Compound, nonionic photoacid generator, and resin composition for photolithography

Abstract

To provide a compound excellent in base resistance.SOLUTION: The compound of the present invention is represented by the following formula (1), where R1 and R4 may be the same or different and are each a hydroxy group, a C1-16 alkoxy group, or a C1-16 alkylthio group; R2, R3, R5 and R6 may be the same or different and are each a hydrogen atom, a hydroxy group, a C1-16 alkoxy group, or a C1-16 alkylthio group; and Rf is a C1-16 hydrocarbon group which may be substituted with a fluorine atom.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound, a photoacid generator, and a resin composition for photolithography. More specifically, the present invention relates to a compound having particularly excellent base resistance, a nonionic photoacid generator containing the compound, and a resin composition for photolithography containing the nonionic photoacid generator. [Background technology]

[0002] Patent Document 1 discloses a photoacid generator and a resin composition for photolithography. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-197146 A Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 does not disclose any specific compounds having particularly excellent base resistance, such as a decomposition rate D of 10% or less, as determined by the method for evaluating base resistance described in the document.

[0005] An object of the present invention is to provide a compound having high base resistance, a nonionic photoacid generator containing said compound, and a resin composition for photolithography containing said nonionic photoacid generator. [Means for solving the problem]

[0006] As a result of intensive research aimed at solving the above problems, the present inventors have found that a compound represented by the following general formula (1) has high base resistance. The present application has been completed based on this finding.

[0007] That is, the present invention provides a compound represented by the following general formula (1).

[0008] [ka]

[0009] [In formula (1), R 1 and R 4 may be the same or different and are a hydroxy group, an alkoxy group having 1 to 16 carbon atoms, or an alkylthio group having 1 to 16 carbon atoms; R 2 , R 3 , R 5 , and R 6 may be the same or different and are a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 16 carbon atoms, or an alkylthio group having 1 to 16 carbon atoms, and Rf is a hydrocarbon group having 1 to 16 carbon atoms which may be substituted with a fluorine atom.]

[0010] In general formula (1), R 1 and R 4 is preferably an alkoxy group having 1 to 16 carbon atoms.

[0011] In general formula (1), R 2 , R 3 , R 5 , and R 6 is preferably a hydrogen atom.

[0012] In general formula (1), Rf is preferably a hydrocarbon group having 1 to 16 carbon atoms and substituted with a fluorine atom.

[0013] The alkoxy group, the alkylthio group, and the hydrocarbon group preferably have 4 to 8 carbon atoms.

[0014] The present invention also provides a nonionic photoacid generator (A) containing the above compound.

[0015] The present invention also provides a resin composition for photolithography (Q) containing the nonionic photoacid generator (A). Effect of the Invention

[0016] The compound of the present invention has high base resistance. A compound with high base resistance has low reactivity with a quencher, which is a base. Therefore, when the compound of the present invention is contained in a composition together with a quencher, the composition is less likely to change over time due to storage. In addition, when the composition is exposed to light, the compound of the present invention acts as a non-ionic photoacid generator, and the base neutralizes the generated acid, thereby obtaining a photoresist pattern (wiring pattern) of a desired shape. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] <Compound> The present invention provides a compound represented by the following general formula (1) (hereinafter, also referred to as the compound of the present invention).

[0018] [ka]

[0019] [In formula (1), R 1 and R 4 may be the same or different and are a hydroxy group, an alkoxy group having 1 to 16 carbon atoms, or an alkylthio group having 1 to 16 carbon atoms; R 2 , R 3 , R 5 , and R 6 may be the same or different and are a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 16 carbon atoms, or an alkylthio group having 1 to 16 carbon atoms, and Rf is a hydrocarbon group having 1 to 16 carbon atoms which may be substituted with a fluorine atom.]

[0020] R 1 ~R 6In the above, the alkoxy group having 1 to 16 carbon atoms includes a linear or branched alkoxy group, an aryloxy group, an aryl-alkyloxy group, and a group in which two or more of these groups are bonded. The linear or branched alkoxy group includes a saturated alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a decyloxy group, and a dodecyloxy group, and an unsaturated alkoxy group such as an allyloxy group. The aryloxy group includes phenoxy and naphthyloxy. The aryl-alkyloxy group includes an alkoxy group having a hydrocarbon group to which an aryl group and an alkyl group are bonded, such as a tolyloxy group and a benzyloxy group. The group in which two or more groups are bonded includes a methoxymethoxy group, an ethoxymethoxy group, a 2-methoxyethoxy group, a 1-methoxyethoxy group, and a benzyloxymethoxy group. The alkoxy group having 1 to 16 carbon atoms may be a siloxy group having 1 to 16 carbon atoms, such as a trimethylsiloxy group, a triethylsiloxy group, a triisopropylsiloxy group, a tert-butyldimethylsiloxy group, and a tert-butyldiphenylsiloxy group. Among them, from the viewpoint of superior resistance to base, a linear or branched alkoxy group, an aryl-alkyloxy group, and a siloxy group having 1 to 16 carbon atoms are preferred, and more preferred are a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a benzyloxy group, and a tert-butyldimethylsiloxy group. The alkoxy group having 1 to 16 carbon atoms preferably has a carbon number of 3 to 10, and more preferably has a carbon number of 4 to 8. By keeping the carbon number within the above range, synthesis is easy and solvent solubility can be improved.

[0021] R 1 ~R 6In the above, the alkylthio group having 1 to 16 carbon atoms includes a linear or branched alkylthio group, an arylthio group, an aryl-alkylthio group, and a group in which two or more of these groups are bonded. The linear or branched alkylthio group includes saturated alkylthio groups such as a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, an isopentylthio group, a neopentylthio group, a tert-pentylthio group, an octylthio group, a decylthio group, and a dodecylthio group, and an unsaturated alkylthio group such as an allylthio group. The arylthio group includes a phenylthio group. The aryl-alkylthio group includes an alkylthio group having a hydrocarbon group to which an aryl group and an alkyl group are bonded, such as a tosylthio group and a benzylthio group. Among these, from the viewpoint of superior resistance to base, a straight-chain or branched alkylthio group is preferred, and more preferred are a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a benzylthio group, an octylthio group, and a dodecylthio group. The alkylthio group having 1 to 16 carbon atoms preferably has a carbon number of 3 to 10, and more preferably has a carbon number of 4 to 8. By keeping the carbon number within the above range, synthesis is easy and solvent solubility can be improved.

[0022] R 1 ~R 6 The number of carbon atoms in the alkoxy group, the alkylthio group, and the hydrocarbon group in each of the above formulas is preferably 3 to 10, and more preferably 4 to 8. When the number of carbon atoms is within the above range, synthesis is easy and solvent solubility can be improved.

[0023] In general formula (1), R 1 and R 4are the same or different and are preferably electron-donating groups having 1 to 16 carbon atoms, such as an alkoxy group having 1 to 16 carbon atoms or an alkylthio group having 1 to 16 carbon atoms, more preferably electron-donating groups having 3 to 10 carbon atoms, such as an alkoxy group having 3 to 10 carbon atoms or an alkylthio group having 3 to 10 carbon atoms, and even more preferably electron-donating groups having 4 to 8 carbon atoms, such as an alkoxy group having 4 to 8 carbon atoms or an alkylthio group having 4 to 8 carbon atoms. By having the number of carbon atoms within the above range, the base resistance is more excellent.

[0024] In addition, in the general formula (1), R 1 and R 4 are the same or different, and from the viewpoint of superior base resistance, are preferably alkoxy groups having 1 to 16 carbon atoms, more preferably alkoxy groups having 3 to 10 carbon atoms, and even more preferably alkoxy groups having 4 to 8 carbon atoms.

[0025] In general formula (1), R 2 , R 3 , R 5 , and R 6 In terms of exhibiting higher base resistance, it is preferable that each of the groups is a hydrogen atom.

[0026] Rf may be a hydrocarbon group having 1 to 16 carbon atoms that is not substituted with a fluorine atom, or a hydrocarbon group having 1 to 16 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. When Rf is a hydrocarbon group having 1 to 16 carbon atoms that is substituted with a fluorine atom, the number of fluorine atoms may be 1 to 34, 1 to 5, 3 to 5, etc.

[0027] Examples of the hydrocarbon group having 1 to 16 carbon atoms in the hydrocarbon group having 1 to 16 carbon atoms which may be substituted with a fluorine atom include linear, branched or cyclic alkyl groups having 1 to 16 carbon atoms, alkenyl groups having 2 to 16 carbon atoms, alkynyl groups having 2 to 16 carbon atoms, and aryl groups having 6 to 12 carbon atoms. The hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms. Having a carbon number within the above range facilitates synthesis and can improve solvent solubility.

[0028] Examples of the alkyl group having 1 to 16 carbon atoms include a linear alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 1 to 16 carbon atoms, and a cyclic alkyl group having 3 to 16 carbon atoms.

[0029] Examples of the linear alkyl group having 1 to 16 carbon atoms include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, a normal pentyl group, a normal hexyl group, a normal heptyl group, a normal octyl group, a normal nonyl group, a normal decyl group, a normal undecyl group, a normal dodecyl group, a normal tridecyl group, a normal tetradecyl group, a normal pentadecyl group, and a normal hexadecyl group.

[0030] Examples of the branched alkyl group having 1 to 16 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group (3-methylbutyl group), a tert-pentyl group, a neopentyl group, a 2,3-dimethylpropyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an isohexyl group (4-methylpentyl group), a 2-methylpentyl group, a 3-methylpentyl group, a hexyl group having a methyl group on the side chain such as a 2-methylhexyl group, a heptyl group having a methyl group on the side chain such as a 2-methylheptyl group, and a 2-methyloctyl group. Examples of the methyl group include an octyl group having a methyl group in the side chain, a nonyl group having a methyl group in the side chain, such as a 2-methylnonyl group, a decyl group having a methyl group in the side chain, such as a 2-methyldecyl group, an undecyl group having a methyl group in the side chain, such as a 2-methylundecyl group, a dodecyl group having a methyl group in the side chain, such as a 2-methyldodecyl group or a methylundecyl group, a tridecyl group having a methyl group in the side chain, such as a 2-methyltridecyl group, a tetradecyl group having a methyl group in the side chain, such as a 2-methyltetradecyl group, and a pentadecyl group having a methyl group in the side chain, such as a 2-methylpentadecyl group.

[0031] The cyclic alkyl group having 3 to 16 carbon atoms may be a monocyclic hydrocarbon group or a polycyclic (bridged ring) hydrocarbon group. As the monocyclic hydrocarbon group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic hydrocarbon group, a cycloalkyl group having 6 to 16 carbon atoms is preferable, and examples thereof include an adamantyl group and an isobornyl group.

[0032] Examples of the alkenyl group having 2 to 16 carbon atoms include linear, branched, or cyclic alkenyl groups such as ethenyl, 1-propenyl, 2-propenyl, 1-buten-1-yl, 2-buten-1-yl, 2-methyl-2-propenyl, 1-cyclopenten-1-yl, 1-cyclohexen-1-yl, 1-decen-1-yl, 1-dodecen-1-yl, and norbornenyl.

[0033] Examples of the alkynyl group having 2 to 16 carbon atoms include linear, branched, or cyclic alkynyl groups such as ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 1-butyn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 2-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 3-methyl-1-butyn-1-yl, 1-methyl-2-butyn-1-yl, 1-methyl-3-butyn-1-yl, 1,1-dimethyl-2-propyn-1-yl, 1-decyn-1-yl, and 1-cyclooctyn-1-yl.

[0034] Examples of the aryl group having 6 to 12 carbon atoms include aromatic hydrocarbon groups which may have an alkyl group, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-azulenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,4-xylyl group, a 2,6-xylyl group, a 3,5-xylyl group, and a 2,4,6-mesityl group.

[0035] Examples of the hydrocarbon group having 1 to 16 carbon atoms in which a hydrogen atom is substituted with a fluorine atom include a linear alkyl group (RF1), a branched alkyl group (RF2), a cyclic alkyl group (RF3), and an aryl group (RF4), in which a hydrogen atom is substituted with a fluorine atom.

[0036] Examples of the linear alkyl group (RF1) in which a hydrogen atom is substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, etc. The number of carbon atoms in RF1 is preferably 1 to 6, more preferably 1 to 4, and further preferably 1 to 3.

[0037] Examples of the branched alkyl group (RF2) in which a hydrogen atom is substituted with a fluorine atom include a hexafluoroisopropyl group, a nonafluoro-tert-butyl group, a perfluoro-2-ethylhexyl group, etc. The number of carbon atoms in RF2 is preferably 2 to 6, and more preferably 2 to 4.

[0038] Examples of the cyclic alkyl group (RF3) in which a hydrogen atom is substituted with a fluorine atom include a heptafluorocyclobutyl group, a nonafluorocyclopentyl group, a perfluorocyclohexyl group, a perfluoro(1-cyclohexyl)methyl group, etc. The number of carbon atoms in RF3 is 6 to 12, and preferably 6.

[0039] Examples of the aryl group (RF4) in which a hydrogen atom is substituted with a fluorine atom include a pentafluorophenyl group, a 3-trifluoromethyltetrafluorophenyl group, a 3,5-bistrifluoromethylphenyl group, etc. RF4 has 6 to 12 carbon atoms, and preferably 6 carbon atoms.

[0040] From the viewpoint of even better base resistance, Rf is preferably a hydrocarbon group substituted with a fluorine atom, more preferably the above-mentioned RF1, RF2, and RF4, still more preferably RF1 and RF4, still more preferably a trifluoromethyl group (CF3), a pentafluoroethyl group (C2F5), a heptafluoropropyl group (C3F7), a nonafluorobutyl group (C4F9), or a pentafluorophenyl group (C6F5), and particularly preferably a pentafluorophenyl group (C6F5).

[0041] The compound of the present invention has a decomposition rate D [%] of preferably 10% or less, more preferably 5% or less. The decomposition rate D can be calculated by calculating the integral ratio of fluorine atoms by fluorine-19 NMR or the like for the compound of the present invention and a mixture of the compound of the present invention and a base which are mixed and allowed to stand at room temperature for 24 hours, and then calculating the decomposition rate D according to the following formula. Decomposition rate D [%]: D = integral ratio of composition / (integral ratio of compound + integral ratio of composition) × 100

[0042] (Synthesis method) The compounds of the present invention can be produced, for example, by the reaction scheme shown below.

[0043] [ka]

[0044] In the above reaction scheme, R 1 ~R 6 and Rf is defined as in formula (1). In the first stage reaction, precursor (P1) is reacted with oxalyl chloride and aluminum chloride in an organic solvent (dichloromethane, etc.). The reaction temperature is -20 to 10°C, and the reaction time is 1 to 6 hours. After the reaction is completed, water is added, the separated oily matter is extracted with an organic solvent, and the volatile matter is distilled off to obtain precursor (P2). This precursor (P2) can be washed with an appropriate organic solvent as necessary, or purified by a recrystallization method.

[0045] In the second stage reaction, the precursor (P2) is reacted with a peroxide in an organic solvent (acetonitrile, methanol, ethanol, isopropanol, chloroform, etc.) under reflux for 6 to 48 hours. After the reaction is completed, the reaction liquid is poured into water, and the precipitated solid is filtered and washed with an appropriate organic solvent to obtain the precursor (P3).

[0046] The peroxide may be any peroxide commonly used in the Bayer-Villiger oxidation reaction, including known organic peroxides (peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, etc.) and inorganic peroxides (hydrogen peroxide, potassium peroxymonosulfate, potassium peroxymonosulfate-potassium hydrogen sulfate-potassium sulfate triple salt, etc.). If necessary, an acid (acetic acid, phosphoric acid, hydrochloric acid, etc.) or an alkali (sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, etc.) may be used in combination.

[0047] In the third reaction, precursor (P3) is mixed and stirred with an organic solvent (acetonitrile, dioxane, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), etc.) to obtain a mixture, which is then reacted with hydroxylamine. The reaction time is 10 minutes to 48 hours, and the reaction temperature is 0 to 50°C. After the reaction is completed, the reaction solution is neutralized with dilute acid. The precipitated solid is filtered, or the separated oil is extracted with an organic solvent, and the volatile matter is distilled off to obtain precursor (P4). This precursor (P4) can be washed with an appropriate organic solvent or purified by recrystallization as necessary.

[0048] In the fourth stage reaction, the precursor (P4), a base (imidazole, pyridine, dimethylaminopyridine, triethylamine, methylmorpholine, etc.), and a sulfonic acid halide represented by RfSO2X are mixed in an organic solvent (acetonitrile, chloroform, dichloromethane, DMF, ethyl acetate, etc.). The reaction temperature is -20 to 30°C, and the reaction time is 1 to 6 hours. After the reaction is completed, the mixture is neutralized with a dilute acid, and the precipitated solid is filtered or the separated oil is extracted with an organic solvent, and the volatile matter is distilled off to obtain the compound represented by general formula (1) as a solid. The obtained solid can be purified by washing with an appropriate organic solvent or recrystallization as necessary.

[0049] <Non-ionic photoacid generator (A)> The compound of the present invention can be used as a nonionic photoacid generator. The nonionic photoacid generator contains at least the compound of the present invention. The nonionic photoacid generator may hereinafter be referred to as the nonionic photoacid generator (A) of the present invention. The nonionic photoacid generator (A) of the present invention may be composed of the compound of the present invention, or may contain components other than the compound of the present invention. In addition, the nonionic photoacid generator (A) of the present invention may contain only one type of the compound of the present invention, or may contain two or more types. The compound of the present invention generates a super strong acid by irradiation with light, so the nonionic photoacid generator (A) containing the compound of the present invention generates a super strong acid by irradiation with light.

[0050] The nonionic photoacid generator (A) of the present invention may be dissolved in advance in a solvent that does not inhibit the reaction, in order to facilitate dissolution in the resin composition for photolithography (Q) described below.

[0051] Examples of the solvent include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.), esters (ethyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc.), ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.), and ether esters (glycol ether monoesters such as ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate (PGMEA)).

[0052] When a solvent is used, the proportion of the solvent used is preferably 15 to 1000 parts by mass, and more preferably 30 to 500 parts by mass, based on 100 parts by mass of the compound of the present invention.

[0053] <Resin composition for photolithography (Q)> The nonionic photoacid generator (A) of the present invention can be used in a resin composition for photolithography. The resin composition for photolithography contains at least the nonionic photoacid generator of the present invention. The resin composition for photolithography may hereinafter be referred to as the resin composition for photolithography (Q) of the present invention. The resin composition for photolithography (Q) of the present invention contains the nonionic photoacid generator (A) of the present invention, and may further contain a base such as a quencher. Since the resin composition for photolithography (Q) of the present invention contains the nonionic photoacid generator (A), the difference in solubility in a developer between an exposed portion and an unexposed portion is created by performing ultraviolet irradiation and post-exposure baking (PEB). The resin composition for photolithography (Q) of the present invention may contain only one type of the nonionic photoacid generator (A) of the present invention, or may contain two or more types.

[0054] The content of the photoacid generator (particularly, the nonionic photoacid generator (A) of the present invention) in the resin composition for photolithography (Q) of the present invention is, for example, 0.3 to 5.0 mass%, preferably 0.5 to 4.5 mass%, and more preferably 1.0 to 4.0 mass%, relative to the total solid content (100 mass%) of the composition.

[0055] Examples of the base include nitrogen atom-containing compounds such as ammonia, triethylamine, and diethylamine (e.g., aliphatic amines, non-aromatic heterocyclic amines, aromatic heterocyclic amines, etc.). The resin composition for photolithography (Q) of the present invention may contain only one type of base or two or more types of bases.

[0056] Examples of the photolithography resin composition (Q) of the present invention include a mixture of a negative-type chemically amplified resin (QN) and a nonionic photoacid generator (A) of the present invention, and a mixture of a positive-type chemically amplified resin (QP) and a nonionic photoacid generator (A) of the present invention.

[0057] The negative-type chemically amplified resin (QN) is composed of a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2).

[0058] The phenolic hydroxyl group-containing resin (QN1) may be a resin containing a phenolic hydroxyl group, such as novolac resin, polyhydroxystyrene, copolymer of hydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, copolymer of styrene and (meth)acrylic acid derivative, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, polyimide containing a phenolic hydroxyl group, polyamic acid containing a phenolic hydroxyl group, and phenol-dicyclopentadiene condensation resin. Among these, novolac resin, polyhydroxystyrene, copolymer of hydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, copolymer of styrene and (meth)acrylic acid derivative, and phenol-xylylene glycol condensation resin are preferred. Note that these phenolic hydroxyl group-containing resins (QN1) may be used alone or in combination of two or more.

[0059] The novolak resin can be obtained, for example, by condensing a phenol with an aldehyde in the presence of a catalyst.

[0060] Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, 1-naphthol, and 2-naphthol. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

[0061] Specific examples of the novolak resin include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, and phenol-naphthol / formaldehyde condensed novolak resin.

[0062] The phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low molecular weight compound as a part of its components.

[0063] Examples of the phenolic low molecular weight compound include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, and 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol. These low molecular weight phenolic compounds may be used alone or in combination of two or more.

[0064] The content of this phenolic low molecular weight compound in the phenolic hydroxyl group-containing resin (QN1) is preferably 40% by weight or less, and more preferably 1 to 30% by weight, when the phenolic hydroxyl group-containing resin (QN1) is taken as 100% by weight.

[0065] The weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2000 or more, more preferably 2000 to 20,000, from the viewpoints of the resolution, thermal shock resistance, thermal stability, film remaining rate, etc. of the resulting insulating film.

[0066] The content of the phenolic hydroxyl group-containing resin (QN1) in the negative-type chemically amplified resin (QN) is preferably 30 to 90 mass %, more preferably 40 to 80 mass %, when the entire composition excluding the solvent is taken as 100 mass %. When the content of the phenolic hydroxyl group-containing resin (QN1) is 30 to 90 mass %, it is preferable because the film formed using the photosensitive insulating resin composition has sufficient developability with an alkaline aqueous solution.

[0067] The crosslinking agent (QN2) may be a compound capable of crosslinking the phenolic hydroxyl group-containing resin (QN1) with the strong acid generated from the nonionic photoacid generator (A) of the present invention.

[0068] Examples of the crosslinking agent (QN2) include bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, poly(hydroxystyrene)-based epoxy compounds, oxetane compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing phenol compounds, carboxymethyl group-containing melamine resins, carboxymethyl group-containing benzoguanamine resins, carboxymethyl group-containing urea resins, carboxymethyl group-containing phenol resins, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, and carboxymethyl group-containing phenol compounds.

[0069] Of these crosslinking agents (QN2), methylol group-containing phenol compounds, methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compounds, methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and acetoxymethyl group-containing phenol compounds are preferred, and methoxymethyl group-containing melamine compounds (e.g., hexamethoxymethylmelamine), methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and the like are more preferred.

[0070] The content of the crosslinking agent (QN2) is usually 5 to 60 mol %, preferably 10 to 50 mol %, and more preferably 15 to 40 mol %, relative to the total acidic functional groups (100 mol %) in the phenolic hydroxyl group-containing resin (QN1), from the viewpoints of reducing the residual film rate, preventing pattern meandering and swelling, and developing properties.

[0071] The positive-type chemically amplified resin (QP) may be a protecting group-introduced resin (QP2) in which a part or all of the hydrogen atoms of the acidic functional group in an alkali-soluble resin (QP1) containing one or more acidic functional groups selected from the group consisting of phenolic hydroxyl groups, carboxyl groups, and sulfonyl groups, are substituted with an acid-dissociable group. The acid-dissociable group is a group that can dissociate in the presence of a strong acid generated from the nonionic photoacid generator (A) of the present invention. The protecting group-introduced resin (QP2) is itself insoluble or poorly soluble in alkali.

[0072] Examples of the alkali-soluble resin (QP1) include a phenolic hydroxyl group-containing resin (QP11), a carboxyl group-containing resin (QP12), and a sulfonic acid group-containing resin (QP13).

[0073] As the phenolic hydroxyl group-containing resin (QP11), those exemplified and explained as the hydroxyl group-containing resin (QN1) can be used.

[0074] The carboxy group-containing resin (QP12) includes a polymer having a carboxy group, and can be obtained, for example, by vinyl polymerization of a carboxy group-containing vinyl monomer (Ba) and, if necessary, a hydrophobic group-containing vinyl monomer (Bb).

[0075] Examples of the carboxyl group-containing vinyl monomer (Ba) include unsaturated monocarboxylic acids ((meth)acrylic acid, crotonic acid, cinnamic acid, etc.), unsaturated polyvalent (divalent to tetravalent) carboxylic acids (maleic anhydride ((anhydride)), itaconic acid, fumaric acid, citraconic acid, etc.), unsaturated polyvalent carboxylic acid alkyl esters (unsaturated polyvalent carboxylic acid alkyl esters having an alkyl group having 1 to 10 carbon atoms, such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, citraconic acid monoalkyl esters, etc.), and salts thereof (alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, amine salts, ammonium salts, etc.). Among these, from the viewpoints of polymerizability and ease of availability, unsaturated monocarboxylic acids are preferred, and (meth)acrylic acid is more preferred.

[0076] Examples of the hydrophobic group-containing vinyl monomer (Bb) include (meth)acrylic acid esters (Bb1) and aromatic hydrocarbon monomers (Bb2).

[0077] Examples of the (meth)acrylic acid ester (Bb1) include alkyl (meth)acrylates having an alkyl group having 1 to 20 carbon atoms (methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.), and alicyclic group-containing (meth)acrylates (dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, etc.).

[0078] Examples of the aromatic hydrocarbon monomer (Bb2) include hydrocarbon monomers having a styrene skeleton (styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, etc.) and vinylnaphthalene.

[0079] The molar ratio of monomers (Ba) / (Bb) charged in the carboxyl group-containing resin (QP12) is usually 10-100 / 0-90, and from the viewpoint of developability, is preferably 10-80 / 20-90, and more preferably 25-85 / 15-75.

[0080] As the sulfonic acid group-containing resin (QP13), a polymer having a sulfonic acid group can be used, and for example, it can be obtained by vinyl polymerization of a sulfonic acid group-containing vinyl monomer (Bc) and, if necessary, the hydrophobic group-containing vinyl monomer (Bb).

[0081] Examples of the sulfonic acid group-containing vinyl monomer (Bc) include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, 2-(meth)acryloylamide-2-methylpropane sulfonic acid, and salts thereof. Examples of the salts include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), primary to tertiary amine salts, ammonium salts, and quaternary ammonium salts.

[0082] The molar ratio of monomers (Bc) / (Bb) charged in the sulfonic acid group-containing resin (QP13) is usually 10-100 / 0-90, and from the viewpoint of developability, is preferably 10-80 / 20-90, and more preferably 25-85 / 15-75.

[0083] The HLB value of the alkali-soluble resin (QP1) preferably falls within different ranges depending on the resin skeleton of the alkali-soluble resin (QP1), but is preferably from 4 to 19, more preferably from 5 to 18, and particularly preferably from 6 to 17. If the HLB value is 4 or more, the developability is even better when development is carried out, and if it is 19 or less, the water resistance of the cured product is even better.

[0084] Note that the HLB value in this specification is the HLB value determined by the Oda method, which is the hydrophilic-hydrophobic balance value and can be calculated from the ratio of the organic value and the inorganic value of the organic compound. <Evaluation Method of HLB> HLB ≒ 10 × inorganic property / organic property

[0085] Also, the inorganic value and the organic value are described in detail on page 501 of the literature "Synthesis and Application of Surfactants" (published by Makino Shoten, written by Oda and Teramura); or on page 198 of "New Introduction to Surfactants" (written by Takehiko Fujimoto, published by Sanyo Chemical Industries, Ltd.).

[0086] Examples of the acid dissociable group in the protecting group-introduced resin (QP2) include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, a cyclic acid dissociable group, and the like. These may be used alone or in combination of two or more.

[0087] Examples of the substituted methyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a phenacyl group, a bromophenacyl group, a methoxyphenacyl group, a methylthiophenacyl group, an α-methylphenacyl group, a cyclopropylmethyl group, a benzyl group, a diphenylmethyl group, a triphenylmethyl group, a bromobenzyl group, a nitrobenzyl group, a methoxybenzyl group, a methylthiobenzyl group, an ethoxybenzyl group, an ethylthiobenzyl group, a piperonyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an i-propoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, and a tert-butoxycarbonylmethyl group.

[0088] Examples of the 1-substituted ethyl group include a 1-methoxyethyl group, a 1-methylthioethyl group, a 1,1-dimethoxyethyl group, a 1-ethoxyethyl group, a 1-ethylthioethyl group, a 1,1-diethoxyethyl group, a 1-ethoxypropyl group, a 1-propoxyethyl group, a 1-cyclohexyloxyethyl group, a 1-phenoxyethyl group, a 1-phenylthioethyl group, a 1,1-diphenoxyethyl group, a 1-benzyloxyethyl group, a 1-benzylthioethyl group, a 1-cyclopropylethyl group, a 1-phenylethyl group, a 1,1-diphenylethyl group, a 1-methoxycarbonylethyl group, a 1-ethoxycarbonylethyl group, a 1-n-propoxycarbonylethyl group, a 1-isopropoxycarbonylethyl group, a 1-n-butoxycarbonylethyl group, and a 1-tert-butoxycarbonylethyl group.

[0089] Examples of the 1-branched alkyl group include an isopropyl group, a sec-butyl group, a tert-butyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, and a 1,1-dimethylbutyl group.

[0090] Examples of the silyl group include tricarbylsilyl groups such as a trimethylsilyl group, an ethyldimethylsilyl group, a diethylmethylsilyl group, a triethylsilyl group, an isopropyldimethylsilyl group, a diisopropylmethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a di-tert-butylmethylsilyl group, a tri-tert-butylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

[0091] Examples of the germyl group include tricarbylgermyl groups such as a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an isopropyldimethylgermyl group, a methyldiisopropylgermyl group, a triisopropylgermyl group, a tert-butyldimethylgermyl group, a di-tert-butylmethylgermyl group, a tri-tert-butylgermyl group, a dimethylphenylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group.

[0092] Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tert-butoxycarbonyl group.

[0093] Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauroyl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group, a succinyl group, a glutaryl group, an adipoyl group, a piperoyl group, a suberoyl group, an azelaoyl group, a sebacoyl group, an acryloyl group, and a propioloyl group. , methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, campholoyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group, and mesyl group.

[0094] Examples of the cyclic acid-dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 3-bromotetrahydropyranyl group, a 4-methoxytetrahydropyranyl group, a 4-methoxytetrahydrothiopyranyl group, and a 3-tetrahydrothiophene-1,1-dioxide group.

[0095] Of these acid-dissociable groups, tert-butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, and tetrahydrothiofuranyl groups are preferred.

[0096] The introduction rate of the acid-dissociable group in the protecting group-introduced resin (QP2) {the ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in the protecting group-introduced resin (QP2)} cannot be generally defined depending on the type of acid-dissociable group and the alkali-soluble resin into which the group is introduced, but is preferably 10 to 100%, more preferably 15 to 100%.

[0097] The weight average molecular weight (hereinafter, referred to as "Mw") of the protecting group-introduced resin (QP2) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably from 1,000 to 150,000, and more preferably from 3,000 to 100,000.

[0098] The ratio (Mw / Mn) of the Mw of the protecting group-introduced resin (QP2) to the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC) is usually 1 to 10, and preferably 1 to 5.

[0099] The content of the nonionic photoacid generator (A) of the present invention based on the mass (100 mass%) of the solid content of the resin composition for photolithography (Q) of the present invention is preferably 0.001 to 20 mass%, more preferably 0.01 to 15 mass%, and particularly preferably 0.05 to 7 mass%. If it is 0.001 mass% or more, the sensitivity to ultraviolet light can be more excellent, and if it is 20 mass% or less, the physical properties of the part insoluble in an alkaline developer can be more excellent.

[0100] A resist using the resin composition for photolithography (Q) of the present invention can be formed, for example, by applying a resin solution dissolved in a predetermined organic solvent (dissolved and dispersed when inorganic fine particles are contained) to a substrate by a known method such as spin coating, curtain coating, roll coating, spray coating, or screen printing, and then drying the solvent by heating or blowing hot air.

[0101] Examples of organic solvents that dissolve the resin composition for photolithography (Q) of the present invention include those that can dissolve the resin composition and can adjust the physical properties (such as viscosity) of the resin solution so that it can be applied to spin coating, etc. For example, known solvents such as N-methylpyrrolidone, DMF, dimethyl sulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, acetone, and xylene can be used.

[0102] Among these solvents, from the viewpoint of drying temperature, etc., those having a boiling point of 200° C. or less (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, acetone, xylene) are preferred. The above solvents may be used alone or in combination of two or more.

[0103] When an organic solvent is used, the amount of the organic solvent is not particularly limited, but is usually preferably 30 to 1,000 parts by mass, more preferably 40 to 900 parts by mass, and particularly preferably 50 to 800 parts by mass, based on the mass (100 parts by mass) of the solid content of the resin composition for photolithography (Q) of the present invention.

[0104] The drying conditions for the resin solution after application vary depending on the solvent used, but are preferably carried out at 50 to 200°C for 2 to 30 minutes, and are appropriately determined based on the amount of residual solvent (mass%) in the resin composition for photolithography (Q) of the present invention after drying.

[0105] After forming a resist on a substrate, the resist is irradiated with light in the shape of a wiring pattern, followed by post-exposure baking (PEB) and alkaline development to form a wiring pattern.

[0106] The light irradiation method may be a method of exposing the resist to active light through a photomask having a wiring pattern. The active light used for the light irradiation may be one that decomposes the nonionic photoacid generator (A) of the present invention in the resin composition for photolithography (Q) of the present invention.

[0107] Examples of actinic rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halogen lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium cadmium lasers, etc.), etc. Among these, high-pressure mercury lamps and ultra-high-pressure mercury lamps are preferred.

[0108] The temperature of post-exposure bake (PEB) is usually 40 to 200°C, preferably 50 to 190°C, and more preferably 60 to 180°C. If it is 40°C or higher, the deprotection reaction or crosslinking reaction can be sufficiently carried out, and the difference in solubility between the UV-irradiated part and the UV-unirradiated part is large, making it easy to form a pattern, while if it is 200°C or lower, productivity is improved. The heating time is usually 0.5 to 120 minutes. If it is 0.5 minutes or more, the time and temperature can be easily controlled, and if it is 120 minutes or less, productivity is improved.

[0109] An example of the alkaline development method is a method of dissolving and removing the wiring pattern shape using an alkaline developer. As the alkaline developer, one that can cause a difference in solubility between the ultraviolet irradiated portion and the ultraviolet unirradiated portion of the photolithography resin composition (Q) of the present invention can be used. Examples of the alkaline developer include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, sodium bicarbonate, and an aqueous tetramethylammonium salt solution. A water-soluble organic solvent may be added to these alkaline developers. Examples of the water-soluble organic solvent include methanol, ethanol, isopropyl alcohol, THF, and N-methylpyrrolidone.

[0110] The developing method includes a dip method, a shower method, and a spray method using an alkaline developer, and the spray method is preferred. The temperature of the developer is preferably 25 to 40° C. The developing time is appropriately determined depending on the thickness of the resist. EXAMPLES

[0111] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, % means % by mass and parts means parts by mass.

[0112] <Production Example 1> <Synthesis of 2,5-dibutoxynaphthalene [precursor (P1-1)]> To 10 parts of 2,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 100 parts of acetonitrile, 43 parts of potassium carbonate, and 21 parts of 1-bromobutane were mixed, and then refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, and potassium carbonate was removed by filtration. Further, after concentrating the filtrate, methanol was added, the obtained solid was filtered, and dried under reduced pressure to obtain 15 parts of a precursor (P1-1) (2,5-dibutoxynaphthalene), which is a light brown solid.

[0113] <Production Example 2> <Synthesis of 2,5-dibutoxy-1,8-aceanthrenequinone [Precursor (P2-1)]> After mixing 230 parts of dichloromethane, 15 parts of aluminum chloride, and 8 parts of oxalyl dichloride, the mixture was cooled to -10°C. To this, 15 parts of 2,5-dibutoxynaphthalene, which is the precursor (P1-1) obtained in Production Example 1, was slowly added, and the reaction was carried out at -10°C for 2 hours. After completion of the reaction, water was added, the organic layer was washed 3 times with water, and the extract was concentrated to obtain a brown solid. This solid was washed with isopropanol and dried to obtain 10 parts of the compound of precursor (P2-1).

[0114] <Production Example 3> <Synthesis of 2,5-dibutoxy-1,8-naphthalic anhydride [Precursor (P3-1)]> To a methanol dispersion of 29 parts containing 1.8 parts of 2,5-dibutoxy-1,8-aceanthrenequinone, which is the precursor (P2-1) obtained in Production Example 2, 10 parts of potassium peroxymonosulfate (double salt) was added at once under a nitrogen atmosphere. This dispersion was refluxed for one day while stirring strongly. After completion of the reaction, the mixture was cooled to room temperature and poured into a large amount of water. The obtained solid was filtered and dried under reduced pressure to obtain 1.5 parts of precursor (P3-1).

[0115] <Production Example 4> <Synthesis of N-hydroxy-2,5-dibutoxy-1,8-naphthalimide [Precursor (P4-1)]> 1.1 parts of the precursor (P3-1) obtained in Production Example 3 was dispersed in 20 parts of acetonitrile, 2.0 parts of an aqueous hydroxylamine solution (Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) was added, and the mixture was stirred at 50° C. for one day to obtain a reaction liquid. This reaction liquid was poured into a dilute aqueous hydrochloric acid solution, and the precipitate was filtered off, washed with water, and dried to obtain 1.1 parts of a precursor (P4-1).

[0116] <Production Example 5> <Synthesis of 2,5-dibromo-6-butoxynaphthalene> 10 parts of 2,5-dibromo-6-naphthol (Tokyo Chemical Industry Co., Ltd.) was mixed with 100 parts of acetonitrile, 11 parts of potassium carbonate, and 6 parts of 1-bromobutane, and the mixture was refluxed for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the potassium carbonate was removed by filtration. Furthermore, the filtrate was concentrated, and then methanol was added thereto. The obtained solid was filtered and dried under reduced pressure to obtain 12 parts of 2,5-dibromo-6-butoxynaphthalene as a light brown solid.

[0117] <Production Example 6> <Synthesis of 2,5-dithiobutyl-6-butoxynaphthalene [precursor (P1-2)]> 2,5-Dibromo-6-butoxynaphthalene obtained in Production Example 5 was mixed with 100 parts of acetonitrile, 20 parts of potassium carbonate, and 10 parts of 1-butanethiol, and reacted for 4 hours at 75° C. After completion of the reaction, the mixture was cooled to room temperature, and the potassium carbonate was removed by filtration. Furthermore, the filtrate was concentrated, and then methanol was added thereto. The obtained solid was filtered and dried under reduced pressure to obtain 12 parts of a precursor (P1-2) as a light brown solid.

[0118] <Production Example 7> <Synthesis of 2,5-dithiobutyl-6-butoxynaphthalene-1,8-acenaphthenequinone [precursor (P2-2)]> 160 parts of dichloromethane, 11 parts of aluminum chloride, and 6 parts of oxalyl chloride were mixed and then cooled to -10°C. 14 parts of 2,5-dithio-butyl-6-butoxynaphthalene, which is the precursor (P1-2) obtained in Production Example 6, was slowly added thereto, and the mixture was reacted at -10°C for 2 hours. After completion of the reaction, water was added, the organic layer was washed three times with water, and the extract was concentrated to obtain a brown solid. This solid was washed with isopropanol and dried to obtain 10 parts of the compound of the precursor (P2-2).

[0119] <Production Example 8> <Synthesis of 2,5-dithio-butyl-6-butoxynaphthalene-1,8-naphthalic anhydride [precursor (P3-2)]> To a dispersion of 1.8 parts of 2,5-dithio-butyl-6-butoxynaphthalene-1,8-aceanthraquinone, which is the precursor (P2-2) obtained in Production Example 7, in 29 parts of methanol, 10 parts of potassium peroxymonosulfate (double salt) was added all at once under a nitrogen atmosphere to obtain a dispersion. This dispersion was refluxed for one day while being strongly stirred. After completion of the reaction, it was cooled to room temperature and poured into a large amount of water. The obtained solid was filtered and dried under reduced pressure to obtain 1.5 parts of the precursor (P3-2).

[0120] <Production Example 9> <Synthesis of N-hydroxy-2,5-dithio-butyl-6-butoxy-1,8-naphthalimide [precursor (P4-2)]> 1.1 parts of the precursor (P3-2) obtained in Production Example 8 was dispersed in 20 parts of acetonitrile, 2.0 parts of an aqueous hydroxylamine solution (manufactured by Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) was added, and the mixture was stirred at 50°C for one day to obtain a reaction solution. This reaction solution was poured into a dilute hydrochloric acid aqueous solution, the precipitate was filtered off, washed with water, and dried to obtain 1.1 parts of the precursor (P4-2).

[0121] <Example 1> <Synthesis of 2,5-dibutoxy-1,8-naphthalimide trifluoromethanesulfonate> 2.5 parts of the precursor (P4-1) synthesized in Production Example 4 was dispersed in 70 parts of dichloromethane, 1.0 parts of pyridine was added, and the mixture was cooled in an ice bath. 2.0 parts of trifluoromethanesulfonic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise to react. After stirring for 1 hour, the reaction solution was poured into ice-cooled dilute hydrochloric acid, washed three times with water, and the extract was concentrated to obtain a light brown solid. This solid was washed with isopropanol and dried to obtain 3.8 parts of the compound of Example 1.

[0122] <Example 2> <Synthesis of 2,5-dibutoxy-1,8-naphthalimide pentafluorobenzenesulfonate> The same procedure as in Example 1 was repeated to obtain 6.8 parts of the compound of Example 2, except that the amount of dichloromethane was changed from 70 parts to 47 parts, 2.0 parts of trifluoromethanesulfonic acid chloride was changed to 3.1 parts of pentafluorobenzenesulfonic acid chloride (manufactured by Aldrich), and the reaction time was changed to 3 hours.

[0123] <Example 3> <Synthesis of 2,5-dithiobutyl-6-butoxynaphthalimide trifluoromethanesulfonate> The same procedure as in Example 1 was repeated, except that the precursor (P4-1) synthesized in Production Example 4 was changed to the precursor (P4-2) synthesized in Production Example 9, to obtain 6.8 parts of the compound of Example 3.

[0124] <Example 4> <Synthesis of 2,5-dimethoxy-1,8-naphthalimide trifluoromethanesulfonate> The same procedures as in Production Examples 1 to 4 and Example 1 were carried out except that 21 parts of 1-bromobutane in Production Example 1 was changed to 15 parts of bromomethane, to obtain 6.8 parts of the compound of Example 4.

[0125] <Example 5> <Synthesis of 2,5-dioctyloxy-1,8-naphthalimide pentafluorobenzenesulfonate> The same procedures as in Preparations 1 to 4 and Example 1 were carried out, except that 21 parts of 1-bromobutane in Preparation 1 was replaced with 30 parts of 1-bromooctane, and 2.0 parts of trifluoromethanesulfonic acid chloride in Example 1 was replaced with 3.1 parts of pentafluorobenzenesulfonyl chloride (manufactured by Aldrich), to obtain 6.8 parts of the compound of Example 5.

[0126] 1 H-NMR and 19 The structures of the compounds of Examples 1 to 5 were identified as follows by F-NMR.

[0127] [ka]

[0128] Compounds of Examples 1 to 5 1 H-NMR data and 19 The F-NMR data is as follows: Example 1 · 1 H-NMR (400MHz, solvent deuterated chloroform): 8.54(2H,dd), 7.32(1H,d), 6.91(1H,d), 4.32(2H,t), 4.25(2H,t), 1.95(4H,m), 1.59(4H,m), 1.01(6H,m) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 2 · 1 H-NMR (400 MHz, solvent deuterated chloroform): 8.55 (1H, d), 8.46 (1H, d), 7.31 (1H, d), 6.89 (1H, d), 4.25 (4H, m), 1.90 (4H, m), 1.58 (4H, m), 1.00 (6H, m) · 19 F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Example 3 · 1H-NMR (400MHz, solvent deuterated chloroform): 7.84(1H,d), 7.57(1H,s), 7.47(1H,d), 4.21(2H,t), 2.89(4H,t), 1.60(4H,m), 1.44(4H,m), 0.92(9H,m) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 4 · 1 H-NMR (400 MHz, solvent deuterated chloroform): 8.10 (2H, m), 7.03 (1H, d), 6.22 (1H, d), 3.92 (3H, s), 3.79 (3H, s) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 5 · 1 H-NMR (400MHz, solvent deuterated chloroform): 8.57(1H,d), 8.49(1H,d), 7.32(1H,d), 6.89(1H,d), 4.28(4H,m), 1.91(4H,m), 1.55(4H,m), 1.30(16H,m), 0.89(6H,m) · 19 F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F)

[0129] <Comparative Example 1> 1,8-Naphthalimide trifluoromethanesulfonate (Aldrich) was used as received.

[0130] <Comparative Example 2> <Synthesis of 2,5-dimethyl-1,8-acenaphthenequinone [precursor (P2-3)]> 320 parts of dichloromethane, 22 parts of aluminum chloride, and 11 parts of oxalyl chloride were mixed and then cooled to -10°C. 15 parts of a precursor (P1-3) of 2,5-dimethylnaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added thereto, and the reaction was carried out at -10°C for 2 hours. After the reaction was completed, water was added, the organic layer was washed three times with water, and the extract was concentrated to obtain a brown solid. This solid was washed with isopropanol and dried to obtain 10 parts of a compound of precursor (P2-3).

[0131] <Synthesis of 2,5-dimethyl-1,8-naphthalic anhydride [precursor (P3-3)]> To a methanol dispersion of 1.6 parts of 2,5-dimethyl-1,8-acephenanthrenequinone (precursor P2-3) in 29 parts, 10 parts of potassium peroxymonosulfate (double salt) was added all at once under a nitrogen atmosphere. This dispersion was refluxed for one day while being strongly stirred. After the reaction was completed, it was cooled to room temperature and poured into a large amount of water. The obtained solid was filtered and dried under reduced pressure to obtain 1.3 parts of precursor (P3-3).

[0132] <Synthesis of N-hydroxy-2,5-dimethyl-1,8-naphthalimide [precursor (P4-3)]> 1.1 parts of precursor (P3-3) was dispersed in 20 parts of acetonitrile, 2.0 parts of an aqueous hydroxylamine solution (manufactured by Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) was added, and the mixture was stirred at 50°C for one day. The reaction solution was poured into a dilute hydrochloric acid aqueous solution, the precipitate was filtered off, washed with water, and dried to obtain 1.2 parts of precursor (P4-3).

[0133] <Synthesis of 2,5-dimethyl-1,8-naphthalimide trifluoromethanesulfonate> 2.5 parts of precursor (P4-3) was dispersed in 47 parts of dichloromethane, 1.0 part of pyridine was added, and then the mixture was cooled in an ice bath. 2.0 parts of trifluoromethanesulfonic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and reacted. After stirring for 1 hour, the reaction solution was poured into ice-cooled dilute hydrochloric acid, washed three times with water, and the extract was concentrated to obtain a light brown solid. This solid was washed with isopropanol and dried to obtain 3.7 parts of the compound of Comparative Example 2.

[0134] <Comparative Example 3> The compound of Comparative Example 3 (2,7-dithioxy-1,8-naphthalimide trifluoromethanesulfonate) was synthesized in the same manner as in the synthesis of the nonionic photoacid generator (A-2) of JP 2019-197146 A, except that trifluoromethanesulfonyl chloride was used instead of nonafluorobutanesulfonyl chloride.

[0135] <Comparative Example 4> The compound of Comparative Example 4 (2,7-dimethylthio-1,8-naphthalimide trifluoromethanesulfonate) was synthesized according to the method for synthesizing the nonionic photoacid generator (A-3) described in JP 2019-197146 A.

[0136] <Comparative Example 5> The compound of Comparative Example 5 (2,6-diisopropyl-1,8-naphthalimide trifluoromethanesulfonate) was synthesized according to the method for synthesizing the nonionic photoacid generator (A-8) described in JP 2019-197146 A.

[0137] 1 H-NMR and 19 The structures of the compounds of Comparative Examples 1 to 5 were identified as follows by F-NMR.

[0138] [ka]

[0139] Compounds of Comparative Examples 1 to 5 1 H-NMR data and 19 The F-NMR data is as follows: Comparative Example 1 · 1 H-NMR: δ7.85(2H,t), 8.32(2H,dd),8.69(2H,dd) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Comparative Example 2 · 1H-NMR (400 MHz, solvent deuterated chloroform): 8.26 (1H, d), 8.03 (1H, d), 7.26 (1H, d), 7.00 (1H, d), 2.62 (3H, s), 2.47 (3H, s) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Comparative Example 3 · 1 H-NMR (400 MHz, solvent deuterated chloroform): 8.04 (2H, d), 7.06 (2H, d), 3.92 (6H, s) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Comparative Example 4 · 1 H-NMR (400 MHz, solvent deuterated chloroform): 7.73 (2H, d), 7.50 (2H, d), 2.46 (6H, s) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Comparative Example 5 · 1 H-NMR (400 MHz, solvent deuterated chloroform): 8.56 (1H, s), 8.07 (1H, s), 7.84 (1H, d), 7.14 (1H, d), 2.88 (2H, m), 1.25 (12H, d) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F)

[0140] [evaluation] To evaluate the performance as a photoacid generator, the compounds of Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated for base resistance by the following method. The results are shown in Table 1.

[0141] <Method of evaluating base resistance> 2 parts of triethylamine were weighed into a capped screw tube, and 200 parts of deuterated chloroform were added and mixed. Then, 3 parts of the compound synthesized in each Example or Comparative Example was added and stirred quickly to obtain a uniform composition. After leaving this solution at room temperature for 24 hours, fluorine-19 NMR analysis was performed to calculate the decomposition rate D [%]. The decomposition rate D was calculated as follows. Decomposition rate D [%]: D = integral ratio of decomposition product / (integral ratio of photoacid generator + integral ratio of decomposition product) x 100

[0142] <Method for evaluating solvent solubility> 0.3 g of each compound of the Examples and Comparative Examples was placed in a test tube, and 0.2 to 0.5 g of propylene glycol monomethyl ether acetate (PGMEA) was added at 25° C. until the photoacid generator was completely dissolved. The solid concentration at the time of dissolution was determined as the solvent solubility.

[0143] [Table 1]

[0144] As is clear from Table 1, the compounds of Examples 1 to 5 had a decomposition rate D of 10% or less, and were found to have excellent base resistance. It was found that the compounds of Examples 1 to 5 had a significantly smaller decomposition rate D than not only Comparative Example 1 (one of the Comparative Examples in JP 2019-197146 A) but also Comparative Examples 2 to 5 (one of the Examples in JP 2019-197146 A or similar compounds).

[0145] In particular, R in the general formula (1) 2 , R 3 , R 5 , and R 6 The compounds of Examples 1, 2, 4, and 5 in which is a hydrogen atom had a decomposition rate D of 5% or less, and were found to have even better base resistance than Example 3.

[0146] The compound of the present invention, which has excellent base resistance, has low reactivity with bases such as quenchers, and therefore when contained in a composition together with a base, the composition undergoes little change over time.

[0147] As is apparent from Table 1, R 1 and R 4 In Examples 1 to 3 and 5, the number of carbon atoms in the electron donating group is 4 to 8, and R 1 and R 4 It was found that the compound had superior solubility in a solvent as compared with Example 4 in which the number of carbon atoms in the electron donating group was 1. [Industrial Applicability]

[0148] The compounds of the present invention are useful as semiconductor materials.

Claims

1. A compound represented by the following general formula (1): 【Chemistry 1】 [In formula (1), R １ and R ４ may be the same or different and are a hydroxy group, an alkoxy group having 1 to 16 carbon atoms, or an alkylthio group having 1 to 16 carbon atoms; R ２ , R ３ , R ５ , and R ６ may be the same or different and are a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 16 carbon atoms, or an alkylthio group having 1 to 16 carbon atoms, and Rf is a hydrocarbon group having 1 to 16 carbon atoms which may be substituted with a fluorine atom.

2. In general formula (1), R １ and R ４ The compound according to claim 1, wherein is an alkoxy group having 1 to 16 carbon atoms.

3. In general formula (1), R ２ , R ３ , R ５ , and R ６ The compound according to claim 1 , wherein is a hydrogen atom.

4. In general formula (1), R ２ , R ３ , R ５ , and R ６ The compound according to claim 2 , wherein is a hydrogen atom.

5. The compound according to claim 1, wherein in general formula (1), Rf is a hydrocarbon group having 1 to 16 carbon atoms substituted with a fluorine atom.

6. The compound according to claim 1, wherein the alkoxy group, the alkylthio group, and the hydrocarbon group each have 4 to 8 carbon atoms.

7. A non-ionic photoacid generator (A) comprising the compound according to any one of claims 1 to 6.

8. A resin composition for photolithography (Q), comprising the nonionic photoacid generator (A) according to claim 7.

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