Compound, photoacid generator, and resin composition for photolithography

Abstract

Provided is a compound that can be solidified.　A compound according to the present invention is represented by general formula (1). In general formula (1), R1 represents an alkylene group. R2 represents an alkyl group which may be substituted or a hydrogen atom. Rf represents a phenyl group in which at least one hydrogen atom may be substituted with a fluorine atom. In the formula, R1 is an alkylene group having 2 or more carbon atoms, or R2 is a hydrogen atom or an alkyl group which is substituted with an alkoxy group.

Description

Compounds, 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 a solidifiable compound, a nonionic photoacid generator containing the compound, and a resin composition for photolithography containing the nonionic photoacid generator.

[0002] Patent Document 1 discloses a photoacid generator and a resin composition for photolithography. Patent Document 2 discloses a sulfonic acid derivative compound.

[0003] Japanese Patent Publication No. 2020-86083, Japanese Patent Publication No. 2017-535595

[0004] Compounds useful as photoacid generators contained in resin compositions for photolithography can have their purity improved by subsequent crystallization after solidification. However, it has become clear that when Rf in general formula (1) of Patent Document 1 is a substituent other than a PFAS (a general term for perfluoroalkyl compounds and polyfluoroalkyl compounds), such as a fluorophenyl group, the compound of general formula (1) does not solidify.

[0005] Therefore, the object of the present invention is to provide a compound that can be solidified, 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) can be solidified even if Rf is not PFAS. 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 R indicates an alkylene group. ２represents an alkyl group or a hydrogen atom which may be substituted. Rf represents a phenyl group in which at least one hydrogen atom may be substituted by a fluorine atom. However, R １ is an alkylene group having 2 or more carbon atoms, or R ２ is an alkyl group or a hydrogen atom substituted with an alkoxy group. ]

[0010] The compound is preferably such that R １ represents a methylene group or an ethylene group, and R ２ represents an alkyl group substituted with an alkoxy group.

[0011] The compound is preferably such that R １ represents an ethylene group, and R ２ represents an alkyl group or a hydrogen atom which may be substituted with an alkoxy group.

[0012] The compound is preferably such that Rf represents a perfluorophenyl group.

[0013] The present invention also provides a nonionic photoacid generator (A) containing the compound.

[0014] The present invention also provides a resin composition (Q) for photolithography containing the nonionic photoacid generator (A).

[0015] The compound of the present invention can be solidified even if Rf is not a PFAS such as a trifluoromethyl group. Therefore, the purity of the compound can be improved by crystallization, and the performance as a photoacid generator is improved.

[0016] <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).

[0017]

[0018] [In the formula (1), R １ represents an alkylene group. R ２ represents an alkyl group or a hydrogen atom which may be substituted. Rf represents a phenyl group in which at least one hydrogen atom may be substituted by a fluorine atom. However, R １is an alkylene group having 2 or more carbon atoms, or R ２ is an alkyl group substituted with an alkoxy group or a hydrogen atom.]

[0019] R １ Examples of the alkylene group in R include an alkylene group having 1 carbon atom (methylene group) and an alkylene group having 2 or more carbon atoms. Examples of the alkylene group having 2 or more carbon atoms include a linear or branched alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 5 carbon atoms, and the like. Examples of the linear or branched alkylene group having 2 to 8 carbon atoms include a methylmethylene group, a dimethylmethylene group, an ethylene group, a 2-methylethylene group, a 1,2-dimethylethylene group, a trimethylene group, a 2-methyl-trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and the like. R １ The alkylene group in R is particularly preferably an alkylene group having 1 or 2 carbon atoms, that is, a methylene group or an ethylene group, and most preferably an ethylene group.

[0020] R ２ From the viewpoints of solidification and high purity, the number of carbon atoms of the alkyl group in the optionally substituted alkyl group in R is preferably 1 to 16, more preferably 1 to 8, and even more preferably 4 to 8.

[0021] 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, a cyclic alkyl group having 3 to 16 carbon atoms, and the like.

[0022] 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, a normal hexadecyl group, and the like.

[0023] The branched alkyl groups having 1 to 16 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.

[0024] The cyclic alkyl group having 3 to 16 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.

[0025] R ２ In the optionally substituted alkyl group, examples of substituted groups include halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, formyl groups, carboxyl groups, carbamoyl groups, alkoxy groups, alkylthio groups, etc., and alkoxy groups are preferred from the viewpoint of solidification and high purity. The number of these substituents may be 1 to 5 or 1 to 3.

[0026] The number of carbon atoms in the alkoxy group is preferably 1 to 16, and more preferably 1 to 5.

[0027] Examples of the alkoxy group include linear or branched alkoxy groups, aryloxy groups, aryl-alkyloxy groups, and groups in which two or more of these are bonded. Examples of the linear or branched alkoxy group 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 the aryloxy group include phenoxy and naphthyloxy. Examples of the aryl-alkyloxy group 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 the group in which two or more are bonded include methoxymethoxy, ethoxymethoxy, 2-methoxyethoxy, 1-methoxyethoxy, and benzyloxymethoxy. Furthermore, the alkoxy group having 1 to 16 carbon atoms may also be a siloxy group having 1 to 16 carbon atoms, such as trimethylsiloxy, triethylsiloxy, triisopropylsiloxy, tert-butyldimethylsiloxy, and tert-butyldiphenylsiloxy. Among these, a linear alkoxy group is preferred from the viewpoint of obtaining an even higher purity, and a methoxy group or ethoxy group is more preferred.

[0028] The number of carbon atoms in the alkylthio group is preferably 1 to 16, and more preferably 1 to 5.

[0029] Examples of alkylthio groups include linear or branched alkylthio groups, arylthio groups, aryl-alkylthio groups, and groups in which two or more of these are bonded. Examples of 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. Examples of arylthio groups include phenylthio groups. Examples of aryl-alkylthio groups include alkylthio groups having a hydrocarbon group to which an aryl group and an alkyl group are bonded, such as tosylthio groups and benzylthio groups. Among these, linear alkylthio groups are preferred from the viewpoint of obtaining even higher purity, and methylthio groups and ethylthio groups are more preferred.

[0030] The aforementioned R １ and R ２ From the perspective of obtaining even higher purity, R １ R represents a methylene group or an ethylene group. ２ R indicates an alkyl group substituted with an alkoxy group, or １ R indicates an ethylene group, ２ It is preferable that this represents an alkyl group or hydrogen atom which may be substituted with an alkoxy group.

[0031] Rf may be a phenyl group that is not substituted with a fluorine atom, or it may be a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom.

[0032] Examples of phenyl groups in which at least one hydrogen atom is substituted with a fluorine atom include monofluorophenyl groups, difluorophenyl groups, trifluorophenyl groups, tetrafluorophenyl groups, and perfluorophenyl groups (pentafluorophenyl groups), with perfluorophenyl groups (pentafluorophenyl groups) being particularly preferred.

[0033] Substituent {-S(R１ ) OOR ２ The bonding position of} is preferably at the 3rd position from the viewpoint of ease of synthesis.

[0034] The compounds of the present invention can be solidified. For example, it can be determined that a solid can be formed by concentrating a solution containing the compounds of the present invention, adding methanol, cooling to -25°C, and confirming that crystals precipitate.

[0035] (Synthesis Method) The compounds of the present invention can be synthesized, for example, by reacting a precursor (P1) obtained by reacting hydroxylamine with a compound of the following general formula (2) with hydroxylamine, and then reacting it with the corresponding benzenesulfonyl chloride.

[0036]

[0037] In the above general formula (2), R １ and R ２ This is the same as the definition in general formula (1).

[0038] The reaction conditions for hydroxy-1,8-naphthalic anhydride and the compound of general formula (2) are 1 to 50 hours at a temperature of -30 to 100°C, and it is preferable to use a reaction solvent and a base catalyst to complete the reaction quickly and in good yield.

[0039] The reaction solvent is not particularly limited, but acetonitrile, tetrahydrofuran, dichloromethane, chloroform, etc. are preferred. As a base catalyst, for example, pyridine, methylmorpholine, dimethylaminopyridine, 2,6-lutidine, triethylamine, imidazole, DBU, sodium hydride, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, etc. are preferred, and are usually added in an amount of 1 to 100 mol% relative to hydroxy-1,8-naphthalic anhydride.

[0040] The molar ratio of hydroxy-1,8-naphthalic anhydride to the compound of general formula (2) is usually 1:1 to 1:4.

[0041] The compound of the present invention, obtained by reacting a precursor (P1) with hydroxylamine and then with the corresponding benzenesulfonyl chloride, can be purified by recrystallization with a suitable organic solvent as needed.

[0042] <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.

[0043] 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.

[0044] 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.).

[0045] 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.

[0046] <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. Because the photolithography resin composition (Q) of the present invention contains the nonionic photoacid generator (A), ultraviolet irradiation and post-exposure heating (PEB) result in a difference in solubility in the developer 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.

[0047] 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.

[0048] 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.

[0049] The negative-type chemically amplified resin (QN) is composed of a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2).

[0050] 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.

[0051] The novolac resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

[0052] 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.

[0053] Specific examples of novolac resins include phenol / formaldehyde condensation novolac resins, cresol / formaldehyde condensation novolac resins, and phenol-naphthol / formaldehyde condensation novolac resins.

[0054] Furthermore, the phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low-molecular-weight compound as part of its components.

[0055] 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.

[0056] The content of this phenolic low molecular weight compound in the phenolic hydroxyl group-containing resin (QN1) is preferably 40% by mass or less, and more preferably 1 to 30% by mass, when the phenolic hydroxyl group-containing resin (QN1) is considered to be 100% by mass.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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).

[0065] As the phenolic hydroxyl group-containing resin (QP11), those exemplified and described as the hydroxyl group-containing resin (QN1) can be used.

[0066] 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).

[0067] 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.

[0068] Examples of the hydrophobic group-containing vinyl monomer (Bb) include (meth)acrylic acid ester (Bb1) and aromatic hydrocarbon monomer (Bb2).

[0069] 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.).

[0070] 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.

[0071] 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.

[0072] 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).

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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

[0077] 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.).

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tert-butoxycarbonyl group.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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%.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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 solvents may be used, or two or more may be used.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] <Example 1> In a triangular flask, 21 parts of 4-bromo-1,8-naphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 27 parts of potassium carbonate, a base catalyst, were dispersed in 400 parts of acetonitrile, the reaction solvent. Then, 30 parts of methoxybutyl thioglycolate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was reacted at 75°C for 6 hours. Next, the potassium carbonate was filtered off, and then 18 parts of a 50% aqueous hydroxylamine solution (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise, and the mixture was reacted at room temperature for 2 hours. After the reaction was complete, the reaction solution was added to deionized water, and then hydrochloric acid was added until the pH reached 5. After stirring for a while, the precipitate was filtered and collected, and dried under reduced pressure at 70°C to obtain a pale yellow solid precursor. The dried precursor was dissolved in 500 parts of dichloromethane and 20 parts of pyridine, then cooled to 10°C, and 42 parts of pentafluorobenzenesulfonyl chloride were added dropwise. After adding the reagents dropwise, the mixture was allowed to react at room temperature for one hour, then washed with deionized water to obtain the reaction solution.

[0105] <Example 2> The same procedure as in Example 1 was followed, except that methoxybutyl thioglycolate was replaced with methoxybutyl mercaptopropionate.

[0106] <Example 3> The same procedure as in Example 1 was followed, except that methoxybutyl thioglycolate was replaced with octyl mercaptopropionate.

[0107] <Example 4> The same procedure as in Example 1 was followed, except that methoxybutyl thioglycolate was replaced with 3-mercaptopropionic acid.

[0108] １ H-NMR and １９ The structures of the compounds contained in the reaction solutions of Examples 1 to 4 were identified by F-NMR as follows.

[0109]

[0110] Compounds contained in the reaction solutions of Examples 1 to 4 １ H-NMR data and １９ The F-NMR results are as follows: Example 1 １ ​¹H-NMR (400 MHz, solvent: heavy chloroform), δ (ppm): 8.65 (m, 2H), 8.45 (d, 1H), 7.82 (t, 1H), 7.67 (d, 1H), 4.25 (t, 2H), 3.93 (s, 2H), 3.31 (m, 1H), 3.22 (s, 3H), 1.75 (m, 2H), 1.09 (d, 3H) １９ F-NMR(400MHｽ, solvent: heavy クロロホルム), δ(ppm):-13 2.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Example 2・ １ ¹H-NMR (400 MHz, solvent: heavy chloroform), δ (ppm): 8.60 (m, 2H), 8.45 (d, 1H), 7.78 (t, 1H), 7.58 (d, 1H), 4.22 (t, 2H), 3.45 (t, 2H), 3.39 (m, 1H), 3.28 (s, 3H), 2.79 (t, 2H), 1.75 (m, 2H), 1.13 (d, 3H) １９ F-NMR(400MHｽ, solvent: heavy クロロホルム), δ(ppm):-13 2.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Example 3・ １ ¹H-NMR (400 MHz, solvent: heavy chloroform), δ (ppm): 8.62 (m, 2H), 8.45 (d, 1H), 7.78 (t, 1H), 7.60 (d, 1H), 4.05 (m, 2H), 3.45 (t, 2H), 2.79 (t, 2H), 1.35 (m, 2H), 1.25 (bs, 7H), 0.85 (m, 6H) １９ F-NMR(400MHｽ, solvent: heavy クロロホルム), δ(ppm):-13 2.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Implementation example 4・ １ ¹H-NMR (400 MHz, solvent: heavy chloroform), δ (ppm): 8.90 (s, ¹H), 8.62 (m, ²H), 8.45 (d, ¹H), 7.78 (t, ¹H), 7.60 (d, ¹H), 3.45 (t, ²H), 2.80 (t, ²H) １９ F-NMR(400MHｽ, solvent: heavy クロロホルム), δ(ppm):-13 2.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F)

[0111] <Comparative Example 1> The same procedure as in Example 1 was followed, except that methoxybutyl thioglycolate was replaced with octyl thioglycolate.

[0112] <Reference Example 1> The same procedure as in Example 1 was followed, except that methoxybutyl thioglycolate was replaced with methoxybutyl mercaptopropionate and pentafluorobenzenesulfonyl chloride was replaced with trifluoromethanesulfonic anhydride (manufactured by Mitsubishi Materials Electronic Chemicals, EF-18).

[0113] １ H-NMR and １９ F-NMR determined the structures of the compounds contained in the reaction solutions of Comparative Example 1 and Reference Example 1 as follows.

[0114]

[0115] H of the compound contained in the reaction solution of Comparative Example 1 and Reference Example 1 １ - NMR data and １９ The F-NMR results are as follows: Comparative Example 1 １ H-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): 8.63 (dd, 2H), 8.45 (d, 1H), 7.81 (t, 1H), 7.65 ( d, 1H), 4.05 (m, 2H), 3.95 (s, 2H), 3.39 (d, 2H), 1.75 (m, 1H), 1.25 (m, 8H), 0.85 (m, 3H)・ １９ F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Reference Example 1 １ H-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): 8.65 (m, 2H), 8.45 (d, 1H), 7.85 (t, 1H), 7.70 (d , 1H), 4.25 (t, 2H), 3.95 (s, 2H), 3.30 (m, 1H), 3.20 (s, 3H), 1.75 (m, 2H), 1.010 (d, 3H)・ １９ F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F)

[0116] ​<Confirmation Test for Solidification> To one part of the reaction solution of each example, comparative example, and reference example, concentrated using a rotary evaporator, 20 parts methanol was added and cooled to -25°C. The presence or absence of crystal precipitation was checked, and if crystals precipitated, solidification was evaluated as "○" (○). If crystals did not precipitate, solidification was evaluated as "×" (×). The results are shown in Table 1.

[0117] <Purity Confirmation Test (HPLC)> HPLC analysis was performed on the reaction solutions of each example, comparative example, and reference example under the following conditions. The purity of the compounds contained was calculated from the peak area ratio obtained by HPLC analysis and is shown in Table 1. Equipment used: Hitachi LaChrome 7000 series or equivalent model Developing solution: Methanol / water / trifluoroacetic acid = 100 / 10 / 1 (wt) Flow rate: 1.0 mL / min Column: GL Sciences Co., Ltd. ODS-3 (4.6 mm I.D. × 250 mm) Oven temperature: 40°C Measurement wavelength: 254 nm Sample injection volume: 10 μL

[0118]

[0119] Table 1 shows that, as in Reference Example 1, when Rf in the general formula (1) corresponds to PFAS, solidification occurs, but as in Comparative Example 1, when Rf in the general formula (1) does not correspond to PFAS, solidification does not occur. Furthermore, it was found that the compounds of Examples 1 to 4 can be solidified even though their structure does not involve Rf in the general formula (1) corresponding to PFAS. In addition, it was found that because solidification is possible in Examples 1 to 4, the compounds contained in the reaction solution can be obtained in high purity. In particular, it was found that in Examples 1 and 3, the compounds contained in the reaction solution can be obtained in even higher purity.

[0120] In summary, the composition of this disclosure and its variations are described below. [1] A compound represented by the general formula (1). [2] R １ R represents a methylene group or an ethylene group, ２ The compound described in [1], wherein R is an alkyl group substituted with an alkoxy group. [3] R １ R indicates an ethylene group, ２[1] A compound wherein Rf is an alkyl group or hydrogen atom which may be substituted with an alkoxy group. [4] A compound according to any one of [1] to [3] wherein Rf is a perfluorophenyl group. [5] A nonionic photoacid generator (A) comprising a compound according to any one of [1] to [4]. [6] A resin composition for photolithography (Q) comprising the nonionic photoacid generator (A) according to [5]. [7] Use of a compound according to any one of [1] to [4] as a nonionic photoacid generator (A). [8] A method for generating acid, comprising the step of irradiating a compound according to any one of [1] to [4] with light. [9] A composition comprising a compound according to any one of [1] to [4] and a photosensitive resin.

[10] A composition comprising a nonionic photoacid generator (A) according to [5] and a photosensitive resin.

[11] A photoresist comprising a compound according to any one of [1] to [4] and a photosensitive resin.

[12] A photoresist comprising the nonionic photoacid generator (A) described in [5] and a photosensitive resin.

[13] A method for producing a photoresist, comprising mixing the compound described in any one of [1] to [4] with a photosensitive resin.

[14] A method for producing a photoresist, comprising mixing the nonionic photoacid generator (A) described in [5] with a photosensitive resin.

[0121] 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 represents an alkylene group. R ２ represents an optionally substituted alkyl group or a hydrogen atom. Rf represents a phenyl group in which at least one hydrogen atom may be substituted with a fluorine atom. However, R １ is an alkylene group having 2 or more carbon atoms, or R ２ is an alkyl group or a hydrogen atom substituted with an alkoxy group. ] 2. R １ R represents a methylene group or an ethylene group. ２ The compound according to claim 1, wherein is an alkyl group substituted with an alkoxy group.

3. R １ R indicates an ethylene group, ２ The compound according to claim 1, wherein is an alkyl group or hydrogen atom which may be substituted with an alkoxy group.

4. The compound according to claim 1, wherein Rf represents a perfluorophenyl group.

5. A nonionic photoacid generator (A) comprising the compound described in any one of claims 1 to 4.

6. A resin composition (Q) for photolithography comprising the nonionic photoacid generator (A) described in claim 5.

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