WO2022224835A1 - Composé, générateur d'acide, composition, produit durci, procédé de production d'un produit durci, motif et procédé de production de motif - Google Patents

Composé, générateur d'acide, composition, produit durci, procédé de production d'un produit durci, motif et procédé de production de motif Download PDF

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WO2022224835A1
WO2022224835A1 PCT/JP2022/017251 JP2022017251W WO2022224835A1 WO 2022224835 A1 WO2022224835 A1 WO 2022224835A1 JP 2022017251 W JP2022017251 W JP 2022017251W WO 2022224835 A1 WO2022224835 A1 WO 2022224835A1
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group
carbon atoms
unsubstituted
compound
acid
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PCT/JP2022/017251
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Japanese (ja)
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依純 松井
智幸 有吉
哲千 中屋敷
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present disclosure relates to a compound suitably used as an acid generator, an acid generator containing the compound, a composition, a cured product thereof, a method for producing a cured product using the composition, a pattern, and a method for producing a pattern. .
  • the acid generator is a substance that generates acid by irradiation with energy rays such as light, heat treatment, or the like.
  • Patent Documents 1 and 2 disclose, as acid generators, photoacid generators or thermal acid generators comprising sulfonic acid derivative compounds. Further, Patent Documents 1 and 2 disclose a negative resist whose solubility in a developer decreases due to the formation of chemical bonds such as polymerization or cross-linking by an acid generated from an acid generator, and an ester group caused by the action of an acid. Alternatively, it is described that an acid generator is used together with a positive resist whose solubility in a developing solution is increased by, for example, breaking the chemical bond of the acetal group. Also, as specific uses, semiconductors, overcoat agents, paints, adhesives, inks, etc. are described.
  • an object of the present invention is to provide a compound with excellent sensitivity to acid generation.
  • an oxime sulfonate compound having a specific structure has excellent acid generation sensitivity, and completed the present invention.
  • the present invention is a compound having a structure represented by the following general formula (A) (hereinafter sometimes referred to as compound A).
  • R 31 represents a group represented by the following general formula (1)
  • R 32 is a group represented by a formula selected from the following general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh)
  • R33 is halogen atom, nitro group, cyano group, -OR 34 , -COR 34 , -OCOR 34 , -COOR 34 , -SR 34 , -SOR 34 , -SO 2 R 34 , -NR 35 R 36 , -NR 35 COR 36 , —CONR 35 R 36 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or represents a group in which one or more of the methylene groups in the hydrocarbon group or the hetero
  • R 35 or R 36 When there are multiple 34 , R 35 or R 36 , they may be the same or different,
  • the substituent that replaces one or more of the hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from Group IIa below.
  • a represents an integer from 1 to 20
  • b represents an integer from 1 to 20
  • c represents an integer from 0 to 18, The sum of a, b and c is 21 or less.
  • R 1 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. , or represents a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ia below
  • R 2 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group having 2 to 20 carbon atoms; a heterocyclic ring-containing group or a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ia below,
  • R 51 represents OR 81 , NR 82 R 83 or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms
  • R 52 and R 53 each independently represent R 81 or OR 81 , R 52 and R 53 may combine to form a ring
  • R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64 , R 65 , R 71 and R 73 are unsubstituted or substituted aryl groups having 6 to 20 carbon atoms
  • represents R 54 , R 57 , R 60 , R 63 , R 66 , R 67 and R 72 each independently represent an unsubstituted or substituted arylene group having 6 to 20 carbon atoms or a single bond
  • R 68 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms
  • R 69 and R 70 each independently represent R 81
  • Group Ia -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-.
  • Group IIa halogen atom, cyano group, nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH or --SO 3 H.
  • R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R' or R", they may be the same can be different.
  • the present invention also provides an acid generator containing the above compound, a composition of the above compound, a cured product of the composition, a method for producing a cured product by curing the composition, a pattern using the composition, and a method for producing a pattern. do.
  • the present invention it is possible to provide a compound with excellent sensitivity to acid generation.
  • the compound of the present invention is also excellent in that a pattern produced from a composition using the compound has a high transmittance of light in the visible light region.
  • the present invention provides an acid generator with high sensitivity to acid generation using the compound, a composition of the compound, a cured product of the composition, a method for producing a cured product by curing the composition, and a pattern using the composition. and a pattern manufacturing method.
  • the present invention relates to a compound, an acid generator, a composition, a cured product, a method for producing a cured product, a pattern, and a method for producing a pattern.
  • the present invention will be described in detail below.
  • R 31 represents a group represented by the following general formula (1)
  • R 32 is a group represented by a formula selected from the following general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh)
  • R 33 is a halogen atom, a nitro group, a cyano group, —OR 34 , —COR 34 , —OCOR 34 , —COOR 34 , —SR 34 , —SOR 34 , —SO 2 R 34 , —NR 35 R 36 , — NR 35 COR 36 , —CONR 35 R 36 , unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted heterocyclic group having 2 to 20 carbon atoms a ring-containing group, or a group in which one or more of the methylene groups in
  • R 35 or R 36 When there are multiple 34 , R 35 or R 36 , they may be the same or different,
  • the substituent that replaces one or more of the hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from Group IIa below.
  • a represents an integer from 1 to 20
  • b represents an integer from 1 to 20
  • c represents an integer from 0 to 18, The sum of a, b and c is 21 or less.
  • R 1 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. , or represents a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ia below
  • R 2 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group having 2 to 20 carbon atoms; a heterocyclic ring-containing group or a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ia below,
  • R 51 represents OR 81 , NR 82 R 83 or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms
  • R 52 and R 53 each independently represent R 81 or OR 81 , R 52 and R 53 may combine to form a ring
  • R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64 , R 65 , R 71 and R 73 are unsubstituted or substituted aryl groups having 6 to 20 carbon atoms
  • represents R 54 , R 57 , R 60 , R 63 , R 66 , R 67 and R 72 each independently represent an unsubstituted or substituted arylene group having 6 to 20 carbon atoms or a single bond
  • R 68 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms
  • R 69 and R 70 each independently represent R 81
  • Group Ia -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-.
  • Group IIa halogen atom, cyano group, nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH or --SO 3 H.
  • R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R' or R", they may be the same can be different.
  • the compound A is represented by the above general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) (such as diketone groups).
  • IVa general formulas
  • IVb general formulas
  • IVc general formulas
  • IVe IVe
  • IVf IVg
  • IVh IVh
  • a group represented by a formula selected from It has a group to be used, so it has excellent sensitivity to acid generation.
  • the compound A contains a structure having an IVa group or the like and a group represented by the general formula (1) (hereinafter sometimes referred to as a specific structure), thereby increasing the light absorption efficiency around 365 nm.
  • the structure of formula (1) corresponding to the acid-generating site is excellent in acid-generating ability. Due to these, compound A is excellent in acid generation efficiency.
  • the above specific structure can provide a desired sensitivity even when added in a small amount, compared to a compound that does not have a combination of the IVa group and the like and the group represented by the general formula (1).
  • the composition has excellent sensitivity to acid generation.
  • the compound A has a high transmittance of light in the visible light region due to the presence of the IVa group and the like. Therefore, it can be suitably used for a resin composition for forming a member that requires transparency.
  • the halogen atom in the general formula (A) includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • the number of carbon atoms in the above general formula (A), formula (1), formulas (IVa) to (IVh), (Ara), (Arb), (Ara1) and (Arb1), and (A1) to (A3) below is 1
  • the hydrocarbon group of -20 is a hydrocarbon group containing no aromatic hydrocarbon ring or heterocyclic ring, and may have a substituent.
  • a hydrocarbon group having a substituent is a group having a structure in which one or more hydrogen atoms in the hydrocarbon group are substituted with a substituent.
  • Preferred examples of the unsubstituted hydrocarbon group include aliphatic hydrocarbon groups, and specific examples include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, and 3 to 20 carbon atoms. and cycloalkylalkyl groups having 4 to 20 carbon atoms.
  • Examples of the hydrocarbon group having a substituent include groups in which one or more hydrogen atoms in the unsubstituted hydrocarbon group are substituted with a substituent. , Group IIb or Group IIc, ie, a halogen atom, a cyano group, a nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH or --SO 3 H.
  • the alkyl group having 1 to 20 carbon atoms may be linear or branched.
  • Straight chain alkyl groups include methyl, ethyl, propyl, butyl, hexyl, heptyl and octyl.
  • Branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl and iso-heptyl.
  • tert-heptyl iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, octadecyl and the like.
  • the alkenyl group having 2 to 20 carbon atoms may be linear or branched. Moreover, it may be a terminal alkenyl group having an unsaturated bond at the terminal, or an internal alkenyl group having an unsaturated bond inside. Terminal alkenyl groups include, for example, vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl and 5-hexenyl.
  • Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3- undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienylallyl and the like.
  • the cycloalkyl group having 3 to 20 carbon atoms includes a saturated monocyclic alkyl group having 3 to 20 carbon atoms, a saturated polycyclic alkyl group having 3 to 20 carbon atoms, and Examples include groups having 4 to 20 carbon atoms in which one or more hydrogen atoms are substituted with an alkyl group.
  • Examples of the saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
  • the above saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentanyl and the like.
  • Examples of the alkyl group substituting a hydrogen atom in the ring of the saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified above for the alkyl group having 1 to 20 carbon atoms.
  • Examples of a group in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group are substituted with an alkyl group include bornyl group and the like.
  • the above cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group.
  • a cycloalkyl group in a cycloalkylalkyl group may be monocyclic or polycyclic.
  • the monocyclic cycloalkylalkyl groups having 4 to 20 carbon atoms include, for example, cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl and cyclooctyl.
  • the polycyclic cycloalkylalkyl groups having 4 to 20 carbon atoms include 3-3-adamantylpropyl and decahydronaphthylpropyl.
  • Groups in which one or more hydrogen atoms in the unsubstituted hydrocarbon group are substituted with a substituent and the substituent is a halogen atom include trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, Heptafluoropropyl, 3-bromopropyl, nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1 , 1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, alkyl halides such as 7H-dodecafluorohexyl, norbornyl-1 Halogenated cycloalkyl or halogenated
  • the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R′ and R′′ includes the above hydrocarbon group having 1 to 20 carbon atoms. and the same groups as those mentioned above.
  • the number of carbon atoms in a group defines the number of carbon atoms in the group after the substitution when hydrogen atoms in the group are substituted with a substituent.
  • the 1 to 20 carbon atoms refers to the number of carbon atoms after the hydrogen atom is substituted, and the hydrogen atom is substituted. It does not refer to the number of carbon atoms before
  • the number of carbon atoms in a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group defines the number of carbon atoms in the group before the substitution.
  • the number of carbon atoms in the group in which the methylene group in the alkyl group having 1 to 20 carbon atoms is replaced with a divalent group is 1 to 1, regardless of the number of carbon atoms after replacement. 20 shall be deemed to be met.
  • the number of carbon atoms in the group after being substituted with a methylene group satisfies the requirement for the number of carbon atoms in the group before substitution.
  • the number of carbon atoms in the general formula (A), formula (1), formulas (IVa) to (IVh), (Ara), (Arb), (Ara1) and (Arb1), and (A1) to (A3) below is 2
  • the heterocyclic ring-containing group of ⁇ 20 is a heterocyclic group or a group in which a heterocyclic ring and a hydrocarbon group are bonded, may have an aromatic hydrocarbon ring-containing group, or has an aliphatic hydrocarbon group may have a substituent. In a group in which a heterocyclic ring and a hydrocarbon group are bonded, a bond may exist on the heterocyclic ring or on the hydrocarbon group.
  • a heterocyclic ring-containing group having a substituent is a group having a structure in which one or more hydrogen atoms in the heterocyclic ring-containing group are substituted with a substituent.
  • the definition of "having 2 to 20 carbon atoms" means the total number of carbon atoms in the heterocyclic ring-containing group. Count including the number of carbon atoms.
  • unsubstituted heterocyclic ring-containing groups include pyridyl group, quinolyl group, thiazolyl group, tetrahydrofuran group, dioxolanyl group, tetrahydropyranyl group, morpholylfuran group, thiophene group, methylthiophene group, hexylthiophene group, benzothiophene group, pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, imidazoline group, pyrazole group, pyrazolidine group, piperidine group, piperazine group, pyrimidyl group, furyl group, thienyl group, benzoxazol-2-yl group, thiazole group, isothiazole groups, oxazole groups, isoxazole groups, heterocyclic groups such as morphonyl groups, and groups in which one or more hydrogen atoms of an alkyl group are substituted
  • heterocyclic ring-containing group having a substituent examples include groups in which one or more hydrogen atoms in the unsubstituted heterocyclic ring-containing group are substituted with a substituent, and the like.
  • the unsubstituted heterocyclic ring-containing group may be one in which a heterocyclic ring and an aromatic hydrocarbon ring having a monocyclic structure are linked, or a heterocyclic ring and an aromatic hydrocarbon ring having a condensed ring structure are linked.
  • a single bond, a carbonyl group, etc. are mentioned as a connection group which connects two aromatic-hydrocarbon rings.
  • Examples of the heterocyclic ring-containing group in which a heterocyclic ring and a monocyclic aromatic hydrocarbon ring are linked include benzothiophene and the like.
  • hydrocarbons in the general formula (A), formula (1), formulas (IVa) to (IVh), (Ara), (Arb), (Ara1) and (Arb1), and (A1) to (A3) below group or a group in which one or more of the methylene groups in the heterocycle-containing group is replaced with a divalent group selected from Group Ia, Group Ib, or Group Ic, a plurality of said divalent groups are adjacent have no structure.
  • the plurality of divalent groups referred to here may be the same or different.
  • the group in which one or more methylene groups of the hydrocarbon group are replaced with a divalent group selected from Group Ia, Group Ib, or Group Ic includes, for example, methylene in the bornyl group, which is a hydrocarbon group A 10-camphoryl group, which is a group in which the group is replaced with -CO-, can be mentioned.
  • Examples of unsubstituted aryl groups having 6 to 20 carbon atoms in formulas (IVa) to (IVh) include phenyl, methylphenyl, ethylphenyl and naphthyl groups.
  • Examples of the unsubstituted arylene group having 6 to 20 carbon atoms in the formulas (IVa) to (IVh) include a phenylene group, a methylphenylene group, an ethylphenylene group and a naphthylene group.
  • Examples of the substituent in the aryl group and arylene group having a substituent include a halogen atom, a cyano group, a nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH and --SO 3 H. be done.
  • a is preferably 1 to 20, more preferably 1 to 10, further preferably 1 or 2, and most preferably 1. . This is because when the number is above, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • b in the general formula (A) of compound A is preferably 1 to 20, more preferably 1 to 10, further preferably 1 or 2, most preferably 1 . This is because when the number is above, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • c in the general formula (A) of compound A is preferably 0 to 18, more preferably 0 to 10, even more preferably 0 to 3, and 0 or 1 Even more preferred. This is because when the number is above, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • the total of a, b and c is preferably 21 or less, more preferably 10 or less, and further preferably 5 or less, on the premise that it is a bondable number in the aromatic ring group Ar. Preferably, it is 2 or more and 3 or less, most preferably. This is because when the number is above, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 31 is a group represented by the general formula (1).
  • the group is preferably a halogen atom, more preferably a fluorine atom. This is because it facilitates the formation of an acid generator having excellent acid generating sensitivity.
  • R 1 in the general formula (1) is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or one or more of the methylene groups in the hydrocarbon group is group Ia below.
  • It is preferably a group substituted with a divalent group selected from It is preferably a hydrocarbon group having up to 20 substituents, and the substituent substituting one or more of the hydrogen atoms of the above-mentioned substituted hydrocarbon group is preferably a halogen atom.
  • the hydrocarbon group represented by R 1 in the general formula (1) is preferably a linear or branched alkyl group.
  • the number of carbon atoms in the group represented by R 1 in the general formula (1) is preferably 1-10, more preferably 1-5. This is because it is easy to synthesize and facilitates the formation of an acid generator having excellent sensitivity to acid generation.
  • R 1 in the above general formula (1) is a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in an alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom. It is preferably a halogenated alkyl having 1 to 20 carbon atoms, and in particular, an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom.
  • R 1 in the above general formula (1) is a perfluoroalkyl group having 1 to 4 carbon atoms.
  • a perfluoroalkyl group having 1 to 2 carbon atoms is particularly preferred, and a perfluoroalkyl group having 1 carbon atom, that is, a trifluoromethyl group, is particularly preferred.
  • R 2 in the above general formula (1) is a cyano group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or one or more methylene groups of the above hydrocarbon group.
  • a hydrocarbon group having a halogen atom as a substituent, or one or more of the methylene groups in the unsubstituted or substituted hydrocarbon group having a halogen atom as a substituent is replaced with -COO- is more preferably a group, more preferably a cyano group or a hydrocarbon group having a halogen atom as a substituent having 1 to 20 carbon atoms. is preferably a hydrocarbon group having a halogen atom as a substituent of . This is because it facilitates the formation of an acid generator having excellent acid generating sensitivity.
  • the hydrocarbon group represented by R 2 in the general formula (1) is preferably a linear or branched alkyl group.
  • the number of carbon atoms in the group represented by R 2 in the general formula (1) is preferably 1-10, more preferably 1-5. This is because it is easy to synthesize and facilitates the formation of an acid generator having excellent sensitivity to acid generation.
  • R 2 in the general formula (1) is a group having 1 to 20 carbon atoms in which one or more hydrogen atoms in an alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom.
  • halogenated alkyl having 1 to 20 carbon atoms and in particular, an alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom.
  • a perhaloalkyl group having 1 to 5 carbon atoms which is a group in which all hydrogen atoms in the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms.
  • R 2 in the above general formula (1) is a perfluoroalkyl group having 1 to 3 carbon atoms.
  • a perfluoroalkyl group having 1 to 2 carbon atoms is particularly preferred, and a perfluoroalkyl group having 1 carbon atom, that is, a trifluoromethyl group, is particularly preferred.
  • R 32 is preferably a group represented by a formula selected from general formulas (IVa), (IVf) and (IVh) above, and particularly preferably a group represented by general formula (IVf). .
  • R 67 in general formula (IVf) above is preferably a single bond. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 68 is preferably an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, especially an unsubstituted or substituted hydrocarbon group having 1 to 5 carbon atoms. is preferably a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, and an unsubstituted hydrocarbon group having 1 to 3 carbon atoms A hydrogen group is most preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • At least one of R 33 is a hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted, or at least one methylene group in the hydrocarbon group is selected from Group Ia below. It is preferable to represent a group substituted with a divalent group such that various functions can be easily imparted to the compound (A).
  • the aromatic ring in the aromatic ring group Ar having 5 to 20 carbon atoms constituting the ring may be a 5- to 7-membered monocyclic ring or a condensed ring.
  • monocyclic rings include monocyclic cycloalkanes such as cyclopentane, cyclohexane and cyclopentene, monocyclic aromatic rings such as benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactam ring.
  • monocyclic heterocycles such as Condensed rings include naphthalene and anthracene, carbazole, fluorene, and the like.
  • the aromatic ring group Ar may have a linked ring structure in which a plurality of aromatic rings are linked by direct bonds, —S—, —O—, nitrogen atoms, or the like.
  • the number of 5 to 20 hydrocarbons constituting the ring is the total number of carbon atoms constituting all rings contained in Ar.
  • the carbazole ring has 12 carbon atoms
  • the fluorene ring has 13 carbon atoms.
  • the aromatic ring group Ar is preferably an aromatic ring group having a structure represented by the following general formula (Ara) or (Arb). This is because, as a result, the compound A becomes a compound having excellent sensitivity to acid generation.
  • X 1 is a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR 41 R 42 , CO, NR 43 or PR 44 ;
  • X2 is an oxygen atom, a sulfur atom, a selenium atom, CR41R42 , CO , NR43 or PR44 ;
  • X 3 is NR 53 ;
  • R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or a heterocyclic ring-containing group having a substituent, or a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ib below.
  • R 53 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 111 , —COR 111 , —OCOR 111 , —COOR 111 , —SR 111 , —SOR 111 , —SO 2 R 111 , —NR 112 R 113 , —NR 112 COR 113 , —CONR 112 R 113 , unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted hydrocarbon group having 2 to 20 carbon atoms or a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ib below, R 111 , R 112 and R 113 are each independently a hydrogen atom,
  • R 112 and R 113 each exist in plural numbers, they may be the same or different,
  • the substituent that replaces one or more hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from the following group IIb .
  • Group Ib -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-.
  • Group IIb halogen atom, cyano group, nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH or --SO 3 H.
  • R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R' or R", they may be the same can be different.
  • a is 1 and b is 1 in the general formula (A), and the following partial structure (A ⁇ ) in the general formula (A) is the following general A group represented by the formula (Ara1) or (Arb1) is preferred.
  • R 141 , R 142 , R 151 and R 152 each independently represent a halogen atom, a nitro group, a cyano group, —OR 121 , —COR 121 , —OCOR 121 , —COOR 121 , —SR 121 , —SOR 121 , —SO 2 R 121 , —NR 122 R 123 , —NR 122 COR 123 , —CONR 122 R 123 , unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, 2 to 2 carbon atoms 20 unsubstituted or substituted heterocyclic ring-containing groups, or one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ic below.
  • R 121 , R 122 and R 123 are each independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group having 2 to 20 carbon atoms.
  • the substituent that replaces one or more hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from the following group IIc , a1 is 0 to 3, a2 is 0 to 3; c1 is 0 to 3; c2 is 0 to 1; *1 represents the binding site with R31 , *2 represents the bonding site with R32 .
  • Group Ic -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-.
  • Group IIc halogen atom, cyano group, nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH or --SO 3 H.
  • R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R' or R", they may be the same can be different.
  • X 1 in the general formulas (Ara) and (Ara1) is preferably a single bond, no bond, CR 41 R 42 , CO, or NR 43 , especially a single bond or no bond.
  • a single bond is preferred, and a single bond is most preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • “No bond” means that there is no direct chemical bond to X 1 , for example, the state in which R 11 and R 20 are not bonded in general formula (A1) below.
  • X 2 in the general formulas (Ara) and (Ara1) is preferably a sulfur atom, CR 41 R 42 or NR 43 , and more preferably CR 41 R 42 or NR 43 .
  • the compound A is a compound having excellent sensitivity to acid generation.
  • it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 41 and R 42 used for X 2 in the general formulas (Ara) and (Ara1) are hydrogen atoms, unsubstituted or substituted hydrocarbon groups having 1 to 20 carbon atoms, or It is preferable that one or more of the methylene groups in the hydrocarbon group is a group substituted with a divalent group selected from the above group Ib, especially a hydrogen atom, or an unsubstituted or A hydrocarbon group having a substituent is preferred, and a hydrogen atom or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms is particularly preferred. This is because the compound A is a compound having excellent sensitivity to acid generation.
  • the number of carbon atoms in the hydrocarbon group represented by R 41 and R 42 used for X 2 in the general formulas (Ara) and (Ara1) is preferably 1 to 15, more preferably 1 to 10. is preferred, and 1 to 5 is particularly preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 43 in the general formulas (Ara) and (Ara1) is a hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted, from the viewpoint of ease of synthesis and excellent sensitivity to acid generation, or It is preferable that one or more of the methylene groups in the hydrocarbon group is a group substituted with a divalent group selected from the group Ib, and among them, an unsubstituted or substituted group having 1 to 20 carbon atoms It is preferably a hydrocarbon group, and particularly preferably an unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
  • the number of carbon atoms in the hydrocarbon group represented by R 43 in the general formulas (Ara) and (Ara1) is preferably 1 to 15, especially from the viewpoint of ease of synthesis and excellent sensitivity to acid generation. , preferably 2 to 10, particularly preferably 2 to 9.
  • the aliphatic hydrocarbon group represented by R 43 in the general formulas (Ara) and (Ara1) is preferably a linear or branched alkyl group from the viewpoint of ease of synthesis and excellent sensitivity to acid generation. Among them, a branched alkyl group is preferable. In the case of branching, it is particularly preferred that the number of carbon atoms is 3-9.
  • a1 in the general formula (Ara1) is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0. This is because when the number is above, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • a2 in the general formula (Ara1) is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0. This is because when the number is above, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • c1 is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0. This is because when the number is above, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • c2 in the general formula (Arb1) is preferably 0 to 1, particularly preferably 0. This is because when the number is above, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • X 2 in the general formula (Ara) or (Ara1) is a sulfur atom
  • X 2 in (Ara1) is a sulfur atom
  • X 2 in general formula (Ara) or (Ara1) above is a sulfur atom
  • compound A particularly preferably has a structure represented by general formula (A1) below. This is because, with such a structure, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 11 and R 20 are a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , -OCOR 90 , -COOR 90 , -SR 90 , -SOR 90 , -SO 2 R 90 , —NR 91 R 92 , —NR 91 COR 92 , —CONR 91 R 92 , a group represented by the following general formula (1), or a formula selected from the above formulas (IVa) to (IVh) group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or the above hydrocarbon or a group in which one or more of the methylene groups in the heterocycle-containing group is replaced with a divalent group selected from Group Ia above, or R 11 and R 20 are combined to form a single represents a
  • R91 and R92 each exist in plural numbers, they may be the same or different,
  • the substituent that replaces one or more of the hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from the above group IIa. .
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 is a group represented by the general formula (1); and at least one of the rest is a group represented by a formula selected from the above formulas (IVa) to (IVh). )
  • R 11 and R 20 in the above general formula (A1) each have a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , or an unsubstituted or substituted group having 1 to 20 carbon atoms; a hydrocarbon group in which one or more of the methylene groups in the hydrocarbon group are replaced with a divalent group selected from the above group Ia , or a single bond, —O -, -S-, -Se-, -CR 41 R 42 -, -CO-, -NR 43 - or -PR 44 -, and among these, hydrogen atom, halogen atom, nitro group, cyano is preferably a single bond, —O— or —NR 43 — formed by combining R 11 and R 20 , and particularly a hydrogen atom or is preferably a single bond. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it
  • R 43 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms.
  • R 43 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms.
  • the methylene groups in the hydrocarbon group is preferably a group substituted with a divalent group selected from the group Ib, among which unsubstituted or substituted having 1 to 20 carbon atoms
  • a hydrocarbon group having a group is preferred, and an unsubstituted hydrocarbon group having 1 to 20 carbon atoms is particularly preferred.
  • the compound A is a compound having excellent sensitivity to acid generation.
  • it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • the number of carbon atoms in the hydrocarbon group represented by R 43 in the general formula (A1) is preferably 1 to 15, more preferably 1 to 10, particularly 1 to 5.
  • the hydrocarbon group represented by R 43 in the general formula (A1) is preferably a linear or branched alkyl group, more preferably a linear alkyl group. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 12 , R 14 , R 15 , R 16 , R 17 and R 19 in general formula (A1) are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , An unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the above hydrocarbon group are replaced with a divalent group selected from the above group Ic Among them, a hydrogen atom, a nitro group and a cyano group are preferred, and a hydrogen atom is particularly preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 13 in the general formula (A1) is a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , an unsubstituted or substituted hydrocarbon having 1 to 20 carbon atoms; group, a group in which one or more of the methylene groups in the hydrocarbon group is replaced with a divalent group selected from the group Ic, the group represented by the general formula (1), or the formula (IVa) ⁇
  • a group represented by (IVh) is preferable, and among them, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above general formula (1), or a group represented by the above formulas (IVa) to (IVh) ) is preferably a group represented by a formula selected from a hydrogen atom, a group represented by the above general formula (1), or a group represented by a formula selected from the above formulas (IVa) to (IV
  • R 18 in the general formula (A1) is a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , an unsubstituted or substituted hydrocarbon having 1 to 20 carbon atoms; group, a group in which one or more of the methylene groups in the hydrocarbon group is replaced with a divalent group selected from the group Ic, a group represented by the general formula (1) or the formula (IVa) ⁇ ( IVh) is preferably a group represented by a formula selected from, among others, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above general formula (1), or the above formula (IVa) ⁇ (IVh) is preferably a group represented by a formula selected from a hydrogen atom, a group represented by the general formula (1) or a formula selected from the above formulas (IVa) to (IVh) is preferably a group, and particularly
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 is ), and at least one of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 is a group represented by the above formula (IVa ) to (IVh).
  • R 13 and R 18 is a group represented by the above general formula (1)
  • the other group is a group represented by a formula selected from the above formulas (IVa) to (IVh).
  • a formula selected from the above formulas (IVa) to (IVh) Preferably.
  • R 13 in general formula (A1) is a group represented by general formula (1) above
  • R 18 in general formula (A1) is a formula selected from formulas (IVa) to (IVh) above. is preferably a group represented by This is because, with such a structure, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • groups represented by formulas selected from general formulas (IVa) to (IVh) are preferred, In particular, it is preferably a group represented by general formula (IVf). This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 67 in general formula (IVf) above is preferably a single bond.
  • R 68 is preferably an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, especially an unsubstituted or substituted hydrocarbon group having 1 to 5 carbon atoms. is preferably a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, and an unsubstituted hydrocarbon group having 1 to 3 carbon atoms A hydrogen group is preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • X 1 in the general formula (Ara) or (Ara1) is preferably a single bond, and X 2 is NR 43.
  • X 1 is a single bond and X 2 is NR 43 in the above general formula (Ara) or (Ara1)
  • compound A has a structure represented by the following general formula (A2) Preferably. This is because, with such a structure, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 12' R 13' , R 14' , R 15' , R 16' , R 17' , R 18' and R 19' are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, - OR 90 , -COR 90 , -OCOR 90 , -COOR 90 , -SR 90 , -SOR 90 , -SO 2 R 90 , -NR 91 R 92 , -NR 91 COR 92 , -CONR 91 R 92 , the above general formula A group represented by (1), a group represented by a formula selected from the above formulas (IVa) to (IVh), an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, carbon unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 atoms, or one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is divalent selected from
  • R91 and R92 each exist in plural numbers, they may be the same or different,
  • the substituent that replaces one or more of the hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from the above group IIa. .
  • R 12′ R 13′ , R 14′ , R 15′ , R 16′ , R 17′ , R 18′ and R 19′ is a group represented by the general formula (1) and at least one of the rest is a group represented by a formula selected from the above formulas (IVa) to (IVh).
  • R 12′ , R 14′ , R 15′ , R 16′ , R 17′ and R 19′ in general formula (A2) are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a divalent divalent group in which one or more methylene groups in the above hydrocarbon group are selected from the above group Ic A group substituted with a group is preferable, and among these, a hydrogen atom, a nitro group, and a cyano group are preferable, and a hydrogen atom is particularly preferable.
  • the compound A is a compound having excellent sensitivity to acid generation.
  • it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 13′ in the general formula (A2) is a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , unsubstituted or substituted carbon having 1 to 20 carbon atoms.
  • ⁇ ( IVh) is preferably a group represented by a formula selected from a hydrogen atom, a group represented by the general formula (1) or a group represented by a formula selected from the above formulas (IVa) to (IVh) is preferred, and a group represented by the general formula (1) is particularly preferred.
  • the compound A is a compound having excellent sensitivity to acid generation.
  • R 18′ in the general formula (A2) is a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , unsubstituted or substituted carbon having 1 to 20 carbon atoms.
  • It is preferably a group represented by a formula selected from ⁇ (IVh), a hydrogen atom, a group represented by the above general formula (1) or a formula selected from the above formulas (IVa) ⁇ (IVh) is preferably a group represented by a formula selected from the above formulas (IVa) to (IVh).
  • R 12′ , R 13′ , R 14′ , R 15′ , R 16′ , R 17′ , R 18′ and R 19′ Any group represented by (1) may be used, and one or more of R 12′ , R 13′ , R 14′ , R 15′ , R 16′ , R 17′ , R 18′ and R 19′ are Any group represented by a formula selected from the above formulas (IVa) to (IVh) may be used.
  • one group of R 13' and R 18' is a group represented by the above general formula (1), and the other group is represented by a formula selected from the above formulas (IVa) to (IVh). It is preferably a group.
  • R 13′ in the general formula (A2) is a group represented by the general formula (1)
  • R 18′ in the general formula (A2) is selected from the formulas (IVa) to (IVh).
  • a group represented by the formula is preferable. This is because, with such a structure, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • groups represented by formulas selected from general formulas (IVa) to (IVh) are preferred, In particular, it is preferably a group represented by general formula (IVf). This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 67 in general formula (IVf) above is preferably a single bond.
  • R 68 is preferably an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, especially an unsubstituted or substituted hydrocarbon group having 1 to 5 carbon atoms. is preferably a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, and an unsubstituted hydrocarbon group having 1 to 3 carbon atoms A hydrogen group is preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 43 in the above general formula (A2) is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or one or more of the methylene groups in the above hydrocarbon group It is preferably a group substituted with a divalent group selected from, among others, preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, particularly carbon An unsubstituted hydrocarbon group having 1 to 20 atoms is preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • the number of carbon atoms in the hydrocarbon group represented by R 43 in the general formula (A2) is preferably 1 to 15, more preferably 2 to 10, particularly 2 to 9. Preferably. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • the hydrocarbon group represented by R 43 in the general formula (A2) is preferably a linear or branched alkyl group, more preferably a branched alkyl group. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation. Furthermore, it is because the solubility to a solvent becomes favorable.
  • X 1 in the general formula (Ara) or (Ara1) is preferably a single bond, and X 2 is CR 41 R 42 .
  • X 1 is a single bond
  • X 2 is CR 41 R 42
  • the compound A is a compound having excellent sensitivity to acid generation.
  • X 1 is a single bond
  • X 2 is CR 41 R 42 in the above general formula (Ara) or (Ara1)
  • compound A is represented by the following general formula (A3)
  • a structure is preferred. This is because, with such a structure, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • the skeleton of formula (A3) also has the advantage of easily obtaining solvent solubility.
  • R12 '' , R13 '' , R14'', R15 '' , R16 '' , R17 '' , R18 '' and R19 '' are a hydrogen atom, a halogen atom, a nitro group , cyano group, —OR 90 , —COR 90 , —OCOR 90 , —COOR 90 , —SR 90 , —SOR 90 , —SO 2 R 90 , —NR 91 R 92 , —NR 91 COR 92 , —CONR 91 R 92 , a group represented by the above general formula (1), a group represented by a formula selected from the above formulas (IVa) to (IVh), and an unsubstituted or substituted group having 1 to 20 carbon atoms One or more of a hydrocarbon group, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a m
  • R91 and R92 each exist in plural numbers, they may be the same or different,
  • the substituent that replaces one or more of the hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from the above group IIa. .
  • R 12'' , R 13'' , R 14'' , R 15'' , R 16'' , R 17'' , R 18'' and R 19'' A group represented by formula (1), and at least one of the remaining groups is a group represented by a formula selected from the above formulas (IVa) to (IVh).
  • R 41 and R 42 are hydrogen atoms, unsubstituted or substituted hydrocarbon groups having 1 to 20 carbon atoms, or one or more methylene groups in the above hydrocarbon groups selected from Group Ib above. It is preferably a group substituted with a divalent group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted, particularly , a hydrogen atom, or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
  • the compound A is a compound having excellent sensitivity to acid generation.
  • it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • the number of carbon atoms in the hydrocarbon group represented by R 41 and R 42 in the general formula (A3) is preferably 1 to 15, more preferably 1 to 10, particularly 1 ⁇ 5 is preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • R 12′′ , R 15′′ , R 16′′ and R 19′′ in the general formula (A3) are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or one or more of the methylene groups in the above hydrocarbon group is replaced with a divalent group selected from the above group Ic Among them, a hydrogen atom, a nitro group and a cyano group are preferred, and a hydrogen atom is particularly preferred. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • At least one of R 13′′ and R 14′′ in the general formula (A3) is a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , unsubstituted having 1 to 20 carbon atoms.
  • R 14 ′′ satisfies these conditions. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • At least one of R 17 ′′ and R 18 ′′ in the general formula (A3) is a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 90 , —COR 90 , or a C 1-20 inorganic group.
  • a substituted or substituted hydrocarbon group a group in which one or more methylene groups in the hydrocarbon group are replaced with a divalent group selected from the above group Ic, represented by the above general formula (1) or a group represented by a group selected from the above formulas (IVa) to (IVh), among which a hydrogen atom, a halogen atom, a nitro group, a cyano group, the above general formula (1) or a group represented by a group selected from the above formulas (IVa) to (IVh), a hydrogen atom, a group represented by the above general formula (1), or a group represented by the above formula (IVa) to A group represented by a group selected from (IVh) is preferable, and a group represented by a group selected from the above formulas (IVa) to (IVh) is particularly preferable.
  • R 17'' preferably satisfies these conditions. This is because the compound A is a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize,
  • R 12′′ , R 13′′ , R 14′′ , R 15′′ , R 16′′ , R 17′′ , R 18′′ and R 19′′ It suffices that at least one of them is a group represented by the general formula (1), and R 12′′ , R 13′′ , R 14′′ , R 15′′ , R 16′′ and R 17′′ , R 18 ′′ and R 19 ′′ may be a group represented by a group selected from the above formulas (IVa) to (IVh).
  • one group of R 13 '' and R 18 '' is a group represented by the above general formula (1), and the other group is a group selected from the above formulas (IVa) to (IVh).
  • one group of R 14′′ and R 17′′ is a group represented by the above general formula (1), and the other group is a group represented by the above formulas (IVa) to ( It is preferably a group represented by a group selected from IVh).
  • R 14'' in the general formula (A3) is a group represented by the general formula (1)
  • R 17'' in the general formula (A3) is from the formulas (IVa) to (IVh). It is preferably a group represented by the selected group. This is because, with such a structure, the compound A becomes a compound having excellent sensitivity to acid generation. In addition, it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • a group represented by a group selected from general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) are preferred, and groups represented by groups selected from general formula (IVf) are particularly preferred.
  • the compound A is a compound having excellent sensitivity to acid generation.
  • it is easy to synthesize, and it becomes easy to form an acid generator having excellent sensitivity to acid generation.
  • the compound A can be produced by any method that yields a compound having a desired structure, and can be synthesized by applying known chemical reactions.
  • the method represented by the following scheme is mentioned. Specifically, an oxime compound is obtained by reacting a known ketone compound with hydroxylamine hydrochloride. Subsequently, the oxime compound is reacted with a sulfonic anhydride. Next, there is a method of obtaining compound A by reacting a compound having a group represented by R 32 , for example, a diketone body such as chloroglyoxylic acid. Reaction conditions such as reaction temperature, reaction time and amount of raw materials used in the production method are not particularly limited, and known conditions may be adopted.
  • the above compound A has a function of generating an acid.
  • a method for generating an acid from the compound A a method commonly used for acid generators can be used. Specific examples include a method of irradiating energy rays, a method of heat treatment, and a method of performing these methods simultaneously or sequentially.
  • the energy rays include g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), visible rays, ultraviolet rays, deep ultraviolet rays, X-rays and charged particle rays.
  • the heating temperature in the heat treatment is, for example, preferably 70° C. or higher and 450° C. or lower, more preferably 100° C. or higher and 300° C. or lower, and may be 150° C. or higher.
  • the heating time in the heat treatment is preferably, for example, 1 minute or more and 100 minutes or less. This is because the effect of obtaining a composition with little color change can be effectively exhibited under the above heat treatment conditions.
  • Examples of applications of the compound A include acid generators, and more specifically, photoacid generators that generate acid by irradiation with energy rays, thermal acid generators that generate acid by heat treatment, and the like. can be done.
  • the use of the acid generator can include the use of addition to a composition containing a resin component.
  • Applications of the composition include, for example, optical filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed circuit boards, semiconductor devices, LED packages, and liquid crystal inlets. Sealing agents, molding materials, putties, glass fiber impregnating agents, fillers, passivation for semiconductors, solar cells, etc.
  • TFT thin film transistor
  • liquid crystal display device organic EL display device
  • interlayer insulating film used for printed circuit board, surface protective film, printed circuit board, or color filter for color TV, PC monitor, mobile information terminal, CCD image sensor , electrode materials for plasma display panels, printing inks, dental compositions, stereolithographic resins, both liquid and dry films, micromechanical parts, glass fiber cable coatings, holographic recording materials, magnetic recording materials, optical switches, Plating masks, etching masks, stencils for screen printing, touch panels such as transparent conductive films, MEMS devices, nanoimprint materials, photofabrication such as two-dimensional and three-dimensional high-density mounting of semiconductor packages, decorative sheets, artificial nails, glass Alternative optical films, electronic paper, optical discs, microlens arrays used in projectors and optical communication lasers, etc., prism lens sheets used in the backlight of liquid crystal display devices, fresnel lens sheets used in projection television screens, etc.
  • Lens parts of lens sheets such as lenticular lens sheets, backlights using such sheets, optical lenses such as microlenses and imaging lenses, optical elements, optical connectors, optical waveguides, insulating packing, heat-shrink rubber Tubes, O-rings, sealants for display devices, protective materials, optical fiber protective materials, adhesives, die-bonding agents, high heat dissipation materials, high heat resistance sealants, members for solar cells, fuel cells, secondary cells, batteries
  • Civil engineering and construction materials such as solid electrolytes, insulation coating materials, photosensitive drums for copiers, gas separation membranes, concrete protection materials, linings, soil injection agents, sealing agents, cold storage materials, glass coatings, foams, etc., tubes and sealing materials ⁇ Coating materials ⁇ Seal materials for sterilization equipment ⁇ Contact lenses ⁇ Oxygen-enriched membranes, medical materials such as biochips, automobile parts, various machine parts, etc.
  • the above application is preferably for a pattern-forming composition, for example, a negative composition that is used together with an acid-curable component. It is preferably for positive compositions used with an acid-decomposable component (also referred to as an "acid-decomposable resin component"), and more specifically, for optical lenses, optical elements, optical connectors, and optical waveguides. It is preferably for compositions used for forming interlayer insulating films and the like used in liquid crystal display devices, organic EL display devices, printed circuit boards, and the like, which require high sensitivity to acid generation.
  • Acid Generator One of the characteristics of the acid generator of the present invention is that it contains the compound A described above. By including the compound A in the acid generator, an acid generator having excellent sensitivity to acid generation can be easily obtained.
  • Compound A The type of the compound A used in the acid generator of the present invention is not particularly limited as long as it can easily provide an acid generator with excellent sensitivity to acid generation. Two or more types may be used.
  • the content of the compound A in the acid generator of the present invention may be any amount that allows an acid generator with excellent acid generation sensitivity to be obtained easily, and is appropriately set according to the type of the acid generator. be.
  • the content of the compound A in the acid generator of the present invention is, for example, 100 parts by mass per 100 parts by mass of the solid content of the acid generator, that is, the solid content of the acid generator is only the compound A.
  • the content of the above compound A in the acid generator of the present invention is less than 100 parts by mass per 100 parts by mass of the solid content of the acid generator, that is, the acid generator is a composition containing the above compound A and other components. For example, it can be more than 20 parts by mass and 99.99 parts by mass or less.
  • the acid generator of the present invention contains components other than the above compound A, from the viewpoint that an acid generator having excellent sensitivity to acid generation can be obtained more easily, the is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 90 parts by mass or more per 100 parts by mass of the solid content of the acid generator. This is because, by setting the upper limit of the content of the compound A within the above range, an acid generator having excellent sensitivity to acid generation can be easily obtained.
  • the upper limit of the content of compound A in the acid generator of the present invention is 99 parts by mass per 100 parts by mass of the solid content of the acid generator. or less, more preferably 95 parts by mass or less, and even more preferably 90 parts by mass or less. This is because when the content of the compound A is within the above range, an acid generator having excellent sensitivity to acid generation can be easily obtained.
  • the solid content includes all components other than the solvent.
  • the content of the compound A indicates the total amount of the compound A when two or more kinds of the compound A are included.
  • the above compound A can be the same as the content described in the above "A. Compound” section, so the explanation here is omitted.
  • the acid generator may contain components other than the compound A described above.
  • examples of such other components include solvents.
  • the solvent is capable of dispersing or dissolving each component in the acid generator. Therefore, even if it is liquid at normal temperature (25° C.) and atmospheric pressure, the compound A is not included in the solvent.
  • Either water or an organic solvent can be used as the solvent.
  • the solvent is preferably an organic solvent. This is because the compound A can be easily dissolved or dispersed.
  • organic solvent examples include carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; monomethyl ether of ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate; polyhydric alcohols such as monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; esters such as ethyl formate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; Lactones such as ⁇ -caprolactone and ⁇ -caprolactone are included.
  • carbonates such as propylene carbonate and diethyl carbonate
  • ketones such as acetone and 2-heptanone
  • the content of the solvent in the acid generator can be 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the acid generator.
  • Components other than the compound A and the solvent include those described in the sections "2. Resin component” and “3. Other components” of "C. Composition” described later. Further, the other components include known compounds used as acid generators.
  • the content of the above-mentioned other components can be appropriately set according to the use of the acid generator. It is more preferably 10 parts by mass or less. This is because the content of the compound A can be easily increased in the acid generator, and an acid generator having excellent sensitivity to acid generation can be obtained more easily.
  • any method may be used as long as the above compound A can be contained in a desired blending amount.
  • the acid generator contains compound A and other components, methods using known mixing means can be used.
  • Uses of the acid generator include use of addition to a composition containing a resin component. Specifically, it can be the same as described in the section "A. Compounds" above.
  • compositions of the present invention contains the compound A described above and a resin component. By containing the above compound A, the resulting composition or the like has excellent sensitivity to acid generation.
  • Compound A used in the composition of the present invention may be of any kind as long as it exhibits an effect of being excellent in sensitivity to acid generation. may
  • the content of the compound A in the composition of the present invention may be any amount that exhibits the effect of improving the sensitivity to acid generation, and is appropriately set according to the type of the resin component used.
  • the content of compound A in the composition of the present invention is, for example, preferably 0.05 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the resin component, and 0.05 parts by mass or more and 20 parts by mass or less. is more preferable. This is because a composition capable of exhibiting an effect of being excellent in sensitivity to acid generation can be easily obtained. Moreover, it is because formation of the composition etc. which coloring was suppressed is easy.
  • the content of compound A in the composition of the present invention is preferably, for example, 0.001 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the solid content of the composition. This is because a composition capable of exhibiting an effect of being excellent in sensitivity to acid generation can be easily obtained. Moreover, it is because formation of the composition etc. which coloring was suppressed is easy.
  • the content of compound A in the composition of the present invention is preferably, for example, 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. This is because a composition capable of exhibiting an effect of being excellent in sensitivity to acid generation can be easily obtained. Moreover, it is because formation of the composition etc. which coloring was suppressed is easy.
  • the above content of compound A indicates the total amount of compound A when two or more types of compound A are included.
  • Resin Component As the resin component, a polymer compound or a component that can become a polymer compound can be used. Further, the resin component may be an acid-reactive component having a structure capable of reacting with the acid generated from the compound A, or may be a non-acid-reactive component that does not react with the acid generated from the compound A. Preferably, the resin component is an acid-reactive component. This is because when the resin component is an acid-reactive component, the above composition can easily obtain the effect of being excellent in the sensitivity to acid generation that compound A has. Moreover, it is because formation of the composition etc. which coloring was suppressed is easy.
  • an acid-reactive component examples include an acid-curable component that is cured by polymerization or cross-linking with an acid generated from compound A, or an acid-decomposable component that increases solubility in a developer with acid generated from compound A. is preferably used.
  • the resin component when the resin component is an acid-curable component, the effect of being excellent in sensitivity to acid generation can be effectively exhibited, and the acid-curable component can be easily cured.
  • the resin component is an acid-decomposable component, the effect of being excellent in sensitivity to acid generation can be effectively exhibited, and the decomposition of the acid-decomposable component is facilitated.
  • a composition can be obtained in which coloration is suppressed in non-development areas without causing a change in solubility in a developer.
  • Examples of the acid-curable component include cationic polymerizable compounds.
  • Examples of the cationic polymerizable compounds include epoxy compounds, cyclic ether compounds such as oxetane compounds, vinyl ether compounds, vinyl compounds, styrenes, spiroorthoesters, bicycloorthoesters, spiroorthocarbonates, lactones, oxazolines, In addition to aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams, aryldialdehydes, and the like, polymerizable or crosslinkable polymers and oligomers having these polymerizable groups in side chains are exemplified.
  • cationically polymerizable compounds include, for example, acid-reactive organic substances described in WO 2017/130896, cationically polymerizable compounds described in WO 2014/084269, WO 2016/132413, etc. Compounds described as compounds can be used.
  • a mixture of a crosslinkable resin and a crosslinker can also be used as the acid-curable component.
  • the crosslinkable resin include two or more selected from polyhydroxystyrene and its derivatives; polyacrylic acid and its derivatives; polymethacrylic acid and its derivatives; hydroxystyrene, acrylic acid, methacrylic acid and their derivatives.
  • polystyrene examples include phenolic hydroxyl group-containing resins (QN) described in JP-A-2018-112670.
  • crosslinkable resin examples include, for example, a resist base resin described in WO 2017/130896, and the component (A) described in JP 2003-192665, whose solubility in an alkaline developer changes under the action of an acid. Resins described as claim 3 of JP-A-2004-323704 and alkali-soluble resins described in JP-A-10-10733 can also be used.
  • the polymer having the alkoxysilyl group for example, a compound in which the alkoxysilyl group is not directly bonded to the aromatic ring can be used.
  • any cross-linking agent may be used as long as it is capable of cross-linking the above cross-linkable resins in the presence of an acid.
  • cross-linking agents include acidic groups such as phenolic hydroxyl groups and carboxyl groups contained in the above resins, such as epoxy group-containing compounds, hydroxyl group-containing compounds, alkoxy group-containing compounds, methylol group-containing compounds, and carboxymethyl group-containing compounds. and a compound capable of reacting in the presence of an acid can be used.
  • the cross-linking agent includes the cross-linking agents described in JP-A-2016-169173 and JP-A-2018-112670.
  • the acid-decomposable component may be any component as long as it increases the solubility in a developer by the acid generated from compound A.
  • it has an acidic group such as a phenolic hydroxyl group, a carboxyl group, a sulfonyl group, and a silanol group.
  • Resins in which some or all of the hydrogen atoms of the acidic groups in the resin are protected with protective groups can be mentioned.
  • the resin having such an acidic group include the crosslinkable resin used together with the crosslinker as the acid-curable component described above.
  • a positive chemical amplification resin described in JP-A-2018-112670 can also be used.
  • the protecting group may be any one as long as it can protect the acidic group.
  • the acid dissociable group described in JP-A-112670 and the like can be mentioned.
  • an alkoxysilyl group is mentioned as said group by which the said silanol group was protected by the protecting group.
  • the polymer having an alkoxysilyl group used as an acid-decomposable component include, for example, the structural unit containing an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring described in JP-A-2019-66828 ( I) and a polymer component (A) having a structural unit (II) containing an acidic group” can be used.
  • the developing solution include the developing solution described in the section "G. Pattern manufacturing method" described later.
  • a component that reacts with an acid in addition to the acid-curable component and the acid-decomposable component, a component that reacts with an acid can be used.
  • a resin having an alkali-soluble group that is insolubilized by an acid can also be used. can be done.
  • Specific examples include acid-insolubilizing resins that cause intramolecular or intermolecular cross-linking reactions by acid-catalyzed dehydration condensation between hydroxyl groups and carboxyl groups, and between carboxyl groups as exemplified below.
  • Acid-insolubilizing resins that cause acid-catalyzed dehydration condensation between carboxyl groups include, for example, resins having a phthalic acid structure in which carboxyl groups undergo dehydration condensation with an acid, as shown below.
  • the non-acid-reactive component is a component that does not react with the acid generated from compound A, more specifically, a component that does not cause hardening, decomposition, or change in solubility in an alkaline developer due to the acid generated from compound A.
  • examples thereof include thermoplastic resins such as polyolefin-based resins, polybutadiene-based resins, polystyrene-based resins, polystyrene/butadiene-based resins, and polystyrene/olefin-based resins.
  • the content of the resin component in the composition of the present invention is not limited as long as it can provide an effect of excellent sensitivity to acid generation, and is appropriately set according to the type of the resin component used. .
  • the content of the resin component in the composition of the present invention can be, for example, 10 parts by mass or more in 100 parts by mass of the solid content of the composition, and is 30 parts by mass or more and 99.9 parts by mass or less. is preferred, and more preferably 50 parts by mass or more and 99 parts by mass or less. This is because it is possible to effectively obtain the effect of obtaining excellent sensitivity to acid generation.
  • the content of the resin component in the composition of the present invention can be, for example, 10 parts by mass or more in 100 parts by mass of the composition, and more preferably 30 parts by mass or more and 99.9 parts by mass or less. , 50 parts by mass or more and 96 parts by mass or less. This is because it is possible to effectively obtain the effect of obtaining excellent sensitivity to acid generation.
  • the composition may contain a solvent.
  • the solvent is capable of dispersing or dissolving each component in the composition. Therefore, even if they are liquid at normal temperature (25° C.) and atmospheric pressure, the compound A and the resin component are not included in the solvent.
  • Either water or an organic solvent can be used as the solvent.
  • the solvent is preferably an organic solvent. This is because the compound A can be easily dissolved or dispersed.
  • the organic solvent may be the same as described in the section "B. Acid generator".
  • the content of the solvent in the composition of the present invention is appropriately set according to the use of the composition, for example, 1 part by mass or more and 99 parts by mass or less per 100 parts by mass of the composition. can do.
  • composition may optionally contain other ingredients.
  • other components can be selected depending on the application of the composition, and examples thereof include benzotriazole-based, triazine-based, and benzoate-based UV absorbers; phenol-based, phosphorus-based, and sulfur-based antioxidants.
  • Antistatic agents composed of cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, etc.; Halogen compounds, phosphoric ester compounds, phosphoramide compounds, melamine compounds, Flame retardants such as fluorine resins or metal oxides, melamine (poly)phosphate, and piperazine (poly)phosphate; hydrocarbons, fatty acids, aliphatic alcohols, aliphatic esters, aliphatic amides, or metal soaps dyes, pigments, coloring agents such as carbon black; fumed silica, fine particle silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, leech Silicic acid inorganic additives such as stone, attapulgite, talc, mica, minnesotite, pyrophyllite, silica; fillers such
  • the above-mentioned other components may also contain acid diffusion control agents such as amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.
  • the sensitizer include compounds described as spectral sensitizers in JP-T-2008-506749.
  • the acid diffusion controller include compounds described as "[D] acid diffusion controller" in JP-A-2019-8300.
  • the content of these other components in the composition of the present invention can be 50 parts by mass or less per 100 parts by mass of the composition.
  • any known method can be used as long as it is a method capable of mixing each of the above components in a desired blending amount.
  • a method of dissolving or dispersing the compound A in a solvent and then adding a resin component to the solvent can be used.
  • the cured product of the present invention is a cured product of the composition described above. Moreover, the resin component contained in the composition is an acid-curable component.
  • the cured product of the present invention uses the composition described above.
  • the resin component is an acid-curable component.
  • the cured product is obtained by curing the acid-curable component, and includes a polymer obtained by polymerizing the acid-curable components or a cross-linked product obtained by crosslinking the acid-curable components.
  • the content of such a composition can be the same as the content described in the section "C. Composition" above, so the description is omitted here.
  • the shape of the cured product in plan view can be appropriately set according to the application of the cured product, and can be, for example, a pattern such as a dot shape or a line shape.
  • the method for producing the cured product is not particularly limited as long as it is a method capable of forming the cured product of the composition into a desired shape.
  • a production method for example, the production method described in the section “E. Production method of cured product” described later can be used.
  • One of the characteristics of the method for producing a cured product of the present invention is to have a curing step of curing the composition described above. Moreover, the resin component contained in the composition is an acid-curable component.
  • the composition described above by using the composition described above, it is possible to effectively exhibit the effect of being excellent in sensitivity to acid generation, and to easily form a cured product in which curing of the acid-curable component has sufficiently progressed. .
  • the curing step in the present invention is a step of curing the composition described above.
  • any method can be used as long as it can cure the acid-curable component, and a method for generating an acid from compound A can be used.
  • the method for generating an acid from compound A may be any method as long as it can generate a desired amount of acid from compound A. Examples include a method of irradiating with energy rays, a method of heat treatment, and a method of performing these simultaneously or in sequence. be able to.
  • the method of irradiating with energy rays, the method of heat treatment, and the like the same methods as those described in the above section "A. Compounds" can be used.
  • the method of generating an acid includes a method of irradiating an energy ray. This is because the effect of being excellent in sensitivity to acid generation can be effectively exhibited, and the acid-curable component can be effectively cured.
  • the above composition contains an acid-curable component as a resin component.
  • the content of such a composition can be the same as the content described in the section "C. Composition" above, so the description is omitted here.
  • the method for producing a cured product of the present invention may optionally include other steps in addition to the above-described curing step.
  • the other steps include, after the curing step, a developing step to obtain a patterned cured product by removing unpolymerized portions in the coating film of the composition, a post-baking step of heat-treating the cured product after the curing step, A pre-baking step of heat-treating the composition to remove the solvent in the composition before the curing step, and a step of forming a coating film of the composition before the curing step can be exemplified.
  • the other steps include a post-baking step.
  • the acid generated from compound A can be effectively diffused. As a result, it becomes easy to form a cured product in which curing of the acid-curable component has progressed sufficiently.
  • Examples of the method for removing the unpolymerized portion in the development step include a method of applying a developer such as an alkaline developer to the unpolymerized portion.
  • a developer such as an alkaline developer
  • alkaline developers those commonly used as alkaline developers such as tetramethylammonium hydroxide (TMAH) aqueous solution, potassium hydroxide aqueous solution, potassium carbonate aqueous solution, etc. can be used.
  • TMAH tetramethylammonium hydroxide
  • solvent developers such as propylene glycol monomethyl ether acetate (PEGMEA) and cyclohexanone can be used.
  • any method can be used as long as it allows contact between the site to be developed and the developer, and known methods such as a shower method, a spray method, and an immersion method can be used.
  • the execution timing of the developing step may be after the curing step.
  • the heating conditions in the post-baking step may be those that can improve the strength of the cured product obtained in the curing step, for example, 200° C. or higher and 250° C. or lower for 20 to 90 minutes.
  • the heating conditions in the prebaking step may be any conditions as long as the solvent in the composition can be removed, for example, 70 to 150° C. for 30 to 300 seconds.
  • the coating film can be formed on a substrate.
  • the base material can be appropriately selected according to the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like.
  • the cured product may be peeled off from the base material, or may be transferred from the base material to another adherend.
  • Pattern The pattern of the present invention is produced using a positive resist comprising the composition described above. Further, the resin component contained in the composition is an acid-decomposable component.
  • the present invention by using the composition described above, the effect of being excellent in acid generation sensitivity can be effectively exhibited, and the decomposition of acid-decomposable components is facilitated. As a result, it becomes easy to form a pattern with excellent dimensional accuracy.
  • the pattern of the present invention employs the composition described above.
  • the resin component is an acid-decomposable component.
  • the pattern is formed by forming a coating film using the composition described above and removing unnecessary portions. Specifically, after forming a coating film, energy rays are irradiated through a predetermined mask or the like, and acid is generated in the irradiated portions to increase the solubility in the developer, and the irradiated portions are developed. is formed by removing
  • the content of such a composition can be the same as the content described in the section "C. Composition" above, so the description is omitted here.
  • the shape of the pattern in plan view can be appropriately set according to the application of the pattern, and can be, for example, a dot shape, a line shape, or the like.
  • the method for producing the pattern is not particularly limited as long as it is a method capable of forming the composition into a desired shape.
  • a manufacturing method for example, the manufacturing method described in the section “G. Pattern manufacturing method” described later can be used.
  • the method for producing a pattern of the present invention includes the steps of forming a coating film using the composition described above, generating an acid from a compound contained in the formed coating film, and generating an acid from the compound. is developed to remove a portion of the coating film to form a pattern.
  • the resin component contained in the composition is an acid-decomposable component.
  • Step of Generating Acid is a step of generating an acid from the compound A contained in the coating film formed using the composition described above.
  • the method for generating an acid from the compound A may be any method as long as it can generate a desired amount of acid from the compound A.
  • a method of irradiating an energy ray, a method of heat treatment, and these simultaneously or A sequential method can be mentioned.
  • the method of irradiating with energy rays, the method of heat treatment, and the like the same methods as those described in the above section "A. Compounds" can be used.
  • the method of generating an acid includes a method of irradiating an energy ray. This is because it is possible to effectively exhibit the effect of obtaining a pattern excellent in dimensional accuracy and the like.
  • the part of the coating film where acid is generated is a part of the coating film in plan view. This is because the step of forming a pattern, which will be described later, can be easily carried out.
  • the plan view shape and thickness of the coating film are appropriately set according to the use of the pattern coating film.
  • the above composition contains an acid-decomposable component as a resin component.
  • the content of such a composition can be the same as the content described in the section "C. Composition" above, so the description is omitted here.
  • the step of forming a pattern in the present invention is a step of forming a pattern by developing the coating film to remove a portion thereof after the step of generating acid from the compound.
  • a method of developing in this step a method of developing using a developer can be mentioned.
  • developer and development method can be the same as those described in the above section "E. Production method of cured product”.
  • the pattern manufacturing method of the present invention includes the step of generating the acid and the step of forming the pattern, but may include other steps as necessary. Such other steps include a step of forming a coating film of the composition before the step of generating the acid, and a heat treatment after the step of forming the coating film to remove the solvent in the coating film.
  • a pre-baking step or the like can be mentioned.
  • the other steps include a post-exposure baking step.
  • the acid generated from compound A can be effectively diffused. As a result, the decomposition of the acid-decomposable component can proceed more effectively.
  • the process of forming the coating film and the process of prebaking may be the same as those described in the above section "E. Method for producing cured product". Further, the conditions for the post-exposure bake step may be, for example, 70° C. or higher and 150° C. or lower for 30 seconds to 300 seconds.
  • Ar is an aromatic ring group having 5 to 20 carbon atoms constituting the ring
  • R 31 represents a group represented by the following general formula (1)
  • R 32 is a group represented by a formula selected from the following general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh)
  • R 33 is a halogen atom, a nitro group, a cyano group, —OR 34 , —COR 34 , —OCOR 34 , —COOR 34 , —SR 34 , —SOR 34 , —SO 2 R 34 , —NR 35 R 36 , — NR 35 COR 36 , —CONR 35 R 36 , unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted heterocyclic group having 2 to 20 carbon atom
  • R 35 or R 36 When there are multiple 34 , R 35 or R 36 , they may be the same or different,
  • the substituent that replaces one or more of the hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from Group IIa below.
  • a represents an integer from 1 to 20
  • b represents an integer from 1 to 20
  • c represents an integer from 0 to 18, The sum of a, b and c is 21 or less.
  • R 1 is an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms. , or represents a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ia below
  • R 2 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted group having 2 to 20 carbon atoms; a heterocyclic ring-containing group or a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ia below,
  • R 51 represents OR 81 , NR 82 R 83 or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms
  • R 52 and R 53 each independently represent R 81 or OR 81 , R 52 and R 53 may combine to form a ring
  • R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64 , R 65 , R 71 and R 73 each independently have an unsubstituted or substituted group having 6 to 20 carbon atoms
  • represents an aryl group with R 54 , R 57 , R 60 , R 63 , R 66 , R 67 and R 72 each independently represent an unsubstituted or substituted arylene group having 6 to 20 carbon atoms or a single bond
  • R 68 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms
  • Group Ia -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-.
  • Group IIa halogen atom, cyano group, nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH or --SO 3 H.
  • R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R' or R", they may be the same can be different.
  • Ar is an aromatic ring group having a structure represented by the following general formula (Ara) or (Arb).
  • X 1 is a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR 41 R 42 , CO, NR 43 or PR 44 ;
  • X2 is an oxygen atom, a sulfur atom, a selenium atom, CR41R42 , CO , NR43 or PR44 ;
  • X 3 is NR 53 ;
  • R 41 , R 42 , R 43 and R 44 are each independently a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or a heterocyclic ring-containing group having a substituent, or a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ib below.
  • R 53 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 111 , —COR 111 , —OCOR 111 , —COOR 111 , —SR 111 , —SOR 111 , —SO 2 R 111 , —NR 112 R 113 , —NR 112 COR 113 , —CONR 112 R 113 , unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted hydrocarbon group having 2 to 20 carbon atoms or a group in which one or more of the methylene groups in the hydrocarbon group or the heterocyclic ring-containing group is replaced with a divalent group selected from Group Ib below, R 111 , R 112 and R 113 are each independently a hydrogen atom,
  • R 112 and R 113 each exist in plural numbers, they may be the same or different,
  • the substituent that replaces one or more hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from the following group IIb .
  • Group Ib -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-.
  • Group IIb halogen atom, cyano group, nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH or --SO 3 H.
  • R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R' or R", they may be the same can be different.
  • said a is 1
  • said b is 1
  • the compound according to [2], wherein the following partial structure (A ⁇ ) in the general formula (A) is a group represented by the following general formula (Ara1) or (Arb1).
  • Ar, R 33 and c are the same as in formula (A).
  • *1 represents the bonding site with R 31 and *2 represents the bonding site with R 32.
  • the substituent that replaces one or more hydrogen atoms in the hydrocarbon group having the substituent and the heterocyclic ring-containing group having the substituent is an atom or group selected from the following group IIc , a1 is 0 to 3, a2 is 0 to 3; c1 is 0 to 3; c2 is 0 to 1; *1 represents the binding site with R31 , *2 represents the bonding site with R32 .
  • Group Ic -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO 2 -, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R''-.
  • Group IIc halogen atom, cyano group, nitro group, --CO--H, --OH, --SH, --NH 2 , --COOH or --SO 3 H.
  • R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R' or R", they may be the same can be different.
  • R 32 is a group represented by any one of general formulas (IVa), (IVf) and (IVh).
  • R 1 is a hydrocarbon group having a halogen atom as a substituent having 1 to 20 carbon atoms
  • R 2 is a cyano group, a hydrocarbon group having 1 to 20 carbon atoms having a halogen atom as a substituent, or a C 1 to 20 unsubstituted group or having a halogen atom as a substituent
  • An acid generator containing the compound according to any one of [1] to [5].
  • the present invention is not limited to the above embodiments.
  • the above embodiment is an example, and any device that has substantially the same configuration as the technical idea described in the claims of the present invention and produces similar effects is the present invention. It is included in the technical scope of the invention.
  • the mixture was heated and stirred at 120° C. for 3 hours on an oil bath. After cooling to room temperature, ion-exchanged water was added to separate oil and water. After washing once with 3% by mass hydrochloric acid and three times with deionized water, the organic layer was concentrated to obtain 52.3 g of the desired intermediate 1-A as a pale red oil in a yield of 94%.
  • reaction solution was poured into ion-exchanged water, and chloroform was added to separate oil and water. After washing with ion-exchanged water three times, 50 g of silica gel was added to the organic layer and filtered. The filtrate was concentrated to obtain the desired crude intermediate 1-B as a yellow oil. It was used for the next reaction without purification.
  • Examples 5-7 and Comparative Examples 1-2 According to the formulation shown in Table 3 below, a resin component, an acid generator and a surfactant were added to propylene glycol monomethyl ether acetate (PGMEA) and stirred at 25°C for 1 hour to give a composition (solid content: 25 mass). % PGMEA solution) was obtained. The following materials were used for each component. In addition, the compounding quantity in Table 3 represents a mass part.
  • Resin component MARUKA LYNKER TST (manufactured by Maruzen Petrochemical, p-hydroxystyrene-styrene-t-butyl acrylate copolymer, acid-decomposable component)
  • Surfactant FZ2122 (manufactured by Dow Corning Toray)
  • Acid generators compounds produced in Examples 1 to 3 (acid generators composed of compounds Nos. 1 to 3)
  • Acid generator Comparative compound No. below. 1, 2
  • the composition prepared above was filtered through a 5 ⁇ m microfilter and spin-coated onto a glass substrate (1300 rpm, 7 s) so that the film thickness after prebaking was 3 ⁇ m. Subsequently, a hot plate was used to pre-bake at 110° C. for 120 seconds to obtain a positive resist film. After exposure using a high-pressure mercury lamp, PEB (Post Exposure Bake) was performed at 120° C. for 120 seconds and developed with a 2.38 mass % tetramethylammonium hydroxide aqueous solution for 10 seconds to obtain a positive pattern.
  • PEB Post Exposure Bake
  • the line width (the width of the portion removed by development) of the pattern obtained with a mask opening of 20 ⁇ m and exposure doses of 20 mJ/cm 2 and 40 mJ/cm 2 was measured using a microscope. It was evaluated that the wider the development width, the higher the sensitivity. Table 3 shows the results.

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Abstract

L'invention concerne un composé ayant une structure représentée par la formule générale (A). (Dans la formule (A), Ar est un groupe cyclique aromatique en C5-20 constituant un cycle, R31 représente un groupe représenté par la formule générale (1), et R32 est un groupe représenté par une formule choisie parmi les formules générales (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) et (IVh) ; voir la description pour les définitions de R33 et a à c.) (voir la description pour les divulgations des formules) (voir les divulgations dans la description pour les symboles dans les formules.)
PCT/JP2022/017251 2021-04-22 2022-04-07 Composé, générateur d'acide, composition, produit durci, procédé de production d'un produit durci, motif et procédé de production de motif WO2022224835A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103389621A (zh) * 2013-07-26 2013-11-13 常州强力先端电子材料有限公司 一种磺酸肟酯类光产酸剂
WO2021049489A1 (fr) * 2019-09-10 2021-03-18 株式会社Adeka Composé, agent de génération d'acide, composition, produit durci, motif et procédés de production de produit durci et de motif
WO2021049470A1 (fr) * 2019-09-10 2021-03-18 株式会社Adeka Composé, agent de génération d'acide, composition, produit durci, motif et procédé de production d'un produit durci et motif
WO2021125132A1 (fr) * 2019-12-20 2021-06-24 株式会社Adeka Composé de carbamoyl-oxime, initiateur de polymérisation et composition polymérisable contenant ledit composé

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103389621A (zh) * 2013-07-26 2013-11-13 常州强力先端电子材料有限公司 一种磺酸肟酯类光产酸剂
WO2021049489A1 (fr) * 2019-09-10 2021-03-18 株式会社Adeka Composé, agent de génération d'acide, composition, produit durci, motif et procédés de production de produit durci et de motif
WO2021049470A1 (fr) * 2019-09-10 2021-03-18 株式会社Adeka Composé, agent de génération d'acide, composition, produit durci, motif et procédé de production d'un produit durci et motif
WO2021125132A1 (fr) * 2019-12-20 2021-06-24 株式会社Adeka Composé de carbamoyl-oxime, initiateur de polymérisation et composition polymérisable contenant ledit composé

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