each of these independently represents an aryl group with 6 to 40 carbon atoms, R Ｅ１６ R represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Ｅ１７ and R Ｅ１８ Each of the following independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 40 carbon atoms; n represents 0 or 1; n1 and n3 independently represent integers from 1 to 12; and n2 represents an integer from 0 to 11. * represents a bond.

[0067] (In formula (E-3), E １ (where n represents an aliphatic ring in which the carbon-carbon bond may be interrupted by a heteroatom and may be substituted with a substituent. n represents 0 or 1.)

[0068] (In formula (E-4), Y represents an alkylene group having 1 to 4 carbon atoms, which may be single-bonded or substituted. Ｅ４１ , R Ｅ４２ and R Ｅ４３ Each of these independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 40 carbon atoms, R Ｅ４１ is R Ｅ４２ or R Ｅ４３ (They may also form a ring together.)

[0069] Examples of the following structures in formula (E-1) include the following groups. (* indicates a link.) (* indicates a link.)

[0070] Examples of the following structures in formula (E-2) include the following groups. (* indicates a link.) (* indicates a link.)

[0071] E in equation (E-3) １ Examples include the following groups: (* indicates a link.)

[0072] Examples of groups represented by formula (E-4) include the following: (* indicates a link.)

[0073] Resin (A-2) can be synthesized, for example, by the following methods: (I): Reaction of reaction materials containing a compound represented by formula (1A) below and a compound represented by formula (1B) below. (II): Reaction of reaction materials containing a compound represented by formula (1A) below, a compound represented by formula (1B) below, and a compound represented by formula (EA) below. (In equation (1A), Q １ , X １and X ２ have the same meanings as Q in formula (A-2), respectively １ , X １ and X ２ in formula (A-2), respectively. In formula (1B), A, Q ２ , X ３ and X ４ have the same meanings as A, Q ２ , X ３ and X ４ in formula (A-2), respectively. In formula (EA), p and Z have the same meanings as p and Z in formula (E), respectively.)

[0074] The above reaction may be carried out, for example, in the presence of a catalyst. The catalyst is, for example, a quaternary phosphonium salt such as tetrabutylphosphonium bromide or ethyltriphenylphosphonium bromide, or a quaternary ammonium salt such as benzyltriethylammonium chloride. An appropriate amount of the catalyst can be selected and used from the range of 0.1 to 20% by mass relative to the total mass of the reaction raw materials used in the reaction. Optimal conditions for the reaction temperature and reaction time can be selected, for example, from the range of 50 to 160°C and 2 to 50 hours.

[0075] Some examples of the compound represented by formula (1B) include the structures illustrated below.

[0076]

[0077] The weight average molecular weight of Resin (A-2) is not particularly limited, but is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 2,500 to 15,000.

[0078] <<Resin (A-3)>> The resin (A) preferably includes a resin having a structural unit represented by the following formula (A-3) (hereinafter also referred to as "Resin (A-3)"). Resin (A-3) corresponds to a polyether resin.

[0079] (In formula (A-3), T ３ represents a group having a monocyclic aliphatic ring constituting the main chain, and Q ３This represents a divalent linking group, A ３ (This represents a monovalent organic group.)

[0080] The resin (A-3) is A in formula (A-3). ３ It may have two or more different structural units represented by formula (A-3).

[0081] Examples of monocyclic aliphatic rings include cycloalkane rings having 4 to 10 carbon atoms. Among these, the cyclohexane ring is preferred.

[0082] A monocyclic aliphatic ring is represented by -Q in formula (A-3). ３ -A ３ Other substituents may be present. Examples of substituents include halogen atoms, C1-C20 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkynyl groups, C1-C20 alkoxy groups, C6-C30 aryl groups, C6-C30 aryloxy groups, amino groups, hydroxyl groups, C1-C20 hydroxyalkyl groups, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, or ether-bond-containing groups.

[0083] Examples of alkyl groups having 1 to 20 carbon atoms include the alkyl groups exemplified in <<vinyl resin>>. Examples of alkenyl groups having 2 to 10 carbon atoms include the alkenyl groups exemplified in <<vinyl resin>>. Examples of alkynyl groups having 2 to 10 carbon atoms include the alkynyl groups exemplified in <<vinyl resin>>. Examples of alkoxy groups having 1 to 20 carbon atoms include the alkoxy groups exemplified in <<vinyl resin>>.

[0084] Examples of aryl groups having 6 to 30 carbon atoms include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group.

[0085] Examples of aryloxy groups having 6 to 30 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, ester groups, amide groups, sulfonyl-containing groups, sulfide-containing groups, and ether-bond-containing groups include those exemplified in <<Resin (A-2)>>>.

[0086] As the structural unit represented by formula (A-3), the structural unit represented by the following formula (Xa) is preferred.

[0087] (In equation (Xa), R ３ This represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, or an amino group. Q ３ This represents a divalent linking group. A ３ (This represents a monovalent organic group.)

[0088] A in equations (A-3) and (Xa) ３ Examples of the number of carbon atoms include 1 to 50. A in formulas (A-3) and (Xa) ３ Examples include aromatic hydrocarbon rings, which may have substituents. Aromatic hydrocarbon rings may be monorings or fused rings. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, pyrene rings, and the like.

[0089] A in equations (A-3) and (Xa) ３In the case of an aromatic hydrocarbon ring which may have substituents, examples of substituents that may have substituents include halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, amino groups, hydroxyl groups, hydroxyalkyl groups having 1 to 20 carbon atoms, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, or ether-bond-containing groups.

[0090] Q in equations (A-3) and (Xa) ３ The number of atoms constituting the divalent linking group in this compound can range from 1 to 60, for example.

[0091] Q ３ Examples include the following linking group (Qa).

[0092] (In equation (Qa), X ５ is -O-, -S-, -COO-, -N(R ａ ) CO- or -N(R ａ ) represents R ａ X represents a hydrogen atom or a monovalent group. ５ However, -N(R ａ )- When A ３ and R ａ They may also form a ring structure together. *1 represents a bond that connects to a monocyclic aliphatic ring. *2 is A ３ (This represents a bonding operation that connects to [another element].)

[0093] The resin (A-3) is, for example, a reaction product of a polymer (X1) having repeating units represented by the following formula (X1) and a compound (X3) having a functional group that can react with an aromatic carboxylic acid (X2) or an epoxy group.

[0094] (In formula (X1), R ３ (This represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a nitro group, or an amino group.)

[0095] The polymer having repeating units represented by formula (X1) may be a commercially available product. Examples of commercially available products include EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.).

[0096] Examples of aromatic carboxylic acids (X2) include monocyclic aromatic carboxylic acids and fused cyclic aromatic carboxylic acids. Examples of monocyclic aromatic carboxylic acids include benzoic acid. Examples of fused cyclic aromatic carboxylic acids include naphthalenecarbon and anthracenecarboxylic acid. Examples of compounds having a functional group that can react with an epoxy group (X3) include phenol compounds, compounds having a thiol group, and compounds having an NH group. Examples of phenol compounds include any compound having a phenolic hydroxyl group, such as phenol, 1-naphthol, 2-naphthol, anthracene-1-ol, anthracene-2-ol, anthracene-9-ol, and 1-hydroxypyrene. Compounds having a thiol group are not particularly limited as long as they have a thiol group, and examples include benzenethiol, naphthalenchiol, propylenethiol, hexanethiol, isopropylthiol, cyclopentylthiol, cyclohexylthiol, allylthiol, isocyanurate thiol, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, thiophenthiol, franticol, etc. Compounds having an NH group are not particularly limited as long as they have an NH group, and examples include aniline, N-methylaniline, N-ethylaniline, N-cyclohexylaniline, N-allylaniline, N-(prop-2-in-1-yl)aniline, aminonaphthalene, methylamine, ethylamine, allylamine, propargylamine, cyclopentylamine, cyclohexylamine, dimethylamine, diethylamine, dipropargylamine, diallylamine, dicyclohexylamine, diphenylamine, dinaphthylamine, cyanuric acid, hydantoin, triazine, 1,3,5-triazinan-2,4-dione, uracil, N-methylacetamide, N-vinylacetamide, 2-pyrrolidine, maleimide, succinimide, piperidine, and N-methylmethacrylamide.

[0097] Examples of resin (A-3) include the following polymers (X-1) to (X-13). The following polymers have two or three repeating units.

[0098] Examples of resin (A-3) include the polymers described in International Publication No. 2011 / 021555. The contents of International Publication No. 2011 / 021555 are incorporated herein to the same extent as if they were fully expressed.

[0099] The weight-average molecular weight of resin (A-3) is not particularly limited, but is preferably 1,000 to 15,000, more preferably 1,500 to 10,000, and particularly preferably 2,000 to 7,000.

[0100] <<Resin (A-4)>> Resin (A) preferably contains at least a resin having a structural unit represented by the following formula (A-4) (hereinafter also referred to as "Resin (A-4)"). Resin (A-4) corresponds to a resin having an ether bond, thioether bond, amide bond, or ester bond in its side chain. Resin (A-4) may be a homopolymer having one type of structural unit, or a copolymer having two or more types of structural units.

[0101] (In formula (A-4), Ar ４ L represents a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or pyrene ring, which may have substituents. ５m5 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, and m5 represents an integer from 0 to 5. When m5 is 2 to 5, multiple L ５ They may be the same or they may be different. ４ Q represents a divalent organic group that makes up the main chain. ４ Q represents a divalent linking group having an ether bond, thioether bond, amide bond, or ester bond. ５ (where k represents a monovalent organic group which may have substituents; k represents an integer from 1 to 3.)

[0102] Ar ４ Examples of substituents it may have include halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, amino groups, hydroxyl groups, hydroxyalkyl groups having 1 to 20 carbon atoms, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, or ether-bond-containing groups.

[0103] T ４ Examples of divalent organic groups include alkylene groups having 1 to 20 carbon atoms, alkenylene groups having 2 to 20 carbon atoms, alkylylene groups having 2 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, ether bond-containing groups, -CO-, -COO-, -NHCO-, or groups formed by combining two or more of these groups. ４ The divalent organic groups include groups formed by combining a methylene group and an aryl group, groups formed by combining a methine group and an aryl group, groups containing alicyclic hydrocarbons, and quaternary carbon atoms in derivatives containing a fluorene structure.

[0104] T ４ The alkylene group may be linear, branched, or cyclic.

[0105] T ４Examples of alkylene groups include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, s-butylene, t-butylene, cyclobutylene, 1-methylcyclopropylene, 2-methylcyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, and 1-ethyl-n-propylene. , cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2, 2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group , 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples include 3-trimethylcyclopropylene group, 1-ethyl-2-methylcyclopropylene group, 2-ethyl-1-methylcyclopropylene group, 2-ethyl-2-methylcyclopropylene group, 2-ethyl-3-methylcyclopropylene group, n-heptylene group, n-octylene group, n-nonylene group, and n-decanylene group.

[0106] In this specification, "alkenylene group" refers to a divalent group that is produced when two hydrogen atoms are lost from an aliphatic hydrocarbon having one carbon-carbon double bond in its molecule, and is generally -C ｎ H ２ｎ－２ It is represented as - (where n is a positive integer greater than or equal to 2). An alkenylene group with 2 to 20 carbon atoms refers to a linear, branched, or cyclic alkenylene group containing 2 to 20 carbon atoms, such as -CH=CH- and -CH=CHCHCH. ２ -, - (CH ３ Examples include C=CH-, etc.

[0107] In this specification, "alkynylene group" refers to a divalent group that is produced when two hydrogen atoms are lost from an aliphatic hydrocarbon having one carbon-carbon triple bond in its molecule, and is generally -C ｎ H ２ｎ－４ It is represented as - (where n is a positive integer greater than or equal to 2). An alkynylene group with 2 to 20 carbon atoms refers to a linear, branched, or cyclic alkynylene group containing 2 to 20 carbon atoms, such as -CH≡CH- and -C≡C-CH ２ -, - (CH ２ ) ２ Examples include -C≡C-.

[0108] T ４At least one hydrogen atom of the divalent organic group may be substituted with a substituent. Examples of such substituents include halogen atoms, C1-C20 alkyl groups, C2-C10 alkenyl groups, C2-C10 alkynyl groups, C1-C20 alkoxy groups, C6-C30 aryl groups, C6-C30 aryloxy groups, amino groups, hydroxyl groups, C1-C20 hydroxyalkyl groups, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, or ether-bond-containing groups. There may be one substituent or multiple substituents. When there are multiple substituents, the substituents may be the same or different.

[0109] Q ５ Examples of monovalent organic groups include linear, branched, or cyclic alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, or groups combining these. ５ At least one hydrogen atom in the monovalent organic group may be substituted with a substituent. ５ Examples of substituents it may have include halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, amino groups, hydroxyl groups, hydroxyalkyl groups having 1 to 20 carbon atoms, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, or ether-bond-containing groups.

[0110] Q ４ Examples include the following linking group (Qb).

[0111] (In formula (Qb), X ６ is -O-, -S-, -COO-, -N(R ｂ) CO- or -N(R ｂ ) represents R ｂ X represents a hydrogen atom or a monovalent group. ６ However, -N(R ｂ )- When Q ５ and R ｂ These may form a ring structure together. *1 is Ar in formula (A-4) ４ This represents a combination with, and *2 is Q in equation (A-4). ５ (This represents a combination of two elements.)

[0112] The resin (A-4) may be one type or a combination of two or more types. For example, Ar ４ It may be a copolymer having multiple structural units of the same type, for example, Ar ４ Ar such that it has a structural unit containing a benzene ring and a structural unit containing a naphthalene ring. ４ Copolymers having multiple structural units of different types are also not excluded from the scope of the present invention.

[0113] Furthermore, in equation (A-4), k is an integer from 1 to 3, for example, Ar ４ In the ring represented by -Q ４ - Q ５ The group represented by may be not just one, but multiple (two or three) bonded together.

[0114] Resin (A-4) can be obtained, for example, by reacting a polymer having a structural unit represented by the following formula (A-4-1) with a carboxylic acid, a phenol compound, a compound having a thiol group, or a compound having an NH group.

[0115] (In formula (A-4-1), Ar ４ , L ５ , m5, k, and T ４ This is Ar in equation (A-4). ４ , L ５ , m5, k, and T ４ These are synonymous. (E is a group containing an epoxy group.)

[0116] Examples of carboxylic acids include carboxylic acids having 1 to 20 carbon atoms. Examples of carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, capric acid, stearic acid, oleic acid, and linoleic acid. Examples of aromatic carboxylic acids include monocyclic aromatic carboxylic acids and fused-ring aromatic carboxylic acids. Examples of monocyclic aromatic carboxylic acids include benzoic acid. Examples of fused-ring aromatic carboxylic acids include naphthalene carboxylic acid and anthracene carboxylic acid.

[0117] The phenolic compound is not particularly limited as long as it is a compound having a phenolic hydroxyl group. Examples of phenolic compounds include phenol, 1-naphthol, 2-naphthol, anthracene-1-ol, anthracene-2-ol, anthracene-9-ol, and 1-hydroxypyrene. The compound having a thiol group is not particularly limited as long as it has a thiol group, and examples include benzenethiol, naphthalenchiol, propylenethol, hexanethiol, isopropylthiol, cyclopentylthiol, cyclohexylthiol, allylthiol, isocyanurate thiol, isocyanurate tris[2-(3-mercaptopropionyloxy)ethyl]ethyl, thiophenethiol, and franticol. Compounds having an NH group are not particularly limited as long as they have an NH group, and examples include aniline, N-methylaniline, N-ethylaniline, N-cyclohexylaniline, N-allylaniline, N-(prop-2-in-1-yl)aniline, aminonaphthalene, methylamine, ethylamine, allylamine, propargylamine, cyclopentylamine, cyclohexylamine, dimethylamine, diethylamine, dipropargylamine, diallylamine, dicyclohexylamine, diphenylamine, dinaphthylamine, cyanuric acid, hydantoin, triazine, 1,3,5-triazinan-2,4-dione, uracil, N-methylacetamide, N-vinylacetamide, 2-pyrrolidine, maleimide, succinimide, piperidine, and N-methylmethacrylamide.

[0118] The carboxylic acids, phenolic compounds, compounds having a thiol group, or compounds having an NH group described above may have substituents. Examples of substituents include halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, amino groups, hydroxyl groups, hydroxyalkyl groups having 1 to 20 carbon atoms, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, sulfonyl-containing groups, thiol groups, sulfide-containing groups, or ether-bond-containing groups.

[0119] The resin (A-4) is not particularly limited, for example, as long as it satisfies the structural unit of formula (A-4-1). It may be manufactured by a method known to the present day. Commercial products may also be used. Examples of commercial products include 1032H60, 157S70, 1031S, YX7700 (all manufactured by Mitsubishi Chemical Corporation), EPPN-201, EOCN-104S, EOCN-103S, EOCN-102S, EOCN-1020, EOCN-1020-70, EOCN-1020-55, NC-2000-L, NC-3000, NC-3000-L, NC-3000-H, N C-3000FH-75M, NC-3100, NC-7000L, NC-7000H, NC-3500, NC-7300-L, XD-1000, XD-1000-H, XD-1000-2L , EPPN-502H, EPPN-502HY, EPPN-501H, EPPN-503, FAE-2500, CER-1020, CER-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), EP ICLON® series (HP-5000, HP-7200, HP-6000, HP-9900-75M, HP-7241, N-660, N-665, N-670, N-673, N-680, N-695, N-655-EXP-S, N-662-EXP-S, N-665-EXP, N-665-EXP-S, N-672-EXP, N-670-EXP-S, N-685) Examples include EXP-S, N-673-80M, N-680-75M, N-690-75M, N-740, N-770, N-775, N-740-80M, N-770-70M, N-865, N-865-80M, TSR-960, TSR-601, 1650-75MPX, EXA-850CRP, 840-S, 850-S, 860, 1055) (all manufactured by DIC Corporation).

[0120] Examples of polymers having a structural unit represented by formula (A-4-1) are given below.

[0121]

[0122] The weight-average molecular weight of resin (A-4) is not particularly limited, but is preferably 800 to 20,000, more preferably 900 to 15,000, and particularly preferably 1,000 to 10,000.

[0123] <<Resin (A-5)>> Resin (A) preferably contains a reaction product of reaction raw materials comprising a compound having two or more epoxy groups and a compound having at least two groups that can react with epoxy groups. Hereinafter, this reaction product will also be referred to as resin (A-5).

[0124] Examples of compounds having two or more epoxy groups include the compound represented by formula (1B), which was also mentioned in the description of resin (A-2). Examples of compounds having at least two groups that can react with epoxy groups include the compound represented by formula (1A), which was also mentioned in the description of resin (A-2).

[0125] Furthermore, examples of compounds having two or more epoxy groups include the compound represented by the following formula (A5-1). (In formula (A5-1), Ar １ and Ar ２ Each of these represents an aromatic ring with 6 to 40 carbon atoms, which may be independently substituted, and Ar １ and Ar ２ At least one of them is a naphthalene ring, L １ represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted, or an alkenylene group having 2 to 10 carbon atoms which may be substituted. １ and T ２ Each of these independently represents a single bond, an ester bond, or an ether bond, and E represents an epoxy group.

[0126] Furthermore, examples of compounds having at least two groups that can react with epoxy groups include the compound represented by the following formula (A5-2). (In formula (A5-2), X １ (This represents a base represented by the following formulas (2), (3), (4), or (0).) (In equations (2), (3), (4), and (0), R １ and R ２Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, and the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, and alkylthio groups having 1 to 10 carbon atoms, and R １ and R ２ They may be bonded to each other to form a ring with 3 to 10 carbon atoms, R ３ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with a group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, halogen atoms, alkoxy groups having 1 to 10 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 10 carbon atoms. * represents a bond. *1 represents a bond that bonds to the carbon atom in formula (A5-2). *2 represents a bond that bonds to the nitrogen atom in formula (A5-2).

[0127] The compound represented by formula (A5-1) may be a commercially available product. Examples of commercially available products include EPICLON HP-4770, HP-6000, and WR-600 (all manufactured by DIC Corporation).

[0128] Furthermore, as the compound represented by formula (A5-1), a compound having two epoxy groups and having the following general formula as described in Japanese Patent Publication No. 2007-262013 may be used. (In formula (A5-3), R ３ represents a hydrogen atom or a methyl group, and Ar independently represents a naphthylene group, a phenylene group, or a naphthylene group or phenylene group having an alkyl group or phenyl group with 1 to 4 carbon atoms as a substituent, R ２ Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n and m are integers from 0 to 2, and either n or m is 1 or greater, R １represents a hydrogen atom or an epoxy group-containing aromatic hydrocarbon group represented by the following formula (A5-3-1). However, the total number of aromatic nuclei in the formula is 2 to 8. Furthermore, in formula (A5-3), the bond position to the naphthalene skeleton may be either of the two rings constituting the naphthalene ring. (In formula (A5-3-1), R ３ (where represents a hydrogen atom or a methyl group, Ar independently represents a naphthylene group, a phenylene group, or a naphthylene or phenylene group having an alkyl group or phenyl group with 1 to 4 carbon atoms as a substituent, and p is an integer of 1 or 2.)

[0129] Specific examples of compounds having at least two groups that are reactive with epoxy groups include the compounds listed below.

[0130] The above reaction may be carried out, for example, in the presence of a catalyst. Examples of catalysts include quaternary phosphonium salts such as tetrabutylphosphonium bromide and ethyltriphenylphosphonium bromide, and quaternary ammonium salts such as benzyltriethylammonium chloride. The amount of catalyst used can be selected from a range of 0.1 to 20% by mass relative to the total mass of the reaction materials used in the reaction. The reaction temperature and time can be selected to the optimal conditions, for example, from a range of 50 to 160°C and 2 to 50 hours.

[0131] The weight-average molecular weight of resin (A-5) is not particularly limited, but is preferably 1,000 to 15,000, more preferably 1,500 to 10,000, and particularly preferably 2,000 to 7,000.

[0132] <<Resin (A-6)>> The resist underlayer film forming composition preferably contains a resin having a composite structural unit represented by the following formula (A-6) (hereinafter also referred to as "resin (A-6)"). Resin (A-6) is a resin obtained by a reaction that generates a covalent bond between the carbon atoms constituting the aromatic ring of the unit structure (A) described later and the carbon atoms in the unit structure (B) described later. In this specification, resin (A-6) may be referred to as "novolac resin".

[0133] (In formula (A-6), A represents a structure having an aromatic ring (unit structure (A)), and B represents a structure having one or more carbon atoms (unit structure (B)).)

[0134] [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.

[0135] (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).

[0136] 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.

[0137] 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).

[0138] (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.

[0139] (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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] (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.

[0145] (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.

[0146] Examples of non-aromatic monocyclic compounds (aliphatic rings, aliphatic monocyclic compounds) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] (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.

[0152] (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.

[0153] (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.

[0154] <<<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.

[0155] 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.

[0156] Preferably, such aromatic ring has 4 to 30 carbon atoms, more preferably 4 to 24 carbon atoms.

[0157] 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.).

[0158] 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.

[0159] The "aromatic ring" may contain at least one heteroatom selected from N, S, and O on, within, or between the rings.

[0160] 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 ２ Examples 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.

[0161] <<<A-2: Examples of the skeleton constituting the unit structure (A)>>> The unit structure (A) has, for example, a skeleton having aromatic rings.

[0162] Preferred aromatic ring skeletons include aromatic amine skeletons, nitrogen-containing aromatic heterocyclic skeletons, and phenol skeletons.

[0163] 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 (A-6). 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 (A-6).

[0164] 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 ２A 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 ２ A 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.

[0165] <<<<<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 These are, independently, hydrogen, O, S, and NR. ｂ , NR ｂCO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group or aromatic ring residue having 2 to 15 carbon atoms, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ (This represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.)

[0166] 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.

[0167] Examples of skeletons represented by formula (A-1a) 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.

[0168] Examples of skeletons represented by formula (A-1b) include the following:

[0169] Examples of skeletons represented by formula (A-1c) include the following:

[0170] <<<<<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 These are, independently, hydrogen, O, S, and NR. ｂ , NR ｂ CO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group or aromatic ring residue having 2 to 15 carbon atoms, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ R represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. ２２Each 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. R is independently a hydrogen atom, O, S, and NR. ｂ , NR ｂ CO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group, aromatic ring residue, or bond with L, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ n1 represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 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 by bonding with each other, or by bonding between nitrogen atoms and Ar ２１ 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.)

[0171] 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.

[0172] Two adjacent R２２ Examples of unsaturated aliphatic rings formed by these elements together include the following rings. These aliphatic rings may have substituents.

[0173] 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.

[0174] <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.

[0175] Furthermore, in the unit structure (A), R in formula (A-2d) １１ R may be a substituent. １１ If R is a substituent or aromatic group, １１For 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.

[0176] 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 with 6 to 30 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, or alkynyl groups with 2 to 10 carbon atoms.)

[0177] 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.)

[0178] Here, X ０ The monocyclic portion containing refers to the monocyclic portion represented by the following formula (AP011) in formula (A-2d).

[0179] 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 with 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. ２２ Each 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.

[0180] <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).

[0181] 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.

[0182] 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, 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.

[0183] 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 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 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.

[0184] <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-.)

[0185] 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 ３２Examples of aromatic rings formed by these rings together with the carbon atoms bonded to them include fluorene rings, benzofluorene rings, and dibenzofluorene rings.

[0186] 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.

[0187] Examples of skeletons represented by formula (A-2b-1) include the following:

[0188] Examples of skeletons represented by formula (A-2b-2) include the following:

[0189]

[0190] Examples of skeletons represented by formula (A-2c-2) or formula (A-2c-3) include the following:

[0191] Examples of skeletons represented by formula (A-2c-4) include the following:

[0192] Examples of skeletons represented by formula (A-2d) include the following:

[0193] Examples of skeletons represented by formula (A-2e) include the following. Note that there may be overlap between specific examples of skeletons represented by formula (A-2d) and specific examples of skeletons represented by formula (A-2e).

[0194] Examples of skeletons represented by formula (A-3a) include the following:

[0195] Examples of skeletons represented by formula (A-3b) include the following:

[0196] Other examples of nitrogen-containing aromatic heterocyclic skeletons include the following:

[0197] <<<<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.

[0198] Examples of phenol skeletons include those represented by the following formula (A-4a). 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.)

[0199] 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. ２ represents 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.

[0200] Ar ４１ Examples of aromatic rings in the residues of the aromatic ring include aromatic rings represented by the following formula (G3). These aromatic rings may have substituents.

[0201] X １ , and X ２Examples 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.

[0202] 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.

[0203] 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 ５１ Each 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.

[0204] 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.

[0205] n11, for example, can each independently represent either 1 or 2.

[0206] 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.

[0207] 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.

[0208] 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-.)

[0209] n31, for example, independently represents 1 or 2. n32 and n33, for example, independently represent 0, 1, or 2.

[0210] Examples of skeletons represented by formula (A-4a) 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.

[0211] Examples of skeletons represented by formula (A-5a) include the following:

[0212] Examples of skeletons represented by formula (A-5b) include the following:

[0213] Examples of skeletons represented by formula (A-5c) include the following:

[0214] Examples of skeletons represented by formula (A-5d) include the following:

[0215] Examples of skeletons represented by formula (A-6a) include the following:

[0216] Examples of skeletons represented by formula (A-6b-1) or formula (A-6b-2) include the following:

[0217] Examples of skeletons represented by formula (A-6c) include the following:

[0218] Examples of skeletons represented by formula (A-6d) include the following:

[0219] Examples of skeletons represented by formula (A-7a), formula (A-7b), or formula (A-7c) include the following:

[0220] Examples of skeletons represented by formula (A-8a-1) or formula (A-8a-2) include the following:

[0221] Examples of skeletons represented by formula (A-8b) include the following:

[0222] Examples of skeletons represented by formula (A-8c) include the following:

[0223] Examples of skeletons represented by formula (A-8d) include the following:

[0224] Examples of skeletons represented by formula (A-8e) include the following:

[0225] Examples of skeletons represented by equation (A-8f) include the following:

[0226] Examples of skeletons represented by formula (A-8g-1) or formula (A-8g-2) include the following:

[0227] Other skeletons of the phenol skeleton include, for example, the following:

[0228] 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).

[0229] (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. ｓａEach 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.

[0230] <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.

[0231] <R ｓｂ , and R ｓｃ > R ｓｂ , and R ｓｃ Examples 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.)

[0232] <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).

[0233] <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.

[0234] <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.

[0235] < X ｓａ and X ｓｂ > X ｓａ and X ｓｂExamples 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.

[0236] Examples of substituents represented by formula (S1) include the following groups. (* indicates a link.)

[0237] Examples of substituents represented by formula (S2) include the following groups. (* indicates a link.)

[0238] Examples of substituents represented by formula (S3) include the following groups. (* indicates a link.)

[0239] Examples of substituents represented by formula (S4) include the following groups. (* indicates a link.)

[0240] Examples of substituents represented by formula (S5) include the following groups. (* indicates a link.)

[0241] Examples of substituents represented by formula (S6) include the following groups. (* indicates a link.)

[0242] Examples of substituents represented by formula (S7) include the following groups. (* indicates a link.)

[0243] Other substituents include, for example, the following groups: (* indicates a link.)

[0244] << (In formula (A-10), R １ R represents a single bond or a divalent organic group with 1 to 20 carbon atoms. ２ (where * represents a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms, and * represents a bond.)

[0245] In formula (A-10), the bond is preferably bonded to a nitrogen atom or an oxygen atom. １ Examples include linear or branched alkylene groups having 1 to 20 carbon atoms, which may be substituted with hydroxyl groups, aryl groups (phenyl groups, substituted phenyl groups, etc.), or halogen atoms. Examples of linear alkylene groups include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, hexylene groups, etc. ２ Examples of these include linear or branched alkyl groups, alkenyl groups, alkynyl groups, and aryl groups having 1 to 20 carbon atoms, which may be substituted with hydroxyl groups, aryl groups (phenyl groups, substituted phenyl groups, etc.), or halogen atoms. Examples of alkyl groups include the alkyl group in formula (B1) described later. Examples of alkenyl groups include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, and 2-methyl-2-propenyl group. Examples of alkynyl groups include ethynyl group, 1-propynyl group, and propargyl group (2-propynyl group). In addition, examples of alkynyl groups include groups in which the double bond of the alkenyl group listed above is replaced with a triple bond.

[0246] 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.

[0247] (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.

[0248]

[0249] (Examples of unit structures composed of nitrogen-containing aromatic heterocyclic skeletons)

[0250] (Examples of unit structures composed of a phenol skeleton)

[0251] <<<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. An aldehyde equivalent is an organic compound that enables covalent bonding with an aromatic ring and is 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 an organic compound having a carbon-carbon unsaturated bond. 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).

[0252] <<<<<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.

[0253] 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.

[0254] Furthermore, the two bonds in formula (B1) can each be covalently bonded to the respective aromatic rings in the two unit structures (A).

[0255] In the definitions of R and R' in formula (B1), refer to (I-3) and (I-4) above for "aromatic ring" and "heterocyclic ring."

[0256] 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.

[0257] Preferably, R and R' are each independently phenyl, naphthalenyl, anthracenyl, phenantrenyl, naphthalenyl, and pyrenyl.

[0258] 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).)

[0259] Examples of Ar aromatic rings include the aromatic ring represented by formula (G1).

[0260] 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.)

[0261] For example, when obtaining resin (A-6), the carbonyl groups in formulas (B-1a) and (B-1b) are converted to *-C-* in formula (B1).

[0262] 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.

[0263]

[0264] <<<<<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).

[0265] 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.

[0266] 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.

[0267] 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.

[0268] 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.

[0269] 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.

[0270] For example, when obtaining resin (A-6), 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 (A-6), 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 *.

[0271] An example of formula (B-2a) is the following compound.

[0272] An example of formula (B-2b) is the following compound.

[0273] An example of formula (B-2c) is the following compound.

[0274] 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.

[0275]

[0276] <<<<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.

[0277] 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).

[0278] 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.

[0279] 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.

[0280] x and y represent the numbers X and Y, respectively, and each can independently represent either 0 or 1.

[0281] 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).

[0282] 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),

[0283] 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.

[0284] 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 to the unit structure (A) is not particularly limited. Needless to say, the structure may include the example structure as part of the whole.

[0285] 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.

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292] 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.

[0293] 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.

[0294] 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).

[0295] 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.

[0296] Novolac resins having the structure represented by formula (A-6) can be prepared by known methods. For example, a cyclic compound 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.

[0297] 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.

[0298] 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).

[0299] 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.

[0300] 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.

[0301] The content of resin (A) in the resist underlayer film forming composition is not particularly limited, but is preferably 30% to 95% by mass, more preferably 50% to 90% by mass, and particularly preferably 60% to 85% by mass relative to the film constituent components in the resist underlayer film forming composition. Film constituent components refer to components in the resist underlayer film forming composition other than the solvent.

[0302] <Photoacid Generator (B)> The photoacid generator (B) has a cation part and an anion part.

[0303] <<Cation part>> The cation part is an aromatic onium cation having a halogen atom bonded to an aromatic ring. Examples of such aromatic onium cations include aromatic sulfonium cations and aromatic iodonium cations. In this invention, the halogen atom in "halogen atom bonded to an aromatic ring" is assumed to be nonionic. Therefore, in the iodonium cation, "I ＋ " is not included in "halogen atoms bonded to an aromatic ring".

[0304] Examples of halogen atoms bonded to an aromatic ring include chlorine, fluorine, bromine, and iodine atoms. The number of halogen atoms bonded to the aromatic ring in the cation is not particularly limited; there may be one or two or more. If there are two or more halogen atoms bonded to the aromatic ring in the cation, these halogen atoms may be bonded to the same aromatic ring or to different aromatic rings. Furthermore, if there are two or more halogen atoms bonded to an aromatic ring, these halogen atoms may be the same halogen atom or to different halogen atoms.

[0305] The cation portion may or may not have an aromatic hydroxyl group. An aromatic hydroxyl group refers to a hydroxyl group bonded to an aromatic ring.

[0306] Examples of aromatic sulfonium cations include the sulfonium cation represented by the following formula (C1-1). Examples of aromatic iodonium cations include the iodonium cation represented by the following formula (C1-2). (In formula (C1-1), 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 equations (ii) to (iv) is, and R １０１ , R １０２ , and R １０３ At least one of them has a halogen atom bonded to an aromatic ring. (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 (C1-2), 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 bonded to each other to form a ring. However, R １０４ , and R １０５ At least one of them has a halogen atom bonded to an aromatic ring.

[0307] 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 20.

[0308] 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, 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.

[0309] Examples of sulfonium cations represented by formula (C1-1) include the sulfonium cation represented by the following formula (C1-1-1). (In formula (C1-1-1), each Ar independently represents an optionally substituted aromatic hydrocarbon group, wherein at least one of the three Ars has a halogen atom bonded to an aromatic ring.)

[0310] 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.

[0311] Examples of sulfonium cations represented by formula (C1-1-1) include the following cations.

[0312] Examples of sulfonium cations represented by formula (C1-1) include the sulfonium cation represented by the following formula (C1-1-2). (In formula (C1-1-2), each Ar independently represents an optionally substituted aromatic hydrocarbon group, provided that at least one of the three Ars has a halogen atom bonded to an aromatic ring.)

[0313] 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.

[0314] Examples of sulfonium cations represented by formula (C1-1-2) include the following cations.

[0315] Examples of iodonium cations represented by formula (C1-2) include the iodonium cation represented by the following formula (C1-2-1). (In formula (C1-2-1), each Ar independently represents an optionally substituted aromatic hydrocarbon group, wherein at least one of the two Ars has a halogen atom bonded to an aromatic ring.)

[0316] 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.

[0317] Examples of iodonium cations represented by formula (C1-2-1) include the following cations.

[0318] Examples of iodonium cations represented by formula (C1-2) include the iodonium cation represented by the following formula (C1-2-2). (In formula (C1-2-2), each Ar independently represents an optionally substituted aromatic hydrocarbon group, provided that at least one of the two Ars has a halogen atom bonded to an aromatic ring.)

[0319] 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.

[0320] Examples of iodonium cations represented by formula (C1-2-2) include the following cations.

[0321] <<Anionic part>> The anionic part is not particularly limited. Examples of anionic parts include sulfonic acid anions. Examples of sulfonic acid anions include R １０１ SO ３ － (R １０１ R represents a monovalent organic group having 1 to 40 carbon atoms. １０１The 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.

[0322] The sulfonate anion may be, for example, the anion represented by the following formula (An), or it may be an anion other than the anion represented by the following formula (An). (In formula (An), R １ R represents a hydrogen atom, a fluorine atom, or a monovalent organic group having 1 to 20 carbon atoms. ２ R represents a divalent linking group. ３ and R ４ Each of these independently represents a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. ５ and R ６ Each of these independently represents a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. n1 represents an integer from 0 to 10. n2 represents an integer from 0 to 10. n3 represents an integer from 1 to 10. If n1 is 2 or more, multiple R ２ They are the same or different. If n2 is 2 or more, there are multiple R ３ They are the same or different, multiple R ４ They are the same or different. If n3 is 2 or more, there are multiple R ５ They are the same or different, multiple R ６ They are either the same or different.

[0323] The sulfonic acid anion may be, for example, an anion containing the substructure represented by the following formula (An-1), or an anion that does not contain the substructure represented by the following formula (An-1). (In formula (An-1), R ａ and R ｂ Each of these independently represents a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. * represents a bond.

[0324] The pKa of the sulfonate anion at 25°C is not particularly limited, but is preferably -6.0 to -1.0, and more preferably -5.0 to -1.5. In this specification, pKa refers to the negative common logarithm of the acid dissociation constant (Ka) in aqueous solution at 25°C, with a base of 10. pKa can be measured or calculated using pKa calculation tools such as neutralization titration, spectrophotometry, or capillary electrophoresis. For example, Patcore's Calculator Plugins can be used as a pKa calculation tool.

[0325] Examples of anions in the anion category include the following:

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332] For example, if the photoacid generator has a cation represented by the following formula, the anion part is a trifluoromethylsulfonate anion (CF ３ SO ３－ )isn't it.

[0333] When thermogravimetric analysis is performed on the photoacid generator in an air atmosphere at 205°C, the mass loss rate after 3 minutes from the start of measurement may be 0% or greater than 0%.

[0334] As the photoacid generator (B), a commercially available product may be used, or a synthesized product may be used. There are no particular restrictions on the method of synthesizing the photoacid generator (B). In the synthesis of the cation part, the anion part, and the photoacid generator, for example, the synthesis methods of photoacid generators, onium salt structures, onium salts, etc., described in Japanese Patent Publication No. 2013-152451, Japanese Patent Publication No. 2014-225005, Japanese Patent Publication No. 2018-199781, Japanese Patent Publication No. 2019-026572, Japanese Patent Publication No. 2019-038764, and International Publication No. 2023 / 223624 can be used as reference. As for the reaction during synthesis, for example, a reaction using Grignard reagent, a reaction using phosphorus pentoxide and methanesulfonic acid, etc. can be used.

[0335] The content of the photoacid generator (B) in the resist underlayer film forming composition is not particularly limited, but is preferably 0.1% to 50% by mass, more preferably 3% to 40% by mass, and particularly preferably 5% to 30% by mass, relative to the resin (A).

[0336] <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).

[0337] 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.

[0338] Examples of linear or cyclic alkyl ketones include methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0339] An example of a cyclic lactone is γ-butyrolactone.

[0340] 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.

[0341] 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.

[0342] These solvents can be used individually or in combination of two or more.

[0343] The mass percentage of the organic solvent in the solvent is not particularly limited, but 50% to 100% by mass is preferred.

[0344] 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.

[0345] <Crosslinking Agent> The resist underlayer film forming composition may contain a crosslinking agent. The crosslinking agent is not particularly limited. The crosslinking agent has a different structure from resin (A) of the present invention.

[0346] 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.

[0347] 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.

[0348] 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.

[0349] 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.

[0350] 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.

[0351] 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.

[0352] 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.

[0353] 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.

[0354] Examples of glycoluryl derivatives represented by formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0355] 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).

[0356] (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.

[0357] (In formula (3d), R １ (This represents a methyl group or an ethyl group.)

[0358] 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.

[0359] Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which one to four methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, and tetramethoxyethylurea.

[0360] 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.)

[0361] 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.

[0362] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0363] 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.

[0364] 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.

[0365] The molecular weight of the crosslinking agent is not particularly limited, but it is preferably 1,000 or less.

[0366] 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 resin (A) of the present invention.

[0367] <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.

[0368] Only one type of curing catalyst may be used, or two or more types may be used in combination.

[0369] 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.

[0370] <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.

[0371] 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.

[0372] 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.

[0373] (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.

[0374] 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.

[0375] 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.

[0376] 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.

[0377] 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).

[0378] 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)

[0379] (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.

[0380] (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.

[0381] 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.

[0382] 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.

[0383] 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).

[0384] 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.

[0385] Examples of resist compositions include the following compositions.

[0386] 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).

[0387] 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.

[0388] 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 periods of groups 3 to 15 of the periodic table.

[0389] 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.

[0390] (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.)

[0391] 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.

[0392] [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.

[0393] Examples of resist films include the following:

[0394] 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.

[0395] (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.)

[0396] Examples of resist materials include the following:

[0397] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0398] (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.

[0399] A resist material comprising a base resin containing a polymer having repeating units represented by the following formula (a).

[0400] (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.

[0401] 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.

[0402] [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.

[0403] 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).

[0404] [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.

[0405] 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.

[0406] A coating comprising a metal oxo-hydroxo network having organic ligands via metal-carbon bonds and / or metal-carboxylate bonds.

[0407] Inorganic oxo / hydroxo-based compositions.

[0408] 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).

[0409] 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.

[0410] An aqueous solution of an inorganic pattern-forming precursor comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0411] 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.

[0412] 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.

[0413] 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.

[0414] 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.

[0415] 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.

[0416] The film can be developed using either a wet process or a dry process.

[0417] 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.

[0418] 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.

[0419] 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.

[0420] 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).

[0421] 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.

[0422] 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.

[0423] 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.

[0424] 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.

[0425] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0426] The weight-average molecular weight (Mw) of the resins shown in the example below was measured 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)

[0427] 〇 Polymer Synthesis The polymers used in the resist underlayer film formation composition were synthesized using the compounds or polymer group A, catalyst group B, solvent group C, separatory solvent group D, and reprecipitation solvent group E shown below. Note that S14 was a commercially available product (manufactured by Nippon Soda Co., Ltd., trade name VP-8000).

[0428] ○ Compound or polymer group A (In the formula, Boc represents the tert-butoxycarbonyl group.)

[0429] ○Catalyst Group B Benzyltriethylammonium chloride: B1 Azobisisobutyronitrile: B2 Tetrabutylphosphonium bromide: B3 4-Hydroxy-TEMPO free radical (1 wt% PGME solution): B4 Ethyltriphenylphosphonium bromide: B5 Methanesulfonic acid: B6 Tetrabutylammonium iodide: B7

[0430] ○ Solvent Group C Propylene glycol monomethyl ether (=PGME): C1 Propylene glycol monomethyl ether acetate (=PGMEA): C2 Cyclohexanone: C3 Tetrahydrofuran: C4 25 wt% sodium hydroxide aqueous solution: C5

[0431] ○Separatory solvent group D: Butyl acetate / water: D1

[0432] ○Reprecipitation solvent group E: Methanol: E1, Methanol / water: E2

[0433] [Synthesis Examples 1 to 10 and 14] The compounds or polymers shown in Table 1 were placed in a flask, nitrogen purging was performed, and the reaction was carried out at the specified temperature and time shown in Table 1. After the reaction was complete, the polymer solution was cooled, and an ion exchange treatment was performed using cation exchange resin and anion exchange resin as needed to obtain the polymer solution (Table 1).

[0434] [Synthesis Examples 11-12] The compounds shown in Table 1 were placed in a flask, nitrogen purging was performed, and the reaction was carried out at the specified temperature and time shown in Table 1. After the reaction was complete, the polymer solution was cooled and reprecipitation was performed using the solvent shown in Table 1. After reprecipitation, the polymer was recovered by filtration and dried overnight at 40°C. After drying, the polymer was dissolved in a solvent in which it dissolves, and an ion exchange treatment was performed using cation exchange resin and anion exchange resin as needed to obtain a polymer solution (Table 1).

[0435]

[0436] The structures and weight-average molecular weights (Mw) of polymers S1 to S15 are shown below.

[0437] (In the formula, Boc represents the tert-butoxycarbonyl group.)

[0438] Preparation of resist underlayer film formation compositions Polymers (S1) to (S15), additives (CL1 to CL3, Ad1 to Ad2, PAG-1 to PAG-15 below), and solvents (PGMEA, PGME, cyclohexanone (CYH)) were mixed in the mass percentages (mass%) shown in Tables 2-1 and 2-2 below, and then filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare resist underlayer film formation compositions (M1 to M28, comparative M1 to comparative M3) (Tables 2-1 and 2-2). Note that the mass percentages (mass%) of the crosslinking agent, catalyst, and PAG in Tables 2-1 and 2-2 represent the mass percentage relative to the polymer. The mass percentage (mass%) of the solvent represents the mass percentage relative to the total solvent. The amount of solvent in each composition was adjusted to an amount suitable for obtaining the desired film thickness.

[0439]

[0440]

[0441]

[0442] [Leaching Test in Resist Solvent] Resist underlayer formation compositions (M1 to M28, comparative M1 to comparative M3) were applied onto a silicon wafer using a spin coater and baked under the baking conditions described in Table 3 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 baked at 100°C for 30 seconds. The resistance to the solvent was confirmed by comparing the film thickness before and after thinner immersion. A reduction in film thickness of 1 Å or less before and after thinner immersion was marked as "○", and a reduction of more than 1 Å was marked as "×". The results are shown in Table 3.

[0443]

[0444] [Preparation of Resist Patterns] The resist underlayer formation compositions M1 to M28 and comparative M1 to comparative M3 were applied to silicon wafers using a spinner. The silicon wafers were baked on a hot plate under the baking conditions shown in Table 3 to obtain a resist underlayer with a thickness of 5 nm. An EUV positive resist solution was spin-coated onto this, and an EUV resist layer was formed by heating at 130°C for 1 minute. Subsequently, exposure was performed using an ASML EUV exposure apparatus (NXE3400) under the conditions of NA = 0.33 and σ = 0.82 / 0.60 (outer / inner). During exposure, exposure was performed through a mask set so that the line width and the width between lines (space width) of the EUV resist would be 14 nm after development, i.e., a resist pattern with a line and space (L / S) of 1 / 1 of 14 nm would be formed. After exposure, post-exposure heating (PEB, 90°C for 1 minute) was performed, followed by cooling to room temperature (25°C) on a cooling plate. A 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name: NMD-3) was used as the photoresist developer, and paddle development was performed for 30 seconds to form a resist pattern. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern.

[0445] [Pattern Collapse Evaluation] The photoresist patterns obtained by preparing the above resist patterns using each of the resist underlayer film forming compositions M1 to M28 and comparative M1 were evaluated for the feasibility of line and space (L / S) formation. A "○" was used if the resist pattern was not collapsed, and a "×" was used if the resist pattern was collapsed. The results are shown in Table 4.

[0446]

[0447] [Roughness Evaluation] In the preparation of the above resist patterns using each of the resist underlayer formation compositions M1 to M28 and comparative M2, the EUV irradiation dose that formed a 14 nm L / S pattern was defined as the optimal irradiation energy, and the roughness at that time was evaluated as LWR (line width roughness), LER (line edge roughness), and SWR (space width roughness). A MetroLER manufactured by Fractilia was used for image analysis. For each roughness, a "○" was used if the roughness was smaller than that of comparative M2, and a "×" was used if it was larger. The results are shown in Table 5.

[0448]

[0449] [Confirmation of the effect of PAG addition] [[Pattern collapse evaluation]] The photoresist patterns obtained by preparing the above resist patterns using each of the resist underlayer film forming compositions M1-M13, M27-M28 and comparative M3 were evaluated for the ability to form 14 nm line and space (L / S). "○" was used to indicate that the target pattern was formed, and "×" was used to indicate that it was not formed. The results are shown in Table 6.

[0450] [Roughness Evaluation] Furthermore, in the preparation of the above resist patterns using the resist underlayer film formation compositions M1-M13, M27-28, and comparative M3, the EUV irradiation dose that formed a 14 nm L / S pattern was defined as the optimal irradiation energy, and the roughness at that time was evaluated as LWR (line width roughness), LER (line edge roughness), and SWR (space width roughness). A MetroLER manufactured by Fractilia was used for image analysis. For each roughness, a "○" was used if the roughness was smaller than that of comparative M3, and a "×" was used if it was larger. The results are shown in Table 6.

[0451]

Claims

A composition for forming a resist underlayer film, comprising a resin (A), a photoacid generator (B), and a solvent (C), The photoacid generator (B) has a cation portion and an anion portion, The cation portion is an aromatic onium cation having a halogen atom bonded to an aromatic ring. A composition for forming a resist underlayer film. 　 The resist underlayer film forming composition according to claim 1, wherein the resin (A) is a resin other than a vinyl resin. 　 The anionic portion is a sulfonic acid anion. The resist underlayer film forming composition according to claim 1, wherein the sulfonic acid anion does not contain a substructure represented by the following formula (An-1). (In formula (An-1), R ａ and R ｂ Each of these independently represents a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. * represents a bond. 　 The resist underlayer film forming composition according to claim 1, wherein the aromatic onium cation is an aromatic sulfonium cation or an aromatic iodonium cation. 　 The aforementioned aromatic sulfonium cation is represented by the following formula (C1-1), The aforementioned aromatic iodonium cation is represented by the following formula (C1-2): The composition for forming a resist underlayer film according to claim 4. In formula (C1-1), R １０１ , R １０２ , and R １０３ each independently represent any one of the following (i) to (iv), R １０１ and R １０２ , R １０２ and R １０３ , or R １０１ and R １０３ may be bonded to each other to form a ring. Provided that at least one of R １０１ , R １０２ , and R １０３ is any one of the following formulas (ii) to (iv), and at least one of R １０１ , R １０２ , and R １０３ has a halogen atom bonded to an aromatic ring. (i) A linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, which may have substituents and may contain halogen atoms, carbonyl groups, ester groups, ether groups, thioether groups, amide groups, lactone rings, or aryl groups. (ii) Aromatic hydrocarbon group which may have substituents and may contain -S- (iii) Aralkyl groups having 7 to 20 carbon atoms, which may have substituents. (iv) A thiophenyl group which may have a substituent In formula (C1-2), 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 bonded to each other to form a ring. However, R １０４ , and R １０５ At least one of them has a halogen atom bonded to an aromatic ring. 　 The anionic portion is a sulfonic acid anion. The resist underlayer film forming composition according to claim 1, wherein the pKa of the sulfonate anion at 25°C is -6.0 to -1.

0. The resist underlayer film forming composition according to claim 1, wherein the resin (A) is at least one of a polyester resin, a polyether resin, a novolac resin, a resin having ether bonds, thioether bonds, amide bonds, or ester bonds in its side chains, a polyimide resin, and a polyamide resin. 　 The aforementioned resin (A) includes a vinyl resin, The resist underlayer film forming composition according to claim 1, wherein the vinyl resin comprises a resin having at least one structural unit represented by the following formula (A-1). (In formula (A-1), R １ X represents a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 20 carbon atoms. ０ represents a single bond, -COO- or -CONH-, L ０ (This represents a monovalent organic group.) 　 The resist underlayer film forming composition according to claim 1, wherein the resin (A) comprises a resin having at least one of a resin having a structural unit represented by the following formula (A-2) and a resin having a structural unit represented by the following formula (A-3). (In formula (A-2), A independently represents a hydrogen atom, a methyl group, or an ethyl group, and Q １ and Q ２ Each of these independently represents a divalent organic group, X １ ~X ４ These terms independently represent a single bond, an ether bond, a thioether bond, an amide bond, or an ester bond. (In formula (A-3), T ３ Q represents a group having a monocyclic aliphatic ring that constitutes the main chain. ３ represents a divalent linking group, Ar ３ (This represents a monovalent organic group.) 　 The resist underlayer film forming composition according to claim 1, wherein the resin (A) comprises a reaction product of a reaction raw material comprising a compound having two or more epoxy groups and a compound having at least two groups that can react with epoxy groups. 　 The resin (A) includes a resin having an ether bond, a thioether bond, an amide bond, or an ester bond in its side chain. The resist underlayer film forming composition according to claim 7, wherein the resin having an ether bond, a thioether bond, an amide bond, or an ester bond in the side chain comprises a resin having at least one structural unit represented by the following formula (A-4). (In formula (A-4), Ar ４ L represents a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, or pyrene ring, which may have substituents. ５ m5 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, and m5 represents an integer from 0 to 5. When m5 is 2 to 5, multiple L ５ They may be the same or they may be different. ４ Q represents a divalent organic group that makes up the main chain. ４ Q represents a divalent linking group having an ether bond, thioether bond, amide bond, or ester bond. ５ (where k represents a monovalent organic group which may have substituents; k represents an integer from 1 to 3.) 　 The resin includes the novolac resin, The resist underlayer film forming composition according to claim 7, wherein the novolac resin comprises a resin having a composite structural unit represented by the following formula (A-6). (In formula (A-6), A represents a structure having an aromatic ring, and B represents a structure having one or more carbon atoms.) 　 The resist underlayer film forming composition according to claim 12, wherein A in formula (A-6) has a skeleton having an aromatic ring, and the skeleton is at least one of an aromatic amine skeleton, a nitrogen-containing aromatic heterocyclic skeleton, and a phenol skeleton. 　 The resist underlayer film forming composition according to claim 12, wherein A in formula (A-6) has a skeleton having an aromatic ring, and the skeleton is at least one of the following formulas (A-1a), (A-1b), (A-1c), (A-2a), (A-2b-1), (A-2b-2), (A-2c-1), (A-2c-2), (A-2c-3), and (A-2c-4), and in the skeleton, at least one hydrogen atom may be replaced by a substituent. (In formulas (A-1a) to (A-1c), Ar １１ Each of these independently represents a residue of an aromatic ring. １１ These are, independently, hydrogen, O, S, and NR. ｂ , NR ｂ CO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group or aromatic ring residue having 2 to 15 carbon atoms, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ (This represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.) (In the formula, Ar ２１ Each of these independently represents a residue of an aromatic ring. R ２１ These are, independently, hydrogen, O, S, and NR. ｂ , NR ｂ CO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group or aromatic ring residue having 2 to 15 carbon atoms, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 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 also form an unsaturated aliphatic ring together. Note that one of the unsaturated bonds in an unsaturated aliphatic ring refers to the unsaturated bond that constitutes the pyrrole ring. R represents, independently, a hydrogen atom, O, S, and NR. ｂ , NR ｂ CO, CO, COO, or linear, branched, or cyclic alkyl groups having 1 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ CO, CO, COO, or a linear, branched, or cyclic alkenyl group having 2 to 15 carbon atoms, which may be interrupted by an aromatic ring, O, S, NR ｂ , NR ｂ R represents a linear, branched, or cyclic alkynyl group, aromatic ring residue, or bond with L, which may be interrupted by CO, CO, COO, or an aromatic ring. ｂ represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 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), respectively, are bonded by two nitrogen atoms bonding to each other, or by two Ar atoms bonding to each other. ２１ They are bonded together by bonding with each other, or by bonding between nitrogen atoms and Ar ２１ 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.) 　 The resist underlayer film forming composition according to claim 12, wherein A in formula (A-6) has a skeleton having an aromatic ring, and the skeleton is at least one of the following formulas (A-4a), (A-5a), (A-5b), (A-5c), (A-5d), and (A-6a), and in the skeleton, at least one hydrogen atom may be replaced by a substituent. (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.) (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. X 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. Y １ This represents a trivalent saturated hydrocarbon group. Y ２ This represents a tetravalent saturated hydrocarbon group. 　 m1 and m2 each represent an integer between 0 and 3, independently of each other. However, the sum of m1 and m2 must be 1 or greater. 　 m3 to m5 each represent an integer between 0 and 3, independently of each other. However, the sum of m3 to m5 must be 1 or greater. 　 m6 through m8 each independently represent an integer between 0 and 3. However, the sum of m6 through m8 must be 1 or greater. 　 m9 through m12 each independently represent an integer between 0 and 3. However, the sum of m9 through m12 must be 1 or greater. (In the formula, Ar ５１ Each of these independently represents a residue in an aromatic ring. n11 each independently represents an integer from 1 to 4. 　 The resist underlayer film forming composition according to claim 14, wherein the substituent in the skeleton, which may replace at least one hydrogen atom, is one or more groups selected from 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, and ether bond-containing groups. 　 The resist underlayer film forming composition according to claim 13, wherein A in formula (A-6) has a skeleton having an aromatic ring, and in the skeleton, at least one hydrogen atom may be replaced with a group represented by the following formula (A-10). (In formula (A-10), R １ R represents a single bond or a divalent organic group with 1 to 20 carbon atoms. ２ (where * represents a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms, and * represents a bond.) 　 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. 　 The resist underlayer film forming composition according to claim 1, further comprising a crosslinking agent. 　 The resist underlayer film forming composition according to claim 19, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents. 　 The resist underlayer film forming composition according to claim 19, wherein the content of the crosslinking agent is 1% by mass to 60% by mass with respect to the resin (A). 　 The resist underlayer film forming composition according to claim 1, further comprising a curing catalyst. 　 The resist underlayer film forming composition according to claim 1, further comprising a surfactant. 　 A resist underlayer film forming composition according to claim 1, used in EB or EUV lithography. 　 The resist underlayer film forming composition according to claim 1, used for forming an underlayer film of a metal-containing resist. 　 A resist underlayer film, which is a cured product of a resist underlayer film forming composition according to any one of claims 1 to 25. Semiconductor substrate and The resist underlayer film according to claim 26, A laminate comprising the following features. 　 A step 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 25, The steps include forming a resist film on the resist underlayer film, A method for manufacturing semiconductor devices, including 　 A step 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 25, The steps include forming a resist film on the resist underlayer film, The steps include irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern, A step of etching the resist underlayer film using the resist pattern as a mask, A pattern formation method, including the following.

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