Compound, nonionic photoacid generator, and resin composition for photolithography

Abstract

Provided is a compound excellent in base resistance.　The compound according to the present invention is represented by formula (1). In formula (1), R1 and R4 may be the same or different and are each a hydroxy group, a C1-30 alkoxy group, or a C1-30 alkylthio group; R2, R3, R5, and R6 may be the same or different and are each a hydrogen atom, a hydroxy group, a C1-30 alkoxy group or a C1-30 alkylthio group; and Rf is a C1-30 hydrocarbon group optionally substituted with a fluorine atom.

Description

Compounds, nonionic photoacid generators, and resin compositions for photolithography

[0001] The present invention relates to compounds, photoacid generators, and resin compositions for photolithography. More specifically, it relates to compounds with excellent basic resistance, nonionic photoacid generators containing said compounds, and resin compositions for photolithography containing said nonionic photoacid generators.

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

[0003] Japanese Patent Publication No. 2019-197146

[0004] Patent Document 1 does not disclose any specific compounds that exhibit particularly excellent base resistance, such as those with a degradation rate D of 10% or less, according to the base resistance evaluation method described in the document.

[0005] The object of the present invention is to provide a compound with high base resistance, a nonionic photoacid generator containing the compound, and a resin composition for photolithography containing the nonionic photoacid generator.

[0006] As a result of diligent research to solve the aforementioned problems, the inventors have found that compounds represented by the following general formula (1) have high base resistance. This application was completed based on this finding.

[0007] In other words, the present invention provides a compound represented by the following general formula (1).

[0008]

[0009] [In formula (1), R １ and R ４ R may be the same or different, and is a hydroxyl group, a carbon-1 to carbon-30 alkoxy group, or a carbon-1 to carbon-30 alkylthio group. ２ , R ３ , R ５ , and R ６may be the same or different and is a hydrogen atom, a hydroxy group, an alkoxy group having 1 to 30 carbon atoms, or an alkylthio group having 1 to 30 carbon atoms, and Rf is a hydrocarbon group having 1 to 30 carbon atoms which may be substituted with a fluorine atom.]

[0010] In general formula (1), R １ and R ４ are preferably alkoxy groups having 1 to 30 carbon atoms.

[0011] In general formula (1), R ２ , R ３ , R ５ , and R ６ are preferably hydrogen atoms.

[0012] In general formula (1), Rf is preferably a hydrocarbon group having 1 to 30 carbon atoms substituted with a fluorine atom.

[0013] It is preferable that the alkoxy group, the alkylthio group, and the hydrocarbon group have 4 to 30 carbon atoms.

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

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

[0016] The compound of the present invention has high base resistance. A compound having 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, there are few changes over time due to the storage of the composition. Further, when the composition is exposed, the compound of the present invention acts as a nonionic photoacid generator, and further the base neutralizes the generated acid, and a photoresist pattern (wiring pattern) of a desired shape can be obtained.

[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]

[0019] [In formula (1), R １and R ４ R may be the same or different, and is a hydroxyl group, a carbon-1 to carbon-30 alkoxy group, or a carbon-1 to carbon-30 alkylthio group. ２ , R ３ , R ５ , and R ６ Rf may be the same or different hydrogen atom, hydroxyl group, C1-C30 alkoxy group, or C1-C30 alkylthio group, and Rf may be a C1-C30 hydrocarbon group substituted with a fluorine atom.

[0020] R １ ~R ６The alkoxy groups having 1 to 30 carbon atoms include linear or branched alkoxy groups, aryloxy groups, aryl-alkyloxy groups, and groups in which two or more of these are bonded. Examples of linear or branched alkoxy groups include saturated alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, decyloxy, and dodecyloxy groups, as well as unsaturated alkoxy groups such as allyloxy groups. Examples of aryloxy groups include phenoxy and naphthyloxy. Examples of aryl-alkyloxy groups include alkoxy groups having a hydrocarbon group to which an aryl group and an alkyl group are bonded, such as tolyloxy and benzyloxy. Examples of groups in which two or more are bonded include methoxymethoxy, ethoxymethoxy, 2-methoxyethoxy, 1-methoxyethoxy, and benzyloxymethoxy. Furthermore, the alkoxy group having 1 to 30 carbon atoms may also be a siloxy group having 1 to 30 carbon atoms, for example, trimethylsiloxy group, triethylsiloxy group, triisopropylsiloxy group, tert-butyldimethylsiloxy group, tert-butyldiphenylsiloxy, etc. Among these, from the viewpoint of superior base resistance, linear or branched alkoxy groups, aryl-alkyloxy groups, and siloxy groups having 1 to 30 carbon atoms are preferred, and more preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, benzyloxy, and tert-butyldimethylsiloxy group. The alkoxy group having 1 to 30 carbon atoms preferably has 3 to 24 or 4 to 30 carbon atoms, and more preferably 4 to 18 carbon atoms. Being within the range of carbon atoms allows for easy synthesis and improved solvent solubility.

[0021] R １ ~R ６The alkylthio group having 1 to 30 carbon atoms in the above includes linear or branched alkylthio groups, arylthio groups, aryl-alkylthio groups, and groups in which two or more of these are bonded. The linear or branched alkylthio groups include saturated alkylthio groups such as methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, isopentylthio group, neopentylthio group, tert-pentylthio group, octylthio group, decylthio group, and dodecylthio group, as well as unsaturated alkylthio groups such as allylthio group. The arylthio group includes phenylthio group. The aryl-alkylthio group includes alkylthio groups having a hydrocarbon group to which an aryl group and an alkyl group are bonded, such as tosylthio group and benzylthio group. In particular, linear or branched alkylthio groups are preferred from the viewpoint of superior base resistance, and more preferably methylthio groups, ethylthio groups, propylthio groups, isopropylthio groups, butylthio groups, benzylthio groups, octylthio groups, and dodecylthio groups. The alkylthio groups having 1 to 30 carbon atoms are preferably 3 to 24 or 4 to 30 carbon atoms, and more preferably 4 to 18 carbon atoms. Being within the range of carbon atoms allows for easy synthesis and improved solvent solubility.

[0022] R １ ~R ６ The carbon number of the alkoxy group, alkylthio group, and hydrocarbon group in the compound is preferably 3 to 24 or 4 to 30, and more preferably 4 to 18. Being within this range of carbon numbers facilitates synthesis and can improve solvent solubility.

[0023] In general formula (1), R １ and R ４Preferably, the carbon atoms are the same or different electron-donating groups having 1 to 30 carbon atoms, such as alkoxy groups having 1 to 30 carbon atoms or alkylthio groups having 1 to 30 carbon atoms. More preferably, from the viewpoint of even better solvent solubility, the carbon atoms are electron-donating groups having 3 to 24 or 4 to 30 carbon atoms, such as alkoxy groups having 3 to 24 or 4 to 30 carbon atoms or alkylthio groups having 3 to 20 or 4 to 30 carbon atoms, and even more preferably, the carbon atoms are electron-donating groups having 4 to 18 carbon atoms, such as alkoxy groups having 4 to 18 carbon atoms or alkylthio groups having 4 to 18 carbon atoms. Being within the aforementioned range of carbon atoms provides superior basic resistance.

[0024] Also, in general formula (1), R １ and R ４ From the viewpoint of having superior base resistance, the alkoxy group is preferably one with 1 to 30 carbon atoms, more preferably one with 3 to 24 carbon atoms, and even more preferably one with 4 to 18 carbon atoms.

[0025] In general formula (1), R ２ , R ３ , R ５ , and R ６ Since these exhibit higher resistance to bases, it is preferable that they are all hydrogen atoms.

[0026] Rf may be a hydrocarbon group having 1 to 30 carbon atoms that is not substituted with fluorine atoms, or it may be a hydrocarbon group having 1 to 30 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. If Rf is a hydrocarbon group having 1 to 30 carbon atoms that is substituted with fluorine atoms, the number of fluorine atoms may be 1 to 62, 1 to 34, 1 to 5, 3 to 5, etc.

[0027] Examples of C1-C30 hydrocarbon groups that may be substituted with fluorine atoms include linear, branched, or cyclic alkyl groups having 1-30 carbon atoms, alkenyl groups having 2-30 carbon atoms, alkynyl groups having 2-30 carbon atoms, and aryl groups having 6-12 carbon atoms. The hydrocarbon group preferably has 1-10 carbon atoms, and more preferably 1-6 carbon atoms. Being within this range of carbon atoms facilitates synthesis and can improve solvent solubility.

[0028] Examples of the C1-C30 alkyl group include linear alkyl groups having C1-C30, branched alkyl groups having C1-C30, and cyclic alkyl groups having C3-C30.

[0029] Examples of the linear alkyl groups having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, and the like.

[0030] The branched alkyl groups having 1 to 30 carbon atoms include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group (3-methylbutyl group), tert-pentyl group, neopentyl group, 2,3-dimethylpropyl group, 1-ethylpropyl group, 2-methylbutyl group, isohexyl group (4-methylpentyl group), 2-methylpentyl group, 3-methylpentyl group, 2-methylhexyl group, and other hexyl groups having methyl groups in their side chains, heptyl groups having methyl groups in their side chains, such as 2-methylheptyl group, and 2-methyloctyl group. Examples include octyl groups having a methyl group in their side chain, nonyl groups having a methyl group in their side chain, such as 2-methylnonyl group, decyl groups having a methyl group in their side chain, such as 2-methyldecyl group, undecyl groups having a methyl group in their side chain, such as 2-methylundecyl group, dodecyl groups having a methyl group in their side chain, such as 2-methyldodecyl group and methylundecyl group, tridecyl groups having a methyl group in their side chain, such as 2-methyltridecyl group, tetradecyl groups having a methyl group in their side chain, such as 2-methyltetradecyl group, and pentadecyl groups having a methyl group in their side chain, such as 2-methylpentadecyl group.

[0031] The cyclic alkyl group having 3 to 30 carbon atoms may be a monocyclic hydrocarbon group or a polycyclic (bridged ring) hydrocarbon group. A cycloalkyl group having 3 to 8 carbon atoms is preferred as the monocyclic hydrocarbon group, such as a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, or cyclooctyl group. A cycloalkyl group having 6 to 16 carbon atoms is preferred as the polycyclic hydrocarbon group, such as an adamantyl group or isobornyl group.

[0032] Examples of the C2-C30 alkenyl group 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, norbornenyl, etc.

[0033] Examples of the alkynyl groups having 2 to 30 carbon atoms include linear, branched, or cyclic alkynyl groups such as ethynyl, 1-propyne-1-yl, 2-propyne-1-yl, 1-butyne-1-yl, 2-butyne-1-yl, 3-butyne-1-yl, 1-pentin-1-yl, 2-pentin-1-yl, 3-pentin-1-yl, 4-pentin-1-yl, 3-methyl-1-butyne-1-yl, 1-methyl-2-butyne-1-yl, 1-methyl-3-butyne-1-yl, 1,1-dimethyl-2-propyne-1-yl, 1-decyne-1-yl, and 1-cyclooctin-1-yl.

[0034] Examples of the aryl group having 6 to 12 carbon atoms include aromatic hydrocarbon groups which may have alkyl groups such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-azlenyl 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 hydrocarbon groups having 1 to 30 carbon atoms in which the hydrogen atoms are substituted with fluorine atoms include linear alkyl groups (RF1), branched alkyl groups (RF2), cyclic alkyl groups (RF3), and aryl groups (RF4), in which the hydrogen atoms are substituted with fluorine atoms.

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

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

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

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

[0040] As for Rf, from the viewpoint of having even better base resistance, a hydrocarbon group substituted with a fluorine atom is preferred, more preferably RF1, RF2, and RF4, and more preferably a trifluoromethyl group (CF ３ ), pentafluoroethyl group (C ２ F ５ ), heptafluoropropyl group (C ３ F ７), nonafluorobutyl group (C ４ F ９ ), pentafluorophenyl group (C ６ F ５ ) is even more preferred, and a pentafluorophenyl group (C ６ F ５ ) is particularly preferable.

[0041] The compound of the present invention preferably has a decomposition rate D [%] of 10% or less, and more preferably 5% or less. The degree of decomposition D can be calculated by determining the integral ratio of fluorine atoms in the compound of the present invention and a mixture of the compound of the present invention and a base, which has been mixed and left to stand at room temperature for 24 hours, using fluorine-19 NMR or the like, and using 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 shown below.

[0043]

[0044] In the above reaction equation, R １ ~R ６ And Rf are the same as defined in formula (1). In the first reaction stage, the precursor (P1) is reacted with oxalyl chloride and aluminum chloride in an organic solvent (such as dichloromethane). The reaction temperature is -20 to 10°C, and the reaction time is 1 to 6 hours. After the reaction is complete, water is added, the separated oily substance is extracted with an organic solvent, and the volatile components are removed by distillation to obtain the precursor (P2). This precursor (P2) can be purified by washing with a suitable organic solvent or by recrystallization as needed.

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

[0046] As the peroxide, those commonly used in the Bayer-Villiger oxidation reaction can be used, including known organic peroxides (peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, etc.) and inorganic peroxides (hydrogen peroxide, potassium peroxymonosulfate, potassium peroxymonosulfate / potassium sulfate / potassium sulfate triple salt, etc.). Acids (acetic acid, phosphoric acid, hydrochloric acid, etc.) or alkalis (sodium hydroxide, sodium bicarbonate, potassium carbonate, etc.) can also be used in combination as needed.

[0047] In the third reaction stage, the 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 complete, the reaction solution is neutralized with dilute acid. The precipitated solid is filtered, or the separated oily substance is extracted with an organic solvent, and then the volatile components are removed by distillation to obtain the precursor (P4). This precursor (P4) can be purified by washing with a suitable organic solvent or by recrystallization as needed.

[0048] In the fourth reaction step, a precursor (P4), a base (imidazole, pyridine, dimethylaminopyridine, triethylamine, methylmorpholine, etc.), and RfSO4 are used. ２ A sulfonic acid halide represented by X is 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 complete, the mixture is neutralized with a dilute acid, and the precipitated solid is filtered, or the separated oily substance is extracted with an organic solvent, and the volatile components are removed by distillation to obtain the compound represented by general formula (1) as a solid. The obtained solid can be purified by washing with a suitable organic solvent or by recrystallization as needed.

[0049] <Nonionic 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 hereafter be referred to as the nonionic photoacid generator (A) of the present invention. The nonionic photoacid generator (A) of the present invention may consist of the compound of the present invention, or it may contain components other than the compound of the present invention. Furthermore, the nonionic photoacid generator (A) of the present invention may contain only one compound of the present invention, or it may contain two or more compounds. Since the compound of the present invention generates a superacid upon light irradiation, the nonionic photoacid generator (A) containing the compound of the present invention generates a superacid upon light irradiation.

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

[0051] Examples of the aforementioned solvents 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 (ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, glycol ether monoesters such as propylene glycol monomethyl ether acetate (PGMEA), etc.).

[0052] When using a solvent, the solvent is preferably used in an amount of 15 to 1000 parts by mass, and more preferably 30 to 500 parts by mass, per 100 parts by mass of the compound of the present invention.

[0053] <Photolithography Resin Composition (Q)> The nonionic photoacid generator (A) of the present invention can be used in a photolithography resin composition. The photolithography resin composition contains at least the nonionic photoacid generator of the present invention. The photolithography resin composition may hereafter be referred to as the photolithography resin composition (Q) of the present invention. The photolithography resin composition (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. Because the photolithography resin composition (Q) of the present invention contains the nonionic photoacid generator (A), by performing ultraviolet irradiation and post-exposure heating (PEB), a difference in solubility in the developer occurs between the exposed and unexposed areas. The photolithography resin composition (Q) of the present invention may contain only one type of the nonionic photoacid generator (A) of the present invention, or it may contain two or more types.

[0054] The content ratio of the photoacid generator (particularly the nonionic photoacid generator (A) of the present invention) in the photolithography resin composition (Q) of the present invention is, for example, 0.3 to 5.0% by mass, preferably 0.5 to 4.5% by mass, and more preferably 1.0 to 4.0% by mass, based on the total solid content (100% by 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 photolithography resin composition (Q) of the present invention may contain only one of the bases or two or more of the bases.

[0056] The photolithography resin composition (Q) of the present invention preferably comprises the nonionic photoacid generator (A) of the present invention and a photosensitive resin such as a negative-type chemical amplification resin (QN) or a positive-type chemical amplification resin (QP). Examples of the photolithography resin composition (Q) of the present invention include a mixture of a negative-type chemical amplification resin (QN) and the nonionic photoacid generator (A) of the present invention, and a mixture of a positive-type chemical amplification resin (QP) and the 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] As the phenolic hydroxyl group-containing resin (QN1), any resin containing phenolic hydroxyl groups can be used. For example, novolac resin, polyhydroxystyrene, copolymer of hydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, styrene and (meth)acrylic acid derivatives, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, polyimide containing phenolic hydroxyl groups, polyamic acid containing phenolic hydroxyl groups, and phenol-dicyclopentadiene condensation resin can be used. Among these, novolac resin, polyhydroxystyrene, copolymer of hydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, styrene and (meth)acrylic acid derivatives, and phenol-xylylene glycol condensation resin are preferred. Note that one or more of these phenolic hydroxyl group-containing resins (QN1) may be used.

[0059] The novolac resin can be obtained, for example, by condensing phenols and aldehydes 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 novolac resins include phenol / formaldehyde condensation novolac resins, cresol / formaldehyde condensation novolac resins, and phenol-naphthol / formaldehyde condensation novolac resins.

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

[0063] Examples of the aforementioned phenolic low molecular weight compounds 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 phenolic low molecular weight compounds may be used individually 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 considered to be 100% by weight.

[0065] The weight-average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2000 or more, and more preferably 2000 to 20000, from the viewpoint of resolution, thermal shock resistance, thermal stability, and residual film rate of the resulting insulating film.

[0066] Furthermore, the content of the phenolic hydroxyl group-containing resin (QN1) in the negative-type chemical amplification resin (QN) is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass, when the total composition excluding the solvent is considered to be 100% by mass. When the content of the phenolic hydroxyl group-containing resin (QN1) is 30 to 90% by mass, it is preferable because the film formed using the photosensitive insulating resin composition has sufficient developability with an alkaline aqueous solution.

[0067] Examples of the crosslinking agent (QN2) include compounds that can crosslink the phenolic hydroxyl group-containing resin (QN1) with a strong acid generated from the nonionic photoacid generator (A) of the present invention.

[0068] Examples of the crosslinking agent (QN2) include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resol resin epoxy compounds, poly(hydroxystyrene) 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] Among these crosslinking agents (QN2), methylol group-containing phenol compounds, methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compounds, methoxymethyl group-containing glycoluryl 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 glycoluryl compounds, methoxymethyl group-containing urea compounds, etc., are even more preferred.

[0070] The content of the crosslinking agent (QN2) is typically 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 viewpoint of reducing the residual film rate, preventing pattern meandering and swelling, and improving developability.

[0071] The positive-type chemical amplification resin (QP) includes a protecting group-introduced resin (QP2) in which some or all of the hydrogen atoms of an acidic functional group in an alkali-soluble resin (QP1) containing one or more acidic functional groups such as phenolic hydroxyl groups, carboxyl groups, and sulfonyl groups are replaced with acid-dissociable groups. The acid-dissociable group is a group that can be dissociated 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 alkali-insoluble or alkali-slightly soluble in itself.

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

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

[0074] The carboxyl group-containing resin (QP12) can be a polymer having a carboxyl group, and can be obtained, for example, by vinyl polymerization of a carboxyl 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 (2-4 valent) carboxylic acids ((anhydride) maleic acid, itaconic acid, fumaric acid, citraconic acid, etc.), unsaturated polyvalent alkyl esters (unsaturated polyvalent alkyl esters having C1-C10 alkyl groups, such as maleic acid monoalkyl ester, fumaric acid monoalkyl ester, citraconic acid monoalkyl ester, 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.). Of these, unsaturated monocarboxylic acids are preferred from the viewpoint of polymerizability and availability, and (meth)acrylic acid is more preferred.

[0076] Examples of the hydrophobic group-containing vinyl monomer (Bb) include (meth)acrylic acid ester (Bb1) and aromatic hydrocarbon monomer (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, sidiclopentenyl (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] In the carboxyl group-containing resin (QP12), the molar ratio of (Ba) / (Bb) charged monomers is usually 10 to 100 / 0 to 90, and from the viewpoint of developability, 10 to 80 / 20 to 90 is preferred, and 25 to 85 / 15 to 75 is more preferred.

[0080] As the sulfonic acid group-containing resin (QP13), a polymer having a sulfonic acid group can be used, 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 salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), primary to tertiary amine salts, ammonium salts, and quaternary ammonium salts.

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

[0083] The preferred HLB value of the alkali-soluble resin (QP1) varies depending on the resin skeleton of the alkali-soluble resin (QP1), but is preferably 4 to 19, more preferably 5 to 18, and particularly preferably 6 to 17. If the HLB value is 4 or higher, the developability is even better during development, and if it is 19 or lower, the water resistance of the cured product is even better.

[0084] In this specification, the HLB value is the HLB value obtained by the Oda method, and represents the hydrophilic-hydrophobic balance value, which can be calculated from the ratio of the organic value to the inorganic value of an organic compound. <Method for evaluating HLB> HLB ≈ 10 × inorganic / organic

[0085] Furthermore, the inorganic and organic values ​​are described in detail on page 501 of the book "Synthesis and Applications of Surfactants" (published by Maki Shoten, authored by Oda and Teramura), or on page 198 of "New Introduction to Surfactants" (authored by Fujimoto Takehiko, published by Sanyo Chemical Industries, Ltd.).

[0086] Examples of acid-dissociable groups in the protecting group-introduced resin (QP2) include substituted methyl groups, 1-substituted ethyl groups, 1-branched alkyl groups, silyl groups, gelmyl groups, alkoxycarbonyl groups, acyl groups, and cyclic acid-dissociable groups. One of these may be used, or two or more may be used.

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

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

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

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

[0091] Examples of the aforementioned gelmyl group include trimethylgelmyl group, ethyldimethylgelmyl group, methyldiethylgelmyl group, triethylgelmyl group, isopropyldimethylgelmyl group, methyldiisopropylgelmyl group, triisopropylgelmyl group, tert-butyldimethylgelmyl group, di-tert-butylmethylgelmyl group, tri-tert-butylgelmyl group, dimethylphenylgelmyl group, methyldiphenylgelmyl group, triphenylgelmyl group, and other tricarboxylgelmyl groups.

[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 aforementioned acyl groups include acetyl group, propionyl group, butyryl group, heptanol group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azerayl group, sebacoyl group, acryloyl group, and propioloyl group. Examples include methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canholoyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, froyl group, tenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group, and mesyl group.

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

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

[0096] The rate of introduction of acid-dissociable groups 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 defined in general terms depending on the type of acid-dissociable group and the alkali-soluble resin into which the group is introduced, but it is preferably 10 to 100%, and more preferably 15 to 100%.

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

[0098] Furthermore, the ratio (Mw / Mn) 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% by mass) of the solid content of the photolithography resin composition (Q) of the present invention, is preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, and particularly preferably 0.05 to 7% by mass. If the content is 0.001% by mass or more, the sensitivity to ultraviolet light can be exhibited even better, and if it is 20% by mass or less, the physical properties of the portion insoluble in alkaline developer can be exhibited even better.

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

[0101] Organic solvents for dissolving the photolithography resin composition (Q) of the present invention include those that can dissolve the resin composition and adjust the resin solution to have physical properties (viscosity, etc.) suitable for application 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] Of these solvents, those with a boiling point of 200°C or lower (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, acetone, xylene) are preferred from the viewpoint of drying temperature, etc. One of the above solvents may be used, or two or more may be used.

[0103] When using an organic solvent, the amount of organic solvent is not particularly limited, but based on the mass of the solid content (100 parts by mass) of the photolithography resin composition (Q) of the present invention, it 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.

[0104] The drying conditions for the resin solution after coating 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 by the amount of residual solvent (mass%) in the photolithography resin composition (Q) of the present invention after drying.

[0105] After forming a resist on the substrate, light irradiation is performed in the shape of the wiring pattern. Subsequently, post-exposure heating (PEB) is performed, followed by alkaline development to form the wiring pattern.

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

[0107] Examples of active light sources 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, and lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium-cadmium lasers, etc.). Of these, high-pressure mercury lamps and ultra-high-pressure mercury lamps are preferred.

[0108] The temperature for post-exposure heating (PEB) is typically 40 to 200°C, preferably 50 to 190°C, and more preferably 60 to 180°C. A temperature of 40°C or higher allows for sufficient deprotection or crosslinking reactions, and the large difference in solubility between the UV-irradiated and un-UV-irradiated areas facilitates pattern formation. A temperature of 200°C or lower improves productivity. The heating time is typically 0.5 to 120 minutes. A heating time of 0.5 minutes or more allows for easy control of time and temperature, while a heating time of 120 minutes or less improves productivity.

[0109] One method of alkaline development is to dissolve and remove the wiring pattern shape using an alkaline developer. As the alkaline developer, one can be used that causes a difference in solubility between the UV-irradiated and un-UV-irradiated areas of the photolithography resin composition (Q) of the present invention. Examples of the alkaline developer include aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, sodium bicarbonate, and 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] Development methods include the dip method, shower method, and spray method using an alkaline developer, with the spray method being preferred. The developer temperature is preferably 25 to 40°C. The development time is appropriately determined according to the thickness of the resist.

[0111] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, % refers to mass%, and parts refers to parts by mass.

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

[0113] <Production Example 2> <Synthesis of 2,5-dibutoxy-1,8-acenaphthenequinone [precursor (P2-1)]> 230 parts of dichloromethane, 15 parts of aluminum chloride, and 8 parts of oxalyl dichloride were mixed and cooled to -10°C. 15 parts of 2,5-dibutoxynaphthalene, the precursor (P1-1) obtained in Production Example 1, were slowly added and reacted at -10°C for 2 hours. After the reaction was complete, 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 precursor (P2-1) compound.

[0114] <Production Example 3> <Synthesis of 2,5-dibutoxy-1,8-naphthalic anhydride [precursor (P3-1)]> To a dispersion of 1.8 parts of 2,5-dibutoxy-1,8-acenaphthenequinone, the precursor (P2-1) obtained in Production Example 2, in 29 parts methanol, 10 parts of potassium peroxymonosulfate (double salt) were added all at once under a nitrogen atmosphere. This dispersion was refluxed for one day with vigorous stirring. After the reaction was complete, it was cooled to room temperature and added to a large amount of water. The resulting 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 precursor (P3-1) obtained in Production Example 3 were dispersed in 20 parts of acetonitrile, and 2.0 parts of hydroxylamine aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) were added and the mixture was stirred at 50°C for one day to obtain a reaction solution. This reaction solution was added to a dilute hydrochloric acid aqueous solution, the precipitate was filtered off, washed with water, and dried to obtain 1.1 parts of precursor (P4-1).

[0116] <Production Example 5> <Synthesis of 2,5-dibromo-6-butoxynaphthalene> 10 parts of 2,5-dibromo-6-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) were 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 complete, the mixture was cooled to room temperature and potassium carbonate was removed by filtration. The filtrate was further concentrated, methanol was added, and the resulting solid was filtered and dried under reduced pressure to obtain 12 parts of 2,5-dibromo-6-butoxynaphthalene, 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 acetonitrile, 20 parts potassium carbonate, and 10 parts 1-butanethiol, and reacted at 75°C for 4 hours. After the reaction was complete, it was cooled to room temperature and potassium carbonate was removed by filtration. The filtrate was further concentrated, methanol was added, the resulting solid was filtered, and dried under reduced pressure to obtain 12 parts of precursor (P1-2), which was 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 cooled to -10°C. 14 parts of 2,5-dithiobutyl-6-butoxynaphthalene, the precursor (P1-2) obtained in Production Example 6, were slowly added and reacted at -10°C for 2 hours. After the reaction was complete, 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 precursor (P2-2) compound.

[0119] <Production Example 8> <Synthesis of 2,5-dithiobutyl-6-butoxynaphthalene-1,8-naphthalic anhydride [precursor (P3-2)]> 1.8 parts of 2,5-dithiobutyl-6-butoxynaphthalene-1,8-acenaphthenequinone, the precursor (P2-2) obtained in Production Example 7, was mixed with 29 parts methanol to obtain a dispersion. Under a nitrogen atmosphere, 10 parts of potassium peroxymonosulfate (double salt) was added all at once to obtain a dispersion. This dispersion was refluxed for one day with vigorous stirring. After the reaction was complete, it was cooled to room temperature and added to a large amount of water. The resulting solid was filtered and dried under reduced pressure to obtain 1.5 parts of precursor (P3-2).

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

[0121] <Example 1> <Synthesis of 2,5-dibutoxy-1,8-naphthalimidetrifluoromethanesulfonate> 2.5 parts of the precursor (P4-1) synthesized in Production Example 4 were dispersed in 70 parts of dichloromethane, 1.0 part of pyridine was added, and the mixture was cooled in an ice bath. 2.0 parts of trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise and the mixture was reacted. After stirring for 1 hour, the reaction mixture was placed in 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> Except that the amount of dichloromethane was changed from 70 parts to 47 parts, 2.0 parts of trifluoromethanesulfonate chloride was changed to 3.1 parts of pentafluorobenzenesulfonic acid chloride (manufactured by Aldrich), and the reaction time was changed to 3 hours, 6.8 parts of the compound of Example 2 was obtained in the same manner as in Example 1.

[0123] <Example 3> <Synthesis of 2,5-dithiobutyl-6-butoxynaphthalimide trifluoromethanesulfonate> 6.8 parts of the compound of Example 3 were obtained in the same manner as in Example 1, except that the precursor (P4-1) synthesized in Production Example 4 was replaced with the precursor (P4-2) synthesized in Production Example 9.

[0124] <Example 4> <Synthesis of 2,5-dimethoxy-1,8-naphthalimidetrifluoromethanesulfonate> 6.8 parts of the compound of Example 4 were obtained in the same manner as in Production Examples 1 to 4 and Example 1, except that 21 parts of 1-bromobutane in Production Example 1 were replaced with 15 parts of bromomethane.

[0125] <Example 5> <Synthesis of 2,5-dioctyloxy-1,8-naphthalimide pentafluorobenzenesulfonate> 6.8 parts of the compound of Example 5 were obtained in the same manner as in Production Examples 1 to 4 and Example 1, except that 21 parts of 1-bromobutane in Production Example 1 were replaced with 30 parts of 1-bromooctane, and 2.0 parts of trifluoromethanesulfonate chloride in Example 1 were replaced with 3.1 parts of pentafluorobenzenesulfone chloride (manufactured by Aldrich).

[0126] <Example 6> <Synthesis of 2,5-didodecyloxy-1,8-naphthalimidetrifluoromethanesulfonate> 3.5 parts of the compound of Example 6 were obtained in the same manner as in Production Examples 1 to 4 and Example 1, except that 21 parts of 1-bromobutane in Production Example 1 were replaced with 40 parts of 1-bromododecane, and 2.2 parts of pyridine and 4.3 parts of trifluoromethanesulfonate in Example 1.

[0127] <Example 7> <Synthesis of 2,5-dioctadecyloxy-1,8-naphthalimidetrifluoromethanesulfonate> 3.3 parts of the compound of Example 7 were obtained in the same manner as in Production Examples 1 to 4 and Example 1, except that 21 parts of 1-bromobutane in Production Example 1 were replaced with 60 parts of 1-bromooctadecane.

[0128] <Example 8> <Synthesis of 2,5-Ditriacontyloxy-1,8-Naphthalimide Trifluoromethanesulfonate> 3.0 parts of the compound of Example 8 was obtained in the same manner as in Production Examples 1 to 4 and Example 1, except that 21 parts of 1-bromobutane in Production Example 1 were replaced with 80 parts of 1-chlorotriacontane, and 2.2 parts of pyridine and 4.3 parts of trifluoromethanesulfonate in Example 1.

[0129] <Example 9> <Synthesis of 2,5-didodecyloxy-1,8-naphthalimide pentafluorobenzenesulfonate> 6.5 parts of the compound of Example 9 were obtained in the same manner as in Production Examples 1 to 4 and Example 1, except that 21 parts of 1-bromobutane in Production Example 1 were replaced with 40 parts of 1-bromododecane, and 2.0 parts of trifluoromethanesulfonate in Example 1 were replaced with 3.1 parts of pentafluorobenzenesulfone chloride (manufactured by Aldrich).

[0130] <Example 10> <Synthesis of 2,5-dioctadecyloxy-1,8-naphthalimide pentafluorobenzenesulfonate> 6.2 parts of the compound of Example 10 were obtained in the same manner as in Production Examples 1 to 4 and Example 1, except that 21 parts of 1-bromobutane in Production Example 1 were replaced with 60 parts of 1-bromooctadecane, and 2.0 parts of the trifluoromethanesulfonate in Example 1 were replaced with 3.1 parts of pentafluorobenzenesulfone chloride (manufactured by Aldrich).

[0131] <Example 11> <Synthesis of 2,5-Ditriacontyloxy-1,8-Naphthalimide Pentafluorobenzenesulfonate> 5.5 parts of the compound of Example 11 were obtained in the same manner as in Production Examples 1 to 4 and Example 1, except that 21 parts of 1-bromobutane in Production Example 1 were replaced with 80 parts of 1-chlorotriacontane, and 2.0 parts of the trifluoromethanesulfonate in Example 1 were replaced with 3.1 parts of pentafluorobenzenesulfone chloride (manufactured by Aldrich).

[0132] １ H-NMR and １９ The structures of the compounds in Examples 1 to 11 were identified by F-NMR as follows.

[0133] ​

[0134]

[0135]

[0136] Compounds of Examples 1 to 11 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 (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 2 １ ¹H-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 １ H-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 (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 4 １ ¹H-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 (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 5 １H-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)

[0137] Example 6 １ H-NMR (400MHz, solvent: deuterated chloroform): 8.54 (2H, dd), 7.32 (1H, d), 6.91 (1H, d), 4.28 (4H, t), 1.90 (4H, m), 1.30 (36H, m), 0.89 (6H, m) ・ １９ F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 7 １ H-NMR (400MHz, solvent: deuterated chloroform): 8.54 (2H, dd), 7.32 (1H, d), 6.91 (1H, d), 4.28 (4H, t), 1.90 (4H, m), 1.20 (60H, m), 0.86 (6H, m) ・ １９ F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 8 １ H-NMR (400MHz, solvent: deuterated chloroform): 8.54 (2H, dd), 7.32 (1H, d), 6.91 (1H, d), 4.28 (4H, t), 1.90 (4H, m), 1.20 (116H, m), 0.86 (6H, m) ・ １９ F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Example 9 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 (36H, m), 0.89 (6H, m) ・ １９F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Example 10 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) , 1.20 (60H, m), 0.86 (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 11 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) , 1.20 (116H, m), 0.86 (6H, m) ・ １９ F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F)

[0138] <Comparative Example 1> 1,8-Naphthalimide Trifluoromethanesulfonate (manufactured by Aldrich) was used as is.

[0139] <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 cooled to -10°C. 15 parts of 2,5-dimethylnaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) precursor (P1-3) were slowly added and reacted at -10°C for 2 hours. After the reaction was complete, 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 precursor (P2-3) compound.

[0140] <Synthesis of 2,5-dimethyl-1,8-naphthalic anhydride [precursor (P3-3)]> 1.6 parts of 2,5-dimethyl-1,8-acenaphthenequinone (precursor P2-3) dispersed in 29 parts methanol was combined with 10 parts of potassium peroxymonosulfate (double salt) under a nitrogen atmosphere. The dispersion was refluxed for one day with vigorous stirring. After the reaction was complete, the mixture was cooled to room temperature and added to a large amount of water. The resulting solid was filtered and dried under reduced pressure to obtain 1.3 parts of precursor (P3-3).

[0141] <Synthesis of N-hydroxy-2,5-dimethyl-1,8-naphthalimide [precursor (P4-3)]> 1.1 parts of precursor (P3-3) were dispersed in 20 parts of acetonitrile, and 2.0 parts of aqueous hydroxylamine solution (manufactured by Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) were added and the mixture was stirred at 50°C for one day. The reaction mixture was added to an aqueous solution of dilute hydrochloric acid, the precipitate was filtered off, washed with water, and dried to obtain 1.2 parts of precursor (P4-3).

[0142] <Synthesis of 2,5-dimethyl-1,8-naphthalimidetrifluoromethanesulfonate> 2.5 parts of the precursor (P4-3) were dispersed in 47 parts of dichloromethane, 1.0 part of pyridine was added, and the mixture was cooled in an ice bath. 2.0 parts of trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise and the reaction was allowed to proceed. After stirring for 1 hour, the reaction mixture was placed in 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.

[0143] <Comparative Example 3> The compound of Comparative Example 3 (2,7-Ditoxic-1,8-Naphthalimide Trifluoromethanesulfonate) was synthesized in the same manner as the synthesis method of the nonionic photoacid generator (A-2) described in Japanese Patent Application Publication No. 2019-197146, except that trifluoromethanesulfonate was used instead of nonafluorobutanesulfonate.

[0144] <Comparative Example 4> The compound of Comparative Example 4 (2,7-dimethylthio-1,8-naphthalimidetrifluoromethanesulfonate) was synthesized according to the method for synthesizing a nonionic photoacid generator (A-3) described in Japanese Patent Publication No. 2019-197146.

[0145] <Comparative Example 5> The compound of Comparative Example 5 (2,6-diisopropyl-1,8-naphthalimidetrifluoromethanesulfonate) was synthesized according to the method for synthesizing a nonionic photoacid generator (A-8) described in Japanese Patent Publication No. 2019-197146.

[0146] １ H-NMR and １９ The structures of the compounds in Comparative Examples 1 to 5 were identified as follows by F-NMR.

[0147]

[0148] Compounds of Comparative Examples 1-5 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 (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Comparative Example 2 １ 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 (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Comparative Example 3 １ ¹H-NMR (400 MHz, solvent: deuterated chloroform): 8.04 (2H, d), 7.06 (2H, d), 3.92 (6H, s) １９ F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Comparative Example 4 １ ¹H-NMR (400 MHz, solvent: deuterated chloroform): 7.73 (2H, d), 7.50 (2H, d), 2.46 (6H, s) １９ F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F) Comparative Example 5 １ ​¹H-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 (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F)

[0149] [Evaluation] As an evaluation of the performance as a photoacid generator, the base resistance of the compounds in Examples 1 to 11 and Comparative Examples 1 to 5 was evaluated using the following method, and the results are shown in Tables 1 and 2.

[0150] <Method for Evaluating Base Resistance> Two parts of triethylamine were weighed into a capped screw tube, and 200 parts of deuterated chloroform were added and mixed. Subsequently, three parts of the compound from each example or comparative example were added, and the mixture was quickly stirred to obtain a homogeneous composition. After allowing this solution to stand at room temperature for 24 hours, fluorine-19 NMR analysis was performed, and the decomposition rate D [%] was calculated. The decomposition rate D was determined as follows: Decomposition rate D [%]: D = integral ratio of decomposition products / (integral ratio of photoacid generator + integral ratio of decomposition products) × 100

[0151] <Method for evaluating solvent solubility> 0.3 g of each compound from 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 a temperature of 25°C until the photoacid generator was completely dissolved. The solid content concentration at this point was defined as the solvent solubility.

[0152]

[0153]

[0154] As is clear from Tables 1 and 2, the compounds of Examples 1 to 11 had a decomposition rate D of 10% or less and were found to have excellent base resistance. In particular, the compounds of Examples 1 to 11 were found to have a significantly lower decomposition rate D compared not only to Comparative Example 1 (one of the comparative examples in Japanese Patent Publication No. 2019-197146) but also to Comparative Examples 2 to 5 (one of the examples or similar compounds in Japanese Patent Publication No. 2019-197146).

[0155] In particular, R in the general formula (1) ２ , R３ , R ５ , and R ６ For the compounds of Examples 1, 2, 4, and 5 - 11 in which R

[0156] is a hydrogen atom, it was found that the decomposition rate D is 5% or less, and they are more excellent in basic resistance than Example 3.

[0157] Also, as is clear from Tables 1 and 2, in Examples 1 - 3 and 5 - 11 in which the number of carbon atoms in the electron - donating groups of R １ and R ４ in the general formula (1) is 4 - 30, it was found that they are more excellent in solubility in a solvent as compared with Example 4 in which the number of carbon atoms in the electron - donating groups of R １ and R ４ in the general formula (1) is 1.

[0158] As a summary above, the configurations of the present disclosure and their variations are appended below. [1] The compound represented by the general formula (1). [2] The compound according to [1], wherein in the general formula (1), R １ and R ４ are alkoxy groups having 1 - 30 carbon atoms. [3] The compound according to [1], wherein in the general formula (1), R ２ , R ３ , R ５ , and R ６ are hydrogen atoms. [4] The compound according to [1], wherein in the general formula (1), R ２ , R ３ , R ５ , and R ６[2] The compound according to [2], wherein Rf is a hydrogen atom. [5] The compound according to any one of [1] to [4], wherein Rf in general formula (1) is a hydrocarbon group having 1 to 30 carbon atoms substituted with a fluorine atom. [6] The compound according to any one of [1] to [5], wherein the alkoxy group, the alkylthio group, and the hydrocarbon group have 4 to 30 carbon atoms. [7] A nonionic photoacid generator (A) comprising the compound according to any one of [1] to [6]. [8] A resin composition for photolithography (Q) comprising the nonionic photoacid generator (A) according to [7]. [9] Use of the compound according to any one of [1] to [6] as a nonionic photoacid generator (A).

[10] A method for generating acid, comprising the step of irradiating the compound according to any one of [1] to [6] with light.

[11] A composition comprising the compound according to any one of [1] to [6] and a photosensitive resin.

[12] A composition comprising the nonionic photoacid generator (A) described in [7] and a photosensitive resin.

[13] A photoresist comprising the compound described in any one of [1] to [6] and a photosensitive resin.

[14] A photoresist comprising the nonionic photoacid generator (A) described in [7] and a photosensitive resin.

[15] A method for producing a photoresist, comprising mixing the compound described in any one of [1] to [6] and a photosensitive resin.

[16] A method for producing a photoresist, comprising mixing the nonionic photoacid generator (A) described in [7] and a photosensitive resin.

[0159]

[17] A compound represented by the general formula (1) above. [However, in formula (1), R １ and R ４ R may be the same or different, and is a hydroxyl group, a carbon-1 to carbon-16 alkoxy group, or a carbon-1 to carbon-16 alkylthio group. ２ , R ３ , R ５ , and R ６ R may be the same or different, and is a hydrogen atom, a hydroxyl group, a carbon-1 to carbon-16 alkoxy group, or a carbon-1 to carbon-16 alkylthio group, and Rf may be a carbon-1 to carbon-16 hydrocarbon group that is substituted with a fluorine atom.

[18] In general formula (1), R １ and R４ The compound described in

[17] , wherein is an alkoxy group having 1 to 16 carbon atoms.

[19] In general formula (1), R ２ , R ３ , R ５ , and R ６ The compound described in

[17] , wherein is a hydrogen atom.

[20] In general formula (1), R ２ , R ３ , R ５ , and R ６ A compound according to

[18] , wherein Rf is a hydrogen atom.

[21] A compound according to any one of

[17] to

[20] , wherein Rf in general formula (1) is a hydrocarbon group having 1 to 16 carbon atoms substituted with a fluorine atom.

[22] A compound according to any one of

[17] to

[21] , wherein the alkoxy group, the alkylthio group, and the hydrocarbon group have 4 to 8 carbon atoms.

[23] A nonionic photoacid generator (A) comprising a compound according to any one of

[17] to

[22] .

[24] A resin composition for photolithography (Q) comprising the nonionic photoacid generator (A) according to

[23] .

[0160] The compounds of the present invention are useful as semiconductor materials.

Claims

1. A compound represented by the following general formula (1). [In formula (1), R １ and R ４ R may be the same or different, and is a hydroxyl group, a carbon-1 to carbon-30 alkoxy group, or a carbon-1 to carbon-30 alkylthio group. ２ , R ３ , R ５ , and R ６ Rf may be the same or different hydrogen atom, hydroxyl group, C1-C30 alkoxy group, or C1-C30 alkylthio group, and Rf may be a C1-C30 hydrocarbon group 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 30 carbon atoms.

3. In the general formula (1), R ２ , R ３ , R ５ , and R ６ are hydrogen atoms, and the compound according to claim 1.

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 Rf in general formula (1) is a hydrocarbon group having 1 to 30 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 have 4 to 30 carbon atoms.

7. A nonionic photoacid generator (A) comprising the compound described in any one of claims 1 to 6.

8. A resin composition (Q) for photolithography comprising the nonionic photoacid generator (A) described in claim 7.

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