Substrate coating agent composition containing nitrogen atom, resist underlayer film, laminate, method for forming resist pattern, and method for manufacturing semiconductor device

Abstract

A substrate coating agent composition containing a nitrogen atom, comprising a resin (G) having a complex unit structure and a solvent, the complex unit structure having: a unit structure (A) having an aromatic ring, and a unit structure (B) having one or more carbon atoms, the resin (G) being a resin obtained by a reaction of generating a covalent bond between a carbon atom of the aromatic ring constituting the unit structure (A) and a carbon atom in the unit structure (B), the unit structure (A) having at least a unit structure (A-I) containing a nitrogen atom, the substrate containing a nitrogen atom being a substrate formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a film containing a nitrogen atom formed of a compound having a bond between a metal atom or a metalloid atom and a nitrogen atom, the resin (G) not being a resin synthesized only from indole and 1-naphthaldehyde.

Description

Technical Field

[0001] This invention relates to a substrate coating composition containing nitrogen atoms, a resist underlayer film, a laminate, a method for forming a resist pattern, and a method for manufacturing a semiconductor device. Background Technology

[0002] The rapid advancement of semiconductor manufacturing processes has led to a strong demand for higher quality and improved properties of the resist underlayer. For example, it is known that when the substrate used as the base of the resist underlayer contains nitrogen atoms, the diffusion of amine components can impair the resist resolution (Patent Documents 1-3). Typically, the resist film is developed immediately after formation, but due to manufacturing processes, development is sometimes performed after a long period following resist film formation. It is known that in such processes, the resist resolution changes compared to immediate exposure after coating. Furthermore, in existing processes where a resist underlayer is used to suppress amine diffusion, considering processes during or after resist image resolution, the formation of the resist underlayer causes changes in reflectivity, deterioration of pattern shape, and increased process load during pattern processing. Therefore, it is desirable to make the resist underlayer as thin as possible.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2008-39811

[0006] Patent Document 2: Japanese Patent Application Publication No. 2008-39815

[0007] Patent Document 3: Japanese Patent Application Publication No. 2010-134437 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] Therefore, the problem to be solved by the present invention is to provide a suitable coating composition that maintains stable resolution even after a long period of storage following the formation of the resist film when using a substrate containing nitrogen atoms, without affecting reflectivity or pattern processing.

[0010] Methods for solving problems

[0011] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved, and completed the present invention with the following main points.

[0012] That is, the present invention includes the following solutions.

[0013] [1] A substrate coating composition containing nitrogen atoms, comprising a resin (G) having a composite unit structure and a solvent, The above-mentioned composite unit structure has the following characteristics: Unit structures with aromatic rings (A), and Unit structures with one or more carbon atoms (B), The resin (G) described above is a resin obtained by reacting carbon atoms of the aromatic ring constituting the above-described unit structure (A) with carbon atoms in the above-described unit structure (B) to form covalent bonds. The aforementioned unit structure (A) has at least a unit structure (AI) containing nitrogen atoms. The substrate containing nitrogen atoms is a substrate formed of a compound having bonds between metal atoms or metalloid atoms and nitrogen atoms, or a substrate having a film containing nitrogen atoms formed of a compound having bonds between metal atoms or metalloid atoms and nitrogen atoms. The resin (G) described above is not a resin synthesized solely from indole and 1-naphthaldehyde.

[0014] [2] According to the substrate coating composition containing nitrogen atoms as described in [1], the above-mentioned unit structure (AI) contains a skeleton having an aromatic ring, wherein the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

[0015] [3] According to the substrate coating composition containing nitrogen atoms as described in [1] or [2], the above-mentioned unit structure (AI) includes a unit structure that does not contain a carbazole backbone.

[0016] [4] The substrate coating composition containing nitrogen atoms according to any one of [1] to [3], wherein the unit structure (AI) contains a skeleton having an aromatic ring, wherein the skeleton is at least any one of the following formulas (A-1a), (A-1b), (A-1c), (A-2a), (A-2b-1) and (A-2b-2), wherein at least one hydrogen atom may be replaced by a substituent in the skeleton.

[0017]

[0018] (In equations (A-1a) to (A-1c), Ar 11 Each residue independently represents an aromatic ring residue. R 11 Each can independently represent a hydrogen atom or a residue of an aromatic ring.

[0019] (where Ar) 21 Each of them independently represents a residue of the aromatic ring.

[0020] R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring.

[0021] R 22 Each of the two R groups independently represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or a residue of an aromatic ring. 22 They can form unsaturated aliphatic rings together. Additionally, one of the unsaturated bonds in an unsaturated aliphatic ring refers to the unsaturated bond that constitutes the pyrrole ring.

[0022] R independently represents a hydrogen atom, a residue of an aromatic ring, or a bond with L. L represents a single bond or a linker. n1 represents 1, and n2 represents 1 or 2. In formula (A-2b-2), when L is a single bond, partial structures (In1) and partial structures (In2) are bonded together by two nitrogen atoms, or by two Ar atoms. 21 They combine with each other, or through nitrogen atoms and Ar atoms. 21 To combine. In equation (A-2b-2), when L is a connecting base, L combines with N or Ar. 21 (Combined.)

[0023] [5] According to the substrate coating composition containing nitrogen atoms as described in [4], in the above-mentioned skeleton, the substituents that can replace at least one hydrogen atom are selected from one or more groups selected from halogen, alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy, amino, hydroxy, hydroxyalkyl, carboxyl, formyl, cyano, nitro, ester, amide, sulfonyl group, thiol group, thioether group and ether bond group.

[0024] [6] The substrate coating composition containing nitrogen atoms according to any one of [1] to [5], wherein the unit structure (B) comprises a unit structure (BI) derived from an aldehyde compound or an aldehyde equivalent.

[0025] [7] The substrate coating composition containing nitrogen atoms according to any one of [1] to [6], wherein the resin (G) is a resin synthesized from reactive raw materials containing amine compounds and aldehyde compounds or aldehyde equivalents.

[0026] [8] According to the substrate coating composition containing nitrogen atoms as described in [7], the amine compound contains a skeleton having an aromatic ring, wherein the skeleton is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

[0027] [9] The substrate coating composition containing nitrogen atoms according to any one of [1] to [8], wherein the solvent comprises a solvent with a boiling point of 160°C or higher.

[0028]

[10] The substrate coating composition containing nitrogen atoms according to any one of [1] to [9] further comprises at least one selected from acids and their salts, and acid-generating agents.

[0029]

[11] The substrate coating composition containing nitrogen atoms according to any one of [1] to

[10] further comprises a crosslinking agent.

[0030]

[12] According to the substrate coating composition containing nitrogen atoms as described in

[11] , the crosslinking agent is selected from at least one of amino plastic crosslinking agents and phenolic plastic crosslinking agents.

[0031]

[13] The substrate coating composition containing nitrogen atoms according to any one of [1] to

[12] further comprises a surfactant.

[0032]

[14] The substrate coating composition containing nitrogen atoms according to any one of [1] to

[13] is used for forming a resist underlayer film.

[0033]

[15] A photoresist underlayer film on a substrate containing nitrogen atoms, which is a cured product of the substrate coating composition containing nitrogen atoms as described in any one of [1] to

[14] .

[0034]

[16] The resist underlayer film according to

[15] has a thickness of less than 10 nm.

[0035]

[17] A stack comprising a substrate containing nitrogen atoms and a resist underlayer film as described in

[15] or

[16] , wherein the substrate containing nitrogen atoms is a substrate formed of a compound having bonds between metal atoms or quasi-metal atoms and nitrogen atoms, or a substrate having a film containing nitrogen atoms formed of a compound having bonds between metal atoms or quasi-metal atoms and nitrogen atoms.

[0036]

[18] According to the stacked body described in

[17] , the lower resist film is a film containing nitrogen atoms, and the film containing nitrogen atoms constitutes the outermost layer of the substrate containing nitrogen atoms.

[0037]

[19] According to the stacked body described in

[17] or

[18] , the aforementioned metal atoms or quasi-metal atoms are

[0038] (i) Silicon, (ii) Titanium, or (iii) Tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or alloys thereof.

[0039]

[20] The compound having bonds between a metal atom or a quasi-metal atom and a nitrogen atom in any one of

[17] to

[19] is SiON, SiN, TiON or TiN.

[0040]

[21] A method for forming a resist pattern for manufacturing a semiconductor includes a step of coating a substrate coating agent composition containing nitrogen atoms, as described in any one of [1] to

[14] , onto a semiconductor substrate containing nitrogen atoms and firing it to form a resist underlayer film.

[0041]

[22] A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a resist underlayer film on a semiconductor substrate containing nitrogen atoms using any one of the substrate coating compositions containing nitrogen atoms as described in [1] to

[14] . The process of forming a resist film on the aforementioned lower resist film; The process of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; The process of etching the resist underlayer film through the aforementioned resist pattern to form a patterned resist underlayer film; and The process of processing a semiconductor substrate containing nitrogen atoms through the patterned resist underlayer film described above.

[0042]

[23] A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a resist underlayer film on a semiconductor substrate containing nitrogen atoms using any one of the substrate coating compositions containing nitrogen atoms as described in [1] to

[14] . The process of forming a hard mask on the lower layer of the above-mentioned resist film; The next step is to form a resist film on the aforementioned hard mask; The process of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; The process of etching the hard mask using the aforementioned resist pattern to form a patterned hard mask; The process of etching the patterned photoresist underlayer film using the patterned hard mask to form the patterned photoresist underlayer film; and The process of processing a semiconductor substrate containing nitrogen atoms through the patterned resist underlayer film described above.

[0043]

[24] A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a resist underlayer film on a semiconductor substrate containing nitrogen atoms using any one of the substrate coating compositions containing nitrogen atoms as described in [1] to

[14] . The process of forming a hard mask on the lower layer of the above-mentioned resist film; The next step is to form a resist film on the aforementioned hard mask; The process of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; The process of etching the hard mask using the aforementioned resist pattern to form a patterned hard mask; The process of etching the patterned photoresist underlayer film through the patterned hard mask to form the patterned photoresist underlayer film. The process of removing the aforementioned hard mask; and The process of processing a semiconductor substrate containing nitrogen atoms through the patterned resist underlayer film described above.

[0044]

[25] A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a resist underlayer film on a semiconductor substrate containing nitrogen atoms using any one of the substrate coating compositions containing nitrogen atoms as described in [1] to

[14] . The process of forming a hard mask on the lower layer of the above-mentioned resist film; The next step is to form a resist film on the aforementioned hard mask; The process of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; The process of etching the hard mask using the aforementioned resist pattern to form a patterned hard mask; The process of etching the patterned photoresist underlayer film through the patterned hard mask to form the patterned photoresist underlayer film. The process of removing the aforementioned hard mask; The process of forming a vapor-deposited film on the resist underlayer after the hard mask is removed; The process of etching the above-mentioned vapor-deposited film; The process of removing the patterned resist underlayer film, leaving the patterned vapor-deposited film; and The process of processing a semiconductor substrate containing nitrogen atoms through the patterned vapor deposition film described above.

[0045]

[26] In the method of manufacturing a semiconductor device according to any one of

[23] to

[25] , the hard mask is formed by coating a composition containing inorganic materials or by vapor deposition of inorganic materials.

[0046]

[27] In the method for manufacturing a semiconductor device according to any one of

[22] to

[26] , the resist film is patterned by nanoimprinting or self-assembly film.

[0047]

[28] The hard mask described above is removed by etching or by an alkaline solution according to the semiconductor device manufacturing method described in

[24] or

[25] .

[0048] The effects of the invention

[0049] According to the present invention, a suitable coating composition can be provided that maintains stable resolution even after long-term storage following the formation of the resist film, without affecting reflectivity or pattern processing. This reduces the process load.

[0050] When the phenolic varnish resin of the present invention is coated on a substrate containing nitrogen atoms, even an ultrathin film such as less than 10 nm can suppress the diffusion of amine components contained in the substrate. When a resist film is provided on a resist film containing the resin, a regular resist pattern with a vertical shape can be formed without compromising the resolution of the resist film.

[0051] Furthermore, obtaining a vertical resist pattern can suppress the diffusion of amine components from the base film, i.e., the substrate, thus exhibiting excellent resolution even after exposure for a long time following the formation of the resist film.

[0052] Furthermore, even when coated with ultrathin films, it exhibits good coating properties for various substrate types and substrates with varying elevations, and demonstrates sufficient curing properties, thus suppressing film thickness fluctuations within the same wafer. Detailed Implementation

[0053] [Substrate coating composition containing nitrogen atoms]

[0054] The nitrogen-containing substrate coating composition of the present invention (hereinafter also simply referred to as "coating composition") comprises a resin (G) having a composite unit structure and a solvent.

[0055] The above-mentioned composite unit structure has: a unit structure with an aromatic ring (A) and a unit structure with more than one carbon atom (B).

[0056] Resin (G) is a resin obtained by reacting carbon atoms of the aromatic ring constituting unit structure (A) with carbon atoms in unit structure (B) to form covalent bonds.

[0057] The unit structure (A) has at least a unit structure (AI) containing nitrogen atoms.

[0058] The substrate containing nitrogen atoms is a substrate formed of a compound having bonds between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a film containing nitrogen atoms formed of a compound having bonds between a metal atom or a metalloid atom and a nitrogen atom.

[0059] Resin (G) is not a resin synthesized solely from indole and 1-naphthaldehyde.

[0060] In this specification, resin (G) is sometimes referred to as "phenolic varnish resin".

[0061] The resin (G), by including the above-mentioned unit structures (A) and (B), can provide a suitable coating composition that maintains stable resolution even after a long period of preservation following the formation of the resist film, without affecting reflectivity or pattern processing.

[0062] The coating composition is a coating agent used for forming a coating film on a substrate containing nitrogen atoms. Preferably, it offers the following advantages: when used for forming a resist underlayer film, even after prolonged exposure following resist film formation, a regular resist pattern with a vertical shape can be formed without compromising the resolution of the resist film. It is generally believed that using a thick-film material as the resist underlayer film can suppress the diffusion of amine components in a nitrogen-containing substrate, but this leads to increased process load in subsequent processing, increased material costs, and further deterioration of the resist shape due to reduced reflection suppression capabilities. Therefore, it is crucial to avoid such adverse effects while simultaneously suppressing the diffusion of amine components. The coating composition of the present invention provides these advantages even when used for forming an ultrathin resist underlayer film with a film thickness of less than 10 nm.

[0063] While not bound by theory, it can be considered that the mechanism by which the phenolic varnish resin of the present invention inhibits the diffusion of amine components differs from that shown in patent documents, which use acidic additives to neutralize amine components and prevent diffusion. Because the aforementioned phenolic varnish resin has a large number of aromatic rings with high carbon content in its backbone, it exhibits high rigidity, thus significantly reducing the intermolecular gaps through which amine components, as contaminants from the substrate, can diffuse, thereby preventing the diffusion of amine components.

[0064] The unit structure (A) has, for example, at least one of an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring.

[0065] Unitary structures (A) include, for example, those without heteroatoms as atoms constituting aromatic rings and atoms bonded to aromatic rings.

[0066] The unit structure (B) preferably comprises a unit structure (BI) derived from an aldehyde compound or an aldehyde equivalent.

[0067] An aldehyde equivalent is an organic compound that can covalently bond with an aromatic ring and has a ketone group; an acetal group; a ketal group; a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl, alkoxy, or halogroup bonded to the α-carbon atom of an alkyl aryl group; or a carbon-carbon unsaturated bond.

[0068] A substrate containing nitrogen atoms is a substrate formed of a compound having bonds between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a film containing nitrogen atoms formed of a compound having bonds between a metal atom or a metalloid atom and a nitrogen atom.

[0069] As a metallic atom or a near-metallic atom, examples can be given.

[0070] (i) Silicon, (ii) Titanium, or (iii) Tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or alloys thereof.

[0071] Furthermore, SiON, SiN, TiON, or TiN are typical examples of compounds that have bonds between metal atoms or near-metal atoms and nitrogen atoms.

[0072] Furthermore, the coating composition, which is one aspect of the present invention, can most effectively exert its effect by being directly coated on a substrate formed of a compound having bonds between metal atoms or quasi-metal atoms and nitrogen atoms; or by being coated on a substrate having a nitrogen-containing film formed of a compound having bonds between metal atoms or quasi-metal atoms and nitrogen atoms, wherein the nitrogen-containing film constitutes the outermost layer of the substrate.

[0073] [I. Definition of Terms]

[0074] In this specification, the definitions of key terms related to the phenolic varnish resin, which is one aspect of the invention of this application, are explained below. Unless otherwise specifically stated, the following definitions apply to phenolic varnish resin.

[0075] (I-1) "Phenolic varnish resin (Novolak resin)"

[0076] The term "phenolic varnish resin" not only refers to phenol-formaldehyde resin (so-called phenolic varnish type phenolic resin) and aniline-formaldehyde resin (so-called phenolic varnish type aniline resin) in a narrow sense, but also broadly includes the following resins in a broad sense: generally, in the presence of an acid catalyst or under equivalent reaction conditions, an organic compound having functional groups capable of covalently bonding with an aromatic ring [e.g., aldehyde group; ketone group; acetal group; ketal group; hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom; hydroxyl, alkoxy, or halogen group bonded to the α-carbon atom (benzyl carbon atom, etc.) of an alkyl aryl group; carbon-carbon unsaturated bonds of divinylbenzene, dicyclopentadiene, etc.] and a compound having an aromatic ring (preferably having heteroatoms such as oxygen, nitrogen, and sulfur atoms as atoms constituting or bonded to the aromatic ring) through covalent bonding (substitution reaction, addition reaction, condensation reaction, or addition-condensation reaction, etc.).

[0077] Therefore, the phenolic varnish resin mentioned in this application is formed by linking multiple compounds having aromatic rings together by an organic compound containing carbon atoms (sometimes referred to as "linking carbon atoms") derived from the above-mentioned functional groups to form covalent bonds with the aromatic rings in a compound having aromatic rings via the linking carbon atoms.

[0078] In this specification, the terms unit structure (A) and unit structure (B) are used as the unit structures constituting the "phenolic varnish 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 functional groups capable of covalently bonding with the aromatic ring of unit structure (A).

[0079] (I-2) "Residues"

[0080] A "residue" is an organic group in which a hydrogen atom bonded to a carbon atom or heteroatom (nitrogen atom, oxygen atom, sulfur atom, etc.) is replaced by a bonding bond. It can be a monovalent group or a polyvalent group. For example, if one hydrogen atom is replaced by one bonding bond, it becomes a monovalent organic group; if two hydrogen atoms are replaced by bonding bonds, it becomes a divalent organic group.

[0081] (I-3) "Aromatic rings" (aromatic groups, aryl groups, arylene groups)

[0082] The term "aromatic ring" refers to a concept encompassing aromatic hydrocarbon rings, aromatic heterocycles, and their residues [sometimes also called "aromatic groups," "aryl" (in the case of monovalent groups), or "arylene" (in the case of divalent groups)]. It includes both monocyclic (aromatic monocyclic) and polycyclic (aromatic polycyclic) forms. In the case of polycyclic forms, at least one monocycle is an aromatic monocycle, and the remaining monocycles forming a fused ring with this aromatic monocycle can be either monocyclic heterocycles (heterocyclic monocycles) or monocyclic alicyclic hydrocarbons (alicyclic monocycles).

[0083] In this specification, heteroaryl groups are included within aryl groups. Heteroarylene groups are included within arylene groups.

[0084] Examples of aromatic rings include benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, isopropylbenzene, anthracene, phenanthrene, benzo[9,10]phenanthrene, benzo[a]anthracene, pyrene, Fluorene, biphenyl, cardinalene, perylene, fluoranthene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, halobenzene, dibenzo[g,p] Aromatic hydrocarbon rings such as acenaphthene, acenaphthene, pentaphenyl, cyclooctatetraene, etc.; more typically, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, pyrene, etc.; furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, pyrrole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindole fluorene, bisindole benzo[a]fluorene, bisindole dibenzo[a]fluorene, purine, quinoline, isoquinoline, chromene, thiathracene, phenothiazine, phenanthrene, etc. azine, Aromatic heterocycles such as ton, acridine, phenazine, carbazole, indolocarbazole, and more typically furan, thiophene, pyrrole, indole, phenylindole, bisindolylfluorene, phenothiazine, carbazole, and indolocarbazole, but not limited to these.

[0085] Aromatic rings (such as benzene rings, naphthalene rings, etc.) can have substituents in any way. Examples of such substituents include the following atoms and groups.

[0086] Halogen atoms A saturated or unsaturated straight-chain, branched, or cyclic hydrocarbon group (-R) that can be interrupted more than once by an oxygen atom in the middle of the hydrocarbon chain. a (This includes alkyl, alkenyl, and alkynyl groups (e.g., propargyl), as well as aryl groups, which can be interrupted more than once by an oxygen atom in the middle of the hydrocarbon chain.) -OR (where R represents the hydrocarbon group -R) a 。 ) aryloxy -NH2, -NHR, or -NR2 (the two Rs can be the same or different), where R represents the aforementioned hydrocarbon group -R. a .

[0087] hydroxyl Hydroxyalkyl carboxyl formyl group cyano Nitro Ester group (e.g., -CO2R or -OCOR, where R represents the aforementioned hydrocarbon group -R) a 。 ) Amide groups [e.g., -NHCOR, -CONHR, -NRCOR (the two Rs can be the same or different) or -CONR2 (the two Rs can be the same or different), where R represents the aforementioned hydrocarbon group -R] a 。 A sulfonyl group (e.g., -SO2R, where R represents the aforementioned hydrocarbon group -R) a Or hydroxyl group -OH. Thiol group (-SH) The group containing sulfide (-SR, where R represents the aforementioned hydrocarbon group -R) a 。 ) Organogroups containing ether bonds [R] 11 -OR 11 (R 11 Each of these groups independently represents an alkyl, phenyl, naphthyl, anthranyl, pyrene, or other aryl group having 1 to 6 carbon atoms, such as methyl or ethyl. (The remaining group represents the residues of the ether compound; for example, an organogroup containing an ether bond, such as methoxy, ethoxy, or phenoxy.) The term "aromatic ring" further includes: an organic group having a fused ring formed by one or more aromatic rings (benzene, naphthalene, anthracene, pyrene, etc.) and one or more aliphatic rings or heterocycles. Furthermore, examples of aliphatic rings include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene; examples of heterocycles include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0088] An "aromatic ring" can be an organogroup having a structure in which two or more aromatic rings are linked by a divalent linker. Examples of divalent linkers include alkylene, arylene, -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO2-. Furthermore, a divalent linker can be a divalent group from which one hydrogen atom has been removed from any of the substituents of the aforementioned aromatic rings.

[0089] (I-4) "Heterocyclic rings"

[0090] "Heterocycle" encompasses both aliphatic and aromatic heterocycles, including both monocyclic (heteromonocyclic) and polycyclic (heteropolycyclic) forms. In the case of a polycyclic form, at least one monocycle is a heteromonocyclic ring, while the remaining monocycles can be aromatic hydrocarbon monocycles or alicyclic monocycles. For aromatic heterocycles, refer to the example in (I-3) above. Similar to the aromatic rings in (I-3) above, substituents may be present.

[0091] (I-5) "Non-aromatic ring" (aliphatic ring)

[0092] The term "non-aromatic monocyclic ring" refers to a monocyclic hydrocarbon that is not aromatic, typically a single ring of an alicyclic compound. It can be called an aliphatic monocyclic ring (and may include aliphatic heterocyclic rings; as long as it is not an aromatic compound, it can contain unsaturated bonds). Similar to the aromatic rings described in (I-3) above, it can have substituents.

[0093] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0094] The term "non-aromatic polycyclic" refers to polycyclic hydrocarbons that are not aromatic, typically alicyclic compounds. They can be called aliphatic polycyclics [and may include aliphatic heterocyclic polycyclics (at least one of the monocyclic rings constituting the polycyclic structure is an aliphatic heterocycle), and can contain unsaturated bonds as long as they are not aromatic compounds]. They include non-aromatic bicyclic, non-aromatic tricyclic, and non-aromatic tetracyclic rings.

[0095] The term "non-aromatic bicycle" in the context of a bicycle refers to a fused ring composed of two monocyclic hydrocarbons that are not aromatic, typically two alicyclic compounds. In this specification, it is sometimes also referred to as an aliphatic bicycle (which may include aliphatic heterocycles; as long as it is not an aromatic compound, it may contain unsaturated bonds). Examples of non-aromatic bicycles include dicyclopentane, dicyclooctane, and dicycloheptene.

[0096] The term "non-aromatic tricyclic ring" refers to a fused ring composed of three monocyclic hydrocarbons that are not aromatic. Typically, it consists of three alicyclic compounds (each of which can be a heterocycle and can contain unsaturated bonds as long as it is not an aromatic compound). Examples of non-aromatic tricyclic rings include tricyclooctane, tricyclononane, and tricyclodecane.

[0097] The term "non-aromatic tetracycle" in the context of a tetracycle refers to a fused ring composed of four monocyclic hydrocarbons that are not aromatic. Typically, it consists of four alicyclic compounds (each of which can be a heterocycle, and as long as it is not an aromatic compound, it can contain unsaturated bonds). Examples of non-aromatic tetracycles include hexadecylhydropyrene.

[0098] (I-6)

[0099] The term "carbon atom constituting part of the ring" refers to the carbon atoms that make up the ring in the context of a hydrocarbon ring without substituents (which can be any of the aromatic, aliphatic, or heterocyclic rings).

[0100] (I-7)

[0101] The term "hydrocarbon group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon. Such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0102] (I-8)

[0103] In the chemical structural formulas showing the unit structures of phenolic varnish resins in this application specification, bonding bonds are sometimes described for convenience. Unless otherwise specified, such bonding bonds can be used at any bonding position in the unit structure, without any limitation on the bonding position in the unit structure.

[0104] <Resin (G)>

[0105] Resin (G) has a composite unit structure.

[0106] The composite unit structure has: a unit structure with an aromatic ring (A) and a unit structure with more than one carbon atom (B).

[0107] The composite unit structure of resin (G) can be represented, for example, by the following formula (AB).

[0108]

[0109] (In equation (AB), A represents the unit structure (A), and B represents the unit structure (B).)

[0110] <<A-1: Unit Structure (A)>>

[0111] The unit structure (A) has an aromatic ring.

[0112] The unit structure (A) may, for example, have at least one of the following: an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom directly bonded to an aromatic ring.

[0113] There is no particular limitation on the number of carbon atoms in the unit structure (A), for example, it is 4 to 100, preferably 4 to 50.

[0114] Preferably, such aromatic rings have 4 to 30, more preferably 4 to 24 carbon atoms.

[0115] Preferably, such aromatic rings are one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings; or fused rings of benzene rings, naphthalene rings, anthracene rings, pyrene rings and heterocycles or aliphatic rings (fluorene rings, benzo[a]fluorene rings, dibenzo[a]fluorene rings, indole rings, carbazole rings, indole[a]carbazole rings, etc.).

[0116] Aromatic rings can have any number of substituents, but from the viewpoint of polymerization reactivity, the substituents can contain a necessary minimum number of heteroatoms. Furthermore, two or more aromatic rings can be linked by a linking group, which can contain a necessary minimum number of heteroatoms. Examples of heteroatoms include, for example, oxygen, nitrogen, and sulfur atoms.

[0117] An "aromatic ring" may contain at least one heteroatom selected from N, S, and O on, within, or between rings.

[0118] Examples of heteroatoms that can be included on the ring include, for example, the nitrogen atom contained in amino groups (e.g., propargylamino) and cyano groups; the oxygen atom contained in formyl groups, hydroxyl groups, carboxyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups (e.g., propargyloxy groups), and aryloxy groups, which are oxygen-containing substituents; and the nitrogen and oxygen atoms contained in nitro groups, which are both oxygen-containing and nitrogen-containing substituents.

[0119] Examples of heteroatoms that can be included within a ring include, for example, the oxygen atom contained in furan and xaton, the nitrogen atom contained in carbazole and pyrrole, and the sulfur atom contained in phenothiazine.

[0120] Examples of heteroatoms that can be included in a linking group of two or more aromatic rings include nitrogen, oxygen, and sulfur atoms contained in -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO2-.

[0121] In this specification, the term "atom constituting an aromatic ring" has the same meaning as "atoms contained within the ring". The term "atoms bonded to the aromatic ring" refers to, for example, "atoms directly bonded to the ring among atoms or groups contained on the ring" and "atoms directly bonded to the ring among atoms contained between the rings".

[0122] For example, the atoms that make up the benzene ring are carbon atoms.

[0123] For example, the atoms that make up the pyrrole ring are carbon atoms and nitrogen atoms.

[0124] For example, the oxygen atom of the hydroxyl group in phenol is not an atom that forms an aromatic ring.

[0125] For example, the oxygen atom of the hydroxyl group in phenol is an atom that is bonded to the benzene ring, and is an atom that is directly bonded to the benzene ring among the groups contained on the benzene ring.

[0126] <<A-2: An example of the skeleton that constitutes the unit structure (A)>>

[0127] The unit structure (A) contains, for example, a framework with aromatic rings.

[0128] The preferred skeletons with aromatic rings are aromatic amine skeletons, nitrogen-containing aromatic heterocyclic skeletons, and phenol skeletons.

[0129] The unit structure (A) is, for example, a residue from a skeleton having two hydrogen atoms removed.

[0130] The aromatic ring skeleton is derived, for example, from an aromatic ring compound during the synthesis of resin (G). The aromatic ring skeleton is, for example, a compound with an aromatic ring from which two hydrogen atoms have been removed.

[0131] A skeleton with an aromatic ring can have substituents.

[0132] Examples of substituents include, for example, halogen groups (halogen atoms), alkyl groups, alkenyl groups, alkynyl groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, hydroxyalkyl groups, carboxyl groups, formyl groups, cyano groups, nitro groups, ester groups, amide groups, groups containing sulfonyl groups, thiols, groups containing thioethers, and groups containing ether bonds.

[0133] Examples of alkyl groups include straight-chain, branched, or cyclic alkyl groups having 1 to 20 carbon atoms.

[0134] Examples of alkenyl groups include straight-chain, branched, or cyclic alkenyl groups with 2 to 10 carbon atoms.

[0135] Examples of alkynyl groups include straight-chain, branched, or cyclic alkynyl groups with 2 to 10 carbon atoms.

[0136] Examples of alkoxy groups include those represented by -OR. Here, R represents a saturated or unsaturated straight-chain, branched, or cyclic hydrocarbon group that can be interrupted more than once by an oxygen atom in the middle of the hydrocarbon chain (-R). a Examples of carbon atoms that can be represented by an alkoxy group include 1 to 20.

[0137] Examples of aryl groups include those with 6 to 30 carbon atoms.

[0138] Examples of aryloxy groups include those with 6 to 30 carbon atoms.

[0139] Examples of amino groups include those represented by -NH2, -NHR, or -NR2. Here, R represents the aforementioned hydrocarbon group -R. a In -NR2, the two Rs can be the same or different.

[0140] Examples of hydroxyalkyl groups include straight-chain, branched, or cyclic hydroxyalkyl groups with 1 to 20 carbon atoms.

[0141] Examples of ester groups include those represented by -CO2R or -OCOR. Here, R represents the aforementioned hydrocarbon group -R. a .

[0142] Examples of amide groups include those represented by -NHCOR, -CONHR, -NRCOR, or -CONR2. Here, R represents the aforementioned hydrocarbon group -R. a When there are two R values, the two R values ​​can be the same or different.

[0143] Examples of groups containing sulfonyl groups include the group represented by -SO2R. Here, R represents the aforementioned hydrocarbon group -R. a Or hydroxyl group -OH.

[0144] Examples of groups containing thioethers include the group represented by -SR. Here, R represents the aforementioned hydrocarbon group -R. a .

[0145] As a group containing an ether bond, R can be cited as an example. 11 -OR 11 The residues of the ether compound containing the ether bond are shown. Here, R 11 Each group independently represents an alkyl group (1-6 carbon atoms), such as methyl, ethyl, alkyl, phenyl, naphthyl, anthraceneyl, pyrene, etc. Groups containing ether bonds can be, for example, organic groups containing ether bonds such as methoxy, ethoxy, or phenoxy.

[0146] <<A-3: Unit Structure (AI)>>

[0147] The unit structure (A) has at least a unit structure (AI) containing nitrogen atoms. The unit structure (AI) contains a framework with an aromatic ring. Here, the unit structure (AI) is a subordinate concept of the unit structure (A), and does not refer to a part of the structure of the unit structure (A).

[0148] The following section describes the skeleton with aromatic rings in the unit structure (AI).

[0149] <<<A-3-1: Aromatic Amine Skeleton>>>

[0150] The so-called aromatic amine skeleton refers to a skeleton that has an aromatic ring and nitrogen atoms bonded to the aromatic ring but not forming a ring.

[0151] Examples of aromatic amine skeletons include, for example, the skeletons shown in formulas (A-1a) to (A-1c) below.

[0152] Furthermore, as will be described later, in the unit structure (AI), the hydrogen atom of the NH group can be replaced by a substituent. Examples of substituents include the substituents described in (I-3) "Aromatic Ring", the substituents described in (A-2) "Examples of the skeleton constituting the unit structure (A)", and the substituents (S) shown in formulas (S1) to (S7) described later.

[0153]

[0154] (In equations (A-1a) to (A-1c), Ar 11 Each residue independently represents an aromatic ring residue. R 11 Each can independently represent a hydrogen atom or a residue of an aromatic ring.

[0155] As Ar 11 and R 11 The aromatic ring in the residues of the aromatic ring can be exemplified by, for example, the aromatic ring shown in the following formula (G1). These aromatic rings may have substituents.

[0156]

[0157] Examples of skeletons that serve as the framework shown in formula (A-1a) include, for example, the following skeletons. 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.

[0158]

[0159] As an example of the skeleton shown in equation (A-1b), the following skeletons can be cited.

[0160]

[0161] Examples of skeletons that can be used as the skeleton shown in equation (A-1c) include the following skeletons.

[0162]

[0163] <<<A-3-2: Nitrogen-containing aromatic heterocyclic skeleton>>>

[0164] The so-called nitrogen-containing aromatic heterocyclic skeleton refers to a skeleton containing an aromatic heterocycle, wherein the aromatic heterocycle contains nitrogen atoms among the atoms constituting the heterocycle.

[0165] Examples of nitrogen-containing aromatic heterocycles include, for example, pyrrole rings, indole rings, pyridine rings, acridine rings, and phenanthrene rings. Azide rings, phenothiazine rings, etc. These nitrogen-containing aromatic heterocycles can have substituents.

[0166] Examples of nitrogen-containing aromatic heterocyclic skeletons include, for example, the skeletons shown in formula (A-2a), formula (A-2b-1), formula (A-2b-2), formula (A-2d), formula (A-2e), formula (A-3a), or formula (A-3b).

[0167] Furthermore, as will be described later, in the unit structure (AI), the hydrogen atom of the NH group can be replaced by a substituent. Examples of substituents include the substituents described in (I-3) "Aromatic Ring", the substituents described in (A-2) "Examples of the skeleton constituting the unit structure (A)", and the substituents (S) shown in formulas (S1) to (S7) described later.

[0168]

[0169] (where Ar) 21 Each of them independently represents a residue of the aromatic ring.

[0170] R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring.

[0171] R 22 Each of the two R groups independently represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or a residue of an aromatic ring. 22 They can form unsaturated aliphatic rings together. Additionally, one of the unsaturated bonds in an unsaturated aliphatic ring refers to the unsaturated bond that constitutes the pyrrole ring.

[0172] R independently represents a hydrogen atom, a residue of an aromatic ring, or a bond with L. L represents a single bond or a linker. n1 represents 1, and n2 represents 1 or 2. In formula (A-2b-2), when L is a single bond, partial structures (In1) and partial structures (In2) are bonded together by two nitrogen atoms, or by two Ar atoms. 21 They combine with each other, or through nitrogen atoms and Ar atoms. 21 To combine. In equation (A-2b-2), when L is a connecting base, L combines with N or Ar. 21 (Combined.)

[0173] As Ar 21 R 21 R 22 The aromatic ring in the residues of R is an example of an aromatic ring represented by the following formula (G2). These aromatic rings may have substituents.

[0174]

[0175] As two adjacent R 22 Unsaturated aliphatic rings formed together can be exemplified by, for example, the following rings. These aliphatic rings may have substituents.

[0176]

[0177] Examples of linking groups in L include (n1+n2) valence saturated hydrocarbon groups with 1 to 5 carbon atoms, and residues of aromatic rings with (n1+n2) hydrogen atoms removed.

[0178] <Formula (A-2d)>

[0179] (In equation (A-2d), R 11 Each can independently represent a hydrogen atom or an aromatic group. Ar represents an aromatic ring moiety, each of which is an independent benzene ring, a fused ring consisting of 2 to 3 benzene rings, or a structure shown in the following formula (Ar01). X 0 Indicates single bond, -O-, -S-, -NR 12 -or-CR 13 R 14 -, R 12 With R 11 Same or different, with R 11 The definitions are the same, R 13 and R 14 Each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. n is 1 or 2, When n is 1, Z represents a monovalent organogroup; when n is 2, Z represents a divalent organogroup. Furthermore, in the unit structure (AI), R in equation (A-2d) 11 It can be a substituent.

[0180] In R 11 In the case of substituents or aromatic groups, R 11 For example, (i) hydroxymethyl, (ii) aryl groups with 6 to 30 carbon atoms, or (iii) a straight-chain, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a straight-chain, 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. However, regarding (ii) and (iii) above, they may be further substituted by substituents containing oxygen atoms, substituents containing sulfur atoms, substituents containing nitrogen atoms, aryl or halogen groups, or regarding (iii) above, the hydrocarbon chain portion may be further interrupted by substituents containing oxygen atoms, substituents containing sulfur atoms, substituents containing nitrogen atoms, or arylene groups.

[0181] As a skeleton shown in formula (A-2d), examples can be given, for example, the skeleton shown in formula (A-2d-1) below.

[0182]

[0183] (R in equation (A-2d-1)) 11 Ar and X 0 Each with R in equation (A-2d) 11 Ar and X 0 They have the same meaning. R 21 It can be an aryl group with 6 to 30 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkynyl group with 2 to 10 carbon atoms.

[0184] Ar in formulas (A-2d) and (A-2d-1) can be, for example, a benzene ring or a naphthalene ring.

[0185] Ar in equations (A-2d) and (A-2d-1) can be the structure shown in equation (Ar01) below.

[0186]

[0187] (R in formula (Ar01)) 11a R in equation (A-2d-1) 11 The meaning is the same, R 21a R in equation (A-2d-1)21 The same meaning, Ar a As in equation (A-2d-1), X has the same meaning. 0a X in equation (A-2d-1) 0 They have the same meaning.

[0188] In formula (Ar01), among the two carbon atoms a and b, b and c, or c and d, the one containing X in formula (A-2d) or formula (A-2d-1) is... 0 The single-ring portion forms a fused ring.

[0189] Here, the so-called inclusion of X 0 The single-loop portion is represented by the single loop shown in the following formula (AP011) in formula (A-2d).

[0190]

[0191] As the skeleton shown in formula (A-2d), the skeleton shown in formula (A-2d-1), the skeleton shown in formula (A-2d-2), and the skeleton shown in formula (A-2d-3) are preferred.

[0192]

[0193] (In equations (A-2d-2) and (A-2d-3), R) 11 Ar and X 0 Each with R in equation (A-2d) 11 Ar and X 0 They have the same meaning.

[0194] L represents a single bond or a divalent linker. For example, a divalent linker can be represented by -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, or -NR. 101 -、-(CR 102 R 103 )m 1 -、-(Ar 101 )m 2 -, -CH2-(Ar 101 )m 2 -CH2- or -(cyclo-R)-. R 101 R 102 and R 103 Each can independently represent a hydrogen atom; a hydrocarbon group with 1 to 5 carbon atoms; or an aryl group with 6 to 30 carbon atoms; m 1 Represents integers from 1 to 10. Furthermore, Ar 101 Each independently represents an arylene group with 6 to 30 carbon atoms; m 2The number of aromatic rings bonded together by single bonds is an integer from 1 to 3. "cyclo-R" indicates a 5- to 8-membered ring, preferably a 6- to 8-membered ring, that can form a fused ring with one or two benzene or naphthalene rings.

[0195] R 22 Each can independently represent an arylene group with 6 to 30 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkyne group with 2 to 10 carbon atoms that can be substituted.

[0196] <Formula (A-2e)>

[0197] (In formula (A-2e), L represents a single bond or divalent linker between any two carbon atoms constituting each azirroyl fused ring.) R 11 and R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring. R 12 and R 22 Each substituent can be represented independently. n1 and n2 each independently represent R 12 and R 22 The number of substituents can be 0. Ar 1 and Ar 2 Each of these can be a benzene ring that independently forms a fused ring with the pyrrole ring portion of formula (A-2e), or a fused ring consisting of 2 to 3 benzene rings. Furthermore, in the unit structure (AI), R in equation (A-2e) 11 and R 21 It can be a substituent.

[0198] In R 11 and R 21 In the case of residues that are substituents or aromatic groups, R 11 and R 21 For example, (i) hydroxymethyl, (ii) aryl groups with 6 to 30 carbon atoms, or (iii) a straight-chain, branched, or cyclic alkoxymethyl group having 2 to 20 carbon atoms; a straight-chain, 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. However, regarding (ii) and (iii) above, they may be further substituted by substituents containing oxygen atoms, substituents containing sulfur atoms, substituents containing nitrogen atoms, aryl or halogen groups, or regarding (iii) above, the hydrocarbon chain portion may be further interrupted by substituents containing oxygen atoms, substituents containing sulfur atoms, substituents containing nitrogen atoms, or arylene groups.

[0199] In formula (A-2e), L is a single bond or a divalent linker. L can bond with any carbon atom that constitutes the various aziridine fused rings, and can bond with the atoms that constitute Ar. 1 Ar 2 That is, in the fused ring of aziridine and It is bonded to aromatic carbon atoms, but preferably to carbon atoms that constitute the pyrrole ring moiety in the fused ring of the azaaryl group.

[0200] The preferred linker group (L) is selected from -O-, -S-, -SO2-, -CO-, -CONH-, -COO-, -NH-, and -(CR). 102 R 103 )m 1 -、-(Ar 101 )m 2 -, -CH2-(Ar 101 )m 2 -CH2- and -(cyclo-R)-. R 102 and R 103 Each can independently represent a hydrogen atom; a hydrocarbon group with 1 to 5 carbon atoms; or an aryl group with 6 to 30 carbon atoms; m 1 Represents integers from 1 to 10. Furthermore, Ar 101 Each represents an arylene group with 6 to 30 carbon atoms; m 2 The number of aromatic rings bonded together by single bonds is an integer from 1 to 3. "cyclo-R" indicates a 5- to 8-membered ring, preferably a 6- to 8-membered ring, that can form a fused ring with one or two benzene or naphthalene rings.

[0201] <Equations (A-3a) and (A-3b)>

[0202] (where Ar) 31 and Ar 32 Each residue in the aromatic ring represents an aromatic ring residue independently, or together with the carbon atom it is bonded to. X represents -O, -S-, -NH-, -CH2-, -CH2-CH2-, or -CH=CH-.

[0203] As Ar 31 and Ar 32The aromatic ring in the residues of the aromatic ring can be exemplified by, for example, the aromatic ring shown in the above formula (G1).

[0204] As Ar 31 and Ar 32 Aromatic rings that form with the carbon atoms bonded to them include, for example, fluorene rings, benzo[a]fluorene rings, dibenzo[a]fluorene rings, etc.

[0205] The resin (G) preferably contains a unit structure (AI) that does not contain a carbazole backbone.

[0206] Here, the term "carbazole skeleton" refers to a skeleton containing a carbazole ring.

[0207] Examples of carbazole skeletons include those shown in formulas (A-2c-1), (A-2c-2), (A-2c-3), or (A-2c-4).

[0208]

[0209] (where Ar) 21 Each of them independently represents a residue of the aromatic ring.

[0210] R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring.

[0211] R independently represents a hydrogen atom, a residue of an aromatic ring, or a bond with L. L represents a single bond or a linker. n1 represents 1, and n2 represents 1 or 2. In formula (A-2c-4), when L is a single bond, partial structures (Ca1) and partial structures (Ca2) are bonded to each other through two nitrogen atoms, or through two Ar atoms. 21 They combine with each other, or through nitrogen atoms and Ar atoms. 21 Combined to form a bond. In equation (A-2c-4), when L is a linking base, L combines with N or Ar. 21 (Combined.)

[0212] Examples of skeletons that serve as the framework shown in formula (A-2a) include, for example, the following skeletons. 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.

[0213]

[0214] As a skeleton shown in formula (A-2b-1), examples of the following skeletons can be cited.

[0215]

[0216] As a skeleton shown in equation (A-2b-2), examples of the following skeletons can be cited.

[0217]

[0218] As a skeleton shown in formula (A-2c-1), examples of the following skeletons can be cited.

[0219] Examples of skeletons that can be represented as the skeletons shown in formula (A-2c-2) or formula (A-2c-3) include the following skeletons.

[0220]

[0221] As a skeleton shown in equation (A-2c-4), examples of the following skeletons can be cited.

[0222]

[0223] As an example of the skeleton shown in formula (A-2d), the following skeletons can be cited.

[0224]

[0225] As an example of the skeleton shown in equation (A-2e), the following skeletons can be cited.

[0226] Furthermore, specific examples of the skeleton shown in equation (A-2d) sometimes overlap with specific examples of the skeleton shown in equation (A-2e).

[0227]

[0228] As an example of the skeleton shown in equation (A-3a), the following skeletons can be cited.

[0229]

[0230] As an example of the skeleton shown in equation (A-3b), the following skeletons can be cited.

[0231]

[0232] Other skeletons that serve as nitrogen-containing aromatic heterocyclic skeletons include, for example, the following skeletons.

[0233]

[0234] Furthermore, the H atom of NH in the aforementioned aromatic ring skeleton, the H atom of hydroxyl group in the aromatic ring skeleton bonded to the aromatic ring, and the hydrogen atom in the aromatic ring skeleton bonded to the aromatic ring can be replaced with substituents.

[0235] Examples of such substituents include the substituents (S) shown in formulas (S1) to (S7) below.

[0236]

[0237] (In equations (S1) to (S7), R sa It represents a monovalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0238] R sb Each can independently represent a single bond or a divalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0239] R sc Each group independently represents a divalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0240] R sd alkynyl Each group independently represents an alkynyl group with 2 to 4 carbon atoms.

[0241] Ar sa Each group independently represents a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0242] Ar sb Each group independently represents a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0243] X sa and X sb Each independently represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms, or X sa and X sb Together with the carbon atom bonded to the hydroxyl group, it forms a carbonyl group.

[0244] n represents an integer from 0 to 5.

[0245] (This represents a bonding bond.)

[0246] <R sa >

[0247] As Rsa Examples of monovalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms include alkyl groups with 1 to 10 carbon atoms and monovalent unsaturated hydrocarbon groups with 2 to 10 carbon atoms.

[0248] A monovalent unsaturated hydrocarbon group with 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When this type of group has two or more carbon-carbon multiple bonds, these bonds can be entirely carbon-carbon double bonds, entirely carbon-carbon triple bonds, or a mixture of both. These multiple carbon-carbon multiple bonds can be conjugated or not.

[0249] <R sb and R sc >

[0250] As R sb and R sc Examples of divalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms include alkylene groups with 1 to 10 carbon atoms and divalent unsaturated hydrocarbon groups with 2 to 10 carbon atoms.

[0251] A divalent unsaturated hydrocarbon group with 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When a divalent unsaturated hydrocarbon group with 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, these multiple bonds can be all carbon-carbon double bonds, all carbon-carbon triple bonds, or a mixture of both. The two or more carbon-carbon multiple bonds can be conjugated or not conjugated.

[0252] As R sb and R sc Examples of such groups include the following.

[0253]

[0254] ( (This represents a bonding bond.)

[0255] <R sd alkynyl >

[0256] R sd alkynyl This refers to an alkynyl group having 2 to 4 carbon atoms. Examples of alkynyl groups having 2 to 4 carbon atoms include ethynyl, 1-propynyl, and propynyl (2-propynyl).

[0257] <Ar sa >

[0258] Ar saThe monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue from an aromatic hydrocarbon with 6 to 20 carbon atoms by removing one hydrogen atom. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, 2,3-dihydro-1H-phenanthrene, pyrene, fluorene, biphenyl, etc.

[0259] <Ar sb >

[0260] Ar sb The divalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue from an aromatic hydrocarbon with 6 to 20 carbon atoms by removing two hydrogen atoms. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, and biphenyl.

[0261] <X sa and X sb >

[0262] As X sa and X sb Monovalent hydrocarbon groups with 1 to 20 carbon atoms can be exemplified by, for example, monovalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms and monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms.

[0263] Examples of monovalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms include alkyl groups with 1 to 10 carbon atoms.

[0264] A monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue from an aromatic hydrocarbon with 6 to 20 carbon atoms by removing one hydrogen atom. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, 2,3-dihydro-1H-phenanthrene, pyrene, fluorene, biphenyl, etc.

[0265] Examples of substituents represented by formula (S1) include the following groups.

[0266]

[0267] ( (This represents a bonding bond.)

[0268] Examples of substituents shown in formula (S2) include the following groups.

[0269]

[0270] ( (This represents a bonding bond.)

[0271] Examples of substituents shown in formula (S3) include the following groups.

[0272]

[0273] ( (This represents a bonding bond.)

[0274] Examples of substituents shown in formula (S4) include the following groups.

[0275]

[0276] ( (This represents a bonding bond.)

[0277] Examples of substituents shown in formula (S5) include the following groups.

[0278]

[0279] ( (This represents a bonding bond.)

[0280] Examples of substituents shown in formula (S6) include the following groups.

[0281]

[0282] ( (This represents a bonding bond.)

[0283] Examples of substituents shown in formula (S7) include the following groups.

[0284]

[0285] ( (This represents a bonding bond.)

[0286] Other substituents include, for example, the following groups.

[0287]

[0288] ( (This represents a bonding bond.)

[0289] As a unit structure (AI), it is preferred to select at least one of the following. In addition, the positions of the two bonds shown in each unit structure described below are merely for convenience and can extend from any possible carbon atom, without limitation on their positions.

[0290] (Examples of unit structures composed of aromatic amine skeletons)

[0291] -NH- can also take the form of a structure in which the hydrogen atom on N is replaced.

[0292]

[0293] (An example of a unit structure composed of a nitrogen-containing aromatic heterocyclic skeleton)

[0294] The unit structure (A) in the resin (G) may include unit structures other than the unit structure (AI).

[0295] Examples of unit structures other than the Algebraic Algebraic (AI) include, for example, unit structures with a phenolic skeleton.

[0296] <<<A-4: Phenolic skeleton>>>

[0297] The so-called phenolic skeleton refers to a skeleton that has an aromatic ring and hydroxyl groups bonded to the aromatic ring.

[0298] There is no particular limitation on the number of hydroxyl groups that are bonded to aromatic rings in the phenolic skeleton; it can be one or more. In the case of multiple hydroxyl groups, the number can be 2 to 10 or 2 to 8. In the case of multiple hydroxyl groups, the hydroxyl groups can be bonded to the same aromatic ring (e.g., a benzene ring) or to different aromatic rings.

[0299] Furthermore, in the unit structure (A), the hydrogen atom of the hydroxyl group bonded to the aromatic ring can be replaced with a substituent. Examples of substituents include the substituent described in "aromatic ring" in (I-3) above, the substituent described in "examples of the skeleton constituting unit structure (A)" in (A-2) above, and the substituent (S) shown in formulas (S1) to (S7) above.

[0300] Examples of phenolic skeletons include, for instance, those shown in formula (A-4) below. 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.

[0301]

[0302] (In the formula, n1, n2, n4, n5, n6, and n9 each independently represent integers from 1 to 4. n3a, n3b, n7a, n7b, n8a, and n8b each independently represent integers from 0 to 4. Among them, the sum of n3a and n3b ​​is 1 or more, the sum of n7a and n7b is 1 or more, and the sum of n8a and n8b is 1 or more.)

[0303] Furthermore, examples of phenolic skeletons include those shown in formulas (A-5a), (A-5b), (A-5c), or (A-5d).

[0304]

[0305] (where Ar) 41 Each of them independently represents a residue of the aromatic ring.

[0306] k1 and k2 each independently represent an integer of 1 or 2.

[0307] X 1 It represents -O-, -CO-, -S-, -SO2-, or alkylene groups that can be substituted with halogen atoms.

[0308] When k1 is 1, X 21 It represents a single bond, -O-, -CO-, -S-, -SO2-, or an alkylene group that can be substituted by a halogen atom.

[0309] When k2 is 1, X 22 It represents a single bond, -O-, -CO-, -S-, -SO2-, or an alkylene group that can be substituted by a halogen atom.

[0310] When k1 is 2, X 21 This indicates a trivalent saturated hydrocarbon group that can be replaced by a halogen atom.

[0311] When k2 is 2, X 22 This indicates a trivalent saturated hydrocarbon group that can be replaced by a halogen atom.

[0312] Y 1 It represents a trivalent saturated hydrocarbon group.

[0313] Y 2 It represents a tetravalent saturated hydrocarbon group.

[0314] m1 and m2 each independently represent integers from 0 to 3. The sum of m1 and m2 is 1 or higher.

[0315] m3 to m5 each independently represent integers from 0 to 3. The sum of m3 to m5 is 1 or higher.

[0316] m6 to m8 each independently represent integers from 0 to 3. The sum of m6 to m8 is 1 or higher.

[0317] m9 to m12 each independently represent integers from 0 to 3. The sum of m9 to m12 is 1 or higher.

[0318] As Ar 41 The aromatic ring in the residues of the aromatic ring can be exemplified by, for example, the aromatic ring shown in the following formula (G3). These aromatic rings may have substituents.

[0319]

[0320] As X 1and X 2 Examples of the number of carbon atoms in the alkylene group that can be replaced by halogen atoms include, for example, 1 to 20. Examples of structures of the alkylene group include, for example, straight-chain, branched, and cyclic structures, as well as combinations of two or more of these. Examples of halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.

[0321] As Y 1 and Y 2 Examples of the number of carbon atoms in the saturated hydrocarbon group include, for example, 1 to 20. Examples of structures for the saturated hydrocarbon group include, for example, straight-chain, branched, and cyclic structures, as well as combinations of two or more of them.

[0322] Furthermore, examples of phenolic skeletons include those shown in formulas (A-6a), (A-6b-1), (A-6b-2), (A-6c), or (A-6d).

[0323]

[0324] (In equations (A-6a), (A-6b-1), (A-6b-2), (A-6c), and (A-6d), Ar 51 Each element independently represents a residue of the aromatic ring. n11 independently represents an integer from 1 to 4. p independently represents 0 or 1. When p is 1, the oxygen atom acts as an ether bond to form a bridging structure between aromatic rings; when p is 0, no ether bond exists to form a bridging structure between aromatic rings. L represents a single bond or a divalent linker.

[0325] As Ar 51 The aromatic ring in the formula (G1) can be exemplified by, for example, the aromatic ring shown in the formula above, preferably a benzene ring or a naphthalene ring.

[0326] As for L, examples include a divalent group from which two hydrogen atoms have been removed from the following structure.

[0327]

[0328] n11, for example, can represent 1 or 2 independently.

[0329] Furthermore, examples of phenolic skeletons include those shown in formula (A-7a), formula (A-7b), or formula (A-7c).

[0330]

[0331] (In equations (A-7a), (A-7b), and (A-7c), Ar) 61 Each element independently represents a residue of the aromatic ring. n21 independently represents an integer from 1 to 4.

[0332] As Ar 61 The aromatic ring in the formula (G1) can be exemplified by, for example, the aromatic ring shown in the formula above, preferably a benzene ring or a naphthalene ring.

[0333] n21, for example, can represent 1 or 2 independently.

[0334] Furthermore, examples of phenolic skeletons include those shown in formulas (A-8a-1), (A-8a-2), (A-8b), (A-8c), (A-8d), (A-8e), (A-8f), (A-8g-1), or (A-8g-2).

[0335]

[0336] 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.

[0337] In equation (A-8a-2), n32 and n33 each independently represent integers from 0 to 4. The sum of n32 and n33 is 1 or more.

[0338] In equation (A-8d), n32 and n33 each independently represent integers from 0 to 4. The sum of n32 and n33 is 1 or more.

[0339] In equation (A-8b), X 1 It represents -O- or -NH-.

[0340] In equation (A-8d), X 2 It represents -O-, -S-, or -CH2-.

[0341] In equation (A-8e), X 3 It represents -S-, -CH2-, or -NH-.

[0342] In equation (A-8f), X 4 Indicates -CO- or -O-, X 5 (This indicates -CH2- or -O-.)

[0343] n31, for example, can represent 1 or 2 independently.

[0344] n32 and n33, for example, can each independently represent 0, 1, or 2.

[0345] Examples of skeletons that serve as the framework shown in formula (A-4) include, for example, the following skeletons. The aromatic rings in these skeletons may have substituents, and the hydrogen atoms of the hydroxyl groups may be replaced by substituents. The same applies to the following skeletons.

[0346]

[0347] As an example of the skeleton shown in formula (A-5a), the following skeletons can be cited.

[0348]

[0349] As an example of the skeleton shown in equation (A-5b), the following skeletons can be cited.

[0350]

[0351] As an example of the skeleton shown in formula (A-5c), the following skeletons can be cited.

[0352]

[0353] As an example of the skeleton shown in formula (A-5d), the following skeletons can be cited.

[0354]

[0355] As an example of the skeleton shown in formula (A-6a), the following skeletons can be cited.

[0356]

[0357] Examples of skeletons that can be represented as the skeletons shown in formula (A-6b-1) or formula (A-6b-2) include the following skeletons.

[0358]

[0359] As an example of the skeleton shown in formula (A-6c), the following skeletons can be cited.

[0360]

[0361] As an example of the skeleton shown in formula (A-6d), the following skeletons can be cited.

[0362]

[0363] Examples of skeletons shown in formulas (A-7a), (A-7b), or (A-7c) include the following skeletons.

[0364]

[0365] Examples of skeletons that can be represented as the skeletons shown in formula (A-8a-1) or formula (A-8a-2) include the following skeletons.

[0366]

[0367] As an example of the skeleton shown in formula (A-8b), the following skeletons can be cited.

[0368]

[0369] As the skeleton shown in formula (A-8c), examples of the following skeletons can be cited.

[0370]

[0371] As an example of the skeleton shown in formula (A-8d), the following skeletons can be cited.

[0372]

[0373] As the skeleton shown in equation (A-8e), examples of the following skeletons can be cited.

[0374]

[0375] As the skeleton shown in equation (A-8f), examples of the following skeletons can be cited.

[0376]

[0377] Examples of skeletons that can be represented as the skeletons shown in formula (A-8g-1) or formula (A-8g-2) include the following skeletons.

[0378]

[0379] Other skeletons that can serve as phenolic skeletons include, for example, the following skeletons.

[0380]

[0381] Furthermore, the H atoms of the hydroxyl groups in the phenolic skeleton that are bound to the aromatic rings and the hydrogen atoms in the phenolic skeleton that are bound to the aromatic rings can be replaced with substituents.

[0382] Examples of such substituents include the substituents (S) shown in formulas (S1) to (S7) above.

[0383] (Examples of unit structures composed of phenolic skeletons)

[0384] <<B-1: Unit Structure (B)>>

[0385] The unit structure (B) has more than one carbon atom.

[0386] The unit structure (B) is preferably, for example, derived from an aldehyde compound or an aldehyde equivalent (BI).

[0387] Unit structure (B) is one or more unit structures containing connecting carbon atoms bonded to the aromatic ring in unit structure (A) [refer to (I-1) above], for example, including the structures shown in formulas (B1), (B2) or (B3) described later. Unit structure (B) can connect two unit structures (A) by covalent bonding with unit structure (A).

[0388] <<B-2: Unit Structure (BI)>>

[0389] The unit structure (B) preferably includes the unit structure (BI). The unit structure (BI) is derived from an aldehyde compound or an aldehyde equivalent.

[0390] Here, unit structure (BI) is a subordinate concept of unit structure (B), and does not refer to a part of the structure of unit structure (B).

[0391] The following is an explanation of the BI (Block Component) structure.

[0392] <<<B-3: Equation (B1)>>>

[0393] The unit structure (BI) includes, for example, the structure shown in equation (B1) below. The unit structure (BI) can be the structure shown in equation (B1) below.

[0394]

[0395] In equation (B1), R and R' can each independently represent a hydrogen atom, an aromatic ring with 6 to 30 carbon atoms that may have substituents, a heterocycle with 3 to 30 carbon atoms that may have substituents, or a straight-chain, branched, or cyclic alkyl group with 10 or fewer carbon atoms that may have substituents. R and R' can form a ring structure together with the carbon atoms they are bonded to. This represents a bonding bond.

[0396] Examples of substituents include hydroxyl, carboxyl, formyl, nitro, alkyl, alkoxy, aryl, aryloxy, cyano, groups in which the H of the hydroxyl group is replaced by the above-mentioned substituent (S), and halogen groups.

[0397] Furthermore, the two bonding bonds in equation (B1) can be covalently bonded to each of the aromatic rings in the two unit structures (A), respectively.

[0398] In the definitions of R and R' in equation (B1), the terms "aromatic ring" and "heterocyclic ring" can be found in (I-3) and (I-4) above.

[0399] In the definitions of R and R' in formula (B1), examples of "alkyl" include, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2 1-Methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl- n-Butyl, 2-Ethyl-n-Butyl, 1,1,2-Trimethyl-n-Propyl, 1,2,2-Trimethyl-n-Propyl, 1-Ethyl-1-Methyl-n-Propyl, 1-Ethyl-2-Methyl-n-Propyl, Cyclohexyl, 1-Methyl-Cyclopentyl, 2-Methyl-Cyclopentyl, 3-Methyl-Cyclopentyl, 1-Ethyl-Cyclobutyl, 2-Ethyl-Cyclobutyl, 3-Ethyl-Cyclobutyl, 1,2-Dimethyl-Cyclobutyl, 1,3-Dimethyl-Cyclobutyl, 2,2-Dimethyl-Cyclobutyl, 2,3-Dimethyl-Cyclobutyl, 2 4-Dimethyl-cyclobutyl, 3,3-Dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptyl, n-octyl, n-nonyl, n-decyl.

[0400] Preferably, R and R' are each independently phenyl, naphthyl, anthraceneyl, phenanthryl, tetraphenyl, or pyrene.

[0401] More preferably, R is a hydrogen atom and R' is a naphthyl group.

[0402] As a ring structure formed by R and R' together with the carbon atoms they are bonded to, examples include structures shown in the following formula.

[0403]

[0404] (In the formula, Ar independently represents the residues of the aromatic ring.) The carbon atom represented in formula (B1) is the carbon atom bonded to R and R'.

[0405] As an aromatic ring of Ar, examples include the aromatic ring shown in formula (G1).

[0406] The unit structure (BI) of the structure represented by formula (B1) is derived from, for example, aldehyde compounds and ketone compounds.

[0407] Examples of aldehyde compounds include, for instance, the compound shown in the following formula (B-1a).

[0408] Examples of ketone compounds include, for instance, the compound shown in formula (B-1b) below.

[0409]

[0410] In equations (B-1a) and (B-1b), R and R' have the same meaning as R and R' in equation (B1). However, R is not a hydrogen atom.

[0411] In formula (B-1b), R and R' can form a ring structure together with the carbon atoms they are bonded to.

[0412] For example, in obtaining resin (G), the carbonyl groups in formulas (B-1a) and (B-1b) are transformed into the carbonyl groups in formula (B1). -C- .

[0413] If we give specific examples of the unit structure (BI) containing the structure shown in formula (B1), then it is as follows. This basically represents the connection point with the unit structure (A). It goes without saying that it can be a structure that includes the illustrated structure within a part of the whole.

[0414]

[0415] <<<B-4: Equation (B2)>>>

[0416] The unit structure (BI) includes, for example, the structure shown in equation (B2) below. The unit structure (BI) can be the structure shown in equation (B2) below.

[0417]

[0418] In equation (B2), Z 0 This refers to an organogroup consisting of 6 to 30 carbon atoms of aromatic ring residues, aliphatic ring residues, or two or more aromatic or aliphatic rings linked by a single bond, which may have substituents. Examples of organogroups consisting of two or more aromatic or aliphatic rings linked by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and dicyclohexyl.

[0419] Examples of substituents include hydroxyl, carboxyl, formyl, nitro, alkyl, alkoxy, aryl, aryloxy, cyano, groups in which the H of the hydroxyl group is replaced by the above-mentioned substituent (S), and halogen groups.

[0420] J 1 and J 2 Each can be independently represented as a directly bonded or potentially substituent-containing divalent organogroup. Preferably, this divalent organogroup is a straight-chain or branched alkylene group with 1 to 6 carbon atoms, which can be substituted by a hydroxyl group, an aryl group (phenyl, substituted phenyl, etc.), or a halogen group (e.g., fluorine). Examples of straight-chain alkylene groups include, for example, methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0421] The unit structure (BI) containing the structure shown in formula (B2) originates, for example, from compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom, compounds having a hydroxyl, alkoxy, or halogroup bonded to an α-carbon atom (such as a benzyl carbon atom) of an alkyl aryl group, or compounds having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0422] Examples of compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom include, for example, compounds represented by the following formula (B-2a).

[0423] Examples of compounds having a hydroxyl, alkoxy, or halogroup bonded to the α-carbon atom (benzyl carbon atom, etc.) of an alkyl aryl group include, for example, the compound shown in formula (B-2b).

[0424] Examples of compounds having two carbon-carbon double bonds include, for example, compounds represented by formula (B-2c) or formula (B-2d).

[0425]

[0426] (In equations (B-2a), (B-2b), and (B-2c), J) 1 J 2 and Z 0 J in equation (B2) 1 J 2 and Z 0 They have the same meaning.

[0427] In equation (B-2a), X a and X b Each can be used independently to represent a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom.

[0428] In equation (B-2b), Y a and Y b Each of these groups independently represents a hydroxyl, alkoxy, or halogroup bonded to the α-carbon atom of an alkyl aryl group (or the carbon atom at the benzyl position, etc.).

[0429] In equation (B-2d), n represents an integer from 0 to 4.

[0430] For example, when obtaining resin (G), X in formula (B-2a) a -J 1 Transformed into equation (B2) -J 1 J 2 -X b J is transformed into equation (B2) 2 - .

[0431] For example, when obtaining resin (G), Y in formula (B-2b) a -J 1 Transformed into equation (B2) -J 1 J 2 -Y b J is transformed into equation (B2) 2 - .

[0432] An example of formula (B-2a) is the following compound.

[0433]

[0434] An example of formula (B-2b) is the following compound.

[0435]

[0436] An example of formula (B-2c) is the following compound.

[0437]

[0438] If we give specific examples of the unit structures containing the structure shown in equation (B2), then the following is a description. This indicates the junction with the unit structure (A). It goes without saying that this can be a unit structure that contains the illustrated structure within a part of the whole.

[0439]

[0440] The unit structure (BI) includes, for example, the structure shown in equation (B3) below. The unit structure (BI) can be the structure shown in equation (B3) below.

[0441] The unit structure (BI) containing the structure shown in formula (B3) originates, for example, from compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom, compounds having a hydroxyl, alkoxy, or halogroup bonded to an α-carbon atom (such as a benzyl carbon atom) of an alkyl aryl group, or compounds having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0442] <<<B-5: Equation (B3)>>>

[0443] In equation (B3), Z is a group that may have substituents and is a fused ring having 4 to 25 carbon atoms, consisting of a monocyclic, bicyclic, tricyclic, or tetracyclic ring. Furthermore, the number of carbon atoms referred to here means the number of carbon atoms forming the ring skeleton of the fused ring (excluding substituents), excluding the number of heteroatoms forming the heterocycle in the case where the monocyclic or fused ring is a heterocycle.

[0444] The aforementioned single rings are single rings whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0) (hereinafter, sometimes referred to as "non-Hückel single rings"). At least one of the single rings constituting the aforementioned two-, three-, and four-ring structures is a single ring whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0), and the remaining single rings can be single rings whose number of π electrons satisfies 4n+2 (n is an integer greater than or equal to 0).

[0445] The aforementioned monocyclic, bicyclic, tricyclic, or tetracyclic fused rings can further form fused rings with one or more aromatic rings to become fused rings of five or more rings. The number of carbon atoms in the fused ring of five or more rings is preferably 40 or less. Here, the number of carbon atoms refers to the number of carbon atoms constituting the ring skeleton of the aforementioned fused ring of five or more rings after removing substituents, excluding the number of heteroatoms constituting the heterocycle in the case where the aforementioned fused ring of five or more rings is a heterocycle.

[0446] If X and Y are the same or different, it indicates -CR 31 R 32 -base, R 31 and R 32 They may be the same or different, representing hydrocarbon groups with 1 to 6 hydrogen or carbon atoms.

[0447] x and y represent numbers in X and Y respectively, and each independently represents 0 or 1.

[0448] In formula (B3) and (B3) At least one of them is bonded to any carbon atom (referred to as "carbon atom Z") of the aforementioned non-Hückel monocycle constituting Z (in the case of x=1, y=1) or extends from carbon atom Z (in the case of x=0, y=0).

[0449] For example, in equation (B3) It combines with any carbon atom (referred to as "carbon atom 1") of the aforementioned non-Hückel monocycle constituting Z (in the case of x=1) or extends from carbon atom 1 (in the case of x=0). In formula (B3) It combines with any carbon atom (referred to as "carbon atom 2") of the aforementioned non-Hückel monocycle constituting Z (in the case of y=1) or extends from carbon atom 2 (in the case of y=0). Carbon atom 1 and carbon atom 2 can be the same or different. In different cases, they can belong to the same non-Hückel monocycle or different non-Hückel monocycles.

[0450] Furthermore, in formula (B3), the connecting carbon atoms other than carbon atom 1 and carbon atom 2 can be included arbitrarily.

[0451] Furthermore, when Z is a fused ring with three or more rings, the arrangement of one or two non-Hückel monocycles to which carbon atoms 1 and 2 belong in equation (B3) and the remaining monocycles in the fused ring is arbitrary. When carbon atoms 1 and 2 belong to different non-Hückel monocycles (referred to as "non-Hückel monocycle 1" and "non-Hückel monocycle 2" respectively), the arrangement of non-Hückel monocycle 1 and non-Hückel monocycle 2 in the fused ring is also arbitrary.

[0452] If we give specific examples of organic groups that include the structure shown in formula (B3), the following will be described. The binding site with the unit structure (A) is not particularly limited. It goes without saying that a structure can contain the illustrated structure as part of a whole.

[0453] Additionally, it also contains bonding bonds ( For example, if the number of bonds exceeds 2, the remaining bonds can be used for bonding with aromatic rings in other polymer chains, cross-linking, etc., and can be bonds with hydrogen bonds.

[0454]

[0455] Below, in equation (B3), the following will be discussed regarding the content of equation (B3). In the formula (B3) The case of only one of them being combined with any carbon atom (referred to as "carbon atom Z") of the aforementioned non-Hückel monocycle constituting Z (in the case of x=1, y=1) or extending from carbon atom Z (in the case of x=0, y=0) will be explained.

[0456] As a more specific structure of formula (B3) in this case, for example, for formula (C31) below, the unit structure (BI) shown in formula (B3) can be formed by p and k1 or p and k2, which can be the bonding bonds. The remaining bonding bonds are bonded to hydrogen atoms.

[0457]

[0458] Furthermore, for the following formula (C32), the unit structure (BI) shown in formula (B3) can be formed by p with k1, p with k2, or p with m among p, k1, k2, and m, which can become bonding bonds. The remaining bonding bonds are bonded to hydrogen atoms.

[0459]

[0460] If we were to give several more specific examples of equation (B3) that are equivalent to equation (C31) or equation (C32), they would be as follows. This indicates the connection point with the unit structure (A).

[0461] For equation (B3), the bonding bonds that connect with other unit structures (e.g., unit structure (A)) extend separately from the aromatic rings in those structures, but for the specific examples described below, such bonding bonds are omitted. It goes without saying that the unit structure can contain the illustrated structure as part of the whole.

[0462]

[0463] Furthermore, in the specific examples described above, there are examples where the polymer terminus can be formed without the bonding bonds from the aromatic ring.

[0464] The composite unit structure in resin (G) may include unit structures other than unit structure (A) and unit structure (B).

[0465] However, resin (G) does not contain resins synthesized solely from indole and 1-naphthaldehyde.

[0466] The resin (G) is preferably a resin synthesized from reactants containing amine compounds and aldehyde compounds or aldehyde equivalents.

[0467] Examples of amine compounds include, for instance, compounds containing a skeleton having an aromatic ring, which is at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

[0468] Examples of aldehyde compounds include, for instance, the compound shown in formula (B-1a) above.

[0469] Examples of aldehyde equivalents include compounds represented by formulas (B-1b), (B-2a), (B-2b), (B-2c), or (B-2d) above.

[0470] Phenolic varnish resins having the structure shown in formula (AB) can be prepared using known methods. For example, they can be prepared by condensing a cyclic compound represented by HAH with an oxygen-containing compound represented by OHC-B, O=CB, RO-B-OR, RO-CH2-B-CH2-OR, etc. Here, A and B have the same meaning as described above. R represents a hydrogen atom, a halogen, or an alkyl group having about 1 to 3 carbon atoms.

[0471] One type of cyclic compound and one type of oxygen-containing compound can be used, or two or more types can 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, relative to 1 mole of the cyclic compound.

[0472] As catalysts used in condensation reactions, inorganic 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 can be used. The amount of catalyst used varies depending on the type of catalyst used, but is typically 0.001 to 10,000 parts by mass relative to 100 parts by mass of the cyclic compound (in the case of multiple compounds, their totality), preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass.

[0473] Although condensation reactions can occur under solvent-free conditions, they are usually carried out using a solvent. There are no particular limitations on the solvent, as long as it can dissolve the reaction substrate and does not hinder the reaction. Examples include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, tetrahydropyran, and dimethyl ether. Alkane, 1,2-dichloromethane, 1,2-dichloroethane, toluene, N-methylpyrrolidone, dimethylformamide, etc. The condensation reaction temperature is typically 40℃ to 200℃, preferably 100℃ to 180℃. The reaction time varies depending on the reaction temperature, typically ranging from 5 minutes to 50 hours, preferably 5 minutes to 24 hours.

[0474] The phenolic varnish resin involved in one aspect of the present invention typically has a weight-average molecular weight of 500 to 100,000, preferably 600 to 50,000, 700 to 10,000, or 800 to 8,000.

[0475] The content of resin (G) in the coating composition is, for example, 25 to 100% by mass relative to the mass of the film-forming component, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.

[0476] Here, the so-called film-forming component refers to the component from which the solvent component has been removed from the coating agent composition.

[0477] The molar ratio of unit structure (A) to unit structure (B) in resin (G) is preferably 30:70 to 70:30, more preferably 30:70 to 50:50, even more preferably 40:60 to 50:50, and particularly preferably 50:55 to 50:50.

[0478] Furthermore, the molar ratio of unit structure (A) to unit structure (B) in resin (G) can also be expressed by the molar ratio of compound (A) which is the raw material of unit structure (A) to compound (B) which is the raw material of unit structure (B).

[0479] The molar ratio of compound (A) to compound (B) is preferably 30:70 to 70:30, more preferably 30:70 to 50:50, even more preferably 40:60 to 50:50, and particularly preferably 50:55 to 50:50. Here, compound (A) can be one type or two or more types. Similarly, compound (B) can be one type or two or more types.

[0480] The proportion (molar ratio) of unit structure (AI) in unit structure (A) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and can be 100 mol%.

[0481] Furthermore, the proportion (molar ratio) of the unit structure (AI) in unit structure (A) can also be expressed by the molar ratio of the compound (AI) that is the raw material of the unit structure (AI) in compound (A).

[0482] The molar ratio of compound (AI) in compound (A) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and can be 100 mol%.

[0483] The proportion (molar ratio) of unit structure (BI) in unit structure (B) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and can be 100 mol%.

[0484] Furthermore, the proportion (molar ratio) of unit structure (BI) in unit structure (B) can also be expressed by the molar ratio of compounds (BI) that are the raw materials of unit structure (BI) in compound (B).

[0485] The molar ratio of compound (BI) in compound (B) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and can be 100 mol%.

[0486] <Solvent>

[0487] The coating composition of one aspect of the present invention comprises a solvent.

[0488] There are no particular limitations on the solvent, as long as it can dissolve the specific phenolic varnish resin and any other ingredients added as needed.

[0489] Examples of solvents include, for instance, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl methanol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate Isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl acetate, ethyl... Ethyl oxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone, etc. These solvents can be used alone or in combination of two or more.

[0490] In addition, solvents with a boiling point above 160°C and solvents with a boiling point below 160°C can be combined and included.

[0491] As such a high-boiling-point solvent, the following compounds, for example, described in International Publication No. 2018 / 131562 (A1), may be preferred.

[0492]

[0493] [R in equation (i)] 1 R 2 and R 3 Each alkyl group represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms (which can be interrupted by an oxygen atom, a sulfur atom, or an amide bond), and these groups can be the same or different, and can combine to form a ring structure.

[0494] Alternatively, 1,6-diacetoxyhexane (boiling point 260°C), tripropylene glycol monomethyl ether (boiling point 242°C), and various high-boiling solvents described in other paragraph 0082 of Japanese Patent Application Publication No. 2021-84974 may be preferred.

[0495] Alternatively, the following materials may be preferred: dipropylene glycol monomethyl ether acetate (boiling point 213°C), diethylene glycol monoethyl ether acetate (boiling point 217°C), diethylene glycol monobutyl ether acetate (boiling point 247°C), dipropylene glycol dimethyl ether (boiling point 171°C), dipropylene glycol monomethyl ether (boiling point 187°C), dipropylene glycol monobutyl ether (boiling point 231°C), and tripropylene glycol monomethyl ether (boiling point 247°C), as described in Japanese Patent Application Publication No. 2019-20701. The following are examples of high-boiling solvents described in paragraphs 0023 to 0031 of this publication: γ-butyrolactone (boiling point 242°C), benzyl alcohol (boiling point 204°C), propylene carbonate (boiling point 205°C), tetraethylene glycol dimethyl ether (boiling point 275°C), 1,6-diacetoxyhexane (boiling point 260°C), dipropylene glycol (boiling point 230°C), 1,3-butanediol diacetate (boiling point 232°C).

[0496] The coating composition, as one aspect of the invention of this application, may contain an acid and / or its salt and / or an acid-generating agent.

[0497] Examples of acids include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthoic acid.

[0498] Salts of the aforementioned acids can also be used as salts. There are no limitations on the salt composition; salts of ammonia derivatives such as trimethylamine salts and triethylamine salts, pyridine derivatives, and morpholine derivatives can be used appropriately.

[0499] Acids and / or their salts may be used alone, or two or more may be used in combination. The mixing amount relative to the total solid content is typically 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass.

[0500] Examples of acid-producing agents include thermal acid-producing agents and photo-producing acid-producing agents.

[0501] Examples of heat-generating acid agents include 2,4,4,6-tetrabromocyclohexadienone, benzoin toluene sulfonate, 2-nitrobenzyl toluene sulfonate, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, K-PURE TAG2700 (manufactured by King Industries), and organic alkyl sulfonates such as SI-45, SI-60, SI-80, SI-100, SI-110, and SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.).

[0502] Photoacid-generating agents produce acid during the exposure of the photoresist. Therefore, the acidity of the underlying film can be adjusted. This is one method to match the acidity of the underlying film with that of the upper photoresist. Furthermore, by adjusting the acidity of the underlying film, the pattern shape of the photoresist formed on the upper layer can be adjusted.

[0503] Examples of photoacid-generating agents included in the coating composition of the present invention include: Salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds, etc.

[0504] As Salt compounds, for example, diphenyliodine Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate and bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Salt compounds, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro n-butane sulfonate, triphenylsulfonium camphor sulfonate, and triphenylsulfonium trifluoromethane sulfonate.

[0505] Examples of sulfonylimide compounds include, for example, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0506] Examples of disulfonyldiazomethane compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0507] Acid-producing agents can be used alone, or two or more can be used in combination.

[0508] When using an acid-generating agent, its proportion is 0.01 to 10 parts by mass, 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass relative to 100 parts by mass of the solid component of the coating agent composition.

[0509] In addition to the above, the coating composition of this invention may also include, as needed, a crosslinking agent, a surfactant, a light absorber, a rheology modifier, an adhesive aid, etc.

[0510] Representative crosslinking agents include amino plastic crosslinking agents and phenolic plastic crosslinking agents.

[0511] As the aforementioned crosslinking agent, a crosslinking agent with high heat resistance can be used. As a crosslinking agent with high heat resistance, a compound containing crosslinking-forming substituents with aromatic rings (e.g., benzene rings, naphthalene rings) within the molecule is preferred.

[0512] Examples of crosslinking agents for amino plastics include highly alkylated, alkoxylated, or alkoxyalkylated melamine, benzoguanidine, glycourea, urea, and their polymers. Preferably, crosslinking agents have at least two crosslinking-forming substituents, such as compounds like methoxymethylated glycourea, butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanidine, butoxymethylated benzoguanidine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds can also be used.

[0513] Preferably, it is selected from at least one of tetramethoxymethyl glycourea and hexamethoxymethyl melamine.

[0514] If we give some specific examples, they are as follows.

[0515]

[0516] Examples of crosslinking agents for phenolic plastics include highly alkylated, alkoxylated, or alkoxyalkylated aromatic compounds and their polymers. Preferably, crosslinking agents have at least two crosslinking-forming substituents in one molecule, such as 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene. Condensates of these compounds can also be used.

[0517] In addition to the above, other examples of such compounds include compounds having a partial structure of the following formula (4), polymers or oligomers having repeating units of the following formula (5).

[0518]

[0519] The above R 11 R 12 R 13 and R 14 Alkyl groups having 1 to 10 hydrogen or carbon atoms can be used as illustrated above. n1 is an integer from 1 to 4, n2 is an integer from 1 to (5-n1), and (n1+n2) represents an integer from 2 to 5. n3 is an integer from 1 to 4, n4 is from 0 to (4-n3), and (n3+n4) represents an integer from 1 to 4. Oligomers and polymers can be used in the range of 2 to 100 or 2 to 50 repeating unit structures.

[0520] If we give some specific examples, they are as follows.

[0521]

[0522] Crosslinking agents such as amino plastic crosslinking agents and phenolic plastic crosslinking agents can be used alone or in combination. Amino plastic crosslinking agents can be manufactured by methods known to them or equivalent methods; in addition, commercially available products can be used.

[0523] Furthermore, the amount of crosslinking agents such as amino plastic crosslinking agents and phenolic plastic crosslinking agents used varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but relative to the total solid content of the coating agent composition involved in this invention, it is 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more, and is 80% by mass or less, 50% by mass or less, 40% by mass or less, 20% by mass or less, or 10% by mass or less.

[0524] In the coating composition of the present invention, surfactants can be mixed in to further improve the coating performance on uneven surfaces in order to avoid the generation of pinholes, streaks, etc.

[0525] Examples of surfactants include, for instance, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol fatty acid esters such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol tristearate; and nonionic surfactants. EF301, EF303, EF352 (manufactured by EF30F Co., Ltd., trade name), EF303, EF352 171. F173, R-30, R-40 (manufactured by Dainippon Co., Ltd., trade name), Fururo FC430, FC43 1 (trade name manufactured by Sumitomo Solar Co., Ltd.), ASUNALA AG710, SALENA S-382, SC101, S Fluorine-based surfactants such as C102, SC103, SC104, SC105, SC106 (trade name manufactured by Asahi Glass Co., Ltd.), Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0526] The amount of these surfactants mixed in relation to the total solids content of the coating composition involved in this invention is typically 2.0% by mass or less, preferably 1.0% by mass or less. These surfactants can be added individually or in combination of two or more.

[0527] As light absorbers, commercially available light absorbers listed in publications such as "Technology and Market of Industrial Pigments" (CMC Publishing) and "Dye Handbook" (Organic Synthetic Chemistry Society) are suitable, including CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; CI Disperse Orange 1, 5, 13, 25, etc. 29, 30, 31, 44, 57, 72 and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; CI Disperse Violet 43; CI Disperse Blue 96; CI Fluorescent Whitening Agent 112, 135 and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. The above-mentioned light absorbers are generally blended in a ratio of 10% by mass or less, preferably 5% by mass or less, relative to the total solid components of the coating composition involved in this invention.

[0528] Rheology modifiers are primarily added to improve the flowability of coating compositions, especially during the baking process, to enhance the uniformity of the resist film thickness and improve the filling ability of the coating composition within pores. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di(n-butyl) maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically blended in proportions of less than 30% by mass relative to the total solids of the coating composition involved in this invention.

[0529] Adhesive additives are primarily used to improve the adhesion between nitrogen-containing substrates or resists and coating agent compositions, especially during development to prevent the resist from peeling off. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium; silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-epoxypropoxypropyltrimethoxysilane; and silanes such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzo[]. Heterocyclic compounds such as azoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. These adhesive aids are typically formulated in proportions of less than 5% by mass, preferably less than 2% by mass, relative to the total solids content of the coating composition involved in this invention.

[0530] The solid content of the coating composition involved in this invention is preferably 0.1 to 70% by mass or 0.1 to 60% by mass. The solid content refers to the percentage of all components contained in the coating composition after the solvent has been removed. A crosslinkable resin may be contained in the solid content at a ratio of 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, or 50 to 90% by mass.

[0531] [Underlying film of resist]

[0532] A nitrogen-containing substrate coating composition, as one aspect of the present invention, can be used to form a photoresist underlayer film on a nitrogen-containing substrate. That is, as a sintered (cured) product of the coating film formed by the nitrogen-containing substrate coating composition, a photoresist underlayer film can be formed on a nitrogen-containing substrate. Another aspect of the present invention is a method for manufacturing a laminate comprising two or more layers, including a nitrogen-containing substrate and a photoresist underlayer film, comprising the steps of: coating at least one side of the nitrogen-containing substrate with a nitrogen-containing substrate coating composition; and firing the resulting coating film to form a photoresist underlayer film. The aforementioned laminate can have a photoresist film stacked on the side opposite to the nitrogen-containing substrate (stacked in the order of substrate / photoresist underlayer film / photoresist film). Furthermore, another aspect of the present invention is the use of a nitrogen-containing substrate coating composition for forming a photoresist underlayer film on a nitrogen-containing substrate.

[0533] Other embodiments of the present invention include a laminate comprising a substrate containing nitrogen atoms and a resist underlayer film of two or more layers. A further embodiment of the present invention includes a laminate in which at least one side of a substrate containing nitrogen atoms is laminated in the order of the resist underlayer film and the resist film described above. A further embodiment of the present invention includes the use of a nitrogen-containing substrate coating agent composition in the manufacture of these laminates or semiconductor devices.

[0534] More specifically, a nitrogen-containing substrate coating agent composition, as described in one aspect of the present invention, is applied to a nitrogen-containing substrate (e.g., silicon nitride substrate (SiN substrate), silicon oxide nitride substrate (SiON substrate), titanium nitride substrate (TiN substrate), or titanium oxide nitride substrate (TiON), etc.) that can be used in the manufacture of semiconductor devices, using a suitable coating method such as a spin coater or a coating machine. Then, firing is performed using a heating means such as a hot plate, thereby forming a photoresist underlayer film on the nitrogen-containing substrate. The firing conditions are appropriately selected from a firing temperature of 80°C to 800°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 500°C (more preferably 150°C to 400°C), and the firing time is 0.5 to 2 minutes. Air, or inactive gases such as nitrogen or argon, can be used as the atmosphere gas during firing. In one embodiment, an oxygen concentration of 1% or less is particularly preferred.

[0535] Here, the thickness of the formed resist film can be, for example, 10–1000 nm, 20–500 nm, 30–400 nm, or 50–300 nm, but from a cost and manufacturing point of view, an ultrathin film with a thickness of less than 10 nm is preferred. The film thickness is preferably 1 to less than 10 nm, more preferably 3 to less than 10 nm. Even with such an ultrathin film, the nitrogen-containing substrate coating agent composition of one aspect of the present invention, by blending with a specific phenolic varnish resin, exhibits good coatability and can maintain a resolution comparable to that of the resist immediately after its formation, even after prolonged exposure following the formation of the resist film.

[0536] Furthermore, an adhesive layer and / or a silicon-containing layer containing 99% by mass or less or 50% by mass or less of Si can also be formed on the resist underlayer film, which is an aspect of the present invention, by coating or vapor deposition. For example, in addition to the method of forming the adhesive layer described in Japanese Patent Application Publication No. 2013-202982, Japanese Patent No. 5827180, and the silicon-containing resist underlayer film (inorganic resist underlayer film) forming composition described in International Publication No. 2009 / 104552 (A1) by spin coating, Si-based inorganic material films can also be formed by CVD or the like.

[0537] Furthermore, by applying the coating agent composition, which is one aspect of the present invention, onto a semiconductor substrate (so-called high-low difference substrate) containing portions having high-low differences and portions not having high-low differences and then firing it, the high-low difference between the portions having high-low differences and the portions not having high-low differences can be reduced.

[0538] [Laminated body]

[0539] The laminate of the present invention comprises a substrate containing nitrogen atoms and a photoresist underlayer film of the present invention.

[0540] The substrate containing nitrogen atoms is a substrate formed of a compound having bonds between a metal atom or a metalloid atom and a nitrogen atom, or a substrate having a film containing nitrogen atoms formed of a compound having bonds between a metal atom or a metalloid atom and a nitrogen atom.

[0541] The resist underlayer film of the present invention is a cured product of the substrate coating composition containing nitrogen atoms of the present invention.

[0542] The resist lower layer film of the present invention is, for example, disposed on a substrate containing nitrogen atoms.

[0543] As one aspect of the present invention, the laminate is preferably a cured product of a substrate coating agent composition containing nitrogen atoms, which is a nitrogen-containing film, and the nitrogen-containing film constitutes the outermost layer of the nitrogen-containing substrate.

[0544] As one aspect of the present invention, the laminate preferably contains a substrate containing nitrogen atoms, and the metal atoms or quasi-metal atoms contained therein are...

[0545] (i) Silicon, (ii) Titanium, or (iii) Tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or alloys thereof.

[0546] As one aspect of the present invention, the stacked body preferably contains a nitrogen-containing substrate in which the compound having bonds between metal atoms or quasi-metal atoms and nitrogen atoms is SiON, SiN, TiON, or TiN.

[0547] [Pattern Formation Method]

[0548] The pattern forming method of the present invention includes at least the step of coating a substrate coating agent composition containing nitrogen atoms onto a semiconductor substrate containing nitrogen atoms and firing it to form a photoresist underlayer film.

[0549] The pattern forming method of the present invention may include the following steps: The process of forming a resist film on the resist underlayer film; The process of irradiating a resist film with light or an electron beam, followed by developing the resist film to obtain a resist pattern; and The process of using a resist pattern as a mask and etching the underlying resist film.

[0550] [Method for manufacturing semiconductor devices]

[0551] (i)

[0552] A method for manufacturing a semiconductor device, as one aspect of the present invention, includes the following steps: The process of forming a photoresist underlayer film on a nitrogen-containing semiconductor substrate using a coating agent composition as an aspect of the present invention. The process of forming a resist film on the resist underlayer film; The process of forming a resist pattern by irradiating a resist film with light or an electron beam and developing it; The process of etching the aforementioned resist underlayer film through a resist pattern to form a patterned resist underlayer film; and A process of processing a semiconductor substrate containing nitrogen atoms through a patterned resist underlayer.

[0553] (ii)

[0554] Furthermore, the method for manufacturing a semiconductor device as an aspect of the present invention includes the following steps: The process of forming a photoresist underlayer film on a nitrogen-containing semiconductor substrate using a coating agent composition as an aspect of the present invention. The process of forming a hard mask on the underlying resist film; The next step is to form a resist film on the hard mask. The process of forming a resist pattern by irradiating a resist film with light or an electron beam and developing it; The process of etching a hard mask using a resist pattern to form a patterned hard mask; The process of etching the aforementioned resist underlayer film through a patterned hard mask to form a patterned resist underlayer film; and A process of processing a semiconductor substrate containing nitrogen atoms through a patterned resist underlayer.

[0555] (iii)

[0556] Furthermore, the method for manufacturing a semiconductor device as an aspect of the present invention includes the following steps: The process of forming a photoresist underlayer film on a nitrogen-containing semiconductor substrate using a coating agent composition as an aspect of the present invention. The process of forming a hard mask on the underlying resist film; The next step is to form a resist film on the hard mask. The process of forming a resist pattern by irradiating a resist film with light or an electron beam and developing it; The process of etching a hard mask using a resist pattern to form a patterned hard mask; The process of etching the above-mentioned photoresist underlayer film through a patterned hard mask to form a patterned photoresist underlayer film. The process of removing the hard mask; and A process of processing a semiconductor substrate containing nitrogen atoms through a patterned resist underlayer.

[0557] (iv)

[0558] Furthermore, the method for manufacturing a semiconductor device as an aspect of the present invention includes the following steps: The process of forming a photoresist underlayer film on a nitrogen-containing semiconductor substrate using a coating agent composition as an aspect of the present invention. The process of forming a hard mask on the underlying resist film; The next step is to form a resist film on the hard mask. The process of forming a resist pattern by irradiating a resist film with light or an electron beam and developing it; The process of etching a hard mask using a resist pattern to form a patterned hard mask; The process of etching the above-mentioned photoresist underlayer film through a patterned hard mask to form a patterned photoresist underlayer film. The process of removing the hard mask; The process of forming a vapor-deposited film (spacer) on the resist underlayer film after the hard mask is removed; The process of etching a vapor-deposited film (spacer); The process of removing the patterned resist underlayer, leaving the patterned vapor-deposited film (spacers); and The process of processing a semiconductor substrate containing nitrogen atoms through a patterned vapor-deposited film (spacer).

[0559] The manufacturing methods described in (i) to (iv) above can be used to process a semiconductor substrate containing nitrogen atoms.

[0560] In this specification, the term "semiconductor substrate containing nitrogen atoms" refers to a semiconductor substrate having the aforementioned nitrogen-containing film on the substrate.

[0561] Examples of semiconductor substrates containing nitrogen atoms include semiconductor substrates having a SiON film, SiN film, TiON film, or TiN film thereon as a film containing nitrogen atoms, and silicon substrates (Si substrates) having a film containing nitrogen atoms thereon.

[0562] The process of forming a resist underlayer film using a coating agent composition as an aspect of the present invention is as described in the section on [Resist Underlayer Film] above.

[0563] A hard mask containing silicon, or a film, can be formed on the resist lower layer film formed by the above process as a second resist lower layer film, and a resist pattern can be formed on it [as described in (ii) to (iv) above].

[0564] Hard masks can be coatings of inorganic materials, or vapor-deposited films of inorganic materials formed by vapor deposition methods such as CVD and PVD. Examples include SiON films, SiN films, or SiO2 films.

[0565] An anti-reflective film (BARC) can be further formed on the hard mask, and a resist shape correction film without anti-reflective capability can be formed.

[0566] In the above-described process of forming the resist pattern, exposure is performed either by using a mask (photomask) to form the specified pattern or by direct drawing. Exposure sources can include, for example, gamma rays, i-rays, KrF excimer lasers, ArF excimer lasers, EUV, and electron beams. After exposure, post-exposure baking is performed as needed. Then, development is carried out with a developer (e.g., 2.38% tetramethylammonium hydroxide aqueous solution, butyl acetate), followed by rinsing with a rinsing solution or pure water to remove the used developer. Finally, post-baking is performed to dry the resist pattern and improve adhesion to the substrate.

[0567] The etching process performed after the above-mentioned resist pattern is formed is carried out by dry etching.

[0568] Additionally, the following gases—CF4, CHF3, CH2F2, CH3F, C4F6, C4F8, O2, N2O, NO2, H2, and He—can be used in the processing of the hard mask (containing a silicon layer), the underlayer of the resist, and the substrate. These gases can be used alone or in mixtures of two or more. Furthermore, argon, nitrogen, carbon dioxide, carbonyl sulfide, sulfur dioxide, neon, or nitrogen trifluoride can be mixed with these gases.

[0569] The aforementioned resist film can be patterned using nanoimprinting or self-assembly film methods.

[0570] For nanoimprinting, a resist composition is formed using a mold (type) that is transparent to the light and has been patterned. Furthermore, for self-assembled film methods, patterning is achieved using self-assembled films with naturally formed nanoscale regular structures, such as diblock polymers (polystyrene-polymethyl methacrylate, etc.).

[0571] In nanoimprint lithography, a silicon-containing layer (hard mask layer) can be selectively formed on a photoresist underlayer by coating or vapor deposition before applying a curable composition that becomes a photoresist film. A bonding layer is then formed on the photoresist underlayer or the silicon-containing layer (hard mask layer) by coating or vapor deposition, and the curable composition that becomes a photoresist film is applied on the bonding layer.

[0572] In addition, wet etching is sometimes performed to simplify the process and reduce damage to the substrate. This suppresses dimensional variations and reduces pattern roughness, resulting in a high yield rate for substrate processing. Therefore, in (iii) to (iv) above, hard masks can be removed by either etching or an alkaline solution. In particular, when using an alkaline solution, there are no restrictions on the composition, but the following components are preferred as the alkaline component.

[0573] Examples of alkaline components include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N... Methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]undecene-7, 1,4-diazabicyclo[2.2.2]octane, hydroxyethylpiperazine, piperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine, 1,5-diazabicyclo[4,3,0]nonene-5, etc. Furthermore, especially from an operational point of view, tetramethylammonium hydroxide and tetraethylammonium hydroxide are particularly preferred, as an inorganic base can be used in combination with a quaternary ammonium hydroxide. As the inorganic base, hydroxides of alkali metals such as potassium hydroxide, sodium hydroxide, and rubidium hydroxide are preferred, with potassium hydroxide being more preferred.

[0574] Example

[0575] The following examples illustrate the content of the present invention in detail, but the present invention is not limited to these examples.

[0576] The weight-average molecular weight Mw and Mw / Mn (polydispersity) of the resins shown in Synthetic Examples 1-16 and Comparative Synthetic Examples 1-4 below were determined by gel permeation chromatography (hereinafter referred to as GPC). A GPC apparatus manufactured by Higashi Soy Co., Ltd. was used in the determination, and the determination conditions are described below.

[0577] GPC column: TSKgel Super-MultiporeHZ-N (2 columns)

[0578] Column temperature: 40℃

[0579] Solvent: Tetrahydrofuran (THF)

[0580] Flow rate: 0.35 ml / min

[0581] Standard sample: Polystyrene (manufactured by Tosoo Corporation)

[0582] Synthesis of resin

[0583] The synthesis of resins (S1) to (S9) used in the lower layer of the resist film, and the synthesis of resin (SS1) as a comparative example, used the following compound groups A to C, catalyst group D, solvent group E, reprecipitation solvent group F, and separation solvent group G.

[0584] ○Compound group A~C

[0585] ○Catalyst group D, Solvent group E, Reprecipitation solvent group F, Separation solvent group G

[0586] Mesylate: D1

[0587] Tetrabutylammonium iodide: D2

[0588] Mercaptopropionic acid: D3

[0589] Propylene glycol monomethyl ether acetate (PGMEA): E1

[0590] Propylene glycol monomethyl ether (PGME): E2

[0591] N-Methyl-2-pyrrolidone: E3

[0592] Cyclohexanone: E4

[0593] 25% sodium hydroxide aqueous solution: E5

[0594] Tetrahydrofuran (THF): E6

[0595] Methanol: F1

[0596] Methanol / Water: F2

[0597] Butyl acetate / water: G1

[0598] [Synthesis example 1]

[0599] 5.0 g of A1, 2.46 g of B1, 0.37 g of D1, and 18.3 g of PGMEA were added to a flask. The mixture was then heated under nitrogen to 150 °C and reacted for approximately 20 hours. After the reaction was stopped, the mixture was redetermined with a methanol-water mixture (F2) and dried to obtain resin (S1). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 1,300. The target compound solution was obtained by dissolving the obtained resin in PGMEA and performing ion exchange for 4 hours using both cation and anion exchange resins. Similarly, ion exchange was performed by dissolving resins insoluble in PGMEA in PGME or cyclohexanone (CYH). The amounts of compounds added as raw materials for the resin, the synthesis conditions, etc., are shown in Table 1.

[0600] [Synthesis Examples 2 to 12]

[0601] Resins (S2) to (S11) and (SS1) were synthesized using the same procedure as in Synthesis Example 1. Furthermore, ion exchange was performed similarly by dissolving polymers insoluble in PGMEA in PGME or CYH. The amounts of compounds that will become raw materials for each resin, the synthesis conditions, etc., are shown in Table 1.

[0602]

[0603] The following shows the structural formulas of the obtained resins (S1) to (S11) and resin (SS1).

[0604]

[0605] [Synthesis example 6']

[0606] S6 6.50 g, C1 4.42 g, D2 0.23 g, E5 7.53 g, and E6 16.7 g were added to a flask. The mixture was heated under nitrogen to 55 °C and reacted for approximately 23 hours. After the reaction was stopped, the organic phase was repeatedly separated using a mixed solvent of butyl acetate and water (G1), concentrated, and then reprecipitated using F2. The resulting resin (S6') was dried to obtain the resin. The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was approximately 1,150. The obtained resin was dissolved in PGMEA, and ion exchange was performed for 4 hours using both cation and anion exchange resins to obtain a solution of the target compound. The amounts of compounds added as raw materials for the resin and the synthesis conditions are shown in Table 2.

[0607] [Synthesis Examples 7' to 11']

[0608] Resins (S7') to (S11') were synthesized using the same procedure as in Synthesis Example 1'. Furthermore, ion exchange was performed similarly by dissolving polymers insoluble in PGMEA in PGME or CYH. The amounts of compounds that will become raw materials for each resin, the synthesis conditions, etc., are shown in Table 2.

[0609]

[0610] The following shows the structural formulas of the obtained resins (S6') to (S11').

[0611]

[0612] Modulation of the underlayer film of the resist

[0613] Resins (S1) to (S5), resins (S6') to (S11'), resin (SS1), crosslinking agent (CL1), acid-generating agent (Ad1), solvent (propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CYH)) and surfactant Megafoc R-30 (manufactured by DIC Corporation, H1) were mixed in the proportions shown in Table 3 below (for crosslinking agent, acid-generating agent and surfactant, the weight is relative to 100 parts by weight of resin; for solvent, the weight is expressed independently of the weight of resin as 100% of the total weight of solvent). The mixture was filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare a photoresist underlayer film material (M1 to M11, Comparative M1) as a substrate coating agent composition containing nitrogen atoms.

[0614] The following shows the structural formulas of the crosslinking agents (CL1) to (CL2) and the acid-producing agents (Ad1) to (Ad2). Additionally, R in the formula represents methyl or methoxyisopropyl (-CH(CH3)CH2OCH3). Multiple Rs may be the same or different.

[0615]

[0616] [Examples 1-11, Comparative Example 1]

[0617] [Coating performance evaluation 1]

[0618] The resist underlayer materials M1 to M11, and comparison M1, were coated using a spin coater onto various substrates (SiON or Si substrates) without surface variations. They were then fired at the specified temperature and time as described in Table 4 under atmospheric conditions to form a resist underlayer film with a thickness of 5 nm. The surface of the formed resist underlayer film was visually inspected to evaluate its coatability. Cases where coating was free of pinholes, unevenness, or craters were marked as "0", and cases where it was not were marked as "×". The results are shown in Table 4. Additionally, results are shown for reference to demonstrate that the coating performance on Si substrates without nitrogen atoms is equivalent to that of conventional materials.

[0619]

[0620] [Coating performance evaluation 2]

[0621] The resist underlayer materials M1 to M11, and comparison M1, were coated onto various substrates using a coating and developing apparatus (ACT-8 or Lithius Pro) manufactured by Tokyo Electron Co., Ltd., and fired at the specified temperature / time as described in Table 5 under atmospheric conditions to form resist underlayer films with a thickness of 5 nm. Additionally, nitrogen-containing substrates (SiON substrates) with deposited SiON films (silicon oxide nitride films) were coated using ACT-8, and silicon wafers (Si substrates) were coated using Lithius Pro. The uniformity of the resist underlayer film thickness within the wafer surface was evaluated by measuring a total of 49 points radially and concentrically along the entire wafer plane. The case where the ratio of the film thickness fluctuation ((maximum film thickness) - (minimum film thickness)) to the average film thickness at 49 points is less than that of Comparative Example 1 is judged as "0", and Comparative Example 1 is marked as "×". Furthermore, a smaller ratio of film thickness fluctuation indicates higher film thickness uniformity within the wafer plane. The results are shown in Table 5. Additionally, to demonstrate that the coating performance is equivalent to conventional materials even on Si substrates without nitrogen atoms, the results are shown as a reference.

[0622] [Coating performance evaluation 3]

[0623] The resist underlayer materials M1 to M11, and comparison M1, were coated onto nitrogen-containing substrates (SiON substrates) with SiON vapor-deposited material using a coating and developing apparatus (ACT (registered trademark)-8) manufactured by Tokyo Electron Co., Ltd. The substrates were then fired at the specified temperature / time as described in Table 5 under atmospheric conditions to form resist underlayer films with a thickness of 5 nm. Surface roughness was then evaluated using AFM (atomic force microscopy) to assess coatability. Cases with no coatability issues were rated as "0", while cases showing pinholes, craters, or other film roughness were rated as "×". The results are shown in Table 5. Additionally, results are shown for reference to demonstrate that the coatability is equivalent to that of conventional materials on Si substrates without nitrogen atoms. "-" in the table indicates that this evaluation was not performed.

[0624]

[0625] According to Tables 4 and 5, the nitrogen-containing substrate coating composition of this application, like conventional material compositions, exhibits excellent coating properties on nitrogen-containing substrates, similar to silicon wafers.

[0626] [Photolithography Evaluation]

[0627] Using a coating and developing apparatus (ACT (registered trademark)-8) manufactured by Tokyo Electron Co., Ltd., resist underlayer materials M1 to M11 and Comparative M1 were coated onto a nitrogen-containing substrate (SiON substrate) on which a SiON film was formed, with the resulting film thickness being 5 nm. The substrates were then fired at the specified temperature / time as described in Table 6 under atmospheric atmosphere to form resist underlayer films. Furthermore, as comparative examples, various substrates without resist underlayer films were prepared, in addition to Comparative Example 1, and tests were also conducted on Comparative Examples 2 to 4. A commercially available ArF (argon fluoride) resist solution (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: SAIL X-206) was coated onto these resist underlayer films, and the films were fired at 85°C for 60 seconds to form a photoresist film with a thickness of 100 nm. After the above treatment, the resist films were left to stand for 48 hours without development. Using an ArF scanner (NSR-S307E, wavelength 193nm, NA=0.85, σ=0.93 / 0.85) manufactured by Nicon Inc., exposure was performed through a mask configured such that the linewidth and spacing of the photoresist formed after development would be 0.1μm, i.e., 0.1μm lines with a spacing (L / S) of 1 / 1. The image was then baked on a hot plate at 95°C for 60 seconds, and after cooling, developed with butyl acetate for 60 seconds, forming positive and negative patterns on the underlying photoresist film.

[0628] The size of the resist pattern immediately after formation was observed using a CD-SEM (length measurement SEM, manufactured by Hitachi High Tech Noroze). The size of the resist pattern developed immediately after formation was compared with that developed after 48 hours. The pattern size was then confirmed again using the same wafer after 48 hours. A change in pattern size less than 4 nm (as in Comparative Example 1) was defined as "0", and a change greater than 4 nm (as in Comparative Example 1) was defined as "×".

[0629] Next, the chip, which could form the target pattern size, was cut and observed using a scanning electron microscope (S-4800) manufactured by Hitachi High Tech Noroges Co., Ltd. Cases where the resist shape was perpendicular and unaffected by poisoning from the nitrogen-containing substrate were marked as "〇", while cases where it was non-perpendicular due to the influence of the substrate were marked as "×". The results are shown in Table 6. In Table 6, "-" indicates that the composition (the substrate coating composition containing nitrogen atoms) was not coated on the substrate.

[0630]

[0631] As described above, the phenolic varnish resins of Examples 1-11 exhibit excellent curability under atmospheric conditions even with film thicknesses less than 10 nm, and can be used as a photoresist underlayer in an ultrathin film state. Furthermore, these effects are not compromised even when triple bonds are introduced into NH groups. Moreover, even with film thicknesses less than 10 nm, good coatability is observed for various vapor-deposited film types, with high in-plane uniformity of film thickness. Furthermore, the structure of the resin in this embodiment can block amine components diffusing from nitrogen-containing substrates such as SiON, SiN, and TiN. Therefore, even after a long period of development following photoresist film formation, the size / shape of the photoresist can be maintained in the same vertical shape as the pattern developed immediately after photoresist film formation. Furthermore, the formed photoresist pattern does not change in size over time, exhibiting excellent pattern retention. Therefore, it is expected to become a widely applicable material for coating nitrogen-containing substrates in various semiconductor manufacturing processes.

Claims

1. A substrate coating composition containing nitrogen atoms, comprising a resin (G) having a composite unit structure and a solvent, The composite unit structure has the following characteristics: Unit structures with aromatic rings (A), and Unit structures with one or more carbon atoms (B), The resin (G) is a resin obtained by reacting carbon atoms of the aromatic ring constituting the unit structure (A) with carbon atoms in the unit structure (B) to form covalent bonds. The unit structure (A) has at least a unit structure (AI) containing nitrogen atoms. The substrate containing nitrogen atoms is a substrate formed of a compound having bonds between metal atoms or metalloid atoms and nitrogen atoms, or a substrate having a film containing nitrogen atoms formed of a compound having bonds between metal atoms or metalloid atoms and nitrogen atoms. The resin (G) is not a resin synthesized solely from indole and 1-naphthaldehyde.

2. The substrate coating composition containing nitrogen atoms according to claim 1, wherein the unit structure (AI) contains a backbone having an aromatic ring, the backbone being at least one of an aromatic amine backbone and a nitrogen-containing aromatic heterocyclic backbone.

3. The substrate coating composition containing nitrogen atoms according to claim 1, wherein the unit structure (AI) comprises a unit structure that does not contain a carbazole backbone.

4. The substrate coating composition containing nitrogen atoms according to claim 1, wherein the unit structure (AI) contains a backbone having an aromatic ring, the backbone being at least any one of the following formulas (A-1a), (A-1b), (A-1c), (A-2a), (A-2b-1), and (A-2b-2), wherein at least one hydrogen atom may be replaced by a substituent in the backbone; In equations (A-1a) to (A-1c), Ar 11 Each independently represents a residue of the aromatic ring; R 11 Each can independently represent a hydrogen atom or a residue of an aromatic ring; In the formula, Ar 21 Each residue independently represents a residue of the aromatic ring; R 21 Each can independently represent a hydrogen atom or a residue of an aromatic ring; R 22 Each independently represents a hydrogen atom, a hydrocarbon group with 1 to 5 carbon atoms, or a residue of an aromatic ring; two adjacent R... 22 They can form unsaturated aliphatic rings together; in addition, one of the unsaturated bonds in the unsaturated aliphatic ring refers to the unsaturated bond that constitutes the pyrrole ring. R independently represents a hydrogen atom, a residue of an aromatic ring, or a bond with L; L represents a single bond or a linker; n1 represents 1, n2 represents 1 or 2; in formula (A-2b-2), when L is a single bond, partial structures (In1) and partial structures (In2) are bonded to each other through two nitrogen atoms, or through two Ar atoms. 21 They combine with each other, or through nitrogen atoms and Ar atoms. 21 To combine; in equation (A-2b-2), when L is a linking base, L combines with N or Ar. 21 Combine.

5. The substrate coating composition containing nitrogen atoms according to claim 4, wherein in the backbone, the substituents that may replace at least one hydrogen atom are selected from one or more groups selected from halogenated, alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy, amino, hydroxyl, hydroxyalkyl, carboxyl, formyl, cyano, nitro, ester, amide, sulfonyl groups, thiol groups, thioether groups, and groups containing ether bonds.

6. The substrate coating composition containing nitrogen atoms according to claim 1, wherein the unit structure (B) comprises a unit structure (BI) derived from an aldehyde compound or an aldehyde equivalent.

7. The substrate coating composition containing nitrogen atoms according to claim 1, wherein the resin (G) is a resin synthesized from reactive raw materials containing amine compounds and aldehyde compounds or aldehyde equivalents.

8. The substrate coating composition containing nitrogen atoms according to claim 7, wherein the amine compound contains a skeleton having an aromatic ring, the skeleton being at least one of an aromatic amine skeleton and a nitrogen-containing aromatic heterocyclic skeleton.

9. The substrate coating composition containing nitrogen atoms according to claim 1, wherein the solvent comprises a solvent with a boiling point of 160°C or higher.

10. The substrate coating composition containing nitrogen atoms according to claim 1, further comprising at least one selected from acids and their salts, and acid-generating agents.

11. The substrate coating composition containing nitrogen atoms according to claim 1, further comprising a crosslinking agent.

12. The substrate coating composition containing nitrogen atoms according to claim 11, wherein the crosslinking agent is at least one selected from amino plastic crosslinking agents and phenolic plastic crosslinking agents.

13. The substrate coating composition containing nitrogen atoms according to claim 1, further comprising a surfactant.

14. The substrate coating composition containing nitrogen atoms according to claim 1, which is used for forming a resist underlayer film.

15. A resist underlayer film on a substrate containing nitrogen atoms, which is a cured product of the substrate coating composition containing nitrogen atoms according to any one of claims 1 to 14.

16. The resist underlayer film according to claim 15, wherein the film thickness is less than 10 nm.

17. A laminate comprising a substrate containing nitrogen atoms and a resist underlayer as claimed in claim 15, wherein the substrate containing nitrogen atoms is a substrate formed of a compound having bonds between metal atoms or metalloid atoms and nitrogen atoms, or a substrate having a nitrogen-containing film formed of a compound having bonds between metal atoms or metalloid atoms and nitrogen atoms.

18. The stack according to claim 17, wherein the lower resist film is a nitrogen-containing film, and the nitrogen-containing film constitutes the outermost layer of the nitrogen-containing substrate.

19. The stacked body according to claim 17, wherein the metal atom or quasi-metal atom is (i) Silicon, (ii) Titanium, or (iii) Tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum or alloys thereof.

20. The stacked body according to claim 17, wherein the compound having bonds between a metal atom or a quasi-metal atom and a nitrogen atom is SiON, SiN, TiON, or TiN.

21. A method for forming a resist pattern for manufacturing a semiconductor, comprising the step of coating a substrate coating agent composition containing nitrogen atoms, as described in any one of claims 1 to 14, onto a semiconductor substrate containing nitrogen atoms and firing it to form a resist underlayer film.

22. A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a photoresist underlayer film on a nitrogen-containing semiconductor substrate using the substrate coating composition containing nitrogen atoms according to any one of claims 1 to 14. The process of forming a resist film on the lower resist film; The process of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; The process of etching the resist underlayer film through the resist pattern to form a patterned resist underlayer film; as well as The process of processing a semiconductor substrate containing nitrogen atoms through the patterned resist underlayer film.

23. A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a photoresist underlayer film on a nitrogen-containing semiconductor substrate using the substrate coating composition containing nitrogen atoms according to any one of claims 1 to 14. The process of forming a hard mask on the underlying resist film; The next step is to form a resist film on the hard mask; The process of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; The process of etching the hard mask through the resist pattern to form a patterned hard mask; The process of etching the resist underlayer film through the patterned hard mask to form the patterned resist underlayer film; as well as The process of processing a semiconductor substrate containing nitrogen atoms through the patterned resist underlayer film.

24. A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a photoresist underlayer film on a nitrogen-containing semiconductor substrate using the substrate coating composition containing nitrogen atoms according to any one of claims 1 to 14. The process of forming a hard mask on the underlying resist film; The next step is to form a resist film on the hard mask; The process of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; The process of etching the hard mask through the resist pattern to form a patterned hard mask; The process of etching the resist underlayer film through the patterned hard mask to form the patterned resist underlayer film; The process of removing the hard mask; as well as The process of processing a semiconductor substrate containing nitrogen atoms through the patterned resist underlayer film.

25. A method for manufacturing a semiconductor device, comprising the following steps: The process of forming a photoresist underlayer film on a nitrogen-containing semiconductor substrate using the substrate coating composition containing nitrogen atoms according to any one of claims 1 to 14. The process of forming a hard mask on the underlying resist film; The next step is to form a resist film on the hard mask; The process of forming a resist pattern by irradiating the resist film with light or an electron beam and developing it; The process of etching the hard mask through the resist pattern to form a patterned hard mask; The process of etching the resist underlayer film through the patterned hard mask to form the patterned resist underlayer film; The process of removing the hard mask; The process of forming a vapor-deposited film on the resist underlayer after the hard mask is removed; The process of processing the vapor-deposited film by etching; The process of removing the patterned resist underlayer film, leaving the patterned vapor-deposited film; and The process of processing a semiconductor substrate containing nitrogen atoms through a patterned vapor deposition film.

26. The method of manufacturing a semiconductor device according to claim 23, wherein the hard mask is formed by coating a composition comprising an inorganic material or by vapor deposition of an inorganic material.

27. The method for manufacturing a semiconductor device according to claim 22, wherein the resist film is patterned by nanoimprinting or self-assembling film.

28. The method of manufacturing a semiconductor device according to claim 24, wherein the hard mask is removed by either etching or an alkaline solution.

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