Compound, composition, cured product, method for producing cured product, and method for producing electronic component

Abstract

A compound represented by general formula (I). (In the formula, X represents a hydrogen atom, an optionally substituted cyclic group having 2-20 ring-forming carbon atoms, an optionally substituted C1-20 chain hydrocarbon group, or the like, and R1-R7 represent a hydrogen atom selected from the group consisting of lt; group Agt; r1, R2, R3, R4, R5, R6, R7, R7, R7, R7, R7, R7, R8, R8, R8, R8, R8, R8, R8, R8, R8, group Agt; a represents an integer of 1 to 10, R1 and R2, R3 and R4, R4 and R5, R5 and R6, and a plurality of R7 and R7 are bonded to each other sometimes to form a ring, and one or more R7 groups selected from the group consisting of lt are present in the molecule, and R1 and R2 groups, R3 and R4 groups, R4 and R5 groups, R5 and R6 groups, and a plurality of R7 groups are bonded to each other to form a ring; group Agt; and a reactive group in the group. And other definitions refer to the description). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to compounds having a specific skeleton. Background Art

[0002] Conventionally, it is known that compounds having a skeleton structure in which a 6-membered ring and a 5-membered ring are condensed have heat resistance.

[0003] Non-Patent Document 1 describes the structure and production method of 11-allyl-10,12-dihydrobisindeno[1,2-b',2',1'-e]pyridine.

[0004] Patent document 1 describes a polymer having a structure containing an indolecarbazole unit on a side chain, a polymer containing the polymer, and a resist underlayer film containing the polymer that does not cause mixing with the resist layer, has high dry etching resistance, has high heat resistance, and has a low amount of sublimated products.

[0005] Furthermore, Patent Document 2 describes that a compound having a predetermined skeleton including two or more indole structures has excellent heat resistance and solvent resistance.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: US2018 / 0356732A1

[0009] Patent Document 2: International Publication No. 2022 / 131346

[0010] Non-patent literature

[0011] Non-patent document 1: J. Chem. Res. (2016), Vol. 40, p428-435 (Abudullah M. AsrI et al.) Summary of the invention

[0012] Problems to be solved by the invention

[0013] An object of the present invention is to provide a compound capable of providing a cured product having excellent heat resistance and solvent resistance, and a composition containing the compound.

[0014] Means for solving problems

[0015] The present inventors have conducted intensive studies and have found that a compound having a specific skeleton and having one or more reactive groups in a molecule and a composition containing the same can provide a cured product having excellent heat resistance and solvent resistance, thereby completing the present invention.

[0016] That is, the present invention provides the following [1] to

[13] .

[0017] [1] A compound represented by the following general formula (I).

[0018] [Chemical formula 1]

[0019]

[0020] (wherein, X represents a hydrogen atom, a substitutable cyclic group having 2 to 20 ring carbon atoms, a substitutable chain hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the chain hydrocarbon group are substituted with a divalent group selected from the following <Group B>,

[0021] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 (hereinafter also referred to as “R 1 ~R 7 ". ) each independently represents a hydrogen atom, a reactive group selected from the following <Group A>, a nitro group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, a group in which one or more methylene groups in the above alkyl group having 1 to 20 carbon atoms are substituted by a divalent group selected from the following <Group B>, a group in which one or more methylene groups in the above aromatic ring group having 6 to 20 carbon atoms are substituted by a divalent group selected from the following <Group B>, or a group in which one or more methylene groups in the above heterocyclic group having 2 to 20 carbon atoms are substituted by a divalent group selected from the following <Group B>,

[0022] <Group A> is a carbon-carbon unsaturated bond group, a cyclic ether group, a hydroxyl group, a mercapto group, an amino group, a halogen atom and a cyano group,

[0023] <Group B> -O-, -CO-, -COO-, -OCO-, -NR 11 -、-NR 11 CO- and -S-,

[0024] R 11 represents a hydrogen atom or a hydrocarbon group,

[0025] a represents an integer of 1 to 10, and when X is a hydrogen atom, a is 1,

[0026] When a is 2 or more, multiple R 1 , R 2 , R 3 , R 4 , R 5 , R6 and R 7 Can be the same or different,

[0027] There are 2 R in the same repeating unit 7 Can be the same or different,

[0028] R 1 With R 2 , R 3 With R 4 , R 4 With R 5 , R 5 With R 6 and multiple R 7 With R 7 Sometimes they bond to each other to form a ring,

[0029] However, the molecule has one or more reactive groups selected from the above-mentioned <Group A>.)

[0030] [2] The compound according to claim 1 represented by the following general formula (IIα), (IIβ) or (IIγ).

[0031] [Chemical formula 2]

[0032]

[0033] (Wherein, X, a, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 As with general formula (I),

[0034] R 21 , R 22 , R 23 , R 24 , R 25 and R 26 (hereinafter also referred to as “R 21 ~R 26 ". ) each independently represents a hydrogen atom, a reactive group selected from the above <Group A>, a nitro group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, a group in which one or more methylene groups in the alkyl group having 1 to 20 carbon atoms are substituted by a divalent group selected from the above <Group B>, a group in which one or more methylene groups in the aromatic ring group having 6 to 20 carbon atoms are substituted by a divalent group selected from the above <Group B>, or a group in which one or more methylene groups in the heterocyclic group having 2 to 20 carbon atoms are substituted by a divalent group selected from the above <Group B>,

[0035] R 21 With R 22 , R 23 With R 24 , R 24 With R 25 and R 25 With R 26 Sometimes they are bonded to each other to form a ring.)

[0036] [3] The compound according to [1] or [2], wherein X is an optionally substituted aromatic ring group having 6 to 20 carbon atoms or an optionally substituted heterocyclic group having 2 to 20 carbon atoms.

[0037] [4] The compound according to [1], which has one or more carbon-carbon unsaturated bonding groups as the reactive groups in the molecule.

[0038] [5] The compound according to [2], which has one or more carbon-carbon unsaturated bonding groups as the reactive groups in the molecule.

[0039] [6] The compound according to any one of [1] to [5], wherein the number of reactive groups selected from the above <Group A> present in the molecule is 2 or more.

[0040] [7] The compound according to any one of [1] to [6], wherein X has a fused ring which may be substituted, or the number of the reactive groups present in the molecule is 3 or more.

[0041] [8] A composition comprising the compound according to any one of [1] to [7].

[0042] [9] The composition according to [8], wherein the composition is used for electronic components.

[0043]

[10] A cured product obtained from the composition described in [8].

[0044]

[11] A method for producing a cured product, comprising the step of curing the composition described in [8].

[0045]

[12] A method for producing an electronic component, comprising the step of removing the cured product after the step of curing the composition according to [8].

[0046]

[13] A compound represented by the following general formula (III).

[0047] [Chemical formula 3]

[0048]

[0049] (wherein, X' represents a hydrogen atom, a substitutable cyclic group having 2 to 20 ring carbon atoms, a substitutable chain hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the chain hydrocarbon group are substituted with a divalent group selected from the following <Group B>,

[0050] R 1 '、R 2 '、R 3 '、R 4 '、R 5 '、R 6 ' and R 7 'respectively independently represent a hydrogen atom, a reactive group selected from the following <Group A>, a nitro group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, a group in which one or more methylene groups in the alkyl group having 1 to 20 carbon atoms are substituted by a divalent group selected from the following <Group B>, a group in which one or more methylene groups in the aromatic ring group having 6 to 20 carbon atoms are substituted by a divalent group selected from the following <Group B>, or a group in which one or more methylene groups in the heterocyclic group having 2 to 20 carbon atoms are substituted by a divalent group selected from the following <Group B>,

[0051] <Group A> is a carbon-carbon unsaturated bond group, a cyclic ether group, a hydroxyl group, a mercapto group, an amino group, a halogen atom and a cyano group,

[0052] <Group B> -O-, -CO-, -COO-, -OCO-, -NR 11 -、-NR 11 CO- and -S-,

[0053] R 11 represents a hydrogen atom or a hydrocarbon group,

[0054] a' represents an integer of 1 to 10. When X' is a hydrogen atom, a is 1.

[0055] When a' is 2 or more, multiple R 1 '、R 2 '、R 3 '、R 4 '、R 5 '、R 6 ' and R 7 'It can be the same or different,

[0056] There are 2 R in the same repeating unit 7 'It can be the same or different,

[0057] R 1 'With R2 ’, R 3 ’ and R 4 ’, R 4 ’ and R 5 ’, R 5 ’ and R 6 ’ and multiple existing Rs 7 ’ and R 7 ’ sometimes bond to each other to form a ring,

[0058] However, it has more than 1 phenolic hydroxyl group in the molecule.)

[0059] Advantages of the Invention

[0060] The compound represented by the general formula (I) of the present invention and the composition containing the same can provide a cured product with excellent heat resistance and solvent resistance. In addition, the cured product obtained by the present invention using the above composition becomes a cured product with excellent heat resistance and solvent resistance. Furthermore, the method for manufacturing an electronic component of the present invention can manufacture high-quality electronic components by using a composition suitable for electronic components that are considered to require high heat resistance and solvent resistance. Furthermore, by using the compound represented by the general formula (III) which is a precursor of the compound of the present invention, the compound of the present invention can be smoothly manufactured. Detailed Description of the Invention

[0061] <A. The compound represented by the general formula (I)>

[0062] The compound represented by the general formula (I) (hereinafter, also referred to as "Compound I".) will be described first. Compound I is a compound having a specific skeleton represented by the above general formula (I), and one of its characteristics is that it has a specified skeleton and has more than 1 reactive group selected from the above <Group A> (hereinafter, also simply referred to as "reactive group".) in the molecule. Preferred examples of Compound I are the compounds represented by the general formulas (IIα), (IIβ), and (IIγ) (hereinafter, also referred to as "Compound IIα", "Compound IIβ", and "Compound IIγ" respectively, and the three are collectively referred to as "Compound IIα-IIγ".)

[0063] It should be noted that "R in the same repeating unit that exists in two" 7 " refers to the two Rs in "(R 7 )2" in formula (I). 7 .

[0064] The carbon-carbon unsaturated bond group in the above-mentioned reactive group represents a group with a carbon-carbon unsaturated bond, and preferably a group with a carbon-carbon unsaturated bond at the terminal can be listed. As the above-mentioned carbon-carbon unsaturated bond group with a carbon-carbon unsaturated bond at the terminal, preferably ethynyl, propargyl, propargyloxy, monopropargylamino, dipropargylamino (di-2-propynylamino) and the like have a carbon-carbon triple bond at the terminal, vinyl, allyl, acryloyl, acryloyloxy, methacryloyl, methacryloyloxy and the like have a carbon-carbon double bond at the terminal. As the carbon-carbon unsaturated bond group becoming a reactive group, a group with a carbon-carbon triple bond at the terminal is particularly preferred, and ethynyl, propargyl, propargyloxy or dipropargylamino is particularly preferred. Because the carbon-carbon unsaturated bond group is the group represented above, it is easy to obtain a cured product with excellent heat resistance and solvent resistance.

[0065] The cyclic ether group in the reactive group is a group having a cyclic ether, preferably a group having a cyclic ether at the end, more preferably an epoxy group or an oxetane group, and particularly preferably an epoxy group such as a glycidyl ether group, a β-glycidyl ether group, or an alicyclic epoxy group. When the cyclic ether group is a group represented above, a cured product having excellent heat resistance can be easily obtained.

[0066] R of formula (I) 1 ~R 7 and R of formula (IIα) to (IIγ) 21 ~R 26 The alkyl group having 1 to 20 carbon atoms may be straight-chain or branched, may have an alicyclic ring, or may be an arylalkyl group. Examples of straight-chain alkyl groups include methyl, ethyl, propyl, butyl, isopentyl, tert-pentyl, hexyl, heptyl, and octyl. Examples of branched alkyl groups include isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like.

[0067] Examples of the alkyl group having an alicyclic ring include cycloalkyl groups such as cyclopentyl and cyclohexyl; cycloalkylalkyl groups such as cyclohexylmethyl; and alkyl groups in which a hydrogen atom in the group is substituted with a heterocyclic ring.

[0068] From the perspective of heat resistance and solvent resistance, R 1 ~R 7 and R 21 ~R 26 The alkyl group other than the arylalkyl group represented has preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 5 carbon atoms.

[0069] The arylalkyl group is a group in which one or more hydrogen atoms in an alkyl group are replaced by an aryl group. Examples of the arylalkyl group include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl. 1 ~R 7 and R 21 ~R 26 The number of carbon atoms of the arylalkyl group represented is preferably 7-20, more preferably 7-15, further preferably 7-10.

[0070] R 1 ~R 7 and R 21 ~R 26 The aromatic ring group having 6 to 20 carbon atoms is a hydrocarbon group containing an aromatic hydrocarbon ring and having a bonding point on the aromatic hydrocarbon ring, and may also contain an aliphatic hydrocarbon group or a heterocyclic ring, but preferably does not contain a heterocyclic ring. When containing an aliphatic hydrocarbon group or a heterocyclic ring, the upper limit of the number of carbon atoms is 20 or less, including the number of carbon atoms of the aliphatic hydrocarbon group or the heterocyclic ring.

[0071] Examples of the aromatic ring group include aryl groups having 6 to 20 carbon atoms.

[0072] Examples of the aryl group having 6 to 20 carbon atoms include aryl groups having a monocyclic structure, a condensed ring structure, or a structure in which two or more aromatic hydrocarbon rings are linked.

[0073] Examples of the aryl group having a monocyclic structure and having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a 2,4,6-trimethylphenyl group.

[0074] Examples of the aryl group having a fused ring structure having 6 to 20 carbon atoms include a naphthyl group, anthryl group, phenanthryl group, pyrenyl group, fluorenyl group, and indenofluorenyl group.

[0075] Examples of the linking group linking the aromatic hydrocarbon rings in the aryl group in which two or more aromatic hydrocarbon rings are linked include a single bond, a sulfide group (—S—), and a carbonyl group.

[0076] Examples of the aryl group formed by linking two or more aromatic hydrocarbon rings include biphenyl, diphenyl sulfide, benzoylphenyl, and a group formed by linking a single ring and a condensed ring or condensed rings to each other via the above-mentioned linking group.

[0077] From the perspective of heat resistance and solvent resistance, R 1 ~R 7 and R 21 ~R 26The number of carbon atoms of the aromatic ring group represented is more preferably 6 to 15, particularly preferably 6 to 10.

[0078] As R 1 ~R 7 and R 21 ~R 26 The heterocyclic group having 2 to 20 carbon atoms represented may include a group obtained by removing one hydrogen atom from a "heterocyclic compound" (hereinafter also referred to as "heterocyclic group I") and a group obtained by replacing the hydrogen atom in the heterocyclic group I with a hydrocarbon group (hereinafter also referred to as "heterocyclic group II"). It should be noted that the epoxy group is included in the reactive group and is therefore not included in the heterocyclic group. The heterocyclic group may be a monocyclic structure or a condensed ring structure. Examples of the heterocyclic group having a condensed ring structure having 2 to 20 carbon atoms include a structure formed by condensation of a heterocyclic ring with a heterocyclic ring or a hydrocarbon ring, i.e., a heterocyclic condensed ring group having 3 to 20 carbon atoms. Specific examples of the heterocyclic group I include pyridyl, quinolyl, thiazolyl, tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, methylthiophenyl, hexylthiophenyl, benzothiophenyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl, piperazinyl, pyrimidinyl, furanyl, thienyl, benzoxazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, and morpholinyl.

[0079] In the heterocyclic group II, examples of the hydrocarbon group that replaces the hydrogen atom in the heterocyclic group I include the following: 11 The same hydrocarbon groups as those exemplified in the hydrocarbon groups represented by . In the heterocyclic group II, the bonding point is on the heterocyclic group I. In the case of the heterocyclic group II, the number of carbon atoms including the carbon number of the hydrocarbon group satisfies "2 to 20".

[0080] From the perspective of heat resistance and solvent resistance, R 1 ~R 7 and R 21 ~R 26 The number of carbon atoms of the heterocyclic group represented is more preferably 2 to 15, particularly preferably 2 to 10, and particularly preferably 2 to 5.

[0081] In the present specification, “a group in which one or more methylene groups in an alkyl group having 1 to 20 carbon atoms are substituted with a divalent group selected from <Group B>” is also referred to as “a methylene-substituted alkyl group having 1 to 20 carbon atoms”.

[0082] Likewise, “a group in which one or more methylene groups in an aromatic ring group having 6 to 20 carbon atoms are substituted with a divalent group selected from <Group B>” is also referred to as a “methylene-substituted aromatic ring group having 6 to 20 carbon atoms”.

[0083] Similarly, “a group in which one or more methylene groups in a heterocyclic group having 2 to 20 carbon atoms are substituted with a divalent group selected from <Group B>” is also referred to as a “methylene-substituted heterocyclic group having 2 to 20 carbon atoms”.

[0084] In the present specification, the carbon number of methylene-substituted alkyl groups, methylene-substituted aromatic ring groups, methylene-substituted heterocyclic groups, and methylene-substituted chain hydrocarbon groups described later is within the range obtained by methylene-substituted groups with the carbon number specified before methylene-substituted groups. For example, in the present specification, the carbon number of a group (e.g., alkoxy group) obtained by replacing one methylene group (-CH2-) in an alkyl group with 20 carbon atoms with "-O-" as a divalent group becomes 19. In addition, the carbon number of methylene-substituted alkyl groups, methylene-substituted aromatic ring groups, and methylene-substituted heterocyclic groups is set to 1 to 20, 6 to 20, and 2 to 20, respectively, when any group in Group B is used, and the carbon number is preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less.

[0085] Furthermore, the above-mentioned various methylene-substituted groups do not have a structure in which a plurality of the above-mentioned divalent groups are adjacent to each other.

[0086] As R of formula (I) 1 With R 2 , R 3 With R 4 , R 4 With R 5 , R 5 With R 6 and multiple R 7 With R 7 When they are bonded to each other to form a ring, the formed ring and R in formulas (IIα) to (IIγ) 21 With R 22 , R 23 With R 24 , R 24 With R 25 and R 25 With R 26 When the rings form a ring together, hydrocarbon rings and heterocyclic rings can be mentioned. Examples of hydrocarbon rings include monocyclic rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, and benzene ring; and condensed rings such as indane ring, fluorene ring, naphthalene ring, and anthracene ring.

[0087] Examples of the heterocyclic ring include monocyclic rings such as a pyrrolidine ring, a pyrrole ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a tetrahydropyridine ring, a lactone ring, and a lactam ring; and condensed rings such as a carbazole ring and an indole ring.

[0088] As the above R 1 With R 2 , R 3With R 4 , R 4 With R 5 , R 5 With R 6 and multiple R 7 With R 7 The ring formed by bonding to each other is preferably a hydrocarbon ring, for example, from the viewpoint of good heat resistance and solvent resistance. Among them, an aromatic hydrocarbon ring in which at least one constituent ring is an aromatic ring is preferred, and an indane ring is most preferred.

[0089] Formula (IIα) to (IIγ) are R in formula (I): 7 With R 7 A compound in which a pyridine ring described in formula (I) is bonded to form an indane ring condensed thereto.

[0090] As R 11 Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aromatic ring group.

[0091] Examples of the alkyl group include R 1 Various alkyl groups are listed as examples.

[0092] Examples of the alkenyl group include vinyl, ethenyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl and 4,8,12-tetradecatrienyl allyl groups, and cyclopentadienyl groups as cyclic alkenyl groups.

[0093] Examples of the aromatic ring group include: 1 etc. The groups listed in the description.

[0094] The above R 1 ~R 7 and R 21 ~R 26 The hydrogen atoms in the represented alkyl group having 1 to 20 carbon atoms, aromatic ring group having 6 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, methylene-substituted alkyl group having 1 to 20 carbon atoms, methylene-substituted aromatic ring group having 6 to 20 carbon atoms, and methylene-substituted heterocyclic group having 2 to 20 carbon atoms may also be substituted by a substituent. Examples of the substituent in this case include, in addition to the reactive groups selected from the above-mentioned <Group A>, halogen atoms, nitro groups, etc.

[0095] In the present specification, unless it is described as "forming a ring" or the like, when a group having a predetermined number of carbon atoms has a substituent, it is assumed that the predetermined number of carbon atoms is satisfied including the number of carbon atoms of the substituent.

[0096] For example, the group substituted with a reactive group includes a group represented by the following formula (f).

[0097] *-L f -(R f )t formula (f)

[0098] (Among them, L f is a group obtained by removing t hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, a group obtained by removing t hydrogen atoms from a methylene-substituted alkyl group having 1 to 20 carbon atoms, a methylene-substituted aromatic ring group having 6 to 20 carbon atoms, or a methylene-substituted heterocyclic group having 2 to 20 carbon atoms, and R f is a reactive group, and t is a number from 1 to 10. )

[0099] t is preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. f Preferably, the group obtained by removing t hydrogen atoms from an alkyl group, an aromatic ring group, a methylene-substituted alkyl group or a methylene-substituted aromatic ring group is used, more preferably an aromatic ring group or a methylene-substituted aromatic ring group is used, and most preferably an aromatic ring group is used. This is because the above-mentioned compound I can form a compound with better heat resistance and solvent resistance.

[0100] The number of carbon atoms of the group represented by formula (f) is preferably 10 or less, and may be 5 or less, or 3 or less. This is because the compound I can form a compound with better heat resistance and solvent resistance.

[0101] Hereinafter, the group represented by the formula (f) and the reactive group are also collectively referred to as a "reactive group-containing group".

[0102] As the group containing a reactive group, a reactive group is particularly preferred because the compound I can form a compound having more excellent heat resistance and solvent resistance.

[0103] The cyclic group having 2 to 20 ring carbon atoms represented by X in formula (I) is a group having a ring having 2 to 20 ring carbon atoms and having a bonding point on the ring to the pyridine ring of formula (I). Examples of the ring having 2 to 20 ring carbon atoms include aromatic rings having 6 to 20 ring carbon atoms and heterocyclic rings having 2 to 20 ring carbon atoms. Examples of the aromatic ring having 6 to 20 ring carbon atoms include hydrocarbon rings formed of carbon and hydrogen. The ring having 2 to 20 ring carbon atoms may be a monocyclic ring or a condensed ring.

[0104] As the aromatic ring having 6 to 20 ring carbon atoms, as a monocyclic ring, a hydrocarbon monocyclic ring formed of carbon atoms and hydrogen atoms such as a benzene ring can be listed, and as a condensed ring, a hydrocarbon condensed ring such as a fluorene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, an indane ring, a pyrene ring, and a benzopyrene ring can be listed, and a ring structure formed by connecting these rings with a connecting group can also be listed. As described below, as X, a hydrocarbon condensed ring is preferred, and fluorene is particularly preferred.

[0105] As heterocyclic rings having 2 to 20 ring carbon atoms, as monocyclic rings, there can be listed heterocyclic rings containing heteroatoms such as furan rings, pyridine rings, pyrimidine rings, thiophene rings, pyrrole rings, imidazole rings, thiazole rings, oxadiazole rings, pyridine rings, and pyrazine rings, and as condensed rings, there can be listed carbazole rings, indole rings, dibenzofuran rings, and dibenzothiophene rings. Among the cyclic groups having 2 to 20 ring carbon atoms, there can also be listed ring structures formed by connecting multiple rings with a linking group, as long as any ring has a bonding point to the pyridine ring of formula (I).

[0106] Examples of the linking group in X include a sulfur atom, a nitrogen atom, a carbonyl group, a carbon atom, and a single bond.

[0107] The term “ring carbon atoms number 2 to 20” refers to the total number of carbon atoms constituting the two or more rings when X is a structure in which two or more rings are linked.

[0108] Examples of the chain hydrocarbon group having 1 to 20 carbon atoms represented by X in formula (I) include 11 A group obtained by removing a-1 hydrogen atoms from the chain alkyl group, chain alkenyl group, etc. in the groups listed in . However, a carbon-carbon unsaturated bond such as *-C=C-* is not assumed to be located at the end of the aliphatic hydrocarbon group as long as both ends are not bonded to carbon atoms.

[0109] In addition, regarding X, in the present specification, "a group in which one or more methylene groups in a chain hydrocarbon group having 2 to 20 carbon atoms are substituted with a divalent group selected from <Group B>" is also referred to as "a methylene-substituted chain hydrocarbon group having 2 to 20 carbon atoms".

[0110] The number of carbon atoms in the chain hydrocarbon group and the methylene-substituted chain hydrocarbon group represented by X is within the range of 1 to 20, preferably 1 to 15, more preferably 1 to 10, and particularly preferably 1 to 5.

[0111] The ring having 2 to 20 carbon atoms represented by X may be substituted with a substituent. Examples of the substituent in this case include a nitro group in addition to the reactive group selected from the above <Group A> or the group represented by formula (f).

[0112] The hydrogen atoms in the chain hydrocarbon group having 1 to 20 carbon atoms may be substituted with a substituent. Examples of the substituent in this case include a nitro group in addition to the reactive groups selected from the above <Group A>.

[0113] Hereinafter, preferred examples of compound I are further described. It should be noted that all the following "reactive group-containing groups" can be independently replaced by "reactive groups", and further replaced by "carbon-carbon unsaturated bond groups" or "propargyl groups or groups containing the same (e.g., propargyl groups or propargyloxy groups)".

[0114] As the reactive group of compound I, a carbon-carbon unsaturated bond group, a cyclic ether group, a hydroxyl group or an amino group is preferred, and a carbon-carbon unsaturated bond group is particularly preferred. This is because when the reactive group is the above group, a cured product with excellent heat resistance and solvent resistance can be obtained.

[0115] Compound I preferably has one or more carbon-carbon unsaturated bond groups in the molecule, in which case it may or may not have reactive groups other than carbon-carbon unsaturated bond groups. It should be noted that as the amino group, there can be listed a primary amino group (-NH2 group), a secondary amino group substituted with a lower alkyl group having 1 to 3 carbon atoms or an acetyl group, etc., preferably a primary amino group or a secondary amino group substituted with a lower alkyl group.

[0116] In compound I, the number of reactive groups present in the molecule is more than 1, preferably more than 2, and particularly preferably more than 3. Because the number of reactive groups present in the molecule is the above-mentioned range, a cured product with excellent heat resistance and solvent resistance can be obtained. The number of reactive groups present in the molecule is less than 10, which is preferred from the perspective of easy synthesis and good storage stability. From this viewpoint, it is more preferably less than 9, and further preferably less than 8. It should be noted that the number of so-called reactive groups here is, for example, 2 if it is a dipropargylamino group.

[0117] In particular, in Compound I, from the perspective of high heat resistance of the cured product of Compound I, it is preferred that (a) the number of reactive groups present in the molecule is 3 or more, or (b) X has a fused ring which may be substituted, and it is most preferred that both conditions (a) and (b) are satisfied.

[0118] As R in formula (I) 1 ~R 6The group represented by is preferably a hydrogen atom, a reactive group selected from the above <Group A> or an alkyl group having 1 to 20 carbon atoms which may be substituted by a reactive group, an aromatic ring group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 methylene atoms or an aromatic ring group having 6 to 20 carbon atoms, wherein a hydrogen atom, a reactive group or an alkyl group having 1 to 20 carbon atoms which may be substituted by a reactive group, an aromatic ring group having 6 to 20 carbon atoms or an aromatic ring group having 1 to 20 carbon atoms is preferably selected from the above <Group A>. The methyl-substituted alkyl group is particularly preferably a hydrogen atom, a reactive group, or an alkyl group having 1 to 10 carbon atoms which may be substituted by a reactive group, an aromatic ring group having 6 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted by a methylene group. A hydrogen atom, a reactive group, an alkyl group having 1 to 5 carbon atoms which may be substituted by a reactive group, or an alkyl group having 1 to 5 carbon atoms substituted by a methylene group is particularly preferred. A hydrogen atom, a reactive group, an alkyl group having 1 to 2 carbon atoms, or an alkyl group having 1 to 2 carbon atoms substituted by a methylene group is most preferred.

[0119] Because R in the general formula (I) 1 ~R 6 The groups represented are the groups represented above, and a cured product having excellent heat resistance and solvent resistance can be obtained.

[0120] Especially R. 1 ~R 6 Preferably, at least one of the groups represented by is a group containing a reactive group. 1 ~R 6 The groups represented are the above-mentioned groups, and a cured product having excellent heat resistance and solvent resistance can be obtained.

[0121] In formula (I), R 1 ~R 6 The total number of reactive groups is preferably 1 to 4, preferably 1 to 3, and particularly preferably 2 to 3. 1 ~R 6 When the number of reactive groups in is within the above-described range, a cured product having excellent heat resistance and solvent resistance can be obtained.

[0122] Preferably, R in formula (I) 1 ~R 6 Medium R 1 , R 2 , R 4 and R 5 Any one or more of the groups are reactive groups, and more preferably R 1 , R 2 and R 5 Any one or more of the groups is a group containing a reactive group, and R is particularly preferred. 1 and R2 Any one or both of them are groups containing reactive groups. 1 and R 2 When any one or both of them are reactive group-containing groups, it is particularly preferred that R 4 and R 5 Any one or both of them are groups containing reactive groups, and R 4 and R 5 In the above case, it is preferred that R 1 and R 2 Both are reactive group-containing groups. Since the position of the reactive group-containing group in formula (I) is the above position, a cured product having excellent heat resistance and solvent resistance can be obtained. In addition, the film-forming property is also excellent.

[0123] In R 1 or R 2 When none of them is a group containing a reactive group, it is preferred that R 4 and R 5 At least one of the groups is a group containing a reactive group.

[0124] The groups at positions other than the preferred positions listed above as the reactive group-containing group may or may not be reactive group-containing groups.

[0125] R in formula (I) 1 ~R 6 The group that is not a group containing a reactive group among the groups represented by is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, a methylene-substituted alkyl group having 1 to 20 carbon atoms, or a methylene-substituted aromatic ring group having 6 to 20 carbon atoms. Among them, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a methylene-substituted alkyl group having 1 to 20 carbon atoms is preferred. A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a methylene-substituted alkyl group having 1 to 5 carbon atoms is particularly preferred. Among them, a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a methylene-substituted alkyl group having 1 to 2 carbon atoms is preferred. In view of easy synthesis and the ability to obtain a compound with excellent storage stability, R in formula (I) is also preferred. 1 ~R 6 One or more of the groups represented by are hydrogen atoms.

[0126] a in formula (I) is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 to 2. When a in formula (I) is the above number, synthesis is easy and a compound having excellent storage stability can be obtained.

[0127] The above R 7 With R7 The ring formed by bonding to each other is preferably a hydrocarbon ring formed only of carbon atoms and hydrogen atoms, for example, from the perspective of good heat resistance, and an aromatic hydrocarbon ring is preferred, and an indane ring condensed with the pyridine ring of formula (I) is particularly preferred. Therefore, compound I is preferably any one of compounds IIα to IIγ.

[0128] In particular, compound I is more preferably compound IIα or compound IIγ, and particularly preferably compound IIα. Since the compound of the present invention has the structure shown above, a cured product having excellent heat resistance and solvent resistance can be obtained.

[0129] About R 21 , R 22 , R 23 , R 24 , R 25 and R 26 The respective preferred groups are the same as those mentioned above 1 , R 2 , R 3 , R 4 , R 5 and R 6 The respective preferred groups are the same.

[0130] In addition, R 21 ~R 26 At least one of the groups represented is a group containing a reactive group. This is because a cured product having excellent heat resistance can be obtained. 21 ~R 26 The total number of reactive groups in R 1 ~R 6 The preferred total number of reactive groups is the same.

[0131] R 21 ~R 26 Among them, R is preferred 21 , R 22 , R 24 and R 25 Any one or more of the groups are reactive groups, and more preferably R 21 , R 22 and R 25 Any one or more of the groups is a group containing a reactive group, and R is particularly preferred. 21 and R 22 Any one or both of them are groups containing reactive groups. 21 and R 22 When any one or both of them are reactive group-containing groups, it is particularly preferred that R 24 and R 25 Any one or both of them are groups containing reactive groups, and R 24 and R25 In the above case, it is preferred that R 21 and R 22 These two groups are reactive groups. They can produce a cured product with excellent heat resistance and solvent resistance. They also have excellent film-forming properties.

[0132] Among them, R 21 ~R 26 In, R 21 or R 22 When none of them is a group containing a reactive group, it is preferred that R 24 and R 25 At least one of the above is a group containing a reactive group. Groups at positions other than the preferred positions for the reactive groups listed above may or may not be groups containing a reactive group.

[0133] R in formula (I) 21 ~R 26 In the case where the group represented by is not a group containing a reactive group, the preferred group is the same as R 1 ~R 6 The same applies to the above groups.

[0134] The X is preferably a ring group having 2 to 20 ring carbon atoms. This is because the compound I can form a compound having better heat resistance and solvent resistance.

[0135] When X is a cyclic group having 2 to 20 ring carbon atoms, the number of carbon atoms constituting the ring is preferably 3 to 18, more preferably 4 to 15, and further preferably 6 to 16. This is because the compound I can form a compound with better heat resistance and solvent resistance.

[0136] X is preferably a hydrocarbon aromatic ring group or an aromatic heterocyclic group, and particularly preferably a hydrocarbon aromatic ring group, because the cured product of the above compound has excellent heat resistance and solvent resistance.

[0137] The ring in the ring group represented by X in formula (I) is preferably a fused ring that may be substituted. From the perspective that the heat resistance of the cured product of compound I is particularly high, it is preferred that X has a fused ring that may be substituted or that X has an amino group formed by two reactive groups bonded together, and it is particularly preferred that it has a fused ring that may be substituted. As the amino group formed by two reactive groups bonded together, dipropargylamino and the like can be cited. As the fused ring, a fused ring formed by 2 to 6 rings is preferred, and a fused ring formed by 2 to 4 rings is particularly preferred. Because the group represented by X in formula (I) is the above-mentioned fused ring, a cured product with particularly excellent heat resistance can be obtained. For example, fluorene is formed by 3 rings, naphthalene is formed by 2 rings, and pyrene is formed by 4 rings.

[0138] Specific examples of X include the following formulae (X1) to (X7). In particular, X is preferably a condensed ring represented by any one of formulae (X1) to (X6) because it has particularly excellent heat resistance.

[0139] [Chemical formula 4]

[0140]

[0141] (Where R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 and R86 (hereinafter also referred to as "R 31 ~R 86 ". ) each independently represents a hydrogen atom, a reactive group selected from the above <Group A>, a bonding point, a nitro group, or an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, a methylene-substituted alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, or a methylene-substituted heterocyclic group having 2 to 20 carbon atoms which may be substituted.

[0142] Among them, R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 40 One of them is the bonding point, R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 One of them is the bonding point, R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 and R 58 One of them is the bonding point, R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 and R 67 One of them is the bonding point, R 68 , R 69 , R 70 , R 71 , R 72 , R 73 and R 74 One of them is the bonding point, R 75 , R 76 , R 77 , R78 , R 79 and R 80 One of them is the bonding point, R 81 , R 82 , R 83 , R 84 , R 85 and R 86 One of them is the bonding point.

[0143] In formulas (X1) to (X7), examples of the alkyl group, the aromatic ring group, the heterocyclic group, the methylene-substituted alkyl group, the methylene-substituted aromatic ring group, and the methylene-substituted heterocyclic group include R 1 The groups described in the above and the like may be substituted by a reactive group, a halogen atom, a nitro group or the like.

[0144] In R 31 ~R 86 When the group represented is not a group containing a reactive group or a bonding point, it is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, a methylene-substituted alkyl group having 1 to 20 carbon atoms, or a methylene-substituted aromatic ring group having 6 to 20 carbon atoms. Among them, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a methylene-substituted alkyl group having 1 to 20 carbon atoms is preferred, and a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a methylene-substituted alkyl group having 1 to 5 carbon atoms is particularly preferred, and a hydrogen atom or an alkyl group having 1 to 2 carbon atoms is further preferred. In addition, in each of the rings of formulae (X1) to (X7), the number of substituents other than hydrogen atoms, bonding points, and reactive group-containing groups is preferably 0 to 2, more preferably 0 to 1, and may be 0. This is because the above-mentioned compound I can form a compound with better heat resistance and solvent resistance, and is easy to synthesize and has excellent storage stability.

[0145] Hereinafter, preferred structures of each of Formulae (X1) to (X7) will be described.

[0146] In formula (X1), R 34 or R 39 The compound serving as a bonding point is preferred because it is easy to synthesize, has excellent storage stability, and can provide a cured product having excellent heat resistance.

[0147] The number of reactive groups in formula (X1) is preferably 1 to 8, more preferably 1 to 6, and particularly preferably 2 to 4. Compounds having the number of reactive groups within the above range are easy to synthesize and have excellent storage stability, and can provide cured products with excellent heat resistance and solvent resistance.

[0148] In formula (X1), preferably selected from R 31 , R 32 , R37 ~R 40 At least one of the groups is a group containing a reactive group, and R 31 , R 32 One or two of them are groups containing reactive groups, and R 31 , R 32 These two are groups containing reactive groups.

[0149] This is because the compound in which the position of the reactive group-containing group in the formula (X1) is the above-mentioned position has excellent solubility in a solvent and can provide a cured product having excellent heat resistance.

[0150] In formula (X2), R 45 The compound serving as a bonding point is preferred because it is easy to synthesize, has excellent storage stability, and can provide a cured product having excellent heat resistance.

[0151] The compound having 1 to 6 reactive groups in formula (X2) is preferred, the compound having 1 to 4 reactive groups is more preferred, and the compound having 1 to 2 reactive groups is particularly preferred. This is because the compound having the number of reactive groups within the above range is easy to synthesize and has excellent storage stability, and can obtain a cured product with excellent heat resistance.

[0152] In formula (X2), preferably R 46 , R 47 or R 48 is a group containing a reactive group, wherein R 46 A group containing a reactive group is preferred because it has excellent solubility in a solvent and can provide a cured product having excellent heat resistance.

[0153] In formula (X3), R 54 Compounds that serve as bonding sites are preferred because they are easy to synthesize, have excellent storage stability, and can provide cured products with excellent heat resistance. 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 and R 58 Each independently may be a reactive group-containing group, or may not be a reactive group-containing group.

[0154] In formula (X4), R 61 or R 64 The compound serving as a bonding point is preferred because it is easy to synthesize, has excellent storage stability, and can provide a cured product having excellent heat resistance.

[0155] In formula (X5), R 72The compound serving as a bonding point is preferred because it is easy to synthesize, has excellent storage stability, and can provide a cured product having excellent heat resistance.

[0156] In formula (X5), R 74 A compound containing a reactive group is preferred because it has excellent solubility in a solvent and can provide a cured product having excellent heat resistance.

[0157] In formula (X6), R 80 The compound serving as a bonding point is preferred because it is easy to synthesize, has excellent storage stability, and can provide a cured product having excellent heat resistance.

[0158] In formula (X7), the number of reactive groups is preferably 1 to 3, and more preferably 1 to 2. This is because a cured product having excellent heat resistance and solvent resistance can be obtained.

[0159] In X, groups at positions other than the positions preferred as the reactive group-containing group or bonding point listed above may or may not be reactive group-containing groups.

[0160] The ring group represented by X in formula (I) is preferably at least one selected from a fluorene ring, a benzene ring, a naphthalene ring, a carbazole ring and a pyrene ring. In view of heat resistance, it is particularly preferably at least one selected from a fluorene ring, a benzene ring, a naphthalene ring and a pyrene ring, particularly preferably at least one selected from a fluorene ring, a naphthalene ring and a pyrene ring, and particularly preferably a fluorene ring.

[0161] The bonding site of the group represented by X in the formula (I) is preferably the para position with respect to the nitrogen atom in the pyridine ring because of easy synthesis and excellent storage stability.

[0162] Examples of compound I that have a propargyl group, a propargyloxy group, an ethynyl group, or a vinyl group as a reactive group include, but are not limited to, the following compounds (101) to (179).

[0163] [Chemical formula 5]

[0164]

[0165] [Chemical formula 6]

[0166]

[0167] [Chemical formula 7]

[0168]

[0169] [Chemical formula 8]

[0170]

[0171] [Chemical formula 9]

[0172]

[0173] [Chemical formula 10]

[0174]

[0175] [Chemical Formula 10A]

[0176]

[0177] Next, the compound represented by the above general formula (III) (hereinafter also referred to as "Compound III") is described. Compound III can be used as a precursor of Compound I.

[0178] In compound III, X', R 1 '、R 2 '、R 3 '、R 4 '、R 5 '、R 6 '、R 7 '、R 11 ', a' and X, R of compound I 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 11 , and a have the same meanings. Regarding X, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 11 All of the above descriptions of X', R' and R' can be respectively equivalent to X', R' and R' except for the preferred type and number of reactive groups. 1 '、R 2 '、R 3 '、R 4 '、R 5 '、R 6 '、R 7 '、R 11', a' (hereinafter also referred to as "X'~a'"). For example, X' is preferably a substitutable aromatic ring group having 6 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, similarly to X, and is also preferably a substitutable condensed ring group or a primary amino group, and is more preferably a substitutable condensed ring group. Compound III is further described below, but in the event of a difference between the description of X~a above and the description of X'~a' of the following compound III, the following description of X'~a' shall take precedence. Compound III is different from compound I in that it must have at least one phenolic hydroxyl group.

[0179] The phenolic hydroxyl group refers to a hydroxyl group directly bonded to an aromatic ring, and is preferably a hydroxyl group directly bonded to a benzene ring constituting a condensed ring or a benzene ring as a monocyclic ring.

[0180] Preferred examples of compound III include the following general formulae (IIIα) to (IIIγ).

[0181] [Chemical formula 11]

[0182]

[0183] (Where X', a', R 1 '、R 2 '、R 3 '、R 4 '、R 5 ' and R 6 'Same as general formula (III),

[0184] R 21 '、R 22 '、R 23 '、R 24 '、R 25 ' and R 26 '(hereinafter also referred to as "R 21 '~R 26 '".) each independently represents a hydrogen atom, a reactive group selected from the above <Group A>, a nitro group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, a group in which one or more methylene groups in the alkyl group having 1 to 20 carbon atoms are substituted by a divalent group selected from the above <Group B>, a group in which one or more methylene groups in the aromatic ring group having 6 to 20 carbon atoms are substituted by a divalent group selected from the above <Group B>, or a group in which one or more methylene groups in the heterocyclic group having 2 to 20 carbon atoms are substituted by a divalent group selected from the above <Group B>,

[0185] R 21'With R 22 'Sometimes they are bonded to each other to form a ring, R 23 'With R 24 'Sometimes they are bonded to each other to form a ring, R 24 'With R 25 'Sometimes they are bonded to each other to form a ring, R 25 'With R 26 'Sometimes they are bonded to each other to form a ring. However, there are one or more phenolic hydroxyl groups in the molecule.)

[0186] R 21 '~R 26 The description and preferred examples of the groups of ' are respectively the same as those of R 21 ~R 26 same.

[0187] The preferred examples of compound III are further described below. The phenolic hydroxyl group described below is a general term for the phenolic hydroxyl group and the group represented by (f') below. All the terms "phenolic hydroxyl group" described below can be replaced by their subordinate concepts, namely "phenolic hydroxyl group".

[0188] *-L f '-(OHp)t' formula (f')

[0189] (Among them, L f ' is an aromatic ring-containing group having 6 to 20 carbon atoms, OHp is a phenolic hydroxyl group, and t' is a number from 1 to 10.)

[0190] The group containing an aromatic ring having 6 to 20 carbon atoms is a group obtained by removing t' hydrogen atoms from an arylalkyl group having 7 to 20 carbon atoms, a group obtained by removing t' hydrogen atoms from a heterocyclic group containing an aromatic hydrocarbon ring having 8 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, preferably has 6 to 10 carbon atoms, and is preferably a phenylene group having 6 to 10 carbon atoms which may be substituted with an alkyl group or an alkoxy group. Examples of the heterocyclic group containing an aromatic hydrocarbon ring having 8 to 20 carbon atoms include a ring formed by condensing a benzene ring such as indole and carbazole with a heterocyclic ring.

[0191] t' is preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, more preferably 1 to 2, and may be 1.

[0192] The reactive group of compound III is a reactive group having a phenolic hydroxyl group, and may or may not have a reactive group other than a phenolic hydroxyl group. When compound III has a reactive group other than a phenolic hydroxyl group, the reactive group may include an amino group.

[0193] This is because when the reactive group is the group represented above, it becomes a precursor that can smoothly produce the compound I.

[0194] In compound III, the number of phenolic hydroxyl groups present in the molecule is 1 or more, but preferably 2 or more. The number of phenolic hydroxyl groups present in the molecule is within the above range, which is advantageous in terms of use as a precursor and providing a cured product with excellent heat resistance and solvent resistance. The number of phenolic hydroxyl groups present in the molecule is preferably 10 or less from the perspective of easy synthesis and good storage stability. From this viewpoint, it is more preferably 8 or less, and further preferably 6 or less.

[0195] As R in formula (III) 1 '~R 6 The group represented by ' is preferably a hydrogen atom, a phenolic hydroxyl group, or an alkyl group having 1 to 20 carbon atoms which may each have a phenolic hydroxyl group, an aromatic ring group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with a methylene group, or an aromatic ring group having 6 to 20 carbon atoms, among which a hydrogen atom, a phenolic hydroxyl group, or an alkyl group having 1 to 10 carbon atoms which may each have a phenolic hydroxyl group, an aromatic ring group having 6 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with a methylene group, particularly preferably a hydrogen atom, a phenolic hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with a methylene group, and most preferably a hydrogen atom, a phenolic hydroxyl group, an alkyl group having 1 to 2 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms.

[0196] Preferred R 3 '、R 4 '、R 5 '、R 6 '、R 23 '、R 24 '、R 25 ' and R 26 At least one of the ' is a phenolic hydroxyl group-containing group, and at least two of the ' are particularly preferably phenolic hydroxyl group-containing groups. 3 '、R 4 '、R 5 '、R 6 At least one of them is a phenolic hydroxyl group, preferably R 23 '、R 24 '、R 25 ' and R 26 At least one of the ' is a phenolic hydroxyl group-containing group. It is particularly preferred that each of the phenolic hydroxyl group-containing groups is a phenolic hydroxyl group.

[0197] Among them, R is preferred 4 '、R 5 '、R 24 ' and R25 At least two of the ' are phenolic hydroxyl-containing groups, and it is particularly preferred that these phenolic hydroxyl-containing groups are phenolic hydroxyl groups.

[0198] R is particularly preferred 1 '~R 6 ' is a phenolic hydroxyl group. 1 '~R 6 The group represented by ' is the above-mentioned group, which is advantageous in that it can be used as a precursor and can provide a cured product having excellent heat resistance and solvent resistance.

[0199] In formula (III), R 1 '~R 6 In the formula (III), the total number of phenolic hydroxyl groups is preferably 3 or less, preferably 2 or less, and may be 1. 1 '~R 6 The number of phenolic hydroxyl groups in ' is within the above-described range, which is advantageous in terms of use as a precursor and providing a cured product having excellent heat resistance and solvent resistance.

[0200] In formula (III), R 1 '~R 6 When any one of them has a phenolic hydroxyl group, it is preferred that R 4 ' and R 5 Any one or both of them are phenolic hydroxyl-containing groups, and R 4 ' and R 5 Any one of them is a phenolic hydroxyl group-containing group. These phenolic hydroxyl group-containing groups are preferably phenolic hydroxyl groups. Since the position of the phenolic hydroxyl group in formula (III) is the above position, it is advantageous in that a cured product having excellent heat resistance and solvent resistance can be obtained.

[0201] As R in formula (III) 1 '~R 6 Among the groups represented by ', preferred groups that are not phenolic hydroxyl group-containing groups include: 1 ~R 6 Preferred groups that are not reactive group-containing groups among the groups represented are the groups listed above, and particularly preferred are hydrogen atoms, alkyl groups having 1 to 2 carbon atoms, or alkoxy groups having 1 to 2 carbon atoms.

[0202] R 21 '、R 22 '、R 23 '、R 24 '、R 25 ' and R 26 'The respective preferred groups are the same as those mentioned above 1 '、R2 '、R 3 '、R 4 '、R 5 ' and R 6 Preferred groups of ' are respectively the same, and the above descriptions can be applied.

[0203] In addition, R 21 '~R 26 'At least one of the groups represented by is a phenolic hydroxyl group-containing group. This is advantageous in that it can be used as a precursor and can provide a cured product having excellent heat resistance and solvent resistance. 21 '~R 26 The preferred total number of phenolic hydroxyl groups in R 1 '~R 6 The preferred total number of phenolic hydroxyl groups is the same as that of '.

[0204] In formula (III), R 21 '~R 26 In the case of having a phenolic hydroxyl group, preferably R 24 ' and R 25 Any one or both of them are phenolic hydroxyl-containing groups, and R 24 ' and R 25 Any one of them is a phenolic hydroxyl group-containing group. In particular, these phenolic hydroxyl group-containing groups are preferably phenolic hydroxyl groups. Since the position of the phenolic hydroxyl group in formula (III) is the above position, the synthesis is easy and the storage stability is excellent.

[0205] As R in formula (I) 21 '~R 26 ' is not a group containing a reactive group, and R 1 '~R 6 The same applies to the above groups.

[0206] X' may have a phenolic hydroxyl group or may not have a phenolic hydroxyl group. The number of phenolic hydroxyl groups in X' is preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0 to 2. This is because it is advantageous in terms of use as a precursor and providing a cured product with excellent heat resistance and solvent resistance.

[0207] X' may contain an amino group instead of a phenolic hydroxyl group. In the case of having an amino group, the total number of active hydrogen atoms and phenolic hydroxyl groups of the amino group is preferably the same number as the number of phenolic hydroxyl groups in the above-mentioned X' (hereinafter, the number of phenolic hydroxyl groups recorded for X'1 to X'7 may be similarly replaced by the total number of active hydrogen atoms and phenolic hydroxyl groups of the amino group).

[0208] Specific examples of X' include groups represented by the following formulae (X'1) to (X'7). When the group represented by X' in formula (III) is a ring represented by any one of formulae (X'1) to (X'6), a cured product with better heat resistance can be obtained, including use as a precursor.

[0209] [Chemical formula 12]

[0210]

[0211] (Where R 31 '、R 32 '、R 33 '、R 34 '、R 35 '、R 36 '、R 37 '、R 38 '、R 39 '、R 40 '、R 41 '、R 42 '、R 43 '、R 44 '、R 45 '、R 46 '、R 47 '、R 48 '、R 49 '、R 50 '、R 51 '、R 52 '、R 53 '、R 54 '、R 55 '、R 56 '、R 57 '、R 58 '、R 59 '、R 60 '、R 61 '、R 62 '、R 63 '、R 64 '、R 65 '、R 66 '、R 67 '、R 68 '、R 69 '、R 70 '、R 71 '、R 72 '、R 73 '、R 74 '、R 75 '、R 76 '、R 77 '、R 78 '、R 79 '、R80 '、R 81 '、R 82 '、R 83 '、R 84 '、R 85 ' and R 86 '(hereinafter also referred to as "R 31 '~R 86 '".) each independently represents a hydrogen atom, a phenolic hydroxyl group, an amino group, a bonding point, a nitro group, or an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, or a heterocyclic group having 2 to 20 carbon atoms which may be substituted.

[0212] Among them, R 31 '、R 32 '、R 33 '、R 34 '、R 35 '、R 36 '、R 37 '、R 38 '、R 39 ' and R 40 One of the ' is the bonding point, R 41 '、R 42 '、R 43 '、R 44 '、R 45 '、R 46 '、R 47 ' and R 48 One of the ' is the bonding point, R 49 '、R 50 '、R 51 '、R 52 '、R 53 '、R 54 '、R 55 '、R 56 '、R 57 ' and R 58 One of the ' is the bonding point, R 59 '、R 60 '、R 61 '、R 62 '、R 63 '、R 64 '、R 65 '、R 66 ' and R 67 One of the ' is the bonding point, R 68 '、R 69 '、R70 '、R 71 '、R 72 '、R 73 ' and R 74 One of the ' is the bonding point, R 75 '、R 76 '、R 77 '、R 78 '、R 79 ' and R 80 One of the ' is the bonding point, R 81 '、R 82 '、R 83 '、R 84 '、R 85 ' and R 86 One of the ' is the bonding point.

[0213] In formulas (X'1) to (X'7), examples of the alkyl group, the aromatic ring group, the heterocyclic group, the methylene-substituted alkyl group, the methylene-substituted aromatic ring group, and the methylene-substituted heterocyclic group include R 1 The groups described in the above may be substituted by a phenolic hydroxyl group, a halogen atom, a nitro group, an amino group or the like.

[0214] X' may or may not have a phenolic hydroxyl group. In the former case, each of the 31 '~R 86 Any one or more of the groups X'1 to X'7 in ' is preferably a group containing a phenolic hydroxyl group, and particularly preferably a phenolic hydroxyl group. 81 '~R 86 Any one or more of the groups represented by ' is preferably a phenolic hydroxyl group-containing group, and more preferably a phenolic hydroxyl group.

[0215] R 31 '~R 86 'Each corresponds to the above R 31 ~R 86 .

[0216] About R 31 '~R 86 The group represented by ' can be used appropriately as a preferred group for the case where it is not a phenolic hydroxyl group or a bonding point. 31 ~R 86 Description of preferred groups when the represented group is not a reactive group-containing group or a bonding point. The preferred number of substituents other than hydrogen atoms, bonding points, phenolic hydroxyl-containing groups and amino groups in the rings of each of formulae (X'1) to (X'7) is the same as the preferred number of substituents other than hydrogen atoms, bonding points and reactive group-containing groups in the rings of each of formulae (X1) to (X7).

[0217] In addition, regarding X'1 to X'7, the description of X1 to X7 can be appropriately used to describe the preferred positions of the bonding points.

[0218] In particular, in each of Formula (X'2) and Formula (X'7), the number of reactive groups, such as phenolic hydroxyl groups, is preferably 1 to 3, and more preferably 1 to 2. This is because a cured product having excellent heat resistance and solvent resistance can be obtained.

[0219] In X', the group at a position other than the position preferred as the phenolic hydroxyl group-containing group and the bonding point listed above may be a group containing a reactive group or may not be a group containing a reactive group.

[0220] As the compound I produced using the compound III as a precursor, a compound having a propargyloxy group, an allyl ether group or a glycidyl group as a reactive group is suitable.

[0221] As compound III, compounds having a phenolic hydroxyl group include the following compounds (1) to (65) in addition to the above-mentioned (168), (169), (171) to (173). Such compound III can also be used as an intermediate for producing compound I having a reactive group such as a propargyloxy group.

[0222] [Chemical formula 13]

[0223]

[0224] [Chemical formula 14]

[0225]

[0226] [Chemical Formula 14A]

[0227]

[0228] [Chemical formula 15]

[0229]

[0230] [Chemical Formula 15A]

[0231]

[0232] The above-mentioned Compound I and Compound III can be manufactured according to known methods. Specifically, by condensing an indanone compound with an aldehyde compound using ammonium acetate, a compound having a diindeno[1,2-b:2',1'-d]pyridine skeleton structure can be manufactured. Furthermore, by introducing a reactive group into its skeleton structure, the above-mentioned Compound I can be manufactured. For example, when a compound having a hydroxyl group is used as the aldehyde compound and the indanone compound, Compound III (Compound I having a hydroxyl group as a reactive group) can be manufactured, and the hydroxyl group in this Compound III can be further replaced with a reactive group other than a hydroxyl group (such as in the following Scheme 1) using a halogen compound and a carbonate such as K2CO3.

[0233] In addition, a reactive group can also be introduced at a specified position in the indeno[1,2-b:2',1'-d]pyridine skeleton structure in Formula (I) using a halogen compound and a base agent such as NaOH (such as in the following Scheme 2).

[0234] In the following Scheme 1 and Scheme 2, Compound IIα where a = 1 is described as Compound I as an example, but Compound IIβ and Compound IIγ can be manufactured by a method according to the preparation methods of other compounds (for example, refer to European Journal of Organic Chemistry (2005), (10), p2045 - 2055, RSC Advances (2015), 5(63), p51183 - 51187). In addition, when a is 2 or more, it can be manufactured by setting the aldehyde compound to be polyfunctional.

[0235] [Chemical formula 16]

[0236] (Scheme 1)

[0237]

[0238] [Chemical formula 17]

[0239] (Scheme 2)

[0240]

[0241] <B. Composition>

[0242] The composition of the present invention is characterized by containing the above-mentioned Compound I. By containing the above-mentioned Compound I in the composition, a cured product having excellent heat resistance can be obtained.

[0243] A composition containing 20 to 100% by mass of the above-mentioned Compound I in the solid content is preferred because a cured product having excellent heat resistance can be obtained. The content in the solid content is more preferably 40 to 100% by mass, particularly preferably 50 to 100% by mass, and can also be 60% by mass or more. Here, the solid content refers to the component obtained by removing the solvent described below from the composition.

[0244] The composition of the present invention may also contain a crosslinking agent. The so-called crosslinking agent is a compound that reacts with compound I, connects multiple molecules through chemical bonds, and is incorporated into the polymer after polymerization to change the physical and chemical properties. By containing a crosslinking agent, a cured product with better heat resistance can be obtained. As the crosslinking agent, for example, phenol compounds, epoxy compounds, cyanate compounds, amine compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, azide compounds, etc. can be listed.

[0245] As phenolic compounds, for example, alkylphenols such as phenol, cresols, and xylenols can be listed; bisphenols such as bisphenol A, bisphenol F, bis(3-methyl-4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)-1-phenylethane; triphenols such as α,α,α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene; phenol resins such as phenol novolac resins and phenol aralkyl resins; resinous phenol derivatives such as straight-chain triphenols, methane-type triphenols, straight-chain tetraphenols, and radial hexanuclear compounds represented by the following general formula, etc.

[0246] [Chemical formula 18]

[0247]

[0248] In the formula, R 13 represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2, and m represents an integer of 0 to 1.

[0249] Examples of the epoxy compound include glycidyl ethers of the above-mentioned phenol compounds, tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, and trimethylolpropane triglycidyl ether.

[0250] Examples of the cyanate resin include compounds obtained by replacing a hydroxyl group of the above-mentioned phenol compound with a cyanate group.

[0251] Examples of the amine compound include aromatic amines such as m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, and 1,3-bis(4-aminophenoxy)benzene; alicyclic amines such as diaminocyclohexane, diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminodicyclo[2.2.1]heptane, and isophoronediamine; and aliphatic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine, and triethylenetetramine.

[0252] Examples of the benzoxazine compound include Pd-type benzoxazine obtained from a diamine compound and a monofunctional phenol compound, and Fa-type benzoxazine obtained from an amine compound and a bifunctional phenol compound.

[0253] Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, a compound in which 1 to 6 hydroxymethyl groups of hexamethylolmelamine are methoxymethylated, or a mixture thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, a compound in which 1 to 6 hydroxymethyl groups of hexamethylolmelamine are acyloxymethylated, or a mixture thereof, and the like.

[0254] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 hydroxymethyl groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which 1 to 4 hydroxymethyl groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof, and the like.

[0255] Examples of the glycoluril compound include tetrakishydroxymethyl glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are methoxymethylated or a mixture thereof, and a compound in which 1 to 4 hydroxymethyl groups of tetrakishydroxymethyl glycoluril are acyloxymethylated or a mixture thereof.

[0256] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, or a mixture thereof, and tetramethoxyethyl urea.

[0257] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate. Examples of the azide compound include 1,1′-biphenyl-4,4′-diazide, 4,4′-methylene diazide, and 4,4′-oxydiazide.

[0258] As the cross-linking agent, a phenol compound and a glycoluril compound are preferred because a cured product having excellent heat resistance can be obtained.

[0259] The content of the cross-linking agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the compound I.

[0260] The composition of the present invention may also contain a solvent. Examples of the solvent include, as required, solvents capable of dissolving or dispersing the above-mentioned components, such as ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropyl alcohol or n-propyl alcohol, isobutyl alcohol or n-butyl alcohol, and amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxy- Ether ester solvents such as butyl ether acetate and ethoxyethyl ether propionate; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene and pinene; paraffin solvents such as mineral spirits, SWASOL#310 (COSMO Matsuyama Oil Company) and SOLVESSO#100 (Exxon Chemical Company); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide (DMAc); N-methylpyrrolidone; dimethyl sulfoxide; water, etc. These solvents can be used alone or as a mixed solvent of two or more.

[0261] Among them, ketones, ether ester solvents and the like, particularly propylene glycol monomethyl ether acetate, cyclohexanone and the like are preferred because they have good solubility in the compound I and the cross-linking agent.

[0262] The content of the solvent is preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 70 parts by mass or more and 95 parts by mass or less, based on 100 parts by mass of the composition.

[0263] The polymerization initiator can be classified into a photopolymerization initiator that generates active species by irradiation with active energy rays and a thermal polymerization initiator that generates active species by heating. Examples of the photopolymerization initiator include photoradical polymerization initiators, photoacid generators, and photobase generators, and examples of the thermal polymerization initiator include thermal radical polymerization initiators, thermal acid generators, and thermal base generators.

[0264] In order to promote the curing reaction of the crosslinking agent, the composition of the present invention may also contain an acid generator as a polymerization initiator. The acid generator may be any compound as long as it can generate an acid under predetermined conditions, and examples thereof include onium salts such as sulfonium salts, iodonium salts, and ammonium salts.

[0265] Specific examples of the acid generator include tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, triethylammonium nonafluorobutanesulfonate, pyridinium nonafluorobutanesulfonate, triethylammonium camphorsulfonate, pyridinium camphorsulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, tetramethylammonium p-toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, Diphenyl iodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyl iodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate p-tert-butoxyphenyl)phenylsulfonium, tri(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxycyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxycyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, Onium salts such as dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, (2-norbornyl)methyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, ethylenebis[methyl(2-oxocyclopentyl)sulfonium trifluoromethanesulfonate], and 1,2'-naphthylcarbonylmethyltetrahydrothiophenium trifluoromethanesulfonate.

[0266] In view of good curability, a thermal acid generator that generates an acid by heat is particularly preferred.

[0267] The content of the acid generator is preferably 50 to 150 parts by mass, more preferably 80 to 120 parts by mass, relative to 100 parts by mass of the crosslinking agent. When the content is within the above range, a composition having excellent curability can be obtained.

[0268] When the compound I has a carbon-carbon double bond, the composition of the present invention may also contain a radical polymerization initiator as a polymerization initiator. As the radical polymerization initiator, any of a photoradical polymerization initiator and a thermal radical polymerization initiator can be used.

[0269] Examples of the photoradical polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin propyl ether, and benzoin butyl ether; benzyl ketals such as benzyl dimethyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-benzyl-1-dimethylamino-1-(4'-morpholinobenzoyl)propane, 2-morpholino-2-(4'-methylmercapto)benzoylpropane, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one, 1-hydroxycyclohexylphenyl ketone, 1-hydroxy-1-benzoyl- Acetophenones such as cyclohexane, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4'-isopropyl)benzoylpropane, N,N-dimethylaminoacetophenone, 1,1-dichloroacetophenone, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane; anthraquinones such as 2-methylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4, Benzophenones such as 4'-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl-4'-methyldiphenyl sulfide; oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; carbazoles such as 3-(2-methyl-2-morpholinopropionyl)-9-methylcarbazole; α-dicarbonyls such as benzil and methyl benzoylformate; Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2005-97141, Japanese Patent Table No. 2006-516246 Oxime esters such as compounds described in Japanese Patent No. 3860170, Japanese Patent No. 3798008, WO2006 / 018973, Japanese Patent Unexamined Patent Publication No. 2011-132215, and WO2015 / 152153; triazines such as p-methoxyphenyl-2,4-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-butoxyphenylvinyl)-s-triazine;Benzoyl peroxide, 2,2'-azobisisobutyronitrile, ethyl anthraquinone, 1,7-bis(9'-acridinyl)heptane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, benzophenone, phenylbiphenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 2-(p-butoxyphenylvinyl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzophenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, etc. ;

[0270] Examples of the thermal radical polymerization initiator include peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 4,4-di(tert-butylperoxy)butyl valerate, and dicumyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile; and tetramethylthiuram disulfide.

[0271] Examples of the photobase generator include carbamate compounds, α-aminoketone compounds, quaternary ammonium compounds, O-acyl oxime compounds, and aminocyclopropenone compounds.

[0272] Examples of the carbamate compound include 1-(2-anthraquinone)ethyl 1-piperidinecarboxylate, 1-(2-anthraquinone)ethyl 1 H-2-ethylimidazole-1-carboxylate, 9-anthrylmethyl 1-piperidinylcarboxylate, 9-anthrylmethyl N,N-diethylcarbamate, 9-anthrylmethyl N-propylcarbamate, 9-anthrylmethyl N-cyclohexylcarbamate, 9-anthrylmethyl 1 H-imidazole-1-carboxylate, 9-anthrylmethyl N,N-dioctylcarbamate, 9-anthrylmethyl 1-(4-hydroxypiperidine)carboxylate, 1-pyrenylmethyl 1-piperidinecarboxylate, bis[1-(2-anthraquinone)ethyl]1,6-hexanediylbiscarbamate, bis(9-anthrylmethyl)1,6-hexanediylbiscarbamate, and the like.

[0273] Examples of the α-aminoketone compound include 1-phenyl-2-(4-morpholinobenzoyl)-2-dimethylaminobutane and 2-(4-methylthiobenzoyl)-2-morpholinopropane.

[0274] Examples of the quaternary ammonium compound serving as a photobase generator include 1-(4-phenylthiophenacyl)-1-azonia-4-azabicyclo[2,2,2]octanetetraphenylborate, 5-(4-phenylthiophenacyl)-1-azoniabicyclo[4,3,0]-5-nonenetetraphenylborate, and 8-(4-phenylthiophenacyl)-1-azoniabicyclo[5,4,0]-7-undecenetetraphenylborate.

[0275] Examples of the aminocyclopropenone compound serving as a photobase generator include 2-diethylamino-3-phenylcyclopropenone, 2-diethylamino-3-(1-naphthyl)cyclopropenone, 2-pyrrolidinyl-3-phenylcyclopropenone, 2-imidazolyl-3-phenylcyclopropenone, and 2-isopropylamino-3-phenylcyclopropenone.

[0276] Examples of the thermal base generator include carbamate derivatives such as 2-(4-biphenyl)-2-propylcarbamate and 1,1-dimethyl-2-cyanoethylcarbamate, urea derivatives such as urea or N,N,N'-trimethylurea, dihydropyridine derivatives such as 1,4-dihydronicotinamide, dicyandiamide, and salts formed from acids and bases such as organic salts or inorganic salts.

[0277] The compounds and compositions of the present invention are excellent in heat resistance, so they can be suitably used for electronic components such as semiconductor sealing materials, circuit substrates, laminated films, laminated substrates, semiconductor resists, semiconductor hard masks, and multilayer flexible films. As examples of electronic components, discrete components (single semiconductors) in which one component has a separate function, such as transistors or diodes, ICs (integrated circuits) obtained by mounting components with multiple functions on one chip, and CPUs such as memory, microprocessors (MPUs), and logic ICs can be cited. Electronic components using the compositions of the present invention can be suitably used for various purposes, such as industrial machinery parts, general machinery parts, automobile / railway / vehicle parts, space / aerospace related parts, electronic / electrical parts, building materials, containers / packaging components, daily necessities, sports / leisure products, and wind power generation frame components, but are not limited to these.

[0278] The composition of the present invention has excellent heat resistance and solvent resistance as shown in the examples described below, and is suitable as a material for electronic components. In particular, as shown in the examples described below, it has excellent embedding properties and flatness, and is suitable as a semiconductor film-forming material. The so-called semiconductor film-forming material is a material required for forming a semiconductor film, including a semiconductor member-forming material required for forming a semiconductor member and a semiconductor process member-forming material required for forming a semiconductor process member.

[0279] The semiconductor member forming material includes materials suitable for various applications, such as insulating film forming materials, barrier film forming materials, sealing material forming materials, and gap filling material forming materials.

[0280] The semiconductor process member forming material includes materials suitable for various applications, such as an underlayer film forming material, a photoresist forming material, an antireflection film forming material, and an intermediate film forming material.

[0281] The semiconductor film is a film used in the manufacture of semiconductors, and specifically, is a general term for a solid layer obtained by applying a semiconductor film-forming material and then distilling off the solvent, or a solidified product obtained by curing the solid layer through a polymerization reaction or the like.

[0282] The semiconductor film is composed of a semiconductor component and a semiconductor process component. The semiconductor component is a component that remains in the semiconductor device as a permanent film, and the semiconductor process component is a component that is used in the semiconductor manufacturing process as a replacement film but does not remain in the semiconductor device.

[0283] Examples of the semiconductor member include insulating films, barrier films, sealing materials, and gap-filling materials.

[0284] Examples of the semiconductor process member include a photoresist, an intermediate film, an underlayer film, and an antireflection film.

[0285] The so-called photoresist, intermediate film, and lower film are components for semiconductor processes used to obtain good patterns. They can be used as a multilayer resist stacked in the order of lower film, intermediate film, and photoresist on a processed substrate such as a silicon wafer.

[0286] The composition for electronic components of the present invention includes substances contained in the cured product of the present invention, and also includes substances that are removed after use in the production process or after use as a replacement film and are not contained in the cured product.

[0287] An example of the composition for electronic components of the present invention is an underlayer film in a multilayer resist material.

[0288] An example of an outline of a semiconductor manufacturing process using a multilayer resist material is shown.

[0289] As a general example of a multilayer resist material, there is a three-layer resist method having two layers under a photoresist layer.

[0290] First, a lower layer film forming material is coated on a substrate to be processed such as a silicon wafer, and the lower layer film is formed by heating. After forming an intermediate film on the lower layer film, a photoresist is coated and patterned by exposure and development. Using the formed pattern as a mask, etching treatment is performed on the intermediate film and the lower layer film in this order under appropriate dry etching conditions. Using the obtained lower layer film pattern as a mask, the substrate to be processed is etched under appropriate dry etching conditions, and the remaining mask is ashed, thereby obtaining a substrate with the target structure.

[0291] The lower layer film forming material requires heat resistance and solvent resistance that will not be deformed by the heat or solvent during the film formation of the intermediate film or the photoresist layer. In addition, in order to accurately perform the transfer using etching, etching tolerance is required. In addition, embedding properties into the unevenness of the substrate and flat film forming properties for forming a film flatly are also required. Therefore, it is particularly suitable for use as the composition of the present invention.

[0292] In addition, since the compound and composition of the present invention have excellent embedding properties into a substrate having unevenness, they can also be used as a gap filling material (embedded planarization film) filled into the recesses formed in the substrate, and can also be used for forming an insulating material (embedded insulating film), a barrier material, a semiconductor resist material other than the above-mentioned lower layer film, and an insulating film for silicon through holes filled into the recesses formed in the substrate.

[0293] <C. Cured product>

[0294] The cured product of the present invention is a cured product obtained by curing the above-mentioned composition. From the viewpoint of excellent heat resistance and solvent resistance, the cured product is preferably a thermoset.

[0295] <D. Method for manufacturing a cured product>

[0296] This manufacturing method has a step of curing the composition.

[0297] In the case of thermal curing, it can be cured by heating using a hot plate such as a heating plate, an air oven, an inert gas oven, a vacuum oven, a hot air circulation oven, etc.

[0298] The heating temperature during thermal curing is preferably 150 to 500 °C, more preferably 200 to 450 °C, and particularly preferably 250 to 400 °C as measured by the above-mentioned heating thermometer. Because by setting the heating temperature within the range shown above, a cured product with excellent heat resistance can be obtained.

[0299] In addition, the curing time is not particularly limited, but from the viewpoint of improving productivity, it is preferably 30 seconds to 60 minutes, and particularly preferably 1 to 30 minutes.

[0300] <E. Method for manufacturing an electronic component>

[0301] This manufacturing method has a step of removing the cured product after the step of curing the above-mentioned composition. For example, after forming a layer of the composition of the present invention on a substrate and curing it to form a cured film, there is a step of etching the cured film to pattern it. In the case of using the present invention as an underlayer film for semiconductor formation, specific examples of this step can be listed as follows.

[0302] A method for manufacturing an electronic component, comprising:

[0303] A step of applying a layer of the composition of the present invention on the surface of a substrate to be processed and then curing the layer to form an underlayer film;

[0304] A step of applying a layer of photoresist on the underlying film;

[0305] A step of disposing a mask on the photoresist layer, exposing the photoresist layer to energy rays through the mask, and then developing the exposed photoresist layer to form a resist pattern; and

[0306] A step of partially removing the underlayer film by transferring the pattern to the underlayer film.

[0307] By partially removing the above-mentioned lower layer film, the corresponding portion of the processed substrate is exposed.

[0308] An intermediate film may be formed between the lower film and the photoresist. As the intermediate film, a conventionally known intermediate film such as a silicon-containing layer or a hard mask layer may be used. For patterned removal of the lower film, known plasma etching may be used.

[0309] Example

[0310] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0311] <Example 1-1>

[0312] 6-Hydroxy-1-indanone 5.0 g (34 mmol), 4-hydroxybenzaldehyde 2.2 g (18 mmol), ammonium acetate 5.5 g (72 mmol), and ethanol 25 g were added to a reaction flask with a reflux tube, and the mixture was refluxed while stirring. After 12 and a half hours, the mixture was returned to room temperature, ion exchange water 17 g was added, and the precipitate was filtered. The filtrate was washed with ethanol / ion exchange water and dried under reduced pressure at 40°C to obtain compound A1 as a light yellow powder.

[0313] Yield: 1.4 g (yield: 21%)

[0314] 1H-NMR(DMSO-d6)δ / ppm: 3.78(s, 4H), 6.82(d, 2H), 6.93(d, 2H), 7.38(d, 2H), 7.45(s, 2H), 7.56(d, 2H), 9.52(s, 3H)

[0315] [Chemical formula 19]

[0316]

[0317] <Example 1-2>

[0318] 23.7 g (160 mmol) of 5-hydroxy-1-indanone, 9.8 g (80 mmol) of 4-hydroxybenzaldehyde, 28.4 g (368 mmol) of ammonium acetate, and 130 g of ethanol were added to a reaction flask with a reflux tube, and the mixture was refluxed while stirring. After 6 and a half hours, the mixture was returned to room temperature and the precipitate was filtered. The filtrate was washed with ethanol / ion exchange water and dried under reduced pressure at 40°C to obtain compound A2 as a light yellow powder.

[0319] Yield: 11.4 g (yield: 38%)

[0320] 1 H-NMR(DMSO-d6)δ / ppm: 3.79(s, 4H), 6.87(d, 2H), 6.93(d, 2H), 6.98(s, 2H), 7.55(d, 2H), 7.83(d, 2H), 9.66(s, 3H)

[0321] [Chemical formula 20]

[0322]

[0323] <Examples 1-3>

[0324] 1-Indanone 7.6 g (58 mmol), 4-hydroxybenzaldehyde 3.5 g (29 mmol), ammonium acetate 8.8 g (12 mmol), and ethanol 50 g were added to a reaction flask with a reflux tube, and the mixture was refluxed while stirring. After 6 hours, the mixture was returned to room temperature and the precipitate was filtered. The filtrate was washed with ethanol / ion exchange water and dried under reduced pressure at 60°C to obtain compound A3 as a yellow powder.

[0325] Yield: 3.0 g (yield: 30%)

[0326] 1H-NMR (DMSO-d6) δ / ppm: 3.92 (s, 4H), 6.98 (d, 2H), 7.41-7.60 (m, 4H), 7.61-7.64 (m, 4H), 8.09 (d, 2H), 9.78 (s, 1H)

[0327] [Chemical formula 21]

[0328]

[0329] <Examples 1-4>

[0330] 1-indanone 30.0 g (227 mmol), 2,4-dihydroxybenzaldehyde 15.7 g (114 mmol), ammonium acetate 70.0 g (908 mmol), ethanol 197 g were added to a reaction flask with a reflux tube, and refluxed while stirring. After 4 and a half hours, the temperature was restored to room temperature and the precipitate was filtered. The precipitate was washed with ethanol / ion exchange water and washed with toluene / DMF, and the filtrate was dried under reduced pressure at 60°C to obtain compound A4 as a light red powder.

[0331] Yield: 5.4 g (yield: 14%)

[0332] 1 H-NMR (DMSO-d6) δ / ppm: 3.83 (d, 4H), 6.42 (d, 1H), 6.54 (d, 1H), 7.27 (d, 1 H), 7.41-7.51(m, 4H), 7.62(d, 2H), 8.09(d, 2H), 9.55(s, 1H), 9.64(s, 1H)

[0333] [Chemical formula 22]

[0334]

[0335] <Examples 1-5>

[0336] (Process 1)

[0337] 19.8 g (103 mmol) of 5,6-dimethoxyindanone, 10.0 g (52 mmol) of 2-fluorenecarboxyaldehyde, 15.9 g (206 mmol) of ammonium acetate, and 139 g of ethanol were added to a reaction flask with a reflux tube, and the mixture was refluxed while stirring. After 3 hours, the mixture was returned to room temperature and the precipitate was filtered. The mixture was washed with ethanol / acetone, washed with NMP, and the filtrate was dried under reduced pressure at 100°C to obtain compound A5 as a yellow powder.

[0338] Yield: 5.1 g (yield: 23%)

[0339] 1H-NMR (DMSO-d6) δ / ppm: 3.84 (s, 10H), 3.95 (s, 6H), 4.06 (s, 2H), 7.25 (s, 2H), 7.39 (m, 1H), 7.46(t, 1H), 7.62(s, 2H), 7.67(d, 1H), 7.80(d, 1H), 8.00(s, 1H), 8.02(d, 1H), 8.09(d, 1H)

[0340] [Chemical formula 23]

[0341]

[0342] (Process 2)

[0343] 4.0 g (7.4 mmol) of compound A5, 12.0 g (60 mmol) of 1-dodecanethiol, 4.8 g (118 mmol) of NaOH, and 40 g of NMP were added to a reaction flask with a reflux tube, and stirred at 120°C. After 2 hours, the mixture was cooled, 20 g of ion exchange water was added, and the mixture was neutralized with dilute hydrochloric acid, and the precipitate was filtered. The mixture was washed with methanol, washed with DMF, and the filtrate was dried under reduced pressure at 100°C to obtain compound A6 as a yellow powder.

[0344] Yield 0.2g (yield 14%)

[0345] 1 H-NMR(DMSO-d6)δ / ppm: 3.77(s, 4H), 3.97(s, 6H), 4.05(s, 2H), 7.01(s, 2H), 7.36-7.48(m, 2H ), 7.59(s, 2H), 7.65(d, 1H), 7.74(d, 1H), 7.95(s, 1H), 8.01(d, 1H), 8.07(d, 1H), 9.23(s, 2H)

[0346] [Chemical formula 24]

[0347]

[0348] <Examples 1-6>

[0349] (Process 1)

[0350] 8.1 g (61 mmol) of 1-indanone, 7.0 g (30 mmol) of 1-pyrenecarboxyaldehyde, 9.8 g (127 mmol) of ammonium acetate, and 70 g of ethanol were added to a reaction flask with a reflux tube, and the mixture was refluxed while stirring. After 7 hours, the mixture was returned to room temperature and the precipitate was filtered. The filtrate was washed with THF / acetone and dried under reduced pressure at 40°C to obtain compound A7 as a yellow powder.

[0351] Yield: 3.0 g (yield: 22%)

[0352] 1H-NMR (CDCl3) δ / ppm: 3.65 (q, 4H), 7.36-7.42 (m, 4H), 7.53 (t, 2H), 7.72 (d , 1H), 7.98 (d, 1H), 8.05 (t, 2H), 8.19 (d, 3H), 8.29 (d, 1H), 8.34-8.39 (m, 3H)

[0353] [Chemical formula 25]

[0354]

[0355] (Process 2)

[0356] Add 2.8 g (6.1 mmol) of compound A7 and 20 g of DMF to a reaction flask with a reflux tube, and stir at room temperature under a nitrogen stream. After adding 6.5 g (78 mmol) of 48% aqueous sodium hydroxide solution, add 9.3 g (79 mmol) of 3-bromo-1-propyne dropwise, and stir at 60 ° C for 12 hours. Add 50 g of ion exchange water to a beaker and add the reaction solution. Methanol is also added and the precipitate is filtered. Wash with ion exchange water / methanol and dry the filtrate under reduced pressure at 40 ° C to obtain compound A8 as a yellow powder.

[0357] Yield 0.6g (yield 16%)

[0358] 1 H-NMR (DMSO-d6) δ / ppm: 1.80 (d, 2H), 1.92 (d, 2H), 2.41-2.47 (m, 6H), 2.72 ( d, 2H), 7.45-7.60 (m, 6H), 8.06-8.20 (m, 5H), 8.36-8.48 (m, 5H), 8.55 (d, 1H)

[0359] [Chemical formula 26]

[0360]

[0361] <Examples 1-7>

[0362] (Process 1)

[0363] 1-indanone 7.6 g (58 mmol), 2-fluorene carboxyaldehyde 6.0 g (31 mmol), ammonium acetate 8.6 g (111 mmol), and ethanol 60 g were added to a reaction flask with a reflux tube, and refluxed while stirring. After 8 hours, the mixture was returned to room temperature and the precipitate was filtered. The mixture was washed with ion exchange water / ethanol, washed with DMF / acetone, and the filtrate was dried under reduced pressure at 40°C to obtain compound A9 as a light yellow powder.

[0364] Yield: 3.9 g (yield: 30%)

[0365] 1 H-NMR (CDCl3) δ / ppm: 3.88 (s, 4H), 4.04 (s, 2H), 7.35-7.63 (m, 10H), 7.73 (s, 1H), 7.88 (d, 1H), 7.96 (d, 1H), 8.30 (d, 2H)

[0366] [Chemical formula 27]

[0367]

[0368] (Process 2)

[0369] To a reaction flask with a reflux tube, add 3.4 g (8.1 mmol) of compound A9, 0.8 g (2.4 mmol) of tetrabutylammonium bromide, and 15 g of cyclopentyl methyl ether, and stir at room temperature under a nitrogen stream. After adding 11.9 g (143 mmol) of 48% aqueous sodium hydroxide solution and 10 g of ion exchange water, add 13.4 g (113 mmol) of 3-bromo-1-propyne dropwise, and stir at 70°C for 13 hours. Add 50 g of hexane to a beaker, add the reaction solution, and filter the precipitate. Dissolve the filtrate in 60 g of dichloromethane, wash with water 3 times, and then distill off the solvent. After crystallization with methyl tert-butyl ether, filter. Compound A10 is obtained as a yellow powder by drying the filtrate under reduced pressure at 40°C.

[0370] Yield 1.5g (yield 28%)

[0371] 1 H-NMR (CDCl3) δ / ppm: 1.62 (q, 4H), 1.92 (s, 2H), 2.42 (dd, 4H), 2.82 (d, 4H), 2.96 (s, 4H), 7.43 -7.54(m, 6H), 7.60(d, 2H), 7.70(dd, 2H), 7.85(d, 1H), 7.93(d, 1H), 8.02(s, 1H), 8.25(d, 2H)

[0372] [Chemical formula 28]

[0373]

[0374] <Example 1-8>

[0375] Add 1.7 g (3.7 mmol) of compound A1 and 31 g of DMF to a reaction flask with a reflux tube, and stir at room temperature under a nitrogen stream. After adding 7.9 g (94 mmol) of 48% sodium hydroxide aqueous solution, add 10.6 g (89 mmol) of 3-bromo-1-propyne dropwise, and stir at 65°C for 17 and a half hours. Add 50 g of ion exchange water to a beaker, add the reaction solution, and filter the precipitate. Wash with ion exchange water / ethanol, and dry the filtrate under reduced pressure at 40°C to obtain compound A11 as a yellow powder.

[0376] Yield 0.7g (yield 32%)

[0377] 1 H-NMR (DMSO-d6) δ / ppm: 2.20 (d, 4H), 2.35 (s, 4H), 2.81 (d, 4H), 3.65 (s, 3H), 4.95 (s, 6H), 7.07 (d, 2H), 7.25 (d, 2H), 7.56-7.58 (m, 6H)

[0378] [Chemical formula 29]

[0379]

[0380] <Example 1-9>

[0381] Add 3.1 g (8.0 mmol) of compound A2, 4.8 g (35 mmol) of potassium carbonate and 44 g of DMF to a reaction flask with a reflux tube, and stir at room temperature under a nitrogen stream. Add 3.7 g (31 mmol) of 3-bromo-1-propyne dropwise, and stir at 60°C for 7 hours. Add 196 g of ion exchange water to a beaker, add the reaction solution, and filter the precipitate. Wash with methanol, dry the filtrate under reduced pressure at 40°C, and obtain compound A12 as a yellow powder.

[0382] Yield: 3.3 g (yield: 83%)

[0383] 1 H-NMR(DMSO-d6)δ / ppm: 3.60(s, 2H), 3.65(s, 1H), 3.88(s, 4H), 4.87(s, 4H), 4.93(s,2H),7.11(d,2H),7.18(d,2H),7.24(s,2H),7.75(d,2H),7.98(d,2H)

[0384] [Chemical formula 30]

[0385]

[0386] <Example 1-10>

[0387] Add 3.1 g (8.0 mmol) of compound A2, 0.8 g (2.4 mmol) of tetrabutylammonium bromide, and 15 g of cyclopentyl methyl ether to a reaction flask with a reflux tube, and stir at room temperature under a nitrogen stream. After adding 12.0 g (144 mmol) of 48% aqueous sodium hydroxide solution and 5 g of ion exchange water, add 7.3 g (61 mmol) of 3-bromo-1-propyne dropwise, and stir at 55°C for 6 and a half hours. Add 16 g of methanol and 10 g of ion exchange water, and filter the precipitate. The filtrate is washed with methanol / ion exchange water and dried under reduced pressure at 50°C to obtain compound A13 as a yellow powder.

[0388] Yield: 3.1 g (yield: 61%)

[0389] 1 H-NMR(DMSO-d6)2.19(d,4H),2.35(s,4H),2.80(d,4H),3.61(s,2H),3.65(s,1H),4.8 8(s, 4H), 4.94(s, 2H), 7.10(d, 2H), 7.25(d, 2H), 7.30(s, 2H), 7.52(d, 2H), 7.89(d, 2H)

[0390] [Chemical formula 31]

[0391]

[0392] <Example 1-11>

[0393] Add 1.0 g (2.9 mmol) of compound A3 and 8 g of DMF to a reaction flask with a reflux tube, and stir at room temperature under a nitrogen stream. After adding 1.3 g (15 mmol) of 48% sodium hydroxide aqueous solution, add 1.8 g (15 mmol) of 3-bromo-1-propyne dropwise, and stir for 3 hours. Add 62 g of ion exchange water to a beaker and add the reaction solution. The precipitate is filtered, washed with ion exchange water / methanol, and the filtrate is dried under reduced pressure at 60°C to obtain compound A14 as a light orange powder.

[0394] Yield: 1.3 g (yield: 86%)

[0395] 1H-NMR (DMSO-d6) δ / ppm: 2.23 (d, 2H), 2.27 (d, 2H), 2.35 (t, 4H), 2.85 (d, 2H), 2.89 (d, 2 H), 3.67(t, 1H), 4.96(d, 2H), 7.28(d, 2H), 7.46-7.57(m, 6H), 7.68(d, 2H), 8.02(d, 2H)

[0396] [Chemical formula 32]

[0397]

[0398] <Example 1-12>

[0399] Add 5.0 g (14 mmol) of compound A4 and 33 g of DMF to a reaction flask with a reflux tube, and stir at room temperature under a nitrogen stream. After adding 7.2 g (87 mmol) of 48% sodium hydroxide aqueous solution, add 10.3 g (87 mmol) of 3-bromo-1-propyne dropwise, and stir at 60-80°C for 4 hours. After removing the salt in the system by filtration, add 160 g of ion exchange water to a beaker and add the reaction solution. The precipitate is filtered, washed with ion exchange water / methanol, and the filtrate is dried under reduced pressure at 60°C to obtain compound A15 as a light orange powder.

[0400] Yield: 1.3 g (yield: 86%)

[0401] 1 H-NMR (DMSO-d6) δ / ppm: 2.23 (d, 2H), 2.27 (d, 2H), 2.35 (t, 4H), 2.85 (d, 2H), 2.89 (d, 2H), 3.53 (t, 1H), 3.6 8(t,1H),4.84(d,2H),4.93(d,2H),6.84(d,1H),6.96(d,2H),7.42-7.54(m,5H),7.62(d,2H),8.12(d,2H)

[0402] [Chemical formula 33]

[0403]

[0404] <Example 1-13>

[0405] (Process 1)

[0406] 29.0 g (219 mmol) of 1-indanone, 24.5 g (110 mmol) of 3-formyl-N-ethylcarbazole, 67.7 g (878 mmol) of ammonium acetate, and 246.1 g of ethanol were added to a reaction flask with a reflux tube, and the mixture was refluxed while stirring. After 1 hour, the mixture was returned to room temperature and the precipitate was filtered. The mixture was washed with acetone, washed with THF, and the filtrate was dried under reduced pressure at 60°C to obtain compound A16 as a light red powder.

[0407] Yield: 9.8 g (yield: 20%)

[0408] 1 H-NMR (DMSO-d6) δ / ppm: 1.41 (t, 3H), 4.05 (s, 4H), 4.55 (q, 2H), 7.25 (t, 1H), 7.43-7.54 (m, 5H) ), 7.62(d, 2H), 7.68(d, 1H), 7.79(d, 1H), 7.89(d, 1H), 8.14(d, 2H), 8.31(d, 1H), 8.66(d, 1H)

[0409] [Chemical formula 34]

[0410]

[0411] (Process 2)

[0412] To a reaction flask with a reflux tube, add 4.0 g (8.9 mmol) of compound A16, 0.9 g (2.7 mmol) of tetrabutylammonium bromide, and 21 g of cyclopentyl methyl ether, and stir at room temperature under a nitrogen stream. After adding 8.9 g (107 mmol) of 48% aqueous sodium hydroxide solution and 4 g of ion exchange water, heat to 70°C. Add 6.4 g (54 mmol) of 3-bromo-1-propyne dropwise, and stir at 85°C for 2 hours. Cool to 30°C, add 48 g of ion exchange water, and filter the precipitate. Wash with methanol / ion exchange water, and dry the filtrate under reduced pressure at 60°C to obtain compound A17 as a light yellow powder.

[0413] Yield: 2.8 g (yield: 52%)

[0414] 1H-NMR (DMSO-d6) δ / ppm: 1.46 (t, 3H), 2.24 (dd, 4H), 2.38 (t, 2H), 2.44 (t, 2H), 2.80 (dd, 2H), 2.84 (dd, 2H), 4.59 (q, 2H ), 7.27(t, 1H), 7.45-7.58(m, 5H), 7.65(d, 2H), 7.70-7.76(m, 4H), 7.93(d, 1H), 8.02(d, 1H), 8.05(d, 2H), 8.36(d, 1H)

[0415] [Chemical formula 35]

[0416]

[0417] <Example 1-14>

[0418] To a reaction flask with a reflux tube, add 2.5 g (4.9 mmol) of compound A6, 0.5 g (1.5 mmol) of tetrabutylammonium bromide, and 25 g of cyclopentyl methyl ether, and stir at room temperature under a nitrogen stream. After adding 8.2 g (98 mmol) of 48% aqueous sodium hydroxide solution and 3 g of ion exchange water, heat to 50°C. Add 7.3 g (61 mmol) of 3-bromo-1-propyne dropwise, and stir at 60°C for 3 hours. Cool to 30°C, remove the insoluble matter in the system, and after distilling off the solvent, add 5 g of cyclopentyl methyl ether, 5 g of ion exchange water, and 15 g of methanol, and filter the precipitate. Wash with methanol / ion exchange water, and dry the filtrate under reduced pressure at 50°C to obtain compound A18 as a yellow powder.

[0419] Yield 0.5g (yield 13%)

[0420] 1 H-NMR (DMSO-d6) δ / ppm: 2.24 (t, 1H), 2.29 (t, 1H), 2.34 (d, 2H), 2.36 (t, 2H), 2.39 (d, 2H) 2.48 (t, 2H), 2.73-2.81 (m, 4H ), 2.90-3.00(m, 4H), 3.58(t, 2H), 3.97(s, 6H), 4.84(d, 4H), 7.35-7.64(m, 7H), 7.76(d, 1H), 7.97(d, 2H), 8.10(d, 1H)

[0421] [Chemical formula 36]

[0422]

[0423] <Example 1-15>

[0424] (Process 1)

[0425] Compound A29 was obtained as a light yellow powder by the same synthesis method except that 6-hydroxy-1-indanone in <Example 1-1> was changed to 5-hydroxy-1-indanone and 4-hydroxybenzaldehyde was changed to 3-hydroxybenzaldehyde.

[0426] (Process 2)

[0427] To a reaction flask with a reflux tube, add 9.0 g (23.7 mmol) of compound A29, 2.3 g (7.1 mmol) of tetrabutylammonium bromide, and 18.0 g of cyclopentyl methyl ether, and stir at room temperature under a nitrogen stream. After adding 35.6 g (427 mmol) of 48% aqueous sodium hydroxide solution, raise the temperature to 60°C. Add 21.7 g (183 mmol) of 3-bromo-1-propyne dropwise, and stir at 60°C for 2 hours. Cool to 30°C, distill off the solvent from the organic phase, add 95 g of methanol, and filter the precipitate. Wash with methanol / ion exchange water, and dry the filtrate under reduced pressure at 40°C to obtain compound A22 as a light yellow powder.

[0428] Yield: 6.5 g (yield: 42.4%)

[0429] 1 H-NMR(DMSO-d6)δ / ppm: 2.22-2.24(m, 2H), 2.26-2.28(m, 2H), 2.35-2.38(m, 4H), 2.81-2.82(m, 2H), 2.85-2.87(m , 2H), 3.58(t, 1H), 3.62(t, 2H), 4.87(d, 2H), 4.87(d, 4H), 7.11-7.14(m, 2H), 7.22-7.29(m, 3H), 7.58-7.63(m, 5H)

[0430] [Chemical formula 37]

[0431]

[0432] <Example 1-16>

[0433] (Process 1)

[0434] Compound A30 was obtained as a light yellow powder by the same synthesis method except that 4-hydroxybenzaldehyde in <Example 1-1> was changed to 3-hydroxybenzaldehyde.

[0435] 1H-NMR (DMSO-d6) δ / ppm: 3.79 (s, 4H), 6.93 (dd, 2H), 6.93 (d, 1H), 7.03 (d, 2H) ,7.08(s,1H),7.15(s,1H),7.40(t,1H),7.86(d,2H)9.65(s,2H),9.67(s,1H)

[0436] (Process 2)

[0437] To a reaction flask with a reflux tube, add 9.0 g (23.7 mmol) of compound A30, 2.3 g (7.1 mmol) of tetrabutylammonium bromide, and 18.0 g of cyclopentyl methyl ether, and stir at room temperature under a nitrogen stream. After adding 35.6 g (427 mmol) of 48% aqueous sodium hydroxide solution, raise the temperature to 60°C. Add 21.7 g (183 mmol) of 3-bromo-1-propyne dropwise, and stir at 60°C for 2 hours. Cool to 30°C, distill off the solvent from the organic phase, add 95 g of methanol, and filter the precipitate. Wash with methanol / ion exchange water, and dry the filtrate under reduced pressure at 40°C to obtain compound A23 as a light yellow powder.

[0438] Yield: 6.9 g (yield: 45.0%)

[0439] 1 H-NMR(DMSO-d6)δ / ppm: 2.22-2.24(m, 2H), 2.26-2.28(m, 2H), 2.35-2.38(m, 4H), 2.81-2.82(m, 2H), 2.85-2.87(m , 2H), 3.58(t, 1H), 3.65(t, 2H), 4.87(d, 2H), 4.97(d, 4H), 7.07-7.10(m, 2H), 7.22-7.29(m, 3H), 7.58-7.63(m, 5H)

[0440] [Chemical formula 38]

[0441]

[0442] <Example 1-17>

[0443] (Process 1)

[0444] Compound A31 was obtained as a light yellow powder by the same synthesis method except that 1-indanone in <Example 1-7> was changed to 5-hydroxy-1-indanone.

[0445] 1H-NMR(DMSO-d6)δ / ppm: 3.85(s, 4H), 4.06(s, 2H), 6.90(dd, 2H), 7.00(d, 2H), 7.38(t, 1H), 7.45( t, 1H), 7.66 (d, 1H), 7.74 (d, 1H), 7.87 (d, 2H), 7.96 (s, 1H), 8.01 (d, 1H), 8.09 (d, 1H), 9.67 (s, 2H)

[0446] (Process 2)

[0447] In a reaction flask with a reflux tube, 14 g (31.0 mmol) of compound A31, 3.00 g (9.3 mmol) of tetrabutylammonium bromide, and 56 g of cyclopentyl methyl ether were added, and stirred at room temperature under a nitrogen stream. After adding 62.0 g (744 mmol) of 48% aqueous sodium hydroxide solution, the temperature was raised to 60°C. 31.0 g (261 mmol) of 3-bromo-1-propyne was added dropwise, and stirred at 60°C for 5 hours. After cooling to 30°C, the insoluble matter in the system was removed, and after the solvent was distilled off, 60 g of cyclopentyl methyl ether, 120 g of ion exchange water, and 60 g of methanol were added, and the precipitate was filtered. The filtrate was washed with methanol / ion exchange water and dried under reduced pressure at 50°C to obtain compound A24 as a yellow powder.

[0448] Yield: 15.2 g (yield: 64.9%)

[0449] 1 H-NMR (DMSO-d6) δ / ppm: 2.48 (dd, 2H), 2.76-2.84 (m, 4H), 2.90-3.00 (m, 4H), 3.62 (dd, 2H), 4.88-4.90 (m, 4H), 7.1 2(dd, 2H), 7.31(d, 2H), 7.41-7.50(m, 2H), 7.62(d, 1H), 7.76(d, 1H), 7.92(d, 2H), 7.97-7.99(m, 2H), 8.11(d, 1H)

[0450] [Chemical formula 39]

[0451]

[0452] <Example 1-18>

[0453] (Process 1)

[0454] Compound A32 was obtained as a light yellow powder by the same synthesis method except that 1-indanone in <Example 1-7> was changed to 6-hydroxy-1-indanone.

[0455] 1 H-NMR (DMSO-d6) δ / ppm: 3.80 (s, 4H), 4.00 (s, 2H), 6.84 (dd, 2H), 7.35-7.39 (m, 3H), 7.4 4(t,1H),7.48(d,2H),7.66(d,1H),7.74(d,1H),7.99(d,2H),8.06(d,1H),9.53(s,2H)

[0456] (Process 2)

[0457] In a reaction flask with a reflux tube, 60 g (132.9 mmol) of compound A32, 12.85 g (39.9 mmol) of tetrabutylammonium bromide, and 360 g of cyclopentyl methyl ether were added, and stirred at room temperature under a nitrogen stream. After adding 265.7 g (3189 mmol) of 48% aqueous sodium hydroxide solution, the temperature was raised to 60°C. 139.1 g (1169 mmol) of 3-bromo-1-propyne was added dropwise, and stirred at 60°C for 3 hours. After cooling to 30°C, the insoluble matter in the system was removed, and after the solvent was distilled off, 60 g of cyclopentyl methyl ether, 120 g of ion exchange water, and 60 g of methanol were added, and the precipitate was filtered. The filtrate was washed with methanol / ion exchange water and dried under reduced pressure at 50°C to obtain compound A25 as a yellow powder.

[0458] Yield: 19.55 g (yield: 19.5%)

[0459] 1 H-NMR (DMSO-d6) δ / ppm: 2.28 (dd, 2H), 2.35-2.45 (m, 6H), 2.45 (t, 2H), 2.80 (td, 4H), 2.95 (d, 4H), 3.66 (t, 2 H), 4.98(d, 4H), 7.08(dd, 2H), 7.42-7.50(m, 2H), 7.56-7.64(m, 5H), 7.76(d, 1H), 7.98(d, 2H), 8.12(d, 1H)

[0460] [Chemical formula 40]

[0461]

[0462] <Example 1-19>

[0463] (Process 1)

[0464] Compound A33 was obtained as a light yellow powder by the same synthesis method except that 4-hydroxybenzaldehyde in <Example 1-1> was changed to 3,4-dihydroxybenzaldehyde.

[0465] 1 H-NMR (DMSO-d6) δ / ppm: 3.91 (s, 4H), 6.96 (d, 4H), 7.09 (s, 1H), 7.16 (s, 1H), 7.48 (d, 2H), 7.79 (d, 2H), 9.78 (s, 4H)

[0466] (Process 2)

[0467] To a reaction flask with a reflux tube, 22.7 g (57.3 mmol) of compound A33, 5.4 g (16.8 mmol) of tetrabutylammonium bromide, and 310 g of tetrahydrofuran were added, and stirred at room temperature under a nitrogen stream. After adding 361 g (988 mmol) of a 25% aqueous solution of tetramethylammonium hydroxide, the temperature was raised to 45°C. 72.3 g (608 mmol) of 3-bromo-1-propyne was added dropwise, and stirred at 45 for 2 hours. After cooling to 30°C and removing the solvent from the organic phase by distillation, 95 g of methanol was added, and the precipitate was filtered. The filtrate was washed with methanol / ion exchange water and dried under reduced pressure at 40°C to obtain compound A26 as a yellow powder.

[0468] Yield: 15.1 g (yield: 37.3%)

[0469] 1 H-NMR(DMSO-d6)δ / ppm: 2.36(s, 8H), 2.83(s, 4H), 3.46(s, 1H), 3.65(s, 3H), 4.78(s , 2H), 4.50(s, 6H), 7.06(d, 2H), 7.16(d, 1H), 7.32(d, 2H), 7.57(s, 3H), 7.59(d, 1H)

[0470] [Chemical formula 41]

[0471]

[0472] <Example 1-20>

[0473] (Process 1)

[0474] Compound A34 was obtained as a light yellow powder by the same method except that 4-hydroxybenzaldehyde in <Example 1-1> was changed to 2-hydroxy-1-naphthaldehyde.

[0475] 1H-NMR (DMSO-d6) δ / ppm: 3.32 (s, 4H), 6.82 (dd, 2H), 7.14-7.17 (m, 1H), 7.30-7.3 5(m, 4H), 7.39(d, 1H), 7.51(d, 2H), 7.91-7.97(m, 2H), 9.54(s, 2H), 9.86(s, 1H)

[0476] (Process 2)

[0477] To a reaction flask with a reflux tube, add 8.0 g (18.6 mmol) of compound A34, 1.8 g (5.6 mmol) of tetrabutylammonium bromide, and 48.0 g of cyclopentyl methyl ether, and stir at room temperature under a nitrogen stream. After adding 32.6 g (391 mmol) of 48% aqueous sodium hydroxide solution, raise the temperature to 60°C. Add 17.1 g (143 mmol) of 3-bromo-1-propyne dropwise, and stir at 60° for 5 hours. Cool to 30°C, distill off the solvent from the organic phase, add 95 g of methanol, and filter the precipitate. Wash with methanol / ion exchange water, and dry the filtrate under reduced pressure at 40°C to obtain compound A27 as a light yellow powder.

[0478] Yield: 2.8 g (yield: 21.6%)

[0479] 1 H-NMR(DMSO-d6)δ / ppm: 2.22-2.24(m, 2H), 2.26-2.28(m, 2H), 2.35-2.38(m, 4H), 2.81-2.82(m, 2H), 2.85-2.87(m , 2H), 3.58(t, 1H), 3.65(t, 2H), 4.87(d, 2H), 4.97(d, 4H), 7.07-7.10(m, 2H), 7.22-7.29(m, 3H), 7.58-7.63(m, 5H)

[0480] [Chemical formula 42]

[0481]

[0482] <Example 1-21>

[0483] (Process 1)

[0484] Compound A35 was obtained as a light yellow powder by the same method except that 4-hydroxybenzaldehyde in <Example 1-1> was replaced with 4-acetamidobenzaldehyde.

[0485] 1H-NMR (DMSO-d6) δ / ppm: 2.10 (s, 3H), 3.79 (s, 4H), 6.84 (dd, 2H), 7.37 (d, 2 H), 7.45(d, 2H), 7.67-7.71(m, 2H), 7.76(d, 2H), 9.52(s, 2H), 10.13(s, 1H)

[0486] (Process 2)

[0487] In a reaction flask with a reflux tube, 60.0 g (143 mmol) of compound A35, 240 g of N-methyl-1-pyrrolidone, and 240 g of ethanol were added, and stirred at room temperature under a nitrogen stream. After adding 179 g (2140 mmol) of 48% aqueous sodium hydroxide solution, the mixture was stirred at 90°C for 10 hours. The mixture was cooled to 30°C, 108 g of ethyl acetate was added, and the precipitate was filtered. The filtrate was washed with ethyl acetate, then washed with methanol / ion exchange water, and the filtrate was dried under reduced pressure at 40°C to obtain compound A36 as a light yellow powder.

[0488] 1 H-NMR(DMSO-d6)δ / ppm: 3.74(s, 4H), 5.36(s, 2H), 6.70(d, 2H), 6.75(d, 2H), 7.29(d, 2H), 7.41(d, 2H), 7.45(d, 2H)

[0489] (Process 3)

[0490] To a reaction flask with a reflux tube, 16.0 g (42.3 mmol) of compound A36, 4.1 g (12.7 mmol) of tetrabutylammonium bromide, and 160 g of cyclopentyl methyl ether were added, and stirred at room temperature under a nitrogen stream. After adding 52.9 g (634 mmol) of 48% aqueous sodium hydroxide solution, the temperature was raised to 65°C. 44.3 g (372 mmol) of 3-bromo-1-propyne was added dropwise, and stirred at 75° for 7 hours. After cooling to 30°C and filtering the precipitate, the organic layer of the filtrate was washed with water 5 times and dried under reduced pressure at 40°C. Compound A28 was obtained as a light yellow powder by washing the obtained solid with methyl isobutyl ketone and drying the filtrate under reduced pressure at 40°C.

[0491] Yield 19.5g (yield 67.5%)

[0492] 1H-NMR (DMSO-d6) δ / ppm: 1.70 (dd, 2H), 2.25 (dd, 4H), 2.37 (t, 2H), 2.54-2.67 (m, 4H), 3.53 (t, 1H), 3.67 (t, 2H), 4.84 ( d, 2H), 4.98 (d, 4H), 7.06 (dd, 2H), 7.30 (t, 1H), 7.47 (t, 1H), 7.59-7.65 (m, 5H), 7.72 (d, 1H), 8.02 (d, 1H), 8.27 (d, 1H)

[0493] [Chemical formula 43]

[0494]

[0495] [Examples 2-1 to 2-25 and Comparative Examples 1 to 4]

[0496] The components were weighed and mixed according to the formulations (parts by mass) shown in Tables 1 to 4, and stirred to dissolve. After confirming that the solid was completely dissolved, the mixture was filtered through a fluororesin filter (pore size 0.2 μm) to prepare a composition for evaluation.

[0497] The components in the table are as follows.

[0498] Compound A8: Compound prepared in Example 1-6

[0499] Compound A10: Compound prepared in Example 1-7

[0500] Compound A11: Compound prepared in Example 1-8

[0501] Compound A12: Compound prepared in Example 1-9

[0502] Compound A13: Compound prepared in Example 1-10

[0503] Compound A14: Compound prepared in Example 1-11

[0504] Compound A15: Compound prepared in Example 1-12

[0505] Compound A17: Compound prepared in Example 1-13

[0506] Compound A18: Compound prepared in Example 1-14

[0507] Compound A22: Compound prepared in Example 1-15

[0508] Compound A23: Compound prepared in Example 1-16

[0509] Compound A24: Compound prepared in Example 1-17

[0510] Compound A25: Compound prepared in Example 1-18

[0511] Compound A26: Compound prepared in Example 1-19

[0512] Compound A27: Compound prepared in Example 1-20

[0513] Compound A28: Compound prepared in Example 1-21

[0514] Compound A20: A compound having the following structure and no reactive group

[0515] Compound A21: A compound other than Compound I having the following structure and a reactive group

[0516] Compound B1 has the following structure, cross-linking agent (glycoluril compound)

[0517] Compound B2 has the following structure, cross-linking agent (phenol compound)

[0518] Compound C1 Bis(4-tert-butylphenyl)iodonium nonafluorobutane sulfonate (polymerization initiator: thermal acid generator)

[0519] Compound D1: Propylene glycol monomethyl ether acetate (PGMEA) solvent

[0520] Compound D2: Cyclohexanone solvent

[0521] [Chemical formula 44]

[0522]

[0523] [Chemical formula 45]

[0524]

[0525] (Fabrication of Evaluation Substrate)

[0526] The prepared evaluation composition was applied to a silicon wafer substrate using a spin coater so that the film thickness after heating was 200 nm. The coated substrate was heated on a hot plate set at 170° C. for 60 seconds and then further heated on a hot plate set at 300° C. for 60 seconds to prepare an evaluation substrate.

[0527] Using this evaluation substrate, various evaluations were performed as follows. The evaluation results are summarized in Tables 1 to 4.

[0528] (Film-forming property)

[0529] The case where the ratio of the film thickness change ((W1-W2) / W1) between the film thickness W1 after heating for 60 seconds on a heating plate set at 170°C in the preparation of the above-mentioned evaluation substrate and the film thickness W2 after further heating for 60 seconds on a heating plate set at 300°C is less than 5%, and the film surface on the evaluation substrate has no discoloration and is uniform when visually observed is set as A+; the case where the ratio of the film thickness change is greater than 5% and less than 10%, and the film surface on the evaluation substrate has no discoloration and is uniform when visually observed is set as A; the case where the surface is uniform but has discoloration such as yellowing or blackening is set as B; and the case where there is discoloration and the surface is uneven due to precipitation or volatilization is set as C.

[0530] When the ratio of the film thickness change is small, the surface is uniform, and there is no discoloration, it can be said that the film-forming property is excellent.

[0531] (Heat resistance evaluation)

[0532] The film thickness at five points on the evaluation substrate was measured using SE-2000 spectroscopic ellipsometer manufactured by Semilab, and the average value was defined as the film thickness before the test.

[0533] The evaluation substrate was heated at 300° C. for 60 seconds, and the film thickness after heating was measured in the same manner as above, which was defined as the post-test film thickness Wa.

[0534] The ratio of the film thickness change before and after the test (Wb-Wa) was set as A when it was less than 3% relative to the film thickness Wb before the test, B when it was 3% or more and less than 5%, C when it was 5% or more and less than 10%, and D when it was 10% or more.

[0535] Although not shown in the data, in the same B evaluation, Examples 2-3, 2-5, 2-6, 2-7, 2-13, 2-14, 2-18, 2-19, and 2-22 further suppressed the ratio of the film thickness change compared to Example 2-4.

[0536] (Evaluation of Solvent Resistance)

[0537] The film thickness at five points on the evaluation substrate was measured using SE-2000 spectroscopic ellipsometer manufactured by Semilab, and the average value was defined as the film thickness before the test.

[0538] The evaluation substrate was immersed in PGMEA at 25° C. for 60 seconds, and then heated at 170° C. for 60 seconds. The film thickness after evaporation of PGMEA was measured in the same manner and was defined as post-test film thickness Wa′.

[0539] A was defined as less than 1% of the ratio of the film thickness change before and after the test (Wb'-Wa') relative to the film thickness Wb' before the test, B as 1% or more and less than 3%, and C as 3% or more.

[0540] (Buried properties, flatness)

[0541] The composition was applied to a SIO2 stepped substrate (500 nm in width, 100 nm in height, and 500 nm in width of the channel) using a spin coater. The film was prepared by heating at 170°C for 60 seconds and at 300°C for 60 seconds. The spin coating conditions were adjusted so that the film thickness from the channel was 200 nm.

[0542] Evaluation of embedding property: Slices of the substrate were prepared, and the case where there was no gap in the step was evaluated as A, and the case where there was a gap was evaluated as B in observation with SEM (S-4800 manufactured by Hitachi High-Tech Corporation).

[0543] Flatness evaluation: Flatness is evaluated by the difference between the thickest part of the film on the wall formed on the substrate and the thinnest part of the film on the channel (film thickness difference). Film thickness difference less than 10nm is set as A, 10nm or more and less than 30nm is set as B, and 30nm or more is set as C.

[0544] The smaller the difference in film thickness is, the higher the flatness is, and the more preferably the film can be used as a material for electronic components, particularly a film-forming material for semiconductors.

[0545] Table 1

[0546]

[0547] Table 2

[0548]

[0549] Table 3

[0550]

[0551] Table 4

[0552]

[0553] As shown in Tables 1 to 3, a film having excellent heat resistance and solvent resistance can be obtained by using the compound I of the present invention. In addition, the compound of the present invention has excellent film-forming properties, and is also good in embedding properties and flatness during film formation.

[0554] On the other hand, as shown in Table 4, when the compound not corresponding to the formula (I) was used, it was found that the heat resistance or solvent resistance was inferior.

Claims

1. A compound represented by the following general formula (I): In the formula, X represents a hydrogen atom, a substitutable cyclic group having 2 to 20 ring carbon atoms, a substitutable chain hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the chain hydrocarbon group are substituted with a divalent group selected from the following Group B, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 each independently represents a hydrogen atom, a reactive group selected from the following Group A, a nitro group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, a group in which one or more methylene groups in the alkyl group having 1 to 20 carbon atoms are substituted by a divalent group selected from the following Group B, a group in which one or more methylene groups in the aromatic ring group having 6 to 20 carbon atoms are substituted by a divalent group selected from the following Group B, or a group in which one or more methylene groups in the heterocyclic group having 2 to 20 carbon atoms are substituted by a divalent group selected from the following Group B, Group A is a carbon-carbon unsaturated bond group, a cyclic ether group, a hydroxyl group, a mercapto group, an amino group, a halogen atom, and a cyano group, Group B is -O-, -CO-, -COO-, -OCO-, -NR 11 -、-NR 11 CO- and -S-, R 11 represents a hydrogen atom or a hydrocarbon group, There are 2 R in the same repeating unit 7 Can be the same or different, R 1 With R 2 Sometimes they bond to each other to form a ring, R 3 With R 4 Sometimes they bond to each other to form a ring, R 4 With R 5 Sometimes they bond to each other to form a ring, R 5 With R 6 Sometimes they bond to each other to form a ring, Multiple existence of R 7 With R 7 Sometimes they bond to each other to form a ring, a represents an integer from 1 to 10, When a is 2 or more, multiple R between multiple repeating units 1 Each other, multiple R 2 Each other, multiple R 3 Each other, multiple R 4 Each other, multiple R 5 Each other, multiple R 6 Each other and multiple R 7 They can be the same or different from each other. However, one or more reactive groups selected from the group A are present in the molecule.

2. The compound according to claim 1, wherein The compound is represented by the following general formula (IIα), (IIβ) or (IIγ), In the formula, X, a, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 As with general formula (I), R 21 , R 22 , R 23 , R 24 , R 25 and R 26 each independently represents a hydrogen atom, a reactive group selected from the group A, a nitro group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, a group in which one or more methylene groups in the alkyl group having 1 to 20 carbon atoms are substituted by a divalent group selected from the group B, a group in which one or more methylene groups in the aromatic ring group having 6 to 20 carbon atoms are substituted by a divalent group selected from the group B, or a group in which one or more methylene groups in the heterocyclic group having 2 to 20 carbon atoms are substituted by a divalent group selected from the group B, R 21 With R 22 Sometimes they bond to each other to form a ring, R 23 With R 24 Sometimes they bond to each other to form a ring, R 24 With R 25 Sometimes they bond to each other to form a ring, R 25 With R 26 Sometimes they are bonded to each other to form a ring.

3. The compound according to claim 1 or 2, wherein X is an optionally substituted aromatic ring group having 6 to 20 ring carbon atoms or an optionally substituted heterocyclic group having 2 to 20 ring carbon atoms.

4. The compound according to claim 1, wherein One or more carbon-carbon unsaturated bonding groups are present in the molecule as the reactive group.

5. The compound according to claim 2, wherein One or more carbon-carbon unsaturated bonding groups are present in the molecule as the reactive group.

6. The compound according to claim 1 or 2, wherein The number of the reactive groups present in the molecule is 2 or more.

7. The compound according to claim 1 or 2, wherein X has a fused ring which may be substituted, or the number of the reactive groups present in the molecule is 3 or more.

8. A composition comprising the compound according to claim 1 or 2.

9. The composition according to claim 8, wherein The composition is used for electronic components.

10. A cured product obtained from the composition according to claim 8.

11. A method for producing a cured product, comprising the step of curing the composition according to claim 8.

12. A method for manufacturing an electronic component, wherein: After the step of curing the composition according to claim 8, there is a step of removing the cured product.

13. A compound represented by the following general formula (III): In the formula, X' represents a hydrogen atom, a substitutable cyclic group having 2 to 20 ring carbon atoms, a substitutable chain hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the chain hydrocarbon group are substituted with a divalent group selected from the following <Group B>, R 1 '、R 2 '、R 3 '、R 4 '、R 5 '、R 6 ' and R 7 'respectively independently represent a hydrogen atom, a reactive group selected from the following group A, a nitro group, an alkyl group having 1 to 20 carbon atoms which may be substituted, an aromatic ring group having 6 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted, a group in which one or more methylene groups in the alkyl group having 1 to 20 carbon atoms are substituted by a divalent group selected from the following group B, a group in which one or more methylene groups in the aromatic ring group having 6 to 20 carbon atoms are substituted by a divalent group selected from the following group B, or a group in which one or more methylene groups in the heterocyclic group having 2 to 20 carbon atoms are substituted by a divalent group selected from the following group B, Group A is a carbon-carbon unsaturated bond group, a cyclic ether group, a hydroxyl group, a mercapto group, an amino group, a halogen atom, and a cyano group, Group B is -O-, -CO-, -COO-, -OCO-, -NR 11 '-、-NR 11 'CO- and -S-, R 11 ' represents a hydrogen atom or a hydrocarbon group, There are 2 R in the same repeating unit 7 'It can be the same or different, R 1 'With R 2 'Sometimes they bond to each other to form a ring, R 3 'With R 4 'Sometimes they bond to each other to form a ring, R 4 'With R 5 'Sometimes they bond to each other to form a ring, R 5 'With R 6 'Sometimes they bond to each other to form a ring, Multiple existence of R 7 'With R 7 'Sometimes they bond to each other to form a ring, a' represents an integer of 1 to 10. When X' is a hydrogen atom, a' is 1. When a' is 2 or more, multiple R between multiple repeating units 1 'Each other, multiple R 2 'Each other, multiple R 3 'Each other, multiple R 4 'Each other, multiple R 5 'Each other, multiple R 6 'Each other and multiple R 7 'They can be the same or different from each other. However, it has one or more phenolic hydroxyl groups in the molecule.

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