WO2020073822A1 - 三苯基硫鎓盐化合物及其应用 - Google Patents

三苯基硫鎓盐化合物及其应用 Download PDF

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WO2020073822A1
WO2020073822A1 PCT/CN2019/108369 CN2019108369W WO2020073822A1 WO 2020073822 A1 WO2020073822 A1 WO 2020073822A1 CN 2019108369 W CN2019108369 W CN 2019108369W WO 2020073822 A1 WO2020073822 A1 WO 2020073822A1
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substituted
unsubstituted
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salt compound
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French (fr)
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钱晓春
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Priority claimed from CN201811172185.9A external-priority patent/CN111018764A/zh
Priority claimed from CN201811171951.XA external-priority patent/CN111018763B/zh
Application filed by Changzhou Tronly New Electronic Materials Co Ltd, Changzhou Tronly Advanced Electronic Materials Co Ltd filed Critical Changzhou Tronly New Electronic Materials Co Ltd
Priority to US17/284,274 priority Critical patent/US11746085B2/en
Priority to KR1020217013626A priority patent/KR102636084B1/ko
Priority to JP2021519803A priority patent/JP7345544B2/ja
Priority to EP19871797.7A priority patent/EP3865473A4/en
Priority to EP23154959.3A priority patent/EP4198019A1/en
Publication of WO2020073822A1 publication Critical patent/WO2020073822A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • 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
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/20—Esters of thiophosphoric acids containing P-halide groups
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • the invention belongs to the technical field of functional organic compounds, and particularly relates to a novel triphenylsulfonium salt compound and its application.
  • the cationic photocuring system Compared with the free radical type, the cationic photocuring system has the advantages of small polymerization inhibition by oxygen, small volume shrinkage during curing, and wider selection of resin types. It is widely used in the manufacture of electronic parts and semiconductor components. Triphenylsulfonium salt has high sensitivity to exposure light sources such as KrF or ArF excimer lasers, and is generally used as a photoacid generator / photoinitiator for chemically amplified resists for mass production of semiconductor devices. However, the cationic structure of triphenylsulfonium salt is symmetrical and has high crystallinity. It has poor solubility in monomers and conventional organic solvents in the photocuring system, resulting in limited addition amount, and it is prone to uneven dispersion in the composition and precipitation during use. And other issues.
  • JP2005091976A and JP2002193925A introduce alkyl, fluoroalkyl and other substituent groups at the para position of the benzene ring group
  • WO2005037778A introduces alkyl groups at the meta position of the benzene ring group. Compared with the unsubstituted ones, they The solubility in the solvent is improved, but the photosensitive activity is greatly reduced.
  • TW201444790A introduces an electron-withdrawing group in the meta position of the benzene ring group. Compared with the unsubstituted one, it can improve the solubility while maintaining the photosensitive activity at the same level.
  • the main object of the present invention is to provide a triphenylsulfonium salt compound and its application to solve the problem that the structure of the triphenylsulfonium salt in the prior art cannot have both high solubility and high sensitivity.
  • the present invention aims to provide a new triphenylsulfonium salt compound through structural improvement based on the existing technology, which has excellent solubility and photosensitive activity and can be used as a resist acid generator A good alternative to photoinitiators for cationic polymerization.
  • triphenylsulfonium salt compound having a structure represented by the following general formula (I) or general formula (III):
  • R 1 represents an electron-withdrawing group
  • R 2 represents an amplifier group
  • Each R 3 independently represents halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl , Any one of substituted or unsubstituted aralkyl, optionally, means that -CH 2 -in the group of R 3 may be substituted by -O-, -S-, and the R 3 group May be connected to each other to form a ring; each R 4 and R 5 independently represents halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy Any one of a group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, and optionally,
  • the provided triphenylsulfonium salt compound may also be a bis-triphenylsulfonium salt compound, which has a structure represented by the general formula (II):
  • R 1 represents an electron-withdrawing group
  • R 2 represents an amplifier group
  • each R 3 independently represents halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl , A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, optionally, the carbon-carbon bond in the group representing R 3 may be- O-, -S- interrupted, and R 3 groups can be connected to each other to form a ring; n represents an integer of 0-5; each R 4 independently represents halogen, nitro, cyano, hydroxy, acyl, acyloxy , Sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstit
  • a photosensitive composition containing any of the triphenylsulfonium salt compounds described above.
  • the application shows that by configuring the electron-withdrawing group and the amplifying group at the meta and para positions of the phenyl ring group of the triphenylsulfonium salt, compared to the unsubstituted Phenylsulfonium salts can have significantly improved solubility and photosensitive activity, and also have obvious performance advantages over existing improved alternatives described in the background art.
  • triphenylsulfonium salt compound having the structure represented by the following general formula (I):
  • R 1 represents an electron-withdrawing group
  • R 2 represents an amplifier group
  • each R 3 independently represents halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl , A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, optionally, represents -CH 2 -in the group of R 3 May be substituted by -O-, -S-, and R 3 groups may be connected to each other to form a ring; each R 4 and R 5 independently represent halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfo Any one of acyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsub
  • the application shows that by arranging the electron-withdrawing group and the amplifying group in the meta and para positions of the phenyl ring group of the triphenylsulfonium salt, compared with the unsubstituted triphenylsulfonium salt, it can have a significant improvement
  • C 1 -C x includes all integer values of carbon numbers between 1 and x in addition to 1 and x, for example, C 1 -C 8 alkyl Include all straight or branched chain alkyl groups of C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 and C 8 . Due to space limitations, the descriptions are not expanded one by one, but their meanings are clear and unambiguously determined by those skilled in the art. It should be understood that the included numerical values can be used as the basis for further modification / limitation.
  • Suitable electron-withdrawing groups R 1 include halogen, cyano, nitro, alkoxy, haloalkyl, acyl, acyloxy, and sulfonyl.
  • Halogen may be fluorine, chlorine, bromine or iodine. In consideration of cost and environmental performance, fluorine is preferred.
  • the alkoxy group may be a C 1 -C 8 linear or branched alkoxy group such as methoxy, ethoxy, or propoxy, preferably a C 1 -C 4 linear or branched alkoxy group.
  • Haloalkyl refers to an alkyl group in which at least one hydrogen atom is substituted with halogen, and the alkyl group may be a linear C 1 -C 8 chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl.
  • Alkyl, or C 3 -C 8 branched alkyl such as isopropyl, isobutyl, sec-butyl, and tert-butyl, or C such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl 3 -C 8 cycloalkyl.
  • the halogenated alkyl group is selected from a fluorine-substituted alkyl group, it is advantageous for the photosensitive activity of the compound, and a C 1 -C 4 perfluoroalkyl group is more preferred.
  • Acyl may have or The structure shown, wherein R 6 represents hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl.
  • R 6 represents hydrogen, fluorine, chlorine, C 1 -C 7 linear or branched alkyl group, or C 1 -C 7 linear or branched fluoroalkyl group (more preferably, C 1 -C 7 linear or branched perfluoroalkyl).
  • the acyl group in the acyloxy group has the same meaning as the acyl group in the above paragraph.
  • the sulfonyl group may be mesyl, difluoromethanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, tosyl, and the like.
  • the electron-withdrawing group R 1 is preferably a halogen, a cyano group, a nitro group, a halogenated alkyl group, or an acyl group, and particularly those specific groups are exemplified among the above groups.
  • the so-called amplifier group refers to a group that has an amplifier effect on the solubility and / or photosensitive activity of the compound.
  • R 2 is selected from halogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aralkyl.
  • Halogen is preferably fluorine.
  • the alkyl group is preferably an unsubstituted alkyl group, which may be a C 1 -C 8 linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, or isopropyl, C 3 -C 8 branched alkyl groups such as isobutyl, sec-butyl, and tert-butyl. More preferably, the alkyl group as amplifying group is a C 1 -C 4 linear or branched alkyl group, including methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
  • the alkoxy group is preferably unsubstituted, wherein the alkyl group has the same meaning as the alkyl group in the above paragraph.
  • the aralkyl group is an aryl-terminated alkyl group. From the point of view of the amplification effect, a phenyl-terminated C 1 -C 8 alkyl group is preferred, and a phenyl-terminated C 1 -C 4 linear alkyl group is more preferred. Radicals, including benzyl, phenethyl, phenylpropyl or phenylbutyl.
  • the combination of the amplifier group and the electron-withdrawing group has a synergistic effect on the microelectronic structure of the triphenylsulfonium salt, improving the performance of the compound. More specifically, the present invention can further improve the solubility of triphenylsulfonium salt by using the above-mentioned amplification group, without negatively affecting the photosensitive activity, and even some compounds show relatively better photosensitive activity.
  • the structure of general formula (I) may optionally contain R 3 substituent groups, provided that it does not negatively affect the photocuring application performance of the compound.
  • R 3 independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted Alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, -CH 2 -in the group may be -O-, -S - substituted, and R 3 groups may be attached to each other to form a ring, wherein the R 3 groups may be attached to each other to form a ring preferably two adjacent R 3 represents a benzene ring to form a ring.
  • n represents the number of R 3 groups, and may be an integer of 0-5.
  • n is 0, at this time, side reactions that may occur in the subsequent photocuring process caused by the substitution group or unknown negative effects on the effect may be avoided.
  • n is 2 and two R 3 represent R 1 and R 2, with the top of the benzene ring, R 1 and R 2 are vertically symmetric, i.e. a triphenyl sulfonium salt of the present invention is represented by the following general formula (IV) Structure shown:
  • R 1 and R 2 have the same meaning as described above, the electron-withdrawing group R 1 is preferably halogen, cyano, nitro, haloalkyl, acyl, R 2 is preferably fluorine, methyl, ethyl, n- Propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyl Oxygen, n-hexyloxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, benzyl, phenethyl, phenylpropyl or phenylbutyl.
  • m represents 0, 1 or 2, more preferably 0 or 1.
  • R 4 is preferably located at the para position of the benzene ring group.
  • the triphenylsulfonium salt contains the symmetric electron-withdrawing group and the amplifying group as shown in the structure above in the upper and lower benzene ring groups under the same anionic part, Compared with the improved triphenylsulfonium salt in the art, the compound exhibits significantly further improved solubility and photosensitive activity.
  • the structure of general formula (I) may optionally contain R 4 substituents, provided that it does not negatively affect the photocuring performance of the compound.
  • Halogen may be fluorine, chlorine, bromine or iodine. In consideration of cost and environmental performance, fluorine is preferred.
  • the acyl group can be selected from: C 2 -C 8 aliphatic acyl groups, such as acetyl, propionyl, butyryl, valeryl, isovaleryl, hexanoyl, octanoyl, heptanoyl, etc .; C 7 -C 12 aromatic Acyl groups such as benzoyl, methylbenzoyl, trimethylbenzoyl, ⁇ -phenylpropionyl, naphthoyl and the like.
  • the acyl group in the acyloxy group may have the same meaning as shown in the above paragraph.
  • the sulfonyl group may be mesyl, difluoromethanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, tosyl, and the like.
  • the alkyl group may be substituted or unsubstituted.
  • the alkyl group may be selected from C 1 -C 8 straight chain, C 3 -C 8 branched chain or C 3 -C 8 cyclic alkyl group, for example: methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl Group, 2-methylpentyl, 1,2-dimethylbutyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.
  • the alkyl group is selected from C 1 -C 4 linear or branched chain alkyl groups, or C 3 -C 6 cyclic alkyl groups.
  • Substituents in substituted alkyl groups include, but are not limited to: halogen (fluorine, chlorine, bromine, iodine), amine groups, hydroxyl groups, and the like.
  • the alkoxy group may be substituted or unsubstituted, and the alkyl group and the substituent may have the same meaning as shown in the above paragraph.
  • the aryl group may be substituted or unsubstituted.
  • the aryl group may be phenyl, naphthyl, anthracenyl, pyrenyl, or the like.
  • a substituent it may be: C 1 -C 4 alkyl such as methyl, ethyl, propyl, butyl, etc., halogen such as fluorine, chlorine, bromine, iodine, C 1 -C 3 alkoxy such as methyl Oxygen, ethoxy, propoxy, acyl, sulfonyl, hydroxyl, amine, nitro, phenyl, etc.
  • Aralkyl is an aryl-terminated alkyl group, which may be substituted or unsubstituted. Among them, the aryl moiety and the substituent may have the same meaning as shown in the above paragraph.
  • the alkyl portion thereof C 1 -C 6 alkylene groups are preferred, including methylene, ethylene and the like.
  • the aralkyl group is benzyl, phenethyl, or phenylpropyl, and optionally, at least one hydrogen on the phenyl is substituted with the substituent shown in the above paragraph.
  • n represents the number of R 4 groups, and may be an integer of 0-5. Preferably, m represents 0, 1 or 2, more preferably 0 or 1. When m is 1, R 4 is preferably located at the para position of the benzene ring group.
  • X - represents a non-nucleophilic anion, including (but not limited to): M -, ClO 4 - , CN -, HSO 4 -, NO 3 -, CF 3 COO -, (BM 4) -, (SbM 6) - , (AsM 6) -, ( PM 6) -, Al [OC (CF 3) 3] 4 -, R 7 SO 3 -, (R 7 SO 2) 3 C -, (R 7 SO 2) 2 N - , B (C 6 M 5) 4 -, Ga (C 6 M 5) 4 - , or [(Rf) b PF 6 - b] -.
  • M represents halogen, such as fluorine, chlorine, bromine, iodine, preferably fluorine.
  • R 7 represents a C 1 -C 20 alkyl group, a C 1 -C 20 perfluoroalkyl group, or a C 6 -C 20 aryl group or substituted aryl group.
  • the alkyl group and the perfluoroalkyl group may be linear or branched Either chain or loop.
  • Rf represents an alkyl group in which ⁇ 80% of hydrogen atoms are replaced by fluorine atoms
  • the alkyl group may include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, etc.
  • Alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, etc., cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • Rf based on the number of moles of hydrogen atoms existing in the alkyl group, the ratio of substitution with fluorine atoms is preferably 80% or more, preferably 90% or more, and more preferably 100%. When the substitution ratio of fluorine atoms is within these ranges, the photosensitivity of the compound becomes better.
  • Rf may include: CF 3 -, CF 3 CF 2 -, (CF 3) 2 CF -, CF 3 CF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 -, (CF 3) 2 CFCF 2 -, CF 3 CF 2 ( CF 3) CF - and (CF 3) 3 C -.
  • b represents an integer of 1-5
  • b Rf groups may be the same as or different from each other.
  • M - anion represented can include: Cl -, Br -, F -.
  • BM 4 -, (SbM 6) -, (AsM 6) -, (PM 6) - anion represented, include: BF 4 -, SbF 6 - , AsF 6 -, PF -.
  • R 7 SO 3 - anion represented may include: CF 3 SO 3 -, C 2 F 5 SO 3 -, C 3 F 7 SO 3 -, C 4 F 9 SO 3 -, C 6 F 5 SO 3 - , C 3 F 7 SO 3 - , p-toluenesulfonate anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, sulfonic acid anion and a sulfonate anion butoxy.
  • (R 7 SO 2) 3 C - anion represented include: (CF 3 SO 2) 3 C -, (C 2 F 5 SO 2) 3 C -, (C 3 F 7 SO 2) 3 C - and (C 4 F 9 SO 2) 3 C -.
  • (R 7 SO 2) 2 N - anion represented include: (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, (C 3 F 7 SO 2) 2 N - and (C 4 F 9 SO 2) 2 N -.
  • B (C 6 M 5) 4 -, Ga (C 6 M 5) 4 - anions represented include: B (C 6 F 5) 4 -, Ga (C 6 F 5) 4 -.
  • [(Rf) b PF 6- b] - anion represented include: (CF 3 CF 2) 2 PF 4 -, (CF 3 CF 2) 3 PF 3 -, [(CF 3) 2 CF] 2 PF 4 -, [(CF 3 ) 2 CF] 3 PF 3 -, (CF 3 CF 2 CF 2) 2 PF 4 -, (CF 3 CF 2 CF 2) 3 PF 3 -, [(CF 3) 2 CFCF 2] 2 PF 4 -, [ (CF 3) 2 CFCF 2] 3 PF 3 -, (CF 3 CF 2 CF 2 CF 2) 2 PF 4 - , and (CF 3 CF 2 CF 2 CF 2) 3 PF 3 - Wait.
  • the method for preparing the triphenylsulfonium salt compound of the present invention is not particularly limited, and a well-known organic synthesis process can be used.
  • a sulfonium salt can be obtained by performing a sulfonation reaction between a commercially available diaryl sulfoxide and an aryl compound, and then, if necessary The anion is introduced through the salt exchange reaction, thereby obtaining the triphenylsulfonium salt compound of the present invention.
  • the triphenylsulfonium salt compound of the present invention has the property of releasing Lewis acid by irradiation of energy rays, and can be used as a resist acid generator and a photoinitiator for cationic polymerization.
  • high-energy radiation such as electron beams or X-rays can also be used.
  • the triphenylsulfonium salt compound of the present invention is mixed with a photosensitive active monomer (such as a cationic polymerizable compound) to form a photosensitive composition, and can be applied to the production of lithography, letterpress printing plates, printed boards, and IC and LSI light In resists, photocurable inks, coatings, adhesives and other fields.
  • a photosensitive active monomer such as a cationic polymerizable compound
  • the triphenylsulfonium salt compound represented by the general formula (I) of the present invention has excellent solubility, high light generation efficiency and photosensitive activity, and has good market application value.
  • the present invention also provides a thioxanthone sulfonium salt having the structure represented by the following general formula (III):
  • R 1 , R 2 , R 3 , R 4 and X - have the same meaning as described above, and n and m each independently represent an integer of 1-5.
  • the above thioxanthone sulfonium salt can be regarded as a structure formed by connecting one R 3 and one R 4 in the general formula (I) to form a keto group, and it is also considered to be able to obtain triphenylsulfide represented by the general formula (I) Similar benefits with onium salt compounds.
  • the preparation method of the compound can be synthesized by referring to the process described in the patent document WO2003072567, the entire content of which is hereby incorporated by reference.
  • triphenylsulfonium salt compound which is a bis-triphenylsulfonium salt compound, and has a structure shown by the general formula (II):
  • R 1 represents an electron-withdrawing group
  • R 2 represents an amplifier group
  • each R 3 independently represents halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl , A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, optionally, the carbon-carbon bond in the group representing R 3 may be- O-, -S- interrupted, and R 3 groups can be connected to each other to form a ring; n represents an integer of 0-5; each R 4 independently represents halogen, nitro, cyano, hydroxy, acyl, acyloxy , Sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstit
  • the application shows that by arranging the electron-withdrawing group and the amplifying group at the meta and para positions of the benzene ring group of the bis-triphenylsulfonium salt, compared to the unsubstituted triphenylsulfonium salt Significantly improved solubility and photosensitive activity, and also has a clear performance advantage over existing improved alternatives described in the background.
  • C 1 -C x includes all integer values of carbon numbers between 1 and x in addition to 1 and x, for example, C 1 -C 8 alkyl Include all straight or branched chain alkyl groups of C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 and C 8 . Due to space limitations, the descriptions are not expanded one by one, but their meanings are clear and unambiguously determined by those skilled in the art. It should be understood that the included numerical values can be used as the basis for further modification / limitation.
  • Suitable electron-withdrawing groups R 1 are selected from halogen, cyano, nitro, haloalkyl, acyl, acyloxy, and sulfonyl.
  • Halogen may be fluorine, chlorine, bromine or iodine. From the viewpoint of environmental performance, fluorine is preferred.
  • Haloalkyl refers to an alkyl group in which at least one hydrogen atom is substituted with halogen, and the alkyl group may be a linear C 1 -C 8 chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl.
  • Alkyl, or C 3 -C 8 branched alkyl such as isopropyl, isobutyl, sec-butyl, and tert-butyl, or C such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl 3 -C 8 cycloalkyl.
  • the halogenated alkyl group is selected from a fluorine-substituted alkyl group, it is advantageous for the photosensitive activity of the compound, and a C 1 -C 4 perfluoroalkyl group is more preferred.
  • Acyl may have or The structure shown, wherein R 6 represents hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl.
  • R 6 represents hydrogen, fluorine, chlorine, C 1 -C 7 linear or branched alkyl group, C 1 -C 7 linear or branched haloalkyl group (more preferably, C 1 -C 7 linear or branched perfluoroalkyl), C 6 -C 12 aryl, or C 7 -C 16 aralkyl.
  • the acyl group in the acyloxy group has the same meaning as the acyl group in the above paragraph.
  • the sulfonyl group may be mesyl, difluoromethanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, tosyl, and the like.
  • the electron-withdrawing group R 1 is preferably halogen, cyano, nitro, haloalkyl, especially those preferred above.
  • the so-called amplifier group refers to a group that has an amplifier effect on the solubility and / or photosensitive activity of the compound.
  • R 2 is selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aralkyl group.
  • the alkyl group is preferably an unsubstituted alkyl group, which may be a C 1 -C 8 linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, or isopropyl, C 3 -C 8 branched alkyl groups such as isobutyl, sec-butyl, and tert-butyl. More preferably, the alkyl group as amplifying group is a C 1 -C 4 linear or branched alkyl group, including methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
  • the alkoxy group is preferably unsubstituted, wherein the alkyl group has the same meaning as shown in the above paragraph.
  • the aralkyl group is an aryl-terminated alkyl group. From the point of view of the amplification effect, a phenyl-terminated C 1 -C 8 alkyl group is preferred, and a phenyl-terminated C 1 -C 4 linear alkyl group is more preferred. Radicals, including benzyl, phenethyl, phenylpropyl or phenylbutyl. Optionally, at least one hydrogen atom in the aralkyl group is substituted with halogen (especially fluorine).
  • the structure of the general formula (II) may optionally contain a R 3 substituent group, provided that it does not adversely affect the photocuring application performance of the compound.
  • R 3 independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted Alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, optionally, the carbon-carbon bond in the group may be replaced by -O-, -S- Interrupted, and R 3 groups can be connected to each other to form a ring.
  • n represents the number of R 3 groups, and may be an integer of 0-5.
  • n is 0, at this time, side reactions that may occur in the subsequent photocuring process caused by the substitution group or unknown negative effects on the effect may be avoided.
  • n is 2 and two R 3 represent the same aromatic ring R 1 and R 2, with the top of the benzene ring, R 1 and R 2 are vertically symmetric, i.e. double the present invention - triphenylsulfonium
  • the onium salt has the structure represented by the following general formula (V):
  • each substituent group has the same meaning as described above.
  • the bis-triphenylsulfonium salt contains symmetric electron-withdrawing groups and amplification groups as shown in the above structure in the upper and lower four benzene ring groups, it is the same as the improvement in the prior art Compared with triphenylsulfonium salt, this compound exhibits significantly further improved solubility and photosensitive activity.
  • the structure of the general formula (II) may optionally contain a R 4 substituent group, provided that it does not negatively affect the photocuring performance of the compound.
  • R 4 independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted Alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, optionally, the carbon-carbon bond in the group may be replaced by -O-, -S- Interrupted, and R 4 groups can be connected to each other to form a ring.
  • Halogen may be fluorine, chlorine, bromine or iodine. In consideration of cost and environmental performance, fluorine is preferred.
  • the acyl group can be selected from: C 2 -C 8 aliphatic acyl groups, such as acetyl, propionyl, butyryl, valeryl, isovaleryl, hexanoyl, octanoyl, heptanoyl, etc .; C 7 -C 12 aromatic Acyl groups such as benzoyl, methylbenzoyl, trimethylbenzoyl, ⁇ -phenylpropionyl, naphthoyl and the like.
  • the acyl group in the acyloxy group may have the same meaning as the acyl group in the above paragraph.
  • the sulfonyl group may be mesyl, difluoromethanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, tosyl, and the like.
  • the alkyl group may be substituted or unsubstituted.
  • the alkyl group may be selected from C 1 -C 8 linear, branched or cyclic alkyl groups, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary Butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1,2 -Dimethylbutyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.
  • the alkyl group is selected from C 1 -C 4 linear or branched chain alkyl groups, or C 3 -C 6 cyclic alkyl groups.
  • Substituents in substituted alkyl groups include, but are not limited to: halogen (fluorine, chlorine, bromine, iodine), amine groups, hydroxyl groups, and the like.
  • the alkoxy group may be substituted or unsubstituted, and the alkyl group and the substituent may have the same meaning as shown in the above paragraph.
  • the aryl group may be substituted or unsubstituted.
  • the aryl group may be phenyl, naphthyl, anthracenyl, pyrenyl, or the like.
  • a substituent it may be: C 1 -C 4 alkyl such as methyl, ethyl, propyl, butyl, etc., halogen such as fluorine, chlorine, bromine, iodine, C 1 -C 3 alkoxy such as methyl Oxygen, ethoxy, propoxy, acyl, sulfonyl, hydroxyl, amine, nitro, phenyl, etc.
  • Aralkyl is an aryl-terminated alkyl group, which may be substituted or unsubstituted. Among them, the aryl moiety and the substituent may have the same meaning as shown in the above paragraph.
  • the alkyl portion thereof C 1 -C 6 alkylene groups are preferred, including methylene, ethylene and the like.
  • the aralkyl group is benzyl, phenethyl, or phenylpropyl, and optionally, at least one hydrogen on the phenyl is substituted with the substituent shown in the above paragraph.
  • R 4 is preferably hydrogen, nitro, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, especially those preferred above.
  • n represents the number of R 4 groups and can be an integer from 0-4. Preferably, m represents 0, 1 or 2, more preferably 0 or 1. When m is 1, R 4 is preferably ortho to the side of the A group.
  • the structure of general formula (II) may optionally contain R 5 substituents, provided that it does not negatively affect the photocuring performance of the compound.
  • R 5 may have the same meaning as the R 4 substituent group described above.
  • R 4 and each R 5 may form a ring with the phenyl and A groups connected to each.
  • p represents the number of R 5 groups and can be an integer from 0-4. Preferably, p represents 0, 1 or 2, more preferably 0 or 1. When p is 1, R 5 is preferably located in the ortho position on the side of the A group.
  • A represents a connecting bond (ie a single bond), * O *, * S *, alkylene or alkenylene, and M represents an empty, * O * ⁇ * S * or Group, wherein, * represents a connecting position, R 8 , R 9 , and R 10 each independently represent hydrogen, a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, C 4 -C 20 cycloalkylalkyl or C 4 -C 20 alkylcycloalkyl.
  • the alkylene group is a C 1 -C 4 linear alkylene group
  • M represents vacancy, it means that the two benzene rings are connected only through the linking group A.
  • A represents a bond.
  • the S atoms on the left and right sides are respectively connected to three benzene rings.
  • the connection position of the S atom is preferably the para position of the group A.
  • X - represents a non-nucleophilic anion, including (but not limited to): Q -, ClO 4 - , CN -, HSO 4 -, NO 3 -, CF 3 COO -, (BQ 4) -, (SbQ 6) - , (AsQ 6) -, ( PQ 6) -, Al [OC (CF 3) 3] 4 -, R 6 SO 3 -, (R 6 SO 2) 3 C -, (R 6 SO 2) 2 N - , B (C 6 Q 5) 4 -, Ga (C 6 Q 5) 4 - , or [(Rf) b PF 6- b] -.
  • Q represents halogen, such as fluorine, chlorine, bromine, and iodine, preferably fluorine.
  • R 6 represents a C 1 -C 20 alkyl group, a C 1 -C 20 perfluoroalkyl group, or a C 6 -C 20 aryl group or substituted aryl group, and the alkyl group and the perfluoroalkyl group may be linear or branched Either chain or loop.
  • Rf represents an alkyl group in which ⁇ 80% of hydrogen atoms are replaced by fluorine atoms
  • the alkyl group may include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, etc.
  • Alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, etc., cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • Rf based on the number of moles of hydrogen atoms existing in the alkyl group, the ratio of substitution with fluorine atoms is preferably 80% or more, preferably 90% or more, and more preferably 100%. When the substitution ratio of fluorine atoms is within these ranges, the photosensitivity of the compound becomes better.
  • Rf may include: CF 3 -, CF 3 CF 2 -, (CF 3) 2 CF -, CF 3 CF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 -, (CF 3) 2 CFCF 2 -, CF 3 CF 2 ( CF 3) CF - and (CF 3) 3 C -.
  • b represents an integer of 1-5
  • b Rf groups may be the same as or different from each other.
  • Q - represents the anion, include: Cl -, Br -, F -.
  • (BQ 4) -, (SbQ 6) -, (AsQ 6) -, (PQ 6) - anion represented, include: BF 4 -, SbF 6 - , AsF 6 -, PF -.
  • R 6 SO 3 - anion represented may include: CF 3 SO 3 -, C 2 F 5 SO 3 -, C 3 F 7 SO 3 -, C 4 F 9 SO 3 -, C 6 F 5 SO 3 - , C 3 F 7 SO 3 - , p-toluenesulfonate anion, benzenesulfonic acid anion, camphorsulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, sulfonic acid anion and a sulfonate anion butoxy.
  • (R 6 SO 2) 3 C - anion represented include: (CF 3 SO 2) 3 C -, (C 2 F 5 SO 2) 3 C -, (C 3 F 7 SO 2) 3 C - and (C 4 F 9 SO 2) 3 C -.
  • (R 6 SO 2) 2 N - represents an anion, include: (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, (C 3 F 7 SO 2) 2 N - and (C 4 F 9 SO 2) 2 N -.
  • B (C 6 Q 5) 4 -, Ga (C 6 Q 5) 4 - anions represented include: B (C 6 F 5) 4 -, Ga (C 6 F 5) 4 -.
  • [(Rf) b PF 6- b] - anion represented include: (CF 3 CF 2) 2 PF 4 -, (CF 3 CF 2) 3 PF 3 -, [(CF 3) 2 CF] 2 PF 4 -, [(CF 3 ) 2 CF] 3 PF 3 -, (CF 3 CF 2 CF 2) 2 PF 4 -, (CF 3 CF 2 CF 2) 3 PF 3 -, [(CF 3) 2 CFCF 2] 2 PF 4 -, [ (CF 3) 2 CFCF 2] 3 PF 3 -, (CF 3 CF 2 CF 2 CF 2) 2 PF 4 - , and (CF 3 CF 2 CF 2 CF 2) 3 PF 3 - Wait.
  • the method for preparing the bis-triphenylsulfonium salt compound of the present invention is not particularly limited, and a well-known organic synthesis process can be used.
  • a sulfonium salt is obtained by a sulfonation reaction of a diaryl sulfoxide and a diaryl compound, and then anion is introduced through a salt exchange reaction as needed, thereby obtaining the present invention Bis-triphenylsulfonium salt compound.
  • the bis-triphenylsulfonium salt compound of the present invention has the property of emitting Lewis acid by irradiation of active energy rays, and can act on acid-reactive organic substances to decompose or polymerize, so it can be used as a photoresist for light Used as acid generator or as a cationic polymerization photoinitiator.
  • high-energy radiation such as electron beams or X-rays can also be used.
  • the bis-triphenylsulfonium salt compound of the present invention is mixed with a photosensitive active monomer (such as a cationic polymerizable compound) to form a photosensitive composition, and can be applied to the production of printing plates for planographic and relief printing, printed circuit boards, ICs, and LSIs In the fields of photoresist, photocurable ink, coating, adhesive and so on.
  • a photosensitive active monomer such as a cationic polymerizable compound
  • the bis-triphenylsulfonium salt compound represented by the general formula (II) of the present invention has excellent solubility, high light generation efficiency and photosensitive activity, and has good market application value.
  • the structure of the target product was confirmed by nuclear magnetic resonance hydrogen spectroscopy and mass spectrometry.
  • the specific characterization results are as follows:
  • the structure of the target product was confirmed by nuclear magnetic resonance hydrogen spectroscopy and mass spectrometry.
  • the specific characterization results are as follows:
  • Example II-1 Referring to the preparation method of Example II-1, using dichlorosulfoxide and the corresponding substituted benzene as starting materials, the compounds C2-C25 shown in Table 2 were prepared.
  • the above compounds were prepared as 0.02 mmol / g acetonitrile solution.
  • a 5.00 g prepared acetonitrile solution was added to a Petri dish with an inner diameter of 100 mm, and then under the irradiation of an ultraviolet lamp (model FL10BL), an energy of 200 mj / cm 2 was received at a light intensity of 0.8 mw / cm 2 .
  • BTB was used as an indicator, and titration was performed with a 0.05N potassium hydroxide ethanol solution. Titrate the corresponding solution before light irradiation to obtain the blank value, subtract the blank value from the titration measurement value, and calculate the acid production rate by the following formula conversion:
  • Acid production rate% (acid titration value-blank value) (mol) / theoretical molar number of compound (mol) ⁇ 100%.
  • Resin B represents a novolak resin obtained by condensation of m-cresol and p-cresol at a molar ratio of 1: 1 under formaldehyde and acid catalysis, with a molecular weight of about 10,000;
  • the photoinitiators are the above-mentioned compounds A-1 to A-38, C-1 to C-25 or the comparative compounds B-1 and B-2, D-1 and D-2.
  • Each component was stirred uniformly at the above ratio and filtered through a membrane filter with a pore size of 1 ⁇ m to prepare a resist composition with a solid content of 40%.
  • the resist composition was evenly coated on the silicon wafer substrate by a spin coater, and dried to obtain a 20 ⁇ m thick photoresist coating.
  • a tetramethylammonium hydroxide solution with a mass fraction of 2.38% was used for development for 5 minutes, then washed with running water, and dried with nitrogen to obtain a 10 ⁇ m line pattern.

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Abstract

本发明公开一种如通式(I)所示的三苯基硫鎓盐化合物，其中R1表示吸电子基团，R2表示增幅基团。相较于未取代的三苯基硫鎓盐，该化合物具有明显提高的溶解性和感光活性，并且相比于现有改进型替代品也具有性能上的明显优势。

Description

三苯基硫鎓盐化合物及其应用 技术领域
本发明属于功能有机化合物技术领域，特别涉及一种新型三苯基硫鎓盐化合物及其应用。
背景技术
阳离子型光固化体系相比于自由基型具有受氧阻聚小、固化时体积收缩小、树脂选用类型更宽泛等优点，被广泛用于电子零件和半导体元器件的制造。三苯基硫鎓盐对KrF或ArF准分子镭射等曝光光源具有高感光活性，通常被用作化学增幅型抗蚀剂的光产酸剂/光引发剂，进行半导体元件的量产。然而三苯基硫鎓盐的阳离子结构对称且结晶性高，在光固化体系单体和常规有机溶剂中溶解性差，导致添加量受限，且容易出现在组合物中分散不均匀、使用中析出等问题。
为提高溶解性，JP2005091976A和JP2002193925A在苯环基团的对位引入烷基、氟代烷基等取代基团，WO2005037778A在苯环基团的间位引入烷基，相比于未取代者，它们在溶剂中的溶解性提高，但感光活性大幅降低。TW201444790A在苯环基团的间位引入吸电子基团，相比于未取代者，它在提高溶解性的同时，能够保持感光活性在同等水平。
优化三苯基硫鎓盐结构以获取具有更佳应用性能的替代品，有持续的技术和市场需求。
发明内容
本发明的主要目的在于提供一种三苯基硫鎓盐化合物及其应用，以解决现有技术中三苯基硫鎓盐结构不能同时兼具高溶解性和高感光性的问题。
针对应用市场的需求，本发明旨在现有技术的基础上，通过结构改进提供一种新型三苯基硫鎓盐化合物，其具有优异的溶解性和感光活性，可作为抗蚀剂产酸剂和阳离子聚合用光引发剂的优质替代品。
根据本发明的一个方面，提供了一种三苯基硫鎓盐化合物，具有如下通式(I)或通式(III)所示结构：
Figure PCTCN2019108369-appb-000001
其中，R 1表示吸电子基团；R 2表示增幅基团；
各R 3各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示所述R 3的基团中的-CH 2-可被-O-、-S-所取代，且R 3基团可彼此相连成环；各R 4和R 5各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示所述R 4和R 5的基团中的-CH 2-可被-O-、-S-、或-CH＝CH-所取代，且R 4基团可彼此相连成环；n和m各自独立地表示0-5的整数；X -表示非亲核性阴离子。
根据本发明的另一个方面，提供的三苯基硫鎓盐化合物还可以是双-三苯基硫鎓盐化合物，具有如通式(II)所示结构：
Figure PCTCN2019108369-appb-000002
其中，R 1表示吸电子基团；R 2表示增幅基团；各R 3各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示R 3的基团中的碳碳键可被-O-、-S-所中断，且R 3基团可彼此相连成环；n表示0-5的整数；各R 4各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示R 4的基团中的碳碳键可被-O-、-S-所中断，且R 4基团可彼此相连成环；m表示0-4的整数；各R 5各自独立地，表示氢、卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示R 5的基团中的碳碳键可被-O-、-S-所中断，且R 5基团可彼此相连成环；p表示0-4的整数；A和M各自独立地表示连接基团；X -表示非亲核性阴离子。
根据本发明的又一方面，提供了一种上述各三苯基硫鎓盐化合物作为抗蚀剂产酸剂和/或阳离子聚合用光引发剂的用途。
根据本发明的又一方面，提供了一种包含上述任一种的三苯基硫鎓盐化合物的感光性组合物。
根据本发明的又一方面，提供了一种上述的感光性组合物在制作平版、凸版用印刷版、印刷基板、光致抗蚀剂，光固化油墨、涂料和粘合剂中的应用。
不受限于已知的任何理论，应用表明，通过在三苯基硫鎓盐的苯环基团的间位和对位分别配置吸电子基团和增幅基团，相较于未取代的三苯基硫鎓盐，能够具有明显提高的溶解性和感光活性，并且相比于背景技术中记载的现有改进型替代品也具有性能上的明显优势。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
现有文献显示，在苯环基团的对位引入取代基有利于提高三苯基硫鎓盐的可溶解性，但会对感光活性产生不利影响。但申请人发现，选自特定范围的对位取代基团与间位吸电子基团相配合时，能够兼顾可溶解性和感光活性。
在本申请一种典型的实施方式中，提供了一种三苯基硫鎓盐化合物，具有如下通式(I)所示结构：
Figure PCTCN2019108369-appb-000003
其中，R 1表示吸电子基团；R 2表示增幅基团；各R 3各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示所述R 3的基团中的-CH 2-可被-O-、-S-所取代，且R 3基团可彼此相连成环；各R 4和R 5各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示所述R 4和R 5的基团中的-CH 2-可被-O-、-S-、或-CH＝CH-所取代，且R 4基团可彼此相连成环；n和m各自独立地表示0-5的整数；X -表示非亲核性阴离子。
应用表明，通过在三苯基硫鎓盐的苯环基团的间位和对位分别配置吸电子基团和增幅基团，相较于未取代的三苯基硫鎓盐，能够具有明显提高的溶解性和感光活性，并且相比于背景技术中记载的现有改进型替代品也具有性能上的明显优势。
以下对通式(I)结构中的各可变基团进行更详细的说明。
需要注明的是，在本申请的说明书中，C 1-C x除了1和x之外，还包括碳数在1到x之间的所有整数值，例如，C 1-C 8的烷基包括C 1、C 2、C 3、C 4、C 5、C 6、C 7和C 8的直链或支链的所有烷基。限于篇幅，说明书中未一一展开描述，但其含义对本领域技术人员而言是明确且可毫无疑义确定的，应当理解的是，包含在内的各数值能够作为进一步修改/限定的基础。
可变基团
(1)R 1吸电子基团
据信，在苯环间位引入吸电子基团能够有效提升硫鎓盐的溶解性，同时不对感光活性产生负面影响。
作为适用的吸电子基团R 1，可例举出卤素、氰基、硝基、烷氧基、卤代烷基、酰基、酰氧基、磺酰基。
卤素可以是氟、氯、溴或碘。从成本和环保性能考虑，优选氟。
烷氧基可以是甲氧基、乙氧基、丙氧基等C 1-C 8的直链或支链烷氧基，优选C 1-C 4的直链或支链烷氧基。
卤代烷基是指至少一个氢原子被卤素取代的烷基，所述烷基可以是甲基、乙基、正丙基、正丁基、正戊基、正己基等C 1-C 8的直链烷基，或是异丙基、异丁基、仲丁基、叔丁基等C 3-C 8的支链烷基，或是环丙基、环丁基、环戊基、环己基等C 3-C 8的环烷基。当卤代烷基选自氟取代的烷基时，对化合物的感光活性是有利的，更优选C 1-C 4的全氟烷基。
酰基可具有
Figure PCTCN2019108369-appb-000004
或
Figure PCTCN2019108369-appb-000005
所示的结构，其中R 6表示氢、卤素、取代或未取代的烷基、取代或未取代的芳基。优选地，R 6表示氢、氟、氯、C 1-C 7的直链或支链的烷基、或C 1-C 7的直链或支链的氟代烷基(更优选地，C 1-C 7的直链或支链的全氟代烷基)。
酰氧基中的酰基具有上段内容中酰基所示的相同含义。
磺酰基可以是甲磺酰基、二氟甲磺酰基、三氟甲磺酰基、苯磺酰基、甲苯磺酰基等。
在本发明的通式(I)中，吸电子基团R 1优选是卤素、氰基、硝基、卤代烷基、酰基，特别是上述各基团中列举那些具体基团。
(2)R 2增幅基团
所谓的增幅基团是指对化合物的溶解性和/或感光活性产生增幅作用的基团。
现有文献报道，在三苯基硫鎓盐的苯环基团的对位引入取代基能够提高溶解性，但会明显降低感光活性。出乎意料地，在苯环基团间位存在吸电子基团R 1的情况下，在对位引入增幅基团R 2，能够对化合物的溶解性和/或感光活性产生增幅作用，且在进一步提升该性能的同时，不会对其它性能产生不利影响。
作为能够表现出增幅作用的基团，R 2选自卤素、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳烷基。
卤素优选是氟。
烷基优选是未取代的烷基，可以是甲基、乙基、正丙基、正丁基、正戊基、正己基等C 1-C 8的直链烷基，或是异丙基、异丁基、仲丁基、叔丁基等C 3-C 8的支链烷基。更优选地，作为增幅基团的烷基是C 1-C 4的直链或支链的烷基，包括甲基、乙基、正丙基、异丙基、正丁基或异丁基。
烷氧基优选是未取代的，其中的烷基具有上段内容中烷基所示的相同含义。
芳烷基是以芳基封端的烷基，从增幅效果看，优选是以苯基封端的C 1-C 8的烷基，更优选是以苯基封端的C 1-C 4的直链烷基，包括苯甲基、苯乙基、苯丙基或苯丁基。
不受限于现有的已知理论，增幅基团和吸电子基团的组合对三苯基硫鎓盐的微观电子结构产生协同性影响，提升化合物的性能。更具体地，本发明通过采用上述增幅基团，能够进一步提升三苯基硫鎓盐的溶解性，同时不对感光活性产生负面影响，甚至部分化合物显示出相对更佳的感光活性。
(3)R 3取代基团
通式(I)结构中可任选地含有R 3取代基团，前提是不对化合物的光固化应用性能产生负面影响。
在此前提条件下，从提供更多同类替代品的角度出发，R 3各自独立地，可表示氢、卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基，任选地，基团中的-CH 2-可被-O-、-S-所取代， 且R 3基团可彼此相连成环，其中的R 3基团可彼此相连成环优选表示相邻的两个R 3与苯环成环。
n表示R 3基团的数量，可以是0-5的整数。
本领域的技术人员基于有机领域的基础理论能够知晓，R 3取代基团的存在能够对所处苯环的共轭结构和三苯基硫鎓的整体结构特性产生影响。不受限于任何理论，这种影响带来的结果通常是难以预期的，其更多依赖于试验的最终呈现。
优选地，n是0，此时可避免取代基团引起的后续光固化进程中可能出现的副反应，或对效果产生的未知负面影响。
更优选地，n是2，且两个R 3分别表示R 1和R 2，与最上方苯环的R 1和R 2上下对称，即本发明的三苯基硫鎓盐为下述通式(IV)所示结构：
Figure PCTCN2019108369-appb-000006
其中，R 1和R 2具有如上文所述的相同含义，吸电子基团R 1优选是卤素、氰基、硝基、卤代烷基、酰基，R 2优选为氟、甲基、乙基、正丙基、正丁基、正戊基、正己基、异丙基、异丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基、正己氧基、异丙氧基、异丁氧基、仲丁氧基、叔丁氧基、苯甲基、苯乙基、苯丙基或苯丁基。m表示0、1或2，更优选0或1。当m取1时，R 4优选位于苯环基团的对位。
出乎意料地，在阴离子部分相同的条件下，当三苯基硫鎓盐在上下两个苯环基团中含有如上述结构所示的对称的吸电子基团和增幅基团时，与现有技术中的改进型三苯基硫鎓盐相比，该化合物呈现出显著进一步提升的溶解性和感光活性。
(4)R 4取代基团
通式(I)结构中可任选地含有R 4取代基团，前提是不对化合物的光固化应用性能产生负面影响。
在此前提条件下，从提供更多同类替代品的角度出发，R 4各自独立地，可表示氢、卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基，任选地，基团中的-CH 2-可被-O-、-S-、或-CH＝CH-所取代，且R 4基团可彼此相连成环，其中的R 4基团可彼此相连成环优选表示相邻的两个R 4与苯环成环。
卤素可以是氟、氯、溴或碘。从成本和环保性能考虑，优选氟。
酰基可选自：C 2-C 8的脂肪族酰基，如乙酰基、丙酰基、丁酰基、戊酰基、异戊酰基、己酰基、辛酰基、庚酰基等；C 7-C 12的芳香族酰基，如苯甲酰基、甲基苯甲酰基、三甲基苯甲酰基、α-苯丙酰基、萘甲酰基等。
酰氧基中的酰基可具有上段内容中所示的相同含义。
磺酰基可以是甲磺酰基、二氟甲磺酰基、三氟甲磺酰基、苯磺酰基、甲苯磺酰基等。
烷基可以是取代或未取代的。所述烷基可选自C 1-C 8的直链、C 3-C 8的支链或C 3-C 8的环状的烷基，例如：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、叔戊基、新戊基、正己基、异己基、3-甲基戊基、2-甲基戊基、1,2-二甲基丁基、环丙基、环戊基、环己基等。优选地，所述烷基选自C 1-C 4的直链或支链烷基、或C 3-C 6的环状烷基。取代烷基中的取代基包括(但不限于)：卤素(氟、氯、溴、碘)、胺基、羟基等。
烷氧基可以是取代或未取代的，其中的烷基和取代基可具有上段内容中所示的相同含义。
芳基可以是取代或未取代的。所述芳基可以是苯基、萘基、蒽基、芘基等。作为取代基，可以是：C 1-C 4的烷基如甲基、乙基、丙基、丁基等，卤素如氟、氯、溴、碘，C 1-C 3的烷氧基如甲氧基、乙氧基、丙氧基，酰基，磺酰基，羟基，胺基，硝基，苯基等。
芳烷基是以芳基封端的烷基，可以是取代或未取代的。其中，芳基部分和取代基可具有上段内容中所示的相同含义。作为其中的烷基部分，优选是C 1-C 6的亚烷基，包括亚甲基、亚乙基等。特别优选地，芳烷基是苄基、苯乙基或苯丙基，任选地，苯基上的至少一个氢被上段内容中所示的取代基所取代。
m表示R 4基团的数量，可以是0-5的整数。优选地，m表示0、1或2，更优选0或1。当m取1时，R 4优选位于苯环基团的对位。
(5)非亲核性阴离子
X -表示非亲核性阴离子，包括(但不限于)：M -、ClO 4 -、CN -、HSO 4 -、NO 3 -、CF 3COO -、(BM 4) -、(SbM 6) -、(AsM 6) -、(PM 6) -、Al[OC(CF 3) 3] 4 -、R 7SO 3 -、(R 7SO 2) 3C -、(R 7SO 2) 2N -、B(C 6M 5) 4 -、Ga(C 6M 5) 4 -或[(Rf) bPF 6- b] -。
M表示卤素，如氟、氯、溴、碘，优选氟。
R 7表示C 1-C 20的烷基、C 1-C 20的全氟烷基、或者C 6-C 20的芳基或取代芳基，烷基和全氟烷基可为直链、支链或者环状中的任意一种。
Rf表示≥80％的氢原子被氟原子取代的烷基，所述烷基可列举：直链烷基如甲基、乙基、丙基、丁基、戊基、己基、辛基等，支链烷基如异丙基、异丁基、仲丁基、叔丁基等，环烷基如环丙基、环丁基、环戊基、环己基等。Rf中，基于烷基原有氢原子的摩尔数，被氟原子取代的比例较佳为80％以上，优选90％以上，更优选为100％。若氟原子取代比例在这些范围内，则化合物的光感应性变得更良好。进一步地，Rf可例举：CF 3 -、CF 3CF 2 -、(CF 3) 2CF -、CF 3CF 2CF 2 -、CF 3CF 2CF 2CF 2 -、(CF 3) 2CFCF 2 -、CF 3CF 2(CF 3)CF -以及(CF 3) 3C -。b表示1-5的整数，且b个Rf基团彼此之间可以相同，也可以不同。
M -表示的阴离子，可例举：Cl -、Br -、F -。
(BM 4) -、(SbM 6) -、(AsM 6) -、(PM 6) -表示的阴离子，可例举：BF 4 -、SbF 6 -、AsF 6 -、PF -。
R 7SO 3 -表示的阴离子，可例举：CF 3SO 3 -、C 2F 5SO 3 -、C 3F 7SO 3 -、C 4F 9SO 3 -、C 6F 5SO 3 -、C 3F 7SO 3 -、对甲苯磺酸根阴离子、苯磺酸根阴离子、樟脑磺酸根阴离子、甲磺酸根阴离子、乙磺酸根阴离子、丙磺酸根阴离子以及丁磺酸根阴离子。
(R 7SO 2) 3C -表示的阴离子，可例举：(CF 3SO 2) 3C -、(C 2F 5SO 2) 3C -、(C 3F 7SO 2) 3C -以及(C 4F 9SO 2) 3C -。
(R 7SO 2) 2N -表示的阴离子，可例举：(CF 3SO 2) 2N -、(C 2F 5SO 2) 2N -、(C 3F 7SO 2) 2N -以及(C 4F 9SO 2) 2N -。
B(C 6M 5) 4 -、Ga(C 6M 5) 4 -表示的阴离子，可例举：B(C 6F 5) 4 -、Ga(C 6F 5) 4 -。
[(Rf) bPF 6-b] -表示的阴离子，可例举：(CF 3CF 2) 2PF 4 -、(CF 3CF 2) 3PF 3 -、[(CF 3) 2CF] 2PF 4 -、[(CF 3) 2CF] 3PF 3 -、(CF 3CF 2CF 2) 2PF 4 -、(CF 3CF 2CF 2) 3PF 3 -、[(CF 3) 2CFCF 2] 2PF 4 -、[(CF 3) 2CFCF 2] 3PF 3 -、(CF 3CF 2CF 2CF 2) 2PF 4 -以及(CF 3CF 2CF 2CF 2) 3PF 3 -等。
制备方法
对制备本发明的三苯基硫鎓盐化合物的方法没有特别的限制，可以采用周知的有机合成工艺。例如，可参考专利文献CN1871212A中记载的制备方法(在此将其全文引入以作为参考)，通过市售的二芳基亚砜与芳基化合物进行锍化反应来得到硫鎓盐，再根据需要经过盐交换反应引入阴离子，由此得到本发明的三苯基硫鎓盐化合物。
应用
本发明的三苯基硫鎓盐化合物具有通过能量射线的照射而放出路易斯酸的特性，可作为抗蚀剂产酸剂和阳离子聚合用光引发剂使用。
作为适用的能量射线，可使用低压、中压、高压或超高压的汞灯、金属卤化灯、LED灯、氙灯、碳弧灯、荧光灯、半导体固体激光、氩激光、He-Cd激光、KrF准分子激光、ArF准分子激光或F 2激光等得到的紫外-可见光区域的能量射线，也可使用电子束或X射线等具有高能量的放射线。
本发明的三苯基硫鎓盐化合物与感光性活性单体(如阳离子聚合性化合物)混合形成感光性组合物，能够应用于制作平版、凸版用印刷版、印刷基板和IC、LSI用的光致抗蚀剂，光固化油墨，涂料，粘合剂等领域中。
本发明上述通式(I)所示的三苯基硫鎓盐化合物具有优异的溶解性、较高的光产生效率和感光活性，有很好的市场应用价值。
引申
作为本发明上述三苯基硫鎓盐化合物的结构引申，本发明还提供一种噻吨酮硫鎓盐，具有如下通式(III)所示的结构：
Figure PCTCN2019108369-appb-000007
其中，R 1、R 2、R 3、R 4和X -具有如上文所述的相同含义，n和m各自独立地表示1-5的整数。
上述噻吨酮硫鎓盐可视为通式(I)中一个R 3和一个R 4相连构成酮基后形成的结构，同时被认为能够取得与通式(I)所示的三苯基硫鎓盐化合物类似的有益效果。
该化合物的制备方法可参考专利文献WO2003072567中记载的工艺合成，在此将其全文引入以作为参考。
代表性地，可通过下述工艺合成：
Figure PCTCN2019108369-appb-000008
在本申请又一种典型的实施方式中，提供了另一种三苯基硫鎓盐化合物，其是双-三苯基硫鎓盐化合物，具有如通式(II)所示结构：
Figure PCTCN2019108369-appb-000009
其中，R 1表示吸电子基团；R 2表示增幅基团；各R 3各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示R 3的基团中的碳碳键可被-O-、-S-所中断，且R 3基团可彼此相连成环；n表示0-5的整数；各R 4各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示R 4的基团中的碳碳键可被-O-、-S-所中断，且R 4基团可彼此相连成环；m表示0-4的整数；各R 5各自独立地，表示氢、卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示R 5的基团中的碳碳键可被-O-、-S-所中断，且R 5基团可彼此相连成环；p表示0-4的整数；A和M各自独立地表示连接基团；X -表示非亲核性阴离子。
应用表明，通过在双-三苯基硫鎓盐的苯环基团的间位和对位分别配置吸电子基团和增幅基团，相较于未取代的三苯基硫鎓盐，能够具有明显提高的溶解性和感光活性，并且相比于背景技术中记载的现有改进型替代品也具有性能上的明显优势。
以下对通式(II)结构中的各可变基团进行更详细的说明。
需要注明的是，在本申请的说明书中，C 1-C x除了1和x之外，还包括碳数在1到x之间的所有整数值，例如，C 1-C 8的烷基包括C 1、C 2、C 3、C 4、C 5、C 6、C 7和C 8的直链或支链的 所有烷基。限于篇幅，说明书中未一一展开描述，但其含义对本领域技术人员而言是明确且可毫无疑义确定的，应当理解的是，包含在内的各数值能够作为进一步修改/限定的基础。
可变基团
(1)R 1吸电子基团
据信，在苯环间位引入吸电子基团能够有效提升硫鎓盐的溶解性，同时不对感光活性产生负面影响。
作为适用的吸电子基团R 1，选自卤素、氰基、硝基、卤代烷基、酰基、酰氧基、磺酰基。
卤素可以是氟、氯、溴或碘。从环保性能考虑，优选是氟。
卤代烷基是指至少一个氢原子被卤素取代的烷基，所述烷基可以是甲基、乙基、正丙基、正丁基、正戊基、正己基等C 1-C 8的直链烷基，或是异丙基、异丁基、仲丁基、叔丁基等C 3-C 8的支链烷基，或是环丙基、环丁基、环戊基、环己基等C 3-C 8的环烷基。当卤代烷基选自氟取代的烷基时，对化合物的感光活性是有利的，更优选C 1-C 4的全氟烷基。
酰基可具有
Figure PCTCN2019108369-appb-000010
或
Figure PCTCN2019108369-appb-000011
所示的结构，其中R 6表示氢、卤素、取代或未取代的烷基、取代或未取代的芳基、取代或未取代的芳烷基。优选地，R 6表示氢、氟、氯、C 1-C 7的直链或支链的烷基、C 1-C 7的直链或支链的卤代烷基(更优选地，C 1-C 7的直链或支链的全氟代烷基)、C 6-C 12的芳基、或C 7-C 16的芳烷基。
酰氧基中的酰基具有上段内容中酰基所示的相同含义。
磺酰基可以是甲磺酰基、二氟甲磺酰基、三氟甲磺酰基、苯磺酰基、甲苯磺酰基等。
在本发明的通式(II)中，吸电子基团R 1优选是卤素、氰基、硝基、卤代烷基，特别是上述优选的那些基团。
(2)R 2增幅基团
所谓的增幅基团是指对化合物的溶解性和/或感光活性产生增幅作用的基团。
现有文献报道，在三苯基硫鎓盐的苯环基团的对位引入取代基能够提高溶解性，但会明显降低感光活性。出乎意料地，在苯环基团间位存在吸电子基团R 1的情况下，在对位引入增幅基团R 2，能够对化合物的溶解性和/或感光活性产生增幅作用，且在进一步提升该性能的同时，不会对其它性能产生不利影响。
作为本发明中能够表现出增幅作用的基团，R 2选自取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳烷基。
烷基优选是未取代的烷基，可以是甲基、乙基、正丙基、正丁基、正戊基、正己基等C 1-C 8的直链烷基，或是异丙基、异丁基、仲丁基、叔丁基等C 3-C 8的支链烷基。更优选地，作为增幅基团的烷基是C 1-C 4的直链或支链的烷基，包括甲基、乙基、正丙基、异丙基、正丁基或异丁基。
烷氧基优选是未取代的，其中的烷基具有上段内容中所示的相同含义。
芳烷基是以芳基封端的烷基，从增幅效果看，优选是以苯基封端的C 1-C 8的烷基，更优选是以苯基封端的C 1-C 4的直链烷基，包括苯甲基、苯乙基、苯丙基或苯丁基。任选地，芳烷基中的至少一个氢原子被卤素(特别是氟)所取代。
通式(II)结构中可任选地含有R 3取代基团，前提是不对化合物的光固化应用性能产生负面影响。
在此前提条件下，从提供更多同类替代品的角度出发，R 3各自独立地，表示氢、卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基，任选地，基团中的碳碳键可被-O-、-S-所中断，且R 3基团可彼此相连成环。
n表示R 3基团的数量，可以是0-5的整数。
本领域的技术人员基于有机领域的基础理论能够知晓，R 3取代基团的存在能够对所处苯环的共轭结构和双-三苯基硫鎓的整体结构特性产生影响。不受限于任何理论，这种影响带来的结果通常是难以预期的，其更多依赖于试验的最终呈现。
优选地，n是0，此时可避免取代基团引起的后续光固化进程中可能出现的副反应，或对效果产生的未知负面影响。
更优选地，n是2，且同一苯环上的两个R 3分别表示R 1和R 2，与最上方苯环的R 1和R 2上下对称，即本发明的双-三苯基硫鎓盐为下述通式(V)所示结构：
Figure PCTCN2019108369-appb-000012
其中，各取代基团具有如上文所述的相同含义。
出乎意料地，当双-三苯基硫鎓盐在上下四个苯环基团中含有如上述结构所示的对称的吸电子基团和增幅基团时，与现有技术中的改进型三苯基硫鎓盐相比，该化合物呈现出显著进一步提升的溶解性和感光活性。
(4)R 4取代基团
通式(II)结构中可任选地含有R 4取代基团，前提是不对化合物的光固化应用性能产生负面影响。
在此前提条件下，从提供更多同类替代品的角度出发，R 4各自独立地，表示氢、卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基，任选地，基团中的碳碳键可被-O-、-S-所中断，且R 4基团可彼此相连成环。
卤素可以是氟、氯、溴或碘。从成本和环保性能考虑，优选氟。
酰基可选自：C 2-C 8的脂肪族酰基，如乙酰基、丙酰基、丁酰基、戊酰基、异戊酰基、己酰基、辛酰基、庚酰基等；C 7-C 12的芳香族酰基，如苯甲酰基、甲基苯甲酰基、三甲基苯甲酰基、α-苯丙酰基、萘甲酰基等。
酰氧基中的酰基可具有上段内容中酰基所示的相同含义。
磺酰基可以是甲磺酰基、二氟甲磺酰基、三氟甲磺酰基、苯磺酰基、甲苯磺酰基等。
烷基可以是取代或未取代的。所述烷基可选自C 1-C 8的直链、支链或环状的烷基，例如：甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、叔戊基、新戊基、正己基、异己基、3-甲基戊基、2-甲基戊基、1，2-二甲基丁基、环丙基、环戊基、环己基等。优选地，所述烷基选自C 1-C 4的直链或支链烷基、或C 3-C 6的环状烷基。取代烷基中的取代基包括(但不限于)：卤素(氟、氯、溴、碘)、胺基、羟基等。
烷氧基可以是取代或未取代的，其中的烷基和取代基可具有上段内容中所示的相同含义。
芳基可以是取代或未取代的。所述芳基可以是苯基、萘基、蒽基、芘基等。作为取代基，可以是：C 1-C 4的烷基如甲基、乙基、丙基、丁基等，卤素如氟、氯、溴、碘，C 1-C 3的烷氧基如甲氧基、乙氧基、丙氧基，酰基，磺酰基，羟基，胺基，硝基，苯基等。
芳烷基是以芳基封端的烷基，可以是取代或未取代的。其中，芳基部分和取代基可具有上段内容中所示的相同含义。作为其中的烷基部分，优选是C 1-C 6的亚烷基，包括亚甲基、亚乙基等。特别优选地，芳烷基是苄基、苯乙基或苯丙基，任选地，苯基上的至少一个氢被上段内容中所示的取代基所取代。
在本发明的通式(II)中，R 4优选是氢、硝基、氰基、取代或未取代的烷基、取代或未取代的烷氧基，特别是上述优选的那些基团。
m表示R 4基团的数量，可以是0-4的整数。优选地，m表示0、1或2，更优选0或1。当m取1时，R 4优选位于A基团侧的邻位。
(5)R 5取代基团
通式(II)结构中可任选地含有R 5取代基团，前提是不对化合物的光固化应用性能产生负面影响。
就选择范围而言，R 5可具有与上述R 4取代基团相同的含义。R 4和各R 5与与各自相连的苯基、A基团可以成环。
p表示R 5基团的数量，可以是0-4的整数。优选地，p表示0、1或2，更优选0或1。当p取1时，R 5优选位于A基团侧的邻位。
(6)连接基团
作为两个三苯基硫鎓结构的连接基团，A表示连接键(即单键)、＊O＊、＊S＊、亚烷基或亚链烯基，M表示空、
Figure PCTCN2019108369-appb-000013
＊O＊、＊S＊或
Figure PCTCN2019108369-appb-000014
基团，其中，*表示连接位，R 8、R 9、R 10各自独立地表示氢、C 1-C 20的直链或支链烷基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基或C 4-C 20的烷基环烷基。
优选地，亚烷基是C 1-C 4的直链亚烷基，亚链烯基是-CH＝CH-。
当M表示空时，代表两个苯环之间仅通过连接基团A相连。M不是空时，优选A表示连接键。
(7)连接位
本发明通式(II)所示的双-三苯基硫鎓盐化合物中，左右两侧的S原子分别与三个苯环相连。在中间的两个苯环上，S原子的连接位优选是基团A的对位。
(8)非亲核性阴离子
X -表示非亲核性阴离子，包括(但不限于)：Q -、ClO 4 -、CN -、HSO 4 -、NO 3 -、CF 3COO -、(BQ 4) -、(SbQ 6) -、(AsQ 6) -、(PQ 6) -、Al[OC(CF 3) 3] 4 -、R 6SO 3 -、(R 6SO 2) 3C -、(R 6SO 2) 2N -、B(C 6Q 5) 4 -、Ga(C 6Q 5) 4 -或[(Rf) bPF 6-b] -。
Q表示卤素，如氟、氯、溴、碘，优选氟。
R 6表示C 1-C 20的烷基、C 1-C 20的全氟烷基、或者C 6-C 20的芳基或取代芳基，烷基和全氟烷基可为直链、支链或者环状中的任意一种。
Rf表示≥80％的氢原子被氟原子取代的烷基，所述烷基可列举：直链烷基如甲基、乙基、丙基、丁基、戊基、己基、辛基等，支链烷基如异丙基、异丁基、仲丁基、叔丁基等，环烷基如环丙基、环丁基、环戊基、环己基等。Rf中，基于烷基原有氢原子的摩尔数，被氟原子取代的比例较佳为80％以上，优选90％以上，更优选为100％。若氟原子取代比例在这些范围内，则化合物的光感应性变得更良好。进一步地，Rf可例举：CF 3 -、CF 3CF 2 -、(CF 3) 2CF -、CF 3CF 2CF 2 -、CF 3CF 2CF 2CF 2 -、(CF 3) 2CFCF 2 -、CF 3CF 2(CF 3)CF -以及(CF 3) 3C -。b表示1-5的整数，且b个Rf基团彼此之间可以相同，也可以不同。
Q -表示的阴离子，可例举：Cl -、Br -、F -。
(BQ 4) -、(SbQ 6) -、(AsQ 6) -、(PQ 6) -表示的阴离子，可例举：BF 4 -、SbF 6 -、AsF 6 -、PF -。
R 6SO 3 -表示的阴离子，可例举：CF 3SO 3 -、C 2F 5SO 3 -、C 3F 7SO 3 -、C 4F 9SO 3 -、C 6F 5SO 3 -、C 3F 7SO 3 -、对甲苯磺酸根阴离子、苯磺酸根阴离子、樟脑磺酸根阴离子、甲磺酸根阴离子、乙磺酸根阴离子、丙磺酸根阴离子以及丁磺酸根阴离子。
(R 6SO 2) 3C -表示的阴离子，可例举：(CF 3SO 2) 3C -、(C 2F 5SO 2) 3C -、(C 3F 7SO 2) 3C -以及(C 4F 9SO 2) 3C -。
(R 6SO 2) 2N -表示的阴离子，可例举：(CF 3SO 2) 2N -、(C 2F 5SO 2) 2N -、(C 3F 7SO 2) 2N -以及(C 4F 9SO 2) 2N -。
B(C 6Q 5) 4 -、Ga(C 6Q 5) 4 -表示的阴离子，可例举：B(C 6F 5) 4 -、Ga(C 6F 5) 4 -。
[(Rf) bPF 6-b] -表示的阴离子，可例举：(CF 3CF 2) 2PF 4 -、(CF 3CF 2) 3PF 3 -、[(CF 3) 2CF] 2PF 4 -、[(CF 3) 2CF] 3PF 3 -、(CF 3CF 2CF 2) 2PF 4 -、(CF 3CF 2CF 2) 3PF 3 -、[(CF 3) 2CFCF 2] 2PF 4 -、[(CF 3) 2CFCF 2] 3PF 3 -、(CF 3CF 2CF 2CF 2) 2PF 4 -以及(CF 3CF 2CF 2CF 2) 3PF 3 -等。
制备方法
对制备本发明的双-三苯基硫鎓盐化合物的方法没有特别的限制，可以采用周知的有机合成工艺。例如，可参考专利文献CN1871212A中记载的制备方法，通过二芳基亚砜与二芳基化合物进行锍化反应来得到硫鎓盐，再根据需要经过盐交换反应引入阴离子，由此得到本发明的双-三苯基硫鎓盐化合物。
应用
本发明的双-三苯基硫鎓盐化合物具有通过活性能量射线的照射而放出路易斯酸的特性，能够作用于酸反应性有机物质而进行分解或聚合，因此可作为光致抗蚀剂的光致产酸剂或者作为阳离子型聚合光引发剂使用。
作为适用的能量射线，可使用低压、中压、高压或超高压的汞灯、金属卤化灯、LED灯、氙灯、碳弧灯、荧光灯、半导体固体激光、氩激光、He-Cd激光、KrF准分子激光、ArF准分子激光或F 2激光等得到的紫外-可见光区域的能量射线，也可使用电子束或X射线等具有高能量的放射线。
本发明的双-三苯基硫鎓盐化合物与感光性活性单体(如阳离子聚合性化合物)混合形成感光性组合物，能够应用于制作平版、凸版用印刷版，印刷基板和IC、LSI用的光致抗蚀剂，光固化油墨，涂料，粘合剂等领域中。
本发明上述通式(II)所示的双-三苯基硫鎓盐化合物具有优异的溶解性、较高的光产生效率和感光活性，有很好的市场应用价值。
以下通过实施例对本发明做进一步详细说明，但不应将其理解为对本发明保护范围的限制。
关于具有通式(I)的三苯基硫鎓盐化合物
制备实施例
实施例I-1：硫鎓盐A-1的制备
(1)中间体a1
Figure PCTCN2019108369-appb-000015
向500mL的四口烧瓶中投入110.0g邻氟甲苯、59.5g二氯亚砜、200mL二氯甲烷，冰水浴冷却，控温5℃左右，分批加入66.5g三氯化铝，约1h加完，继续搅拌2h，液相跟踪反应至完全。将产物的二氯甲烷溶液倒入500g冰水中，不断搅拌，分出二氯甲烷层，水洗二氯甲烷层，旋蒸二氯甲烷产物溶液，得淡黄色固体106g，即中间体a1，收率79.7％，HPLC纯度：98％。
中间体产物的结构通过核磁共振氢谱及质谱得到确认，具体表征结果如下： 1H-NMR(CDCl 3，500MHz)：2.3312(6H，s)，7.2438-7.3305(6H，m)。MS(m/Z)：267(M+H) +。
(2)中间体b1
Figure PCTCN2019108369-appb-000016
向500mL的四口烧瓶中投入66.5g中间体a1、200mL醋酐，冰水浴搅拌，控温0℃左右，滴加35g浓硫酸(质量分数70％)，约1h滴加完，滴加完后向反应体系中分批加入27g甲氧基苯，继续搅拌12h，接着缓慢滴加100mL去离子冰水，将溶液用苯萃取2-3次，分出水层，合并苯层水洗一次，将水层合并即得到中间体b1的水溶液。
(3)目标产物即化合物A-1
Figure PCTCN2019108369-appb-000017
在上述中间体b1的水溶液中加入46g KPF 6固体进行离子交换，搅拌下适当补充去离子水，随着KPF 6固体的溶解，目标产物A-1逐渐析出，过滤干燥得77.8g白色固体，收率62.0％，HPLC纯度：99％。
目标产物的结构通过核磁共振氢谱及质谱得到确认，具体表征结果如下：
1H-NMR(DCl 3，500MHz)：2.3312(6H，s)，3.7345(3H，s)，6.8038-7.2818(10H，m)。
MS(m/Z)：357(M) +。
实施例I-2：硫鎓盐A-2的制备
(1)中间体a2
Figure PCTCN2019108369-appb-000018
向1500mL的四口烧瓶中投入12.7g异丙基噻吨酮(ITX)和800mL乙腈与水的混合溶液(乙腈75％，水25％)，搅拌加热到35℃，全部溶解后，加入107.9g硝酸铈铵，室温下搅拌反应约1h，液相跟踪至反应完全。反应结束后加入500mL水，二乙醚多次萃取混合物，合并有机层，硫酸镁干燥，旋蒸得到12.5g中间体a2，收率79.7％，HPLC纯度：98％。
中间体产物的结构通过核磁共振氢谱得到确认，具体表征结果如下： 1H-NMR(CDCl 3，500MHz)：1.2167-2.8743(7H，m)，7.5912-7.9532(7H，m)。
(2)中间体b2
Figure PCTCN2019108369-appb-000019
向500mL的四口烧瓶中投入67.5g中间体a1、200mL醋酐，冰水浴搅拌，控温0℃左右，滴加36g浓硫酸(质量分数70％)，约1h滴加完，滴加完后向反应体系中分批加入27.5g邻氟甲苯，继续搅拌12h，接着缓慢滴加100mL去离子冰水，将溶液用苯萃取2-3次，分出水层，合并苯层水洗一次，将水层合并即得到中间体b1的水溶液。
(3)目标产物即化合物A-2
Figure PCTCN2019108369-appb-000020
在上述中间体b2的水溶液中加入46g KPF 6固体进行离子交换，搅拌下适当补充去离子水，随着KPF 6固体的溶解，目标产物A-2逐渐析出，过滤干燥得77.8g白色固体，收率62.0％，HPLC纯度：99％。
目标产物的结构通过核磁共振氢谱及质谱得到确认，具体表征结果如下： 1H-NMR(DCl 3，500MHz)：1.2034-1.2045(6H，d)，2.3312(3H，s)，2.8732-2.8745(1H，m)，6.9908-7.7221(10H，m)。
MS(m/Z)：363(M) +。
参照实施例1的制备方法，制备如表1中所示的化合物3-38。
目标产物的结构及其MS(m/Z)和 1H-NMR数据列于表1。
表1
Figure PCTCN2019108369-appb-000021
Figure PCTCN2019108369-appb-000022
Figure PCTCN2019108369-appb-000023
Figure PCTCN2019108369-appb-000024
Figure PCTCN2019108369-appb-000025
Figure PCTCN2019108369-appb-000026
Figure PCTCN2019108369-appb-000027
Figure PCTCN2019108369-appb-000028
关于具有通式(II)的三苯基硫鎓盐化合物
制备实施例
实施例II-1：硫鎓盐C-1的制备
(1)中间体a1
Figure PCTCN2019108369-appb-000029
向500mL的四口烧瓶中投入110.0g邻氟甲苯、59.5g二氯亚砜、200mL二氯甲烷，冰水浴冷却，控温5℃左右，分批加入66.5g三氯化铝，约1h加完，继续搅拌2h，液相跟踪反应至完全。将产物的二氯甲烷溶液倒入500g冰水中，不断搅拌，分出二氯甲烷层，水洗二氯甲烷层，旋蒸二氯甲烷产物溶液，得淡黄色固体106g，即中间体a1，收率79.7％，HPLC纯度：98％。
中间体的产物结构通过核磁共振氢谱及质谱得到确认，具体表征结果如下：
1H-NMR(CDCl 3，500MHz)：2.3512(6H，s)，7.2438-7.3305(6H，m)。
MS(m/Z)：267(M+H) +。
(2)中间体b’1
Figure PCTCN2019108369-appb-000030
向500mL的四口烧瓶中投入66.5g中间体a1、200mL醋酐，冰水浴搅拌，控温0℃左右，滴加35g浓硫酸(质量分数70％)，约1h滴加完，滴加完后向反应体系中分批加入23.3g二苯硫醚，继续搅拌12h，接着缓慢滴加100mL去离子冰水，将溶液用苯萃取2-3次，分出水层，合并苯层水洗一次，将水层合并即得到中间体b’1的水溶液。
(3)目标产物即化合物C-1
Figure PCTCN2019108369-appb-000031
在上述中间体b’1的水溶液中加入179.5g四-(五氟苯)硼酸钾盐固体进行离子交换，搅拌下适当补充去离子水，随着四-(五氟苯)硼酸钾盐固体的溶解，目标产物C-1逐渐析出，过滤干燥得158g白色固体，收率62.0％，HPLC纯度：99％。
目标产物的结构通过核磁共振氢谱及质谱得到确认，具体表征结果如下：
1H-NMR(CDCl 3，500MHz)：2.3512(12H，s)，6.8038-7.2818(20H，m)。
MS(m/Z)：684(M) +。
实施例II-2
参照实施例II-1的制备方法，以二氯亚砜与相应的取代苯为起始原料，制备如表2中所示的化合物C2-C25。
目标产物的结构及其MS(m/Z)和 1H-NMR数据列于表2。
表2
Figure PCTCN2019108369-appb-000032
Figure PCTCN2019108369-appb-000033
Figure PCTCN2019108369-appb-000034
Figure PCTCN2019108369-appb-000035
Figure PCTCN2019108369-appb-000036
性能评价
通过配置示例性光固化组合物，对本发明的通式(I)、(II)所示化合物作为光引发剂的应用性能进行测试。
1、溶解性能测试
测定本发明化合物A-1～A-38、C-1～C-25以及对比例化合物B-1和B-2、D-1和D-2在3-乙基-3-羟甲基氧杂环丁烷单体中的溶解度，以20℃条件下100g溶剂中溶解的最大克数计算。
Figure PCTCN2019108369-appb-000037
测试结果示于表3和表4中。
2、产酸率的测定
将上述化合物分别配置成0.02mmol/g的乙腈溶液。在内径为100mm的培养皿中加入5.00g调制的乙腈溶液，然后在紫外灯(型号FL10BL)照射下，以0.8mw/cm 2的光强累计接收200mj/cm 2的能量。对于曝光后的溶液，以BTB作为指示剂，用0.05N的氢氧化钾乙醇溶液进行滴定。将相应的光照前的溶液进行滴定得到空白值，将滴定测定值扣除空白值，通过以下公式换算求出产酸率：
产酸率％＝(酸滴定值-空白值)(mol)/化合物理论摩尔数(mol)×100％。
测试结果示于表3和表4中。
3、感光度测试
通过配置示例性光致抗蚀剂，对本发明通式(I)和(II)所示化合物的感光度进行测试。
光致抗蚀剂的组成：
Figure PCTCN2019108369-appb-000038
其中，
树脂A表示
Figure PCTCN2019108369-appb-000039
树脂B表示间甲酚和对甲酚以摩尔比1:1在甲醛和酸催化条件下缩合而得到的酚醛清漆树脂，分子量为10000左右；
光引发剂为上述化合物A-1～A-38、C-1～C-25或者对比例化合物B-1和B-2、D-1和D-2。
将各组分按上述比例搅拌均匀，通过孔径1μm的膜过滤器进行过滤，制备成固含量为40％的抗蚀剂组合物。
将抗蚀剂组合物通过旋转涂布机均匀涂布在硅晶片基板上，烘干得到20μm厚的光致抗蚀剂涂层。130℃预烘烤6min，然后使用TME-150RSC进行图案曝光(i线)，利用热板在75℃进行5min曝光。然后采用质量分数为2.38％的四甲基氢氧化铵溶液显影5min，再用流水清洗，氮气吹干，得到10μm线条图案。测定看不到图案残渣的最低限度的曝光量，即形成抗蚀剂图案所需的最低曝光量，数值越低，说明引发剂的感光度越高。
测试结果示于表3和表4中。
表3
Figure PCTCN2019108369-appb-000040
Figure PCTCN2019108369-appb-000041
由表3的测试结果可以看出，本发明的硫鎓盐化合物表现出了令人满意的溶解度，且产酸率和感光活性优异，相比于现有的改进型三苯基硫鎓盐B-1和B-2，性能优势明显，具有广阔的应用前景。
表4
Figure PCTCN2019108369-appb-000042
Figure PCTCN2019108369-appb-000043
由表4的测试结果可以看出，本发明通式(II)所示的双-三苯基硫鎓盐化合物表现出了令人满意的溶解度，且产酸率和感光活性优异，相比于现有的改进型三苯基硫鎓盐D-1和D-2，性能优势明显，具有广阔的应用前景。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (25)

  1. 三苯基硫鎓盐化合物，具有如下通式(I)或通式(II)或通式(III)所示结构：
    Figure PCTCN2019108369-appb-100001
    其中，
    R 1表示吸电子基团；
    R 2表示增幅基团；
    各R 3各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，任选地，表示所述通式(I)中的R 3的基团中的-CH 2-可被-O-、-S-所取代，表示所述通式(II)中的R 3的基团中的碳碳键可被-O-、-S-所中断，且R 3基团可彼此相连成环；
    各R 4和R 5各自独立地表示卤素、硝基、氰基、羟基、酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷 基中的任意一种，任选地，表示所述通式(I)中所述R 4的基团中的-CH 2-可被-O-、-S-、或-CH＝CH-所取代，表示所述通式(II)中的R 4和所述R 5的基团中的碳碳键可被-O-、-S-所中断，且R 4基团可彼此相连成环，R 5基团可彼此相连成环；
    所述通式(I)中，n和m各自独立地表示0-5的任意一个整数；所述通式(II)中n表示0-5的任意一个整数，m和p各自独立地表示0-4的任意一个整数，所述通式(III)中n和m各自独立地表示1-5的整数，
    X -表示非亲核性阴离子，
    通式(II)中，A和M各自独立地表示连接基团。
  2. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述R 1选自卤素、氰基、硝基、烷氧基、卤代烷基、酰基、酰氧基、磺酰基中的任意一种，优选所述R 1选自卤素、氰基、硝基、卤代烷基、酰基中的任意一种。
  3. 根据权利要求2所述的三苯基硫鎓盐化合物，其特征在于：作为所述R 1的所述卤素是氟、氯、溴或碘，优选氟。
  4. 根据权利要求2所述的三苯基硫鎓盐化合物，其特征在于：作为所述R 1的所述烷氧基是C 1-C 8的直链或支链烷氧基中的任意一种，优选为C 1-C 4的直链或支链烷氧基中的任意一种。
  5. 根据权利要求2所述的三苯基硫鎓盐化合物，其特征在于：作为所述R 1的所述卤代烷基中的烷基是C 1-C 8的直链烷基、或是C 3-C 8的支链烷基、或是C 3-C 8的环烷基，优选卤代烷基是C 1-C 4的全氟烷基中的任意一种。
  6. 根据权利要求2所述的三苯基硫鎓盐化合物，其特征在于：作为所述R 1的所述酰基或所述酰氧基中的酰基各自独立地具有
    Figure PCTCN2019108369-appb-100002
    所示的结构，其中R 6表示氢、卤素、取代或未取代的烷基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种；优选地，R 6表示氢、氟、氯、C 1-C 7的直链或支链的烷基、或C 1-C 7的直链或支链的氟代烷基中的任意一种，优选所述氟代烷基是C 1-C 7的直链或支链的全氟代烷基。
  7. 根据权利要求2所述的三苯基硫鎓盐化合物，其特征在于：作为所述R 1的所述磺酰基是甲磺酰基、二氟甲磺酰基、三氟甲磺酰基、苯磺酰基、甲苯磺酰基。
  8. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述R 2选自卤素、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳烷基中的任意一种，优选所述通式(II)中的所述R 2选自取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳烷基中的任意一种，优选作为所述R 2的所述卤素为氟。
  9. 根据权利要求8所述的三苯基硫鎓盐化合物，其特征在于：作为所述R 2的所述烷基是未取代的C 1-C 8的直链烷基或C 3-C 8的支链烷基，优选是C 1-C 4的直链或支链的烷基。
  10. 根据权利要求8所述的三苯基硫鎓盐化合物，其特征在于：作为所述R 2的所述烷氧基是未取代的，其中所述烷氧基中的烷基是未取代的C 1-C 8的直链烷基或C 3-C 8的支链烷基，优选是C 1-C 4的直链或支链的烷基。
  11. 根据权利要求8所述的三苯基硫鎓盐化合物，其特征在于：作为所述R 2的所述芳烷基是以苯基封端的C 1-C 8的烷基，优选是以苯基封端的C 1-C 4的直链烷基。
  12. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述通式(I)中和所述通式(II)中的n是0。
  13. 根据权利要求1至11中任一项所述的三苯基硫鎓盐化合物，其特征在于：所述通式(I)中和所述通式(II)中的n是2，且两个R 3分别表示所述R 1和所述R 2，所述化合物具有通式(IV)所示结构或通式(V)所示结构：
    Figure PCTCN2019108369-appb-100003
  14. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述m表示0、1或2，优选0或1；当m取1时，通式(I)中的R 4位于苯环基团的S的对位，通式(II)中的R 4位于苯环基团的A基团的邻位。
  15. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述X -表示M -、ClO 4 -、CN -、HSO 4 -、NO 3 -、CF 3COO -、(BM 4) -、(SbM 6) -、(AsM 6) -、(PM 6) -、Al[OC(CF 3) 3] 4 -、R 7SO 3 -、(R 7SO 2) 3C -、(R 7SO 2) 2N -、B(C 6M 5) 4 -、Ga(C 6M 5) 4 -或[(Rf) bPF 6-b] -，其中M表示卤素，R 7表示C 1-C 20的烷基、C 1-C 20的全氟烷基、C 6-C 20的芳基或取代芳基中的任意一种，Rf表示≥80％的氢原子被氟原子取代的烷基，b表示1-5的任意一个整数，且各个Rf基团彼此之间可以相同，也可以不同。
  16. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述通式(I)和所述通式(III)中，各所述R 4各自独立地选自酰基、酰氧基、磺酰基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳烷基中的任意一种，形成所述R 4的各基团中的-CH 2-可被-O-、-S-、或-CH＝CH-所取代，所述取代所用的取代基为C 1-C 4的烷基、卤素、C 1-C 3的烷氧基、酰基、磺酰基、羟基、胺基、硝基、苯基中的任意一种； 当R 4有多个时，相邻所述R 4与所述R 4相连的苯基可以成环，优选所述酰基和酰氧基中酰基为C 2-C 8的脂肪族酰基、C 7-C 12的芳香族酰基，优选所述磺酰基为苯磺酰基、甲苯磺酰基，所述烷基和所述烷氧基中的烷基优选为C 1-C 8的直链、C 3-C 8的支链、C 3-C 8的环烷基。
  17. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述通式(II)中，各所述R 4和各所述R 5各自独立地选自硝基、氰基、取代或未取代的烷基、取代或未取代的烷氧基中的任意一种，形成所述R 4和所述R 5的各基团中的-CH 2-可被-O-、-S-、或-CH＝CH-所取代，所述R 4和各所述R 5与与各自相连的苯基、A可以成环。
  18. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述p表示0、1或2，优选0或1，所述p表示1时，所述R 5位于苯环基团的A基团的邻位。
  19. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述A表示连接键、＊O＊、＊S＊、亚烷基或亚链烯基，优选所述亚烷基是C 1-C 4的直链亚烷基，优选所述亚链烯基是-CH＝CH-。
  20. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：M表示空、
    Figure PCTCN2019108369-appb-100004
    ＊O＊、＊S＊或
    Figure PCTCN2019108369-appb-100005
    基团，其中，R 8、R 9、R 10各自独立地表示氢、C 1-C 20的直链或支链烷基、C 3-C 20的环烷基、C 4-C 20的环烷基烷基或C 4-C 20的烷基环烷基中的任意一种。
  21. 根据权利要求20所述的三苯基硫鎓盐化合物，其特征在于：M不为空，A为连接键。
  22. 根据权利要求1所述的三苯基硫鎓盐化合物，其特征在于：所述通式(II)中，在与A直接相连的两个苯环上，S原子的连接位是基团A的对位。
  23. 权利要求1-22中任一项所述的三苯基硫鎓盐化合物作为抗蚀剂产酸剂和/或阳离子聚合用光引发剂的用途。
  24. 包含权利要求1-22中任一项所述的三苯基硫鎓盐化合物的感光性组合物。
  25. 权利要求24所述的感光性组合物在制作平版、凸版用印刷版、印刷基板、光致抗蚀剂，光固化油墨、涂料和粘合剂中的应用。
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