Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
  • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
  • C07D221/04—Ortho- or peri-condensed ring systems
  • C07D221/18—Ring systems of four or more rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
  • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
  • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/13—Morphological aspects
  • C08G2261/135—Cross-linked structures
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used

Definitions

• the present invention relates to a compound having a specific skeleton.
• Non-Patent Document 1 describes the structure of 11-allyl-10,12-dihydrodiindino[1,2-b',2',1'-e]pyridine and a method for producing it.
• Patent Document 1 describes a polymer having a structure containing an indolocarbazole unit in the side chain, and a polymer containing this polymer, and describes that a resist underlayer film containing the polymer does not cause intermixing with a resist layer, has high dry etching resistance, has high heat resistance, and produces a small amount of sublimation.
• Patent Document 2 describes that a compound having a specific skeleton containing two or more indole structures has excellent heat resistance and solvent resistance.
• the object of the present invention is to provide a compound that gives a cured product with excellent heat resistance and solvent resistance, and a composition containing the compound.
• X represents a hydrogen atom, an optionally substituted cyclic group having 2 to 20 ring carbon atoms, an optionally substituted 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 (hereinafter also referred to as "R 1 to R 7 ”) each independently represent a hydrogen atom, a reactive group selected from the following ⁇ Group A>, a nitro group, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic ring group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, a group in which one or more
• R 21 , R 22 , R 23 , R 24 , R 25 and R 26 (hereinafter also referred to as "R 21 to R 26 ") each independently represent a hydrogen atom, a reactive group selected from the above ⁇ Group A>, a nitro group, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic ring group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, a group in which one or more methylene groups in the alkyl group having 1 to 20 carbon atoms are substituted with a divalent group selected from the above ⁇ Group B>, a group in which one or more methylene groups in the
• a method for producing a cured product comprising a step of curing the composition described in [8].
• a method for producing an electronic component comprising the step of curing the composition according to [8], followed by the step of removing the cured product.
• the compound represented by general formula (I) of the present invention and a composition containing the compound provide a cured product having excellent heat resistance and solvent resistance.
• the cured product obtained by the present invention uses the above composition and has excellent heat resistance and solvent resistance.
• the method for producing electronic components of the present invention can produce high-quality electronic components using a composition suitable for electronic components that require high heat resistance and solvent resistance.
• the compound of the present invention can be successfully produced by using a compound represented by general formula (III), which is a precursor of the compound of the present invention.
• Compound represented by general formula (I)> 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 general formula (I), and one of its characteristics is that it has a specific skeleton and has one or more reactive groups (hereinafter also simply referred to as "reactive groups”) selected from the above ⁇ Group A> in the molecule.
• Suitable examples of compound I are compounds represented by the general formulae (II ⁇ ), (II ⁇ ), and (II ⁇ ) (hereinafter also referred to as “compound II ⁇ ”, “compound II ⁇ ”, and “compound II ⁇ ”, respectively, and the three types are also collectively referred to as “compounds II ⁇ to II ⁇ ”).
• compound II ⁇ compounds represented by the general formulae (II ⁇ ), (II ⁇ ), and (II ⁇ )
• compound II ⁇ compound II ⁇
• compound II ⁇ compound II ⁇
• compound II ⁇ compound II ⁇
• compound II ⁇ compound II ⁇
• the carbon-carbon unsaturated bond group refers to a group having a carbon-carbon unsaturated bond, and a group having a carbon-carbon unsaturated bond at the end is preferred.
• Preferred examples of the carbon-carbon unsaturated bond group having a carbon-carbon unsaturated bond at the end include groups having a carbon-carbon triple bond at the end, such as ethynyl groups, propargyl groups, propargyloxy groups, monopropargylamino groups, and dipropargylamino groups (di-2-propynylamino groups), and groups having a carbon-carbon double bond at the end, such as vinyl groups, allyl groups, acrylic groups, acryloyloxy groups, methacryl groups, and methacryloxy groups.
• the carbon-carbon unsaturated bond group as a reactive group, a group having a carbon-carbon triple bond at the end is particularly preferred, and in particular, an ethynyl group, a propargyl group, a propargyloxy group, or a dipropargylamino group is preferred. This is because when the carbon-carbon unsaturated bond group is a group represented by the above, a cured product having excellent heat resistance and solvent resistance is easily obtained.
• the cyclic ether group refers to a group having a cyclic ether, and preferably has a cyclic ether at the end.
• epoxy groups and oxetanyl groups are more preferable, and epoxy groups such as glycidyl ether groups, ⁇ -glycidyl ether groups, and alicyclic epoxy groups are particularly preferable. This is because when the cyclic ether group is a group represented by the above, a cured product with excellent heat resistance can be obtained.
• the alkyl groups having 1 to 20 carbon atoms represented by R 1 to R 7 in formula (I) and R 21 to R 26 in formulas (II ⁇ ) to (II ⁇ ) may be linear or branched, may have an alicyclic ring, or may be an arylalkyl group.
• Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl, and octyl.
• branched alkyl groups include Iso-propyl, sec-butyl, tert-butyl, Iso-butyl, Iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, Iso-heptyl, tert-heptyl, Iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, and octadecyl.
• Examples of groups 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 is substituted with a heterocyclic ring.
• the alkyl groups other than the arylalkyl groups represented by R 1 to R 7 and R 21 to R 26 preferably have 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.
• the arylalkyl group refers to a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group.
• Examples of the arylalkyl group include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl, and naphthylpropyl groups.
• the number of carbon atoms in the arylalkyl groups represented by R 1 to R 7 and R 21 to R 26 is preferably 7 to 20, more preferably 7 to 15, and even more preferably 7 to 10.
• the aromatic ring group having 6 to 20 carbon atoms represented by R 1 to R 7 and R 21 to R 26 is a hydrocarbon group containing an aromatic hydrocarbon ring, with a bond present on the aromatic hydrocarbon ring, and may contain an aliphatic hydrocarbon group or a heterocycle, but preferably does not contain a heterocycle. When it contains an aliphatic hydrocarbon group or a heterocycle, the upper limit of the number of carbon atoms, including the number of carbon atoms in the aliphatic hydrocarbon group or the heterocycle, is 20 or less.
• the aromatic ring group includes an aryl group having 6 to 20 carbon atoms.
• 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 together.
• Examples of the aryl group having a monocyclic structure and having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, and 2,4,6-trimethylphenyl.
• Examples of aryl groups having a fused ring structure and having 6 to 20 carbon atoms include naphthyl, anthracenyl, phenanthryl, pyrenyl, fluorenyl, and indenofluorenyl.
• examples of the linking group linking the aromatic hydrocarbon rings together include a single bond, a sulfide group (-S-), and a carbonyl group.
• examples of aryl groups in which two or more aromatic hydrocarbon rings are linked include biphenyl, diphenyl sulfide, benzoylphenyl, and groups in which a single ring and a condensed ring are linked by the above-mentioned linking groups, or condensed rings are linked to each other.
• the aromatic ring groups represented by R 1 to R 7 and R 21 to R 26 more preferably have 6 to 15 carbon atoms, and particularly preferably 6 to 10 carbon atoms.
• heterocyclic group having 2 to 20 carbon atoms represented by R 1 to R 7 and R 21 to R 26 examples include a group in which one hydrogen atom has been removed from a "heterocyclic compound" (hereinafter also referred to as “heterocyclic group I”), and a group in which a hydrogen atom in the heterocyclic group I has been substituted with a hydrocarbon group (hereinafter also referred to as “heterocyclic group II").
• heterocyclic group II a group in which a hydrogen atom in the heterocyclic group I has been substituted with a hydrocarbon group.
• an epoxy group is included in the reactive group, and is therefore not included in the heterocyclic group.
• the heterocyclic group may have a monocyclic structure or a condensed ring structure.
• heterocyclic group having a condensed ring structure having 2 to 20 carbon atoms examples include a heterocycle-containing condensed ring group having 3 to 20 carbon atoms, which is a structure in which a heterocycle and a heterocycle or a hydrocarbon ring are condensed.
• heterocyclic group I examples include pyridyl, quinolyl, thiazolyl, tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, methylthiophenyl, hexylthiophenyl, benzothiophenyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl, piperazinyl, pyrimidinyl, furyl, thienyl, benzoxazol-2-yl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, morpholinyl, and the like.
• heterocyclic group II examples of the hydrocarbon group substituting the hydrogen atom in the heterocyclic group I include the same as those exemplified as the hydrocarbon group represented by R11 described below.
• the bond is present on the heterocyclic group I.
• the number of carbon atoms, including the number of carbon atoms in the hydrocarbon group satisfies "2 to 20 carbon atoms.”
• the heterocyclic groups represented by R 1 to R 7 and R 21 to R 26 preferably have 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 5 carbon atoms.
• 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”.
• 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”.
• a "heterocyclic group having 2 to 20 carbon atoms in which one or more methylene groups 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".
• the number of carbon atoms in the methylene-substituted alkyl group, methylene-substituted aromatic ring group, methylene-substituted heterocyclic group, and methylene-substituted linear hydrocarbon group described below is within the range in which a group having a predetermined number of carbon atoms before the methylene substitution is substituted with methylene.
• the number of carbon atoms in a group e.g., an alkoxy group in which one methylene group (-CH 2 -) in an alkyl group having 20 carbon atoms is substituted with a divalent group "-O-" is 19.
• the number of carbon atoms in the methylene-substituted alkyl group, methylene-substituted aromatic ring group, and methylene-substituted heterocyclic group is within the range of 1 to 20, 6 to 20, and 2 to 20, respectively, regardless of which group in Group B is adopted, and is preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less.
• the various methylene-substituted groups do not have a structure in which a plurality of the divalent groups are adjacent to each other.
• hydrocarbon ring examples include a monocyclic ring such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, or a benzene ring; and a condensed ring such as an indane ring, a fluorene ring, a naphthalene ring, or an anthracene ring.
• a monocyclic ring such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, or a benzene ring
• condensed ring such as an indane ring, a fluorene ring, a naphthalene ring, or an anthracene ring.
• heterocyclic ring examples 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.
• the rings formed by bonding together R1 and R2 , R3 and R4 , R4 and R5 , R5 and R6 , and a plurality of R7s and R7s are preferably hydrocarbon rings, which have good heat resistance and solvent resistance, and are particularly preferably aromatic hydrocarbon rings in which at least one of the constituent rings is an aromatic ring, and are most preferably indan rings.
• Formulae (II ⁇ ) to (II ⁇ ) are those in which R 7 and R 7 in formula (I) are bonded to form an indane ring that is condensed with the pyridine ring described in formula (I).
• the hydrocarbon group represented by R 11 includes an alkyl group, an alkenyl group, and an aromatic ring group.
• alkyl group examples include the various alkyl groups mentioned as examples of R1 , etc.
• alkenyl group examples include chain alkenyl groups such as vinyl, ethylene, 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, and cyclic alkenyl groups such as cyclopentadienyl.
• aromatic ring group examples include the groups mentioned in the explanation of R1 and the like.
• the number of carbon atoms of the substituent is also included in the specified number of carbon atoms.
• the group substituted with a reactive group includes a group represented by the following formula (f). * -Lf- ( Rf )t Formula (f) (wherein Lf 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; Rf is a reactive group; and t is a number from 1 to 10.)
• L f is preferably a group in which t hydrogen atoms have been removed from an alkyl group, an aromatic ring group, a methylene-substituted alkyl group, or a methylene-substituted aromatic ring group, more preferably an aromatic ring group or a methylene-substituted aromatic ring group, and most preferably an aromatic ring group. This is because compound I can form a compound having superior heat resistance and solvent resistance.
• the number of carbon atoms in the group represented by formula (f) is preferably 10 or less, may be 5 or less, or may be 3 or less, because Compound I can form a compound having superior heat resistance and solvent resistance.
• the group represented by formula (f) and the reactive group will be collectively referred to as a "reactive group-containing group.”
• a reactive group is particularly preferred because Compound I can form a compound having superior heat resistance and solvent resistance.
• 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 bond on said ring that bonds to the pyridine ring of formula (I).
• rings 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.
• aromatic rings having 6 to 20 ring carbon atoms include hydrocarbon rings composed of carbon and hydrogen.
• the ring having 2 to 20 ring carbon atoms may be a monocyclic ring or a fused ring.
• examples of the monocyclic ring include a hydrocarbon monocyclic ring consisting of carbon atoms and hydrogen atoms such as a benzene ring
• examples of the condensed ring include 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, and also examples of ring structures in which these are linked by a linking group.
• X is preferably a hydrocarbon condensed ring, and particularly preferably fluorene.
• the heterocyclic ring having 2 to 20 ring-constituting carbon atoms include, as monocyclic rings, hetero-based monocyclic rings containing a heteroatom such as a furan ring, a pyridine ring, a pyrimidine ring, a thiophene ring, a pyrrole ring, an imidazole ring, a thiazole ring, an oxadiazole ring, a pyridine ring, and a pyrazine ring, and examples of the fused rings include a carbazole ring, an indole ring, a dibenzofuran ring, and a dibenzothiophene ring.
• Examples of the ring group having 2 to 20 ring-constituting carbon atoms include a ring structure in which a plurality of rings are linked by a linking group, and it is sufficient that any one of the rings has a bond that bonds to the pyridine ring of formula (I).
• Examples of the linking group for X include a sulfur atom, a nitrogen atom, a carbonyl group, a carbon atom, and a single bond.
• the term "2 to 20 ring carbon atoms" means, when X is a structure in which two or more rings are linked, the total number of carbon atoms constituting these two or more rings.
• Examples of the chain hydrocarbon group having 1 to 20 carbon atoms represented by X in formula (I) include, among the groups listed for R 11 , chain alkyl groups, chain alkenyl groups, etc., in which a-1 hydrogen atoms have been deleted.
• a chain hydrocarbon group having 2 to 20 carbon atoms, in which one or more methylene groups 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".
• the chain hydrocarbon group and methylene-substituted chain hydrocarbon group represented by X have 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
• the ring having 2 to 20 carbon atoms represented by X may be substituted with a substituent.
• substituents include a reactive group selected from the above group A or a group represented by formula (f), as well as a nitro group.
• the hydrogen atoms in the chain hydrocarbon group having 1 to 20 carbon atoms may be substituted with a substituent, and examples of the substituent in this case include reactive groups selected from the above group A, as well as a nitro group.
• the reactive group of compound I is preferably a carbon-carbon unsaturated bond group, a cyclic ether group, a hydroxyl group, or an amino group, and is particularly preferably a carbon-carbon unsaturated bond group, because the reactive group being one of the above groups makes it possible to obtain a cured product having excellent heat resistance and solvent resistance.
• Compound I preferably has one or more carbon-carbon unsaturated bond groups in the molecule, and in that case, it may or may not have a reactive group other than the carbon-carbon unsaturated bond group.
• amino group examples include 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, and the primary amino group or a secondary amino group substituted with a lower alkyl group is preferred.
• the number of reactive groups present in the molecule is 1 or more, preferably 2 or more, particularly preferably 3 or more.
• the number of reactive groups present in the molecule is within the above range, and a cured product excellent in heat resistance and solvent resistance can be obtained.
• the number of reactive groups present in the molecule is preferably 10 or less, in terms of easy synthesis and good storage stability, and from this viewpoint, it is more preferably 9 or less, and even more preferably 8 or less.
• the number of reactive groups here is counted as 2 if it is, for example, a dipropargylamino group.
• compound I (a) has three or more reactive groups in the molecule, or (b) has a fused ring in which X may be substituted, and it is most preferable that compound I satisfies both conditions (a) and (b).
• the groups represented by R 1 to R 6 in formula (I) are preferably a hydrogen atom, a reactive group selected from the above-mentioned ⁇ Group A>, or 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, each of which may be substituted with a reactive group, and among these, a hydrogen atom, a reactive group, or an alkyl group having 1 to 20 carbon atoms, an aromatic ring group having 6 to 20 carbon atoms, or a methylene-substituted alkyl group having 1 to 20 carbon atoms, each of which may be substituted with a reactive group, is particularly preferable.
• the groups represented by R 1 to R 6 in general formula (I) are the above-mentioned groups, a cured product having excellent heat resistance and solvent resistance can be obtained.
• At least one of the groups represented by R 1 to R 6 is a reactive group-containing group. This is because, when the groups represented by R 1 to R 6 in general formula (II) are the above-mentioned groups, a cured product having excellent heat resistance and solvent resistance can be obtained.
• the total number of reactive groups is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 2 to 3. This is because, when the number of reactive groups in R 1 to R 6 in general formula (I) is within the above range, a cured product having excellent heat resistance and solvent resistance can be obtained.
• R 1 to R 6 in formula (I) it is preferable that any one or more of R 1 , R 2 , R 4 and R 5 are reactive group-containing groups, more preferably any one or more of R 1 , R 2 and R 5 are reactive group-containing groups, and particularly preferably any one or both of R 1 and R 2 are reactive group-containing groups.
• R 1 and R 2 are reactive group-containing groups
• R 4 and R 5 are reactive group-containing groups
• even more preferably that any one of R 4 and R 5 is reactive group-containing groups.
• both R 1 and R 2 are reactive group-containing groups. This is because the position of the reactive group-containing group in formula (I) is as described above, a cured product excellent in heat resistance and solvent resistance can be obtained. This is also because it has excellent film-forming properties.
• R 4 and R 5 are reactive group-containing groups.
• Groups at positions other than the above-mentioned preferred positions for the reactive group-containing group may or may not be reactive group-containing groups.
• those that are not reactive group-containing groups are preferably hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 6 to 20 carbon atoms, methylene-substituted alkyl groups having 1 to 20 carbon atoms, or methylene-substituted aromatic ring groups having 6 to 20 carbon atoms, among which hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or methylene-substituted alkyl groups having 1 to 20 carbon atoms are preferred, and in particular hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or methylene-substituted alkyl groups having 1 to 5 carbon atoms are preferred, among which hydrogen atoms, alkyl groups having 1 to 2 carbon atoms, or methylene-substituted alkyl groups having 1 to 2 carbon atoms are preferred. It is also preferred that one or more of the groups represented by R 1
• a is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.
• a in formula (I) is the above number, a compound that is easy to synthesize and has excellent storage stability can be obtained.
• the ring formed by R7 and R7 bonding to each other is preferably a hydrocarbon ring consisting of only carbon atoms and hydrogen atoms, for example, because of its good heat resistance, and is particularly preferably an aromatic hydrocarbon ring, and is particularly preferably an indane ring condensed with the pyridine ring of formula (I). Therefore, it is preferable that compound I is any one of compounds II ⁇ to II ⁇ .
• compound I is more preferably compound II ⁇ or compound II ⁇ , and is particularly preferably compound II ⁇ . This is because the compound of the present invention has the structure represented above, and a cured product having excellent heat resistance and solvent resistance can be obtained.
• R21 , R22 , R23 , R24 , R25 and R26 are the same as the preferred groups for each of R1 , R2 , R3 , R4 , R5 and R6 . It is also preferred that one or more of the groups represented by R 21 to R 26 are reactive group-containing groups, since this allows for a cured product with excellent heat resistance to be obtained.
• the total number of preferred reactive groups in R 21 to R 26 is the same as the total number of preferred reactive groups in R 1 to R 6 .
• R 21 to R 26 it is preferable that any one or more of R 21 , R 22 , R 24 and R 25 are reactive group-containing groups, it is more preferable that any one or more of R 21 , R 22 and R 25 are reactive group-containing groups, and it is particularly preferable that any one or both of R 21 and R 22 are reactive group-containing groups.
• R 21 and R 22 are reactive group-containing groups
• R 24 and R 25 are reactive group-containing groups
• it is preferable that both R 24 and R 25 are reactive group-containing groups.
• both R 21 and R 22 are reactive group-containing groups. This is because a cured product having excellent heat resistance and solvent resistance can be obtained. This is also because it has excellent film-forming properties.
• R 21 to R 26 when neither R 21 nor R 22 is a reactive group-containing group, it is preferable that at least one of R 24 and R 25 is a reactive group-containing group from the viewpoint of heat resistance and solvent resistance. Groups at positions other than the above-mentioned positions preferred for reactive groups may or may not be reactive group-containing groups.
• preferred groups that are not reactive group-containing groups are the same as those described above for R 1 to R 6 .
• the above X is preferably a ring group having 2 to 20 ring carbon atoms. This is because compound I can form a compound with superior heat resistance and solvent resistance.
• the number of carbon atoms constituting the ring is preferably 3 to 18, more preferably 4 to 15, and even more preferably 6 to 16. This is because compound I can form a compound with superior heat resistance and solvent resistance.
• X is preferably a hydrocarbon-based aromatic ring group or an aromatic heterocyclic group, and more preferably a hydrocarbon-based aromatic ring group. This is because the above compounds provide excellent heat resistance and solvent resistance of the cured product.
• the ring in the ring group represented by X in formula (I) is preferably a fused ring which may be substituted. It is preferable that X has a fused ring which may be substituted or an amino group to which two reactive groups are bonded, in that the heat resistance of the cured product of compound I is particularly high, and it is particularly preferable that X has a fused ring which may be substituted.
• An example of an amino group to which two reactive groups are bonded is a dipropargylamino group.
• a fused ring consisting of 2 to 6 rings is preferable, and a fused ring consisting of 2 to 4 rings is particularly preferable.
• X examples include the following formulae (X1) to (X7):
• X is preferably a fused ring represented by any one of formulae (X1) to (X6) in terms of excellent heat resistance.
• R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 and R 40 is a bond
• one of R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 is a bond
• one of R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 and R 58 is a bond
• R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 and R 67 is a bond
• One of R 69 , R 70 , R 71 , R 72 , R 73 and R 74 is a bond
• one of R 75 , R 76 , R 77 , R 78 , R 79 and R 80 is a bond
• 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 the groups explained for R1 and the like, and these may be substituted with a reactive group, a halogen atom, a nitro group, or the like.
• R 31 to R 86 are not reactive group-containing groups or bonds, they are preferably hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 6 to 20 carbon atoms, methylene-substituted alkyl groups having 1 to 20 carbon atoms, or methylene-substituted aromatic ring groups having 6 to 20 carbon atoms, among which hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or methylene-substituted alkyl groups having 1 to 20 carbon atoms are preferred, and in particular hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or methylene-substituted alkyl groups having 1 to 5 carbon atoms are more preferred, and among which hydrogen atoms or alkyl groups having 1 to 2 carbon atoms are even more preferred.
• the number of substituents other than hydrogen atoms, bonds, and reactive group-containing groups is preferably 0 to 2, more preferably 0 to 1, and may be 0. This is because the compound I can form a compound having excellent heat resistance and solvent resistance, and is easy to synthesize and has excellent storage stability.
• the number of reactive groups in formula (X1) is preferably 1 to 8, more preferably 1 to 6, and particularly preferably 2 to 4. This is because compounds having a number of reactive groups within the above range are easy to synthesize, have excellent storage stability, and can give cured products with excellent heat resistance and solvent resistance.
• R 31 , R 32 , and R 37 to R 40 are reactive group-containing groups, and in particular, it is preferable that one or both of R 31 and R 32 are reactive group-containing groups, and it is particularly preferable that both of R 31 and R 32 are reactive group-containing groups. This is because a compound in which the position of the reactive group-containing group in formula (X1) is the above-mentioned position can give a cured product that has excellent solubility in solvents and excellent heat resistance.
• the compound has 1 to 6 reactive groups in formula (X2), more preferably 1 to 4, and particularly preferably 1 to 2. This is because compounds having a number of reactive groups within the above range are easy to synthesize, have excellent storage stability, and give cured products with excellent heat resistance.
• R 46 , R 47 or R 48 is a reactive group-containing group, and among these, it is preferable that R 46 is a reactive group-containing group, since a cured product having excellent solubility in solvents and excellent heat resistance can be obtained.
• R 54 is a bond because it is easy to synthesize, has excellent storage stability, and can give a cured product with excellent heat resistance.
• R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 and R 58 each independently may or may not be a reactive group-containing group.
• the number of reactive groups is preferably 1 to 3, and more preferably 1 to 2. This is because a cured product with excellent heat resistance and solvent resistance can be obtained.
• groups at positions other than the positions preferred for the reactive group-containing groups or bonds listed above may or may not be reactive group-containing groups.
• 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, and is particularly preferably at least one selected from a fluorene ring, a benzene ring, a naphthalene ring, and a pyrene ring in terms of heat resistance, and is particularly preferably at least one selected from a fluorene ring, a naphthalene ring, and a pyrene ring, and is particularly preferably a fluorene ring.
• the bonding position of the group represented by X in formula (I) is preferably para to the nitrogen atom in the pyridine ring, as this allows for easy synthesis and excellent storage stability.
• 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).
• compound III the compound represented by the above general formula (III) (hereinafter also referred to as “compound III”) will be described.
• Compound III can be used as a precursor of compound I.
• X', R 1 ', R 2 ', R 3 ', R 4 ', R 5 ', R 6 ', R 7 ', R 11 ', and a' are the same as X, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 11 , and a in compound I, and the above descriptions regarding X, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 11 , and a in compound I (hereinafter also referred to as "X to a”) all apply to X', R 1 ', R 2 ', R 3 ', R 4 ', R 5 ', R 6 ', R 7 ' , R 11 , and a, respectively, except for the preferred type or number of reactive groups.
• X' is preferably an aromatic ring group having 6 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, which may be substituted, and is preferably a fused ring group which may be substituted, or has a primary amino group, and is more preferably a fused ring group which may be substituted.
• Compound III will be further described below, but in the event of any difference between the above description of X to a and the description of X' to a' of Compound III below, the following description of X' to a' shall take precedence.
• Compound III differs from Compound I in that it is necessary to have at least one phenolic hydroxyl group.
• 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 monocyclic benzene ring.
• Preferred examples of compound III include the following general formulae (III ⁇ ) to (III ⁇ ).
• R 21 ', R 22 ', R 23 ', R 24 ', R 25 ' and R 26 ' each independently represent a hydrogen atom, a reactive group selected from the above ⁇ Group A>, a nitro group, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic ring group having 6 to 20 carbon atoms, an optionally substituted heterocyclic group having 2 to 20 carbon atoms, a group in which one or more methylene groups in the alkyl group having 1 to 20 carbon atoms are substituted with 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 atom
• phenolic hydroxyl group-containing group is a general term for phenolic hydroxyl groups and groups represented by the following (f').
• the term "phenolic hydroxyl group-containing group” described below can all be replaced with its subordinate concept, "phenolic hydroxyl group”.
• L f ' is an aromatic ring-containing group having 6 to 20 carbon atoms
• OHp is a phenolic hydroxyl group
• t ' is a number from 1 to 10.
• the aromatic ring-containing group having 6 to 20 carbon atoms is a group obtained by deleting t' hydrogen atoms from an arylalkyl group having 7 to 20 carbon atoms, an aromatic hydrocarbon ring-containing heterocyclic group having 8 to 20 carbon atoms, or a group obtained by deleting t' hydrogen atoms from an aryl group having 6 to 20 carbon atoms, preferably having 6 to 10 carbon atoms, and more 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 aromatic hydrocarbon ring-containing heterocyclic group having 8 to 20 carbon atoms include rings in which a benzene ring and a heterocycle are condensed, such as indole and carbazole.
• t' is preferably 1 to 8, more preferably 1 to 5, particularly preferably 1 to 3, and even more preferably 1 or 2, and may be 1.
• the reactive group of the compound III has a phenolic hydroxyl group, and may or may not have a reactive group other than the phenolic hydroxyl group.
• the reactive group may be an amino group. This is because the reactive group is a group represented by the above formula, which serves as a precursor for successfully producing compound I.
• the number of phenolic hydroxyl groups present in the molecule is 1 or more, and preferably 2 or more. Having the number of phenolic hydroxyl groups present in the molecule within the above range is advantageous in that it gives a cured product with excellent heat resistance and solvent resistance, including when used as a precursor.
• the number of phenolic hydroxyl groups present in the molecule is preferably 10 or less, in terms of ease of synthesis and good storage stability, and from this viewpoint, it is more preferably 8 or less, and even more preferably 6 or less.
• the groups represented by R 1' to R 6' in formula (III) are preferably a hydrogen atom, a phenolic hydroxyl group, or 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, each of which may have a phenolic hydroxyl group; among these, a hydrogen atom, a phenolic hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, an aromatic ring group having 6 to 10 carbon atoms, or a methylene-substituted alkyl group having 1 to 10 carbon atoms, each of which may have a phenolic hydroxyl group, is preferred; in particular, a hydrogen atom, a phenolic hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or
• At least one of R 3' , R 4' , R 5' , R 6' , R 23' , R 24' , R 25' and R 26' is preferably a phenolic hydroxyl group-containing group, and particularly preferably at least two of them are phenolic hydroxyl group-containing groups.
• at least one of R 3' , R 4' , R 5' and R 6' is a phenolic hydroxyl group-containing group
• at least one of R 23' , R 24' , R 25' and R 26' is a phenolic hydroxyl group-containing group.
• each of the phenolic hydroxyl groups is a phenolic hydroxyl group.
• R 4 ' , R 5 ' , R 24 ' , and R 25 ' are phenolic hydroxyl group-containing groups, and it is particularly preferred that these phenolic hydroxyl group-containing groups are phenolic hydroxyl groups.
• At least one of the groups represented by R 1' to R 6' is a phenolic hydroxyl group-containing group, since the groups represented by R 1' to R 6' are the above-mentioned groups, which is advantageous in that a cured product having excellent heat resistance and solvent resistance can be obtained, including when used as a precursor.
• the total number of phenolic hydroxyl groups is preferably 3 or less, more preferably 2 or less, and may be 1.
• the number of phenolic hydroxyl groups in R 1' to R 6' in formula (III) is within the above range, it is advantageous in that a cured product having excellent heat resistance and solvent resistance can be obtained, including when used as a precursor.
• R 4' and R 5' are phenolic hydroxyl group-containing groups, and it is particularly preferable that either one of R 4' and R 5' is a phenolic hydroxyl group-containing group. It is preferable that these phenolic hydroxyl group-containing groups are phenolic hydroxyl groups. This is because the position of the phenolic hydroxyl group in formula (III) is as described above, which is advantageous in terms of providing a cured product with excellent heat resistance and solvent resistance.
• preferred groups which are not phenolic hydroxyl group-containing groups include those listed above as preferred groups which are not reactive group-containing groups among the groups represented by R 1 to R 6 , and in particular, a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or an alkoxy group having 1 to 2 carbon atoms is preferred.
• R 21 ' , R 22 ' , R 23 ' , R 24 ' , R 25 ' and R 26 ' are the same as the preferred groups of R 1 ', R 2 ', R 3 ', R 4 ', R 5 ' and R 6 ', respectively, and the above explanations can be used. It is also preferred that one or more of the groups represented by R 21 ' to R 26 ' are phenolic hydroxyl group-containing groups. This is because it is advantageous in terms of giving a cured product having excellent heat resistance and solvent resistance, including when used as a precursor.
• the preferred total number of phenolic hydroxyl groups in R 21 ' to R 26 ' is the same as the preferred total number of phenolic hydroxyl groups in R 1 ' to R 6 ' .
• R 21 ' to R 26 ' in formula (III) have a phenolic hydroxyl group
• R 24 ' and R 25 ' are phenolic hydroxyl group-containing groups
• R 24 ' and R 25 ' is a phenolic hydroxyl group-containing group
• these phenolic hydroxyl group-containing groups are phenolic hydroxyl groups. This is because the position of the phenolic hydroxyl group in formula (III) is as described above, which makes synthesis easy and provides excellent storage stability.
• preferred groups which are not reactive group-containing groups are the same as those described above for R 1 ' to R 6 ' .
• X' may 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 providing a cured product having excellent heat resistance and solvent resistance, including when used as a precursor.
• X' may contain an amino group instead of a phenolic hydroxyl group, and when it has an amino group, it is preferable that the total number of active hydrogens of the amino group and phenolic hydroxyl groups is the same as the number of phenolic hydroxyl groups in X' (hereinafter, the numbers of phenolic hydroxyl groups described for X'1 to X'7 can be similarly replaced with the total number of active hydrogens of the amino group and phenolic hydroxyl groups).
• X' include groups represented by the following formulae (X'1) to (X'7).
• 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 having better heat resistance can be obtained, including when used as a precursor.
• R 31 ', R 32 ', R 33 ', R 34 ', R 35 ', R 36 ', R 37 ', R 38 ', R 39 ' and R 40 ' is a bond
• one of R 41 ', R 42 ', R 43 ', R 44 ', R 45 ', R 46 ', R 47 ' and R 48 ' is a bond
• one of R 49 ', R 50 ', R 51 ', R 52 ', R 53 ', R 54 ', R 55 ', R 56 ', R 57 ' and R 58 ' is a bond
• One of R 68 ', R 69 ', R 70 ', R 71 ', R 72 ', R 73 ' and R 74 ' is a bond, one of R 75 ' , R 76 ', R 77 ',
• 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 the groups explained for R1 , etc., and may be substituted with a phenolic hydroxyl group, a halogen atom, a nitro group, an amino group, etc.
• X' may or may not have a phenolic hydroxyl group.
• the groups corresponding to X'1 to X'7 in R 31 ' to R 86 ' it is preferable that any one or more are phenolic hydroxyl group-containing groups, and it is particularly preferable that they are phenolic hydroxyl groups.
• the groups represented by R 81 ' to R 86 ', which are the groups corresponding to X'7 it is preferable that any one or more are phenolic hydroxyl group-containing groups, and it is more preferable that they are phenolic hydroxyl groups.
• R 31 ' to R 86 ' corresponds to R 31 to R 86 described above, respectively.
• the groups represented by R 31 ' to R 86 ' as a preferred group which is not a phenolic hydroxyl group or a bond, the explanation of the preferred groups which are not a reactive group-containing group or a bond for the groups represented by R 31 to R 86 can be used as appropriate.
• the preferred number of substituents other than hydrogen atoms, bonds, phenolic hydroxyl group-containing groups, and amino groups is the same as the preferred number of substituents other than hydrogen atoms, bonds, and reactive group-containing groups in each ring of formulas (X1) to (X7).
• the explanation of the preferred positions of the bonds can be appropriately applied from the explanation of X1 to X7.
• the number of reactive groups for example 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.
• the groups at positions other than the phenolic hydroxyl group-containing groups and the positions preferred for bonds listed above may or may not be reactive group-containing groups.
• the compound I to be produced using the compound III as a precursor one having a propargyloxy group, an allyl ether group, or a glycidyl group as a reactive group is preferred.
• Compound III which has a phenolic hydroxyl group, includes the above compounds (168), (169), (171) to (173), as well as the following compounds (1) to (65). Such compounds III can also be used as intermediates for producing compounds I which have a reactive group such as a propargyloxy group.
• the compounds I and III can be produced according to known methods. Specifically, a compound having a diindenopyridine skeleton structure can be produced by condensing an indanone compound and an aldehyde compound using ammonium acetate. Furthermore, the compound I can be produced by introducing a reactive group into the skeleton structure. For example, when a compound having a hydroxyl group is used as an aldehyde compound or an indanone compound, compound III (compound I having a hydroxyl group as a reactive group) can be produced, and the hydroxyl group in the compound III can be further replaced with a reactive group other than a hydroxyl group using a halogen compound and a carbonate such as K2CO3 (for example, the following scheme 1).
• composition of the present invention is characterized by containing the above-mentioned compound I.
• a cured product having excellent heat resistance can be obtained.
• a composition containing 20 to 100% by mass of the compound I in the solid content is preferred because it produces a cured product with excellent heat resistance.
• the content in the solid content is more preferably 40 to 100% by mass, particularly preferably 50 to 100% by mass, and may be 60% by mass or more.
• the solid content here refers to the components of the composition excluding the solvent described below.
• the composition of the present invention may contain a crosslinking agent.
• a crosslinking agent refers to a compound that reacts with compound I to link multiple molecules through a chemical bond, is incorporated into the polymer after polymerization, and changes the physical and chemical properties. By containing a crosslinking agent, a cured product with better heat resistance can be obtained.
• crosslinking agents include phenol compounds, epoxy compounds, cyanate compounds, amine compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, and azide compounds.
• Phenol compounds include, for example, alkylphenols such as phenol, cresols, and xylenols; bisphenols such as bisphenol A, bisphenol F, bis(3-methyl-4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)-1-phenylethane; trisphenols such as ⁇ , ⁇ , ⁇ '-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene; phenol resins such as phenol novolac resin and phenol aralkyl resin; and resinous phenol derivatives such as linear trisphenols, methane-type trisphenols, linear tetrakisphenols, and radial hexanuclear compounds represented by the following general formula.
• alkylphenols such as phenol, cresols, and xylenols
• bisphenols such as bisphenol A, bisphenol F, bis(3-methyl-4-hydroxyphenyl)propane,
• R 13 represents an alkyl group having 1 to 4 carbon atoms
• n represents an integer of 0 to 2
• m represents an integer of 0 to 1.
• epoxy compounds include glycidyl ethers of the above-mentioned phenol compounds, tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, etc.
• Cyanate resins include, for example, compounds in which the hydroxyl groups of the phenol compounds are replaced with cyanate groups.
• Amine compounds include aromatic amines such as m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, and 1,3-bis(4-aminophenoxy)benzene; alicyclic amines such as diaminocyclohexane, diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo[2.2.1]heptane, and isophoronediamine; and aliphatic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine, and triethylenetetramine.
• aromatic amines such as m-phenylenediamine, p-phenylenediamine, 4,
• benzoxazine compounds examples include P-d type benzoxazines obtained from diamine compounds and monofunctional phenol compounds, and F-a type benzoxazines obtained from amine compounds and bifunctional phenol compounds.
• melamine compounds include hexamethylol melamine, hexamethoxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated or mixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated or mixtures thereof, etc.
• guanamine compounds include tetramethylol guanamine, tetramethoxymethyl guanamine, compounds in which one to four methylol groups of tetramethylol guanamine are methoxymethylated or mixtures thereof, tetramethoxyethyl guanamine, tetraacyloxyguanamine, compounds in which one to four methylol groups of tetramethylol guanamine are acyloxymethylated or mixtures thereof, etc.
• glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 methylol groups of tetramethylol glycoluril are methoxymethylated or mixtures thereof, and compounds in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated or mixtures thereof.
• urea compounds include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea in which one to four methylol groups are methoxymethylated or mixtures thereof, tetramethoxyethyl urea, etc.
• isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.
• azide compounds include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidene bisazide, and 4,4'-oxybisazide.
• Phenol compounds and glycoluril compounds are preferred as the crosslinking agent, as they produce a cured product with excellent heat resistance.
• the content of the crosslinking agent is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of compound I.
• the composition of the present invention may contain a solvent.
• the solvent is usually a solvent capable of dissolving or dispersing each of the above-mentioned components as necessary, for example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl
• ether ester solvents such as butyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate, etc.; BTX solvents such as benzene, toluene, xylene, etc.; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, etc.; terpene hydrocarbon oils such as turpentine oil, D-limonene, pinene, etc.; paraffin solvents such as mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (Exxon Chemical Co., Ltd.), etc.; Examples of such solvents include halogenated aliphatic hydrocarbon solvents such as carbon dioxide, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane
• ketones, ether ester solvents, and especially propylene glycol monomethyl ether acetate and cyclohexanone are preferred because they have good solubility for compound I and the crosslinking agent.
• 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, per 100 parts by mass of the composition.
• Polymerization initiators can be classified into photopolymerization initiators, which generate active species when irradiated with active energy rays, and thermal polymerization initiators, which generate active species when heated.
• Photopolymerization initiators include photoradical polymerization initiators, photoacid generators, and photobase generators
• thermal polymerization initiators include thermal radical polymerization initiators, thermal acid generators, and thermal base generators.
• the composition of the present invention may contain an acid generator as a polymerization initiator to promote the curing reaction of the crosslinking agent.
• the acid generator may be any compound capable of generating an acid under specified conditions, and examples of the acid generator include onium salts such as sulfonium salts, iodonium salts, and ammonium salts.
• acid generators include tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, triethylammonium nonafluorobutanesulfonate, pyridinium nonafluorobutanesulfonate, triethylammonium camphorsulfonate, pyridinium camphorsulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, tetramethylammonium p-toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, and (p-tert-butoxyphenyl)phenyl trifluoromethanesulfonate.
• Thermal acid generators that generate acid when heated are particularly preferred because of their good curing properties.
• the content of the acid generator is preferably 50 to 150 parts by mass, and more preferably 80 to 120 parts by mass, per 100 parts by mass of the crosslinking agent. If the content is within the above range, a composition with excellent curing properties is obtained.
• the composition of the present invention may contain a radical polymerization initiator as a polymerization initiator.
• a radical polymerization initiator either a photoradical polymerization initiator or a thermal radical polymerization initiator can be used.
• photoradical polymerization initiators include benzoins such as benzoin, benzoin methyl ether, benzoin propyl ether, and benzoin butyl ether; benzil ketals such as benzil dimethyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-benzyl-1-dimethylamino-1-(4'-morpholinobenzoyl)propane, 2-morpholyl-2-(4'-methylmercapto)benzoylpropane, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1-benzoylcyclohexane, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4'-isopropyl)benzoylpropane, N,N-di Aceto
• thermal radical polymerization initiators include peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 4,4-di(t-butylperoxy)butylvalerate, and dicumyl peroxide; azo compounds such as 2,2'-azobisisobutyronitrile; and tetramethylthiuranium disulfide.
• peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 4,4-di(t-butylperoxy)butylvalerate, and dicumyl peroxide
• azo compounds such as 2,2'-azobisisobutyronitrile
• tetramethylthiuranium disulfide t
• Photobase generators include carbamate compounds, ⁇ -aminoketone compounds, quaternary ammonium compounds, O-acyloxime compounds, aminocyclopropenone compounds, etc.
• carbamate compound examples include 1-(2-anthraquinonyl)ethyl 1-piperidinecarboxylate, 1-(2-anthraquinonyl)ethyl 1H-2-ethylimidazole-1-carboxylate, 9-anthrylmethyl 1-piperidinecarboxylate, 9-anthrylmethyl N,N-diethylcarbamate, 9-anthrylmethyl N-propylcarbamate, 9-anthrylmethyl N-cyclohexylcarbamate, 9-anthrylmethyl 1H-imidazole-1-carboxylate, 9-anthrylmethyl N,N-dioctylcarbamate, 9-anthrylmethyl 1-(4-hydroxypiperidine)carboxylate, 1-pyrenylmethyl 1-piperidinecarboxylate, bis[1-(2-anthraquinonyl)ethyl] 1,6-hexanediylbiscarbamate, and bis(9-anthrylmethyl
• Examples of the ⁇ -aminoketone compound include 1-phenyl-2-(4-morpholinobenzoyl)-2-dimethylaminobutane, 2-(4-methylthiobenzoyl)-2-morpholinopropane, and the like.
• Thermal base generators include carbamate derivatives such as 2-(4-biphenyl)-2-propyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate, urea derivatives such as urea and N,N,N'-trimethylurea, dihydropyridine derivatives such as 1,4-dihydronicotinamide, dicyandiamide, and salts of acids and bases such as organic salts and inorganic salts.
• carbamate derivatives such as 2-(4-biphenyl)-2-propyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate
• urea derivatives such as urea and N,N,N'-trimethylurea
• dihydropyridine derivatives such as 1,4-dihydronicotinamide, dicyandiamide
• salts of acids and bases such as organic salts and inorganic salts.
• the compounds and compositions of the present invention have excellent heat resistance and can be suitably used for electronic component applications such as semiconductor encapsulants, circuit boards, build-up films, build-up boards, semiconductor resists, semiconductor hard masks, and multilayer flexible films.
• electronic component applications such as semiconductor encapsulants, circuit boards, build-up films, build-up boards, semiconductor resists, semiconductor hard masks, and multilayer flexible films.
• electronic components include discrete devices (individual semiconductors) such as transistors and diodes, each of which has a single function; integrated circuits (ICs) that have multiple functional devices on a single chip; and CPUs such as memories, microprocessors (MPUs), and logic ICs.
• compositions of the present invention can be suitably used for a variety of applications, including, but not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, space and aviation-related parts, electronic and electrical parts, building materials, containers and packaging materials, daily necessities, sports and leisure goods, and housing materials for wind power generation.
• the composition of the present invention has excellent heat resistance and solvent resistance and is suitable as a material for electronic components, and as shown in the examples below in particular, has excellent embedding properties and flatness and is suitable as a film-forming material for semiconductors.
• Semiconductor film-forming materials are materials necessary for forming semiconductor films, and consist of semiconductor member-forming materials necessary for forming semiconductor members and semiconductor process member-forming materials necessary for forming semiconductor process members.
• the above-mentioned semiconductor component forming materials include materials suitable for each application.
• insulating film forming materials, barrier film forming materials, sealing material forming materials, gap fill material forming materials, etc. can be mentioned.
• the above-mentioned semiconductor process component forming materials include materials suitable for each application.
• materials for forming underlayer films materials for forming photoresists, materials for forming anti-reflective films, materials for forming intermediate films, etc.
• the semiconductor film is a film used in the manufacture of semiconductors. Specifically, it is a general term for a solid layer formed by applying a semiconductor film-forming material and then evaporating the solvent, or a hardened product formed by hardening the solid layer through a polymerization reaction or the like.
• the semiconductor film is made up of semiconductor materials and semiconductor process materials.
• Semiconductor materials refer to materials that remain on semiconductor devices as permanent films, while semiconductor process materials refer to materials that are used in the semiconductor manufacturing process as sacrificial films but do not remain on semiconductor devices.
• Examples of the semiconductor components include insulating films, barrier films, sealing materials, gap fill materials, etc.
• Examples of the semiconductor process members include photoresists, intermediate films, underlayer films, and anti-reflective films.
• Photoresists, intermediate films, and underlayer films are semiconductor processing components used for the purpose of obtaining good patterns, and can be used as multi-layer resists in which an underlayer film, an intermediate film, and a photoresist are laminated in that order on a substrate to be processed, such as a silicon wafer.
• the electronic component composition of the present invention includes those that are contained in the cured product of the present invention, as well as those that are used in the manufacturing process, such as as a sacrificial film, and then removed, and are not contained in the cured product.
• An example of the composition for electronic parts of the present invention is an underlayer film in a multi-layer resist material.
• a typical example of a multi-layer resist material is a three-layer resist method having two layers on the bottom of a photoresist layer.
• an underlayer film forming material is applied to a substrate to be processed such as a silicon wafer, and an underlayer film is formed by heating.
• a photoresist is applied, and a pattern is formed by exposure and development.
• the formed pattern as a mask the intermediate film and the underlayer film are etched in that order under appropriate dry etching conditions.
• the substrate to be processed is etched under appropriate dry etching conditions, and the remaining mask is ashed to obtain a substrate with the desired structure.
• the material for forming the underlayer film must be heat-resistant and solvent-resistant so that it will not deform due to heat or solvents when forming the intermediate film or photoresist layer, and must also be etch-resistant so that transfer by etching can be performed accurately. It must also be able to fill in the unevenness of the substrate and have flat properties so that the film can be formed evenly, making it particularly suitable for use with the composition of the present invention.
• the compound and composition of the present invention have excellent embedding properties in uneven substrates, they can also be used as gap fill materials (embedded planarizing films) that are filled into recesses formed in substrates, and can also be used to form insulating materials (embedded insulating films) that are filled into recesses formed in substrates, barrier materials, semiconductor resist materials other than the above-mentioned underlayer films, and insulating films for through-silicon vias.
• the cured product of the present invention is a cured product obtained by curing the above-mentioned composition.
• a thermoset product is preferred because the cured product has excellent heat resistance and solvent resistance.
• the method includes curing the composition.
• the composition can be cured by heating using a hot plate or other hot plate, or an atmospheric oven, an inert gas oven, a vacuum oven, a hot air circulation oven, or the like.
• 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. This is because, when the heating temperature is within the above range, a cured product having excellent heat resistance can be obtained.
• the curing time is not particularly limited, but from the viewpoint of improving productivity, it is preferably from 30 seconds to 60 minutes, and particularly preferably from 1 to 30 minutes.
• the present production method includes a step of removing the cured product after the step of curing the composition.
• the method includes a step of forming a layer of the composition of the present invention on a substrate, curing the layer to form a cured film, and then etching the cured film to pattern it.
• this step include the following.
• a layer of the composition of the present invention onto a surface of a substrate to be processed and then curing the layer to form an underlayer film; applying a layer of photoresist over the underlayer film; placing 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 partially removing the underlying film by transferring the pattern to the underlying film. By partially removing the underlying film, the corresponding portion of the substrate to be processed is exposed.
• An intermediate film may be formed between the underlayer film and the photoresist.
• a conventionally known layer such as a silicon-containing layer or a hard mask layer may be used.
• Well-known plasma etching may be used to remove the underlayer film by patterning.
• Example 1-1 In a reaction flask equipped with a reflux condenser, 5.0 g (34 mmol) of 6-hydroxy-1-indanone, 2.2 g (18 mmol) of 4-hydroxybenzaldehyde, 5.5 g (72 mmol) of ammonium acetate, and 25 g of ethanol were placed and refluxed with stirring. After 12 and a half hours, the mixture was returned to room temperature, 17 g of ion-exchanged water was added, and the precipitate was filtered. The mixture was washed with ethanol/ion-exchanged water, and the residue was dried under reduced pressure at 40° C. to obtain compound A1 as a pale yellow powder.
• Example 1-2 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 placed in a reaction flask equipped with a reflux condenser and refluxed with stirring. After six and a half hours, the mixture was returned to room temperature and the precipitate was filtered. The mixture was washed with ethanol/ion-exchanged water, and the residue was dried under reduced pressure at 40° C. to obtain compound A2 as a pale yellow powder.
• Example 1-3 7.6 g (58 mmol) of 1-indanone, 3.5 g (29 mmol) of 4-hydroxybenzaldehyde, 8.8 g (12 mmol) of ammonium acetate, and 50 g of ethanol were placed in a reaction flask equipped with a reflux condenser and refluxed with stirring. After 6 hours, the mixture was returned to room temperature and the precipitate was filtered. The precipitate was washed with ethanol/ion-exchanged water, and the filtered residue was dried under reduced pressure at 60° C. to obtain compound A3 as a yellow powder.
• Example 1-4 In a reaction flask equipped with a reflux condenser, 30.0 g (227 mmol) of 1-indanone, 15.7 g (114 mmol) of 2,4-dihydroxybenzaldehyde, 70.0 g (908 mmol) of ammonium acetate, and 197 g of ethanol were placed and refluxed with stirring. After 4.5 hours, the mixture was returned to room temperature and the precipitate was filtered. The precipitate was washed with ethanol/ion-exchanged water and toluene/DMF, and the filter cake was dried under reduced pressure at 60°C to obtain compound A4 as a pale pink powder.
• Step 1 In a reaction flask equipped with a reflux condenser, 19.8 g (103 mmol) of 5,6-dimethoxyindanone, 10.0 g (52 mmol) of 2-fluorenecarboxaldehyde, 15.9 g (206 mmol) of ammonium acetate, and 139 g of ethanol were placed and refluxed with stirring. After 3 hours, the mixture was returned to room temperature and the precipitate was filtered. The mixture was washed with ethanol/acetone and NMP, and the residue was dried under reduced pressure at 100° C. to obtain compound A5 as a yellow powder.
• Step 2 In a reaction flask equipped with a reflux condenser, 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 placed and stirred at 120° C. After 2 hours, the mixture was cooled, 20 g of ion-exchanged water was placed, neutralized with dilute hydrochloric acid, and the precipitate was filtered. The mixture was washed with methanol and DMF, and the residue was dried under reduced pressure at 100° C. to obtain compound A6 as a yellow powder.
• Step 1 In a reaction flask equipped with a reflux condenser, 8.1 g (61 mmol) of 1-indanone, 7.0 g (30 mmol) of 1-pyrenecarboxaldehyde, 9.8 g (127 mmol) of ammonium acetate, and 70 g of ethanol were placed and refluxed with stirring. After 7 hours, the mixture was returned to room temperature and the precipitate was filtered. The precipitate was washed with THF/acetone and dried under reduced pressure at 40°C to obtain compound A7 as a yellow powder.
• Step 2 2.8 g (6.1 mmol) of compound A7 and 20 g of DMF were placed in a reaction flask equipped with a reflux condenser, and stirred at room temperature under a nitrogen flow. 6.5 g (78 mmol) of 48% aqueous sodium hydroxide solution was added, and 9.3 g (79 mmol) of 3-bromo-1-propyne was then dropped and stirred at 60°C for 12 hours. 50 g of ion-exchanged water was placed in a beaker, and the reaction solution was added. Methanol was also added, and the precipitate was filtered.
• Step 1-7 (Step 1) 7.6 g (58 mmol) of 1-indanone, 6.0 g (31 mmol) of 2-fluorenecarboxaldehyde, 8.6 g (111 mmol) of ammonium acetate, and 60 g of ethanol were placed in a reaction flask equipped with a reflux condenser, and refluxed with stirring. After 8 hours, the mixture was returned to room temperature, and the precipitate was filtered. The mixture was washed with ion-exchanged water/ethanol, and then washed with DMF/acetone, and the residue was dried under reduced pressure at 40° C. to obtain compound A9 as a pale yellow powder.
• Step 2 In a reaction flask equipped with a reflux condenser, 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 were added and stirred at room temperature under a nitrogen flow. After adding 11.9 g (143 mmol) of 48% aqueous sodium hydroxide solution and 10 g of ion-exchanged water, 13.4 g (113 mmol) of 3-bromo-1-propyne was dropped and stirred at 70°C for 13 hours.
• Example 1-8> In a reaction flask equipped with a reflux condenser, 1.7 g (3.7 mmol) of compound A1 and 31 g of DMF were placed and stirred at room temperature under a nitrogen flow. After placing 7.9 g (94 mmol) of 48% aqueous sodium hydroxide solution, 10.6 g (89 mmol) of 3-bromo-1-propyne was added dropwise and stirred at 65°C for 17.5 hours. 50 g of ion-exchanged water was placed in a beaker, the reaction solution was added, and the precipitate was filtered.
• Example 1-9 In a reaction flask equipped with a reflux condenser, 3.1 g (8.0 mmol) of compound A2, 4.8 g (35 mmol) of potassium carbonate, and 44 g of DMF were placed and stirred at room temperature under a nitrogen flow. 3.7 g (31 mmol) of 3-bromo-1-propyne was added dropwise and stirred at 60°C for 7 hours. 196 g of ion-exchanged water was placed in a beaker, the reaction solution was added, and the precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 40°C to obtain compound A12 as a yellow powder.
• Example 1-10> In a reaction flask equipped with a reflux condenser, 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 were placed and stirred at room temperature under a nitrogen flow. After placing 12.0 g (144 mmol) of 48% aqueous sodium hydroxide solution and 5 g of ion-exchanged water, 7.3 g (61 mmol) of 3-bromo-1-propyne was dropped and stirred at 55°C for 6.5 hours.
• Example 1-11> In a reaction flask equipped with a reflux condenser, 1.0 g (2.9 mmol) of compound A3 and 8 g of DMF were placed and stirred at room temperature under a nitrogen flow. After placing 1.3 g (15 mmol) of 48% aqueous sodium hydroxide solution, 1.8 g (15 mmol) of 3-bromo-1-propyne was added dropwise and stirred for 3 hours. 62 g of ion-exchanged water was placed in a beaker, and the reaction solution was added. The precipitate was filtered and washed with ion-exchanged water/methanol, and the residue was dried under reduced pressure at 60°C to obtain compound A14 as a pale orange powder.
• Example 1-12 In a reaction flask equipped with a reflux condenser, 5.0 g (14 mmol) of compound A4 and 33 g of DMF were placed and stirred at room temperature under a nitrogen flow. After placing 7.2 g (87 mmol) of 48% aqueous sodium hydroxide solution, 10.3 g (87 mmol) of 3-bromo-1-propyne was added dropwise and stirred at 60 to 80°C for 4 hours. After removing the salt in the system by filtration, 160 g of ion-exchanged water was placed in a beaker and the reaction solution was added.
• Step 1-13> (Step 1) 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 placed in a reaction flask equipped with a reflux condenser and refluxed with stirring. After one hour, the mixture was returned to room temperature and the precipitate was filtered. The mixture was washed with acetone and then with THF, and the filter cake was dried under reduced pressure at 60°C to obtain compound A16 as a pale pink powder.
• Step 2 In a reaction flask equipped with a reflux condenser, 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 were added and stirred at room temperature under a nitrogen flow. After adding 8.9 g (107 mmol) of 48% aqueous sodium hydroxide solution and 4 g of ion-exchanged water, the temperature was raised to 70°C. 6.4 g (54 mmol) of 3-bromo-1-propyne was dropped and stirred at 85°C for 2 hours.
• Example 1-14> In a reaction flask equipped with a reflux condenser, 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 were added, and the mixture was stirred at room temperature under a nitrogen flow. After adding 8.2 g (98 mmol) of 48% aqueous sodium hydroxide solution and 3 g of ion-exchanged water, the mixture was heated to 50°C. 7.3 g (61 mmol) of 3-bromo-1-propyne was dropped, and the mixture was stirred at 60°C for 3 hours.
• Step 1 Compound A29 was obtained as a pale yellow powder by the same synthesis method as in Example 1-1, except that 6-hydroxy-1-indanone was changed to 5-hydroxy-1-indanone and 4-hydroxybenzaldehyde was changed to 3-hydroxybenzaldehyde.
• Step 2 In a reaction flask equipped with a reflux condenser, 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 were added and stirred at room temperature under nitrogen flow.
• Step 1 Compound A30 was obtained as a pale yellow powder in the same manner as in Example 1-1, except that 4-hydroxybenzaldehyde was changed to 3-hydroxybenzaldehyde.
• Step 2 In a reaction flask equipped with a reflux condenser, 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 were added and stirred at room temperature under nitrogen flow. 35.6 g (427 mmol) of 48% aqueous sodium hydroxide solution was added and then heated to 60°C. 21.7 g (183 mmol) of 3-bromo-1-propyne was added dropwise and stirred at 60°C for 2 hours. After cooling to 30°C and distilling off the solvent from the organic phase, 95 g of methanol was added and the precipitate was filtered.
• Step 1 Compound A31 was obtained as a pale yellow powder in the same manner as in Example 1-7, except that 1-indanone was changed to 5-hydroxy-1-indanone.
• Step 2 In a reaction flask equipped with a reflux condenser, 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 nitrogen flow. 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 dropped and stirred at 60°C for 5 hours.
• Step 1 Compound A32 was obtained as a pale yellow powder in the same manner as in Example 1-7, except that 1-indanone was changed to 6-hydroxy-1-indanone.
• Step 2 In a reaction flask equipped with a reflux condenser, 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 nitrogen flow. 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 dropped and stirred at 60°C for 3 hours.
• Step 1 Compound A33 was obtained as a pale yellow powder in the same manner as in Example 1-1, except that 4-hydroxybenzaldehyde was replaced with 3,4-dihydroxybenzaldehyde.
• Step 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 nitrogen flow.
• Step 1 Compound A34 was obtained as a pale yellow powder in the same manner as in Example 1-1, except that 4-hydroxybenzaldehyde was replaced with 2-hydroxy-1-naphthaldehyde.
• Step 2 In a reaction flask equipped with a reflux condenser, 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 were added and stirred at room temperature under nitrogen flow. 32.6 g (391 mmol) of 48% aqueous sodium hydroxide solution was added and then heated to 60°C. 17.1 g (143 mmol) of 3-bromo-1-propyne was added dropwise and stirred at 60°C for 5 hours. After cooling to 30°C and distilling off the solvent from the organic phase, 95 g of methanol was added and the precipitate was filtered.
• Step 1 Compound A35 was obtained as a pale yellow powder in the same manner as in Example 1-1, except that 4-hydroxybenzaldehyde was replaced with 4-acetamidobenzaldehyde.
• Step 2 In a reaction flask equipped with a reflux condenser, 60.0 g (143 mmol) of compound A35, 240 g of N-methyl-1-pyrrolidone, and 240 g of ethanol were placed and stirred at room temperature under a nitrogen flow. 179 g (2140 mmol) of 48% aqueous sodium hydroxide solution was added and then 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.
• Examples 2-1 to 2-25 and Comparative Examples 1 to 4 Each component was weighed out and mixed according to the composition (parts by mass) shown in Tables 1 to 4, and dissolved by stirring. After confirming that the solid was completely dissolved, the mixture was filtered through a fluororesin filter (pore size: 0.2 ⁇ m) to obtain a composition for evaluation.
• a fluororesin filter pore size: 0.2 ⁇ m
• the prepared composition for evaluation was applied to a silicon wafer substrate using a spin coater so that the film thickness after heating would be 200 nm.
• the substrate after application was heated on a hot plate set at 170° C. for 60 seconds, and then heated on a hot plate set at 300° C. for an additional 60 seconds to obtain a substrate for evaluation.
• various evaluations were carried out as follows. The evaluation results are summarized in Tables 1 to 4.
• the ratio of change in film thickness W1 after heating for 60 seconds on a hot plate set at 170°C to the film thickness W2 after another 60 seconds on a hot plate set at 300°C was less than 5%, and the film surface on the evaluation substrate was visually observed to be uniform without discoloration. If the ratio of change in film thickness was 5% or more and less than 10%, and the film surface on the evaluation substrate was visually observed to be uniform without discoloration, the film was rated A+. If the film surface was uniform but discolored, such as yellowing or blackening, the film was rated B.
• the film was rated C.
• the rate of change in film thickness is small, the surface is uniform, and there is no discoloration, the film-forming properties are deemed to be excellent.
• the film thickness was measured at five points on the evaluation substrate using a Semilab SE-2000 spectroscopic ellipsometer, and the average value was taken as the pre-test film thickness.
• 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, and was taken as the post-test film thickness Wa.
• the rate of change in film thickness before and after the test was rated as A if it was less than 3% compared to the film thickness Wb before the test, B if it was 3% or more but less than 5%, C if it was 5% or more but less than 10%, and D if it was 10% or more.
• the rate of change in film thickness was further suppressed in Examples 2-3, 2-5, 2-6, 2-7, 2-13, 2-14, 2-18, 2-19, and 2-22 compared to Example 2-4.
• the composition was applied to a SiO2 stepped substrate (500 nm wide, 100 nm high wall, 500 nm wide trench) using a spin coater. A film was produced by heating at 170°C for 60 seconds and at 300°C for 60 seconds. The spin coat conditions were adjusted so that the film thickness from the trench was 200 nm. Evaluation of embeddability: A slice of the substrate was prepared, and when observed with a SEM (S-4800, manufactured by Hitachi High-Technologies Corporation), those that were embedded in the step without any voids were rated A, and those that had voids were rated B.
• SEM S-4800, manufactured by Hitachi High-Technologies Corporation
• Flatness evaluation Flatness was evaluated from the difference (film thickness difference) between the thickest part of the film formed on the wall of the substrate and the thinnest part of the film formed on the trench.
• a film thickness difference of less than 10 nm was rated as A, 10 nm or more but less than 30 nm was rated as B, and 30 nm or more was rated as C.

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