WO2005037778A1 - トリアリールスルホニウム塩の製造法 - Google Patents
トリアリールスルホニウム塩の製造法 Download PDFInfo
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- WO2005037778A1 WO2005037778A1 PCT/JP2004/014604 JP2004014604W WO2005037778A1 WO 2005037778 A1 WO2005037778 A1 WO 2005037778A1 JP 2004014604 W JP2004014604 W JP 2004014604W WO 2005037778 A1 WO2005037778 A1 WO 2005037778A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
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- 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
Definitions
- the present invention provides a triarylsulfonate salt which is useful as an acid generator for a resist or a photoinitiated polymerization initiator and differs only in the structure of one of the three aromatic rings in the cation moiety. For a new production method.
- Triarylsulfonium salts are widely used as photoacid generators in photolithography processes in the semiconductor manufacturing field.
- triarylsulfonium salts can be easily exchanged into various counter-ones using triarylsulfonium halides (eg, chlorides, bromides, etc.) as intermediates.
- triarylsulfonium halides eg, chlorides, bromides, etc.
- Examples of the method for synthesizing triarylsulfo-dum bromide include (1) a method of reacting diaryl sulfoxide with a Grignard reagent (see, for example, Non-Patent Document 1, Non-Patent Document 2, etc.), (2) A method in which a diaryl sulfoxide and an aromatic hydrocarbon are subjected to a condensation reaction in the presence of aluminum salt (for example, see Non-Patent Document 3); (3) a salt of diaryl dichlorosulfide with an aromatic hydrocarbon (For example, see Non-Patent Document 4), (4) a method of reacting diaryl sulfide with diaryliodium salt (for example, Non-Patent Document 5). See, for example).
- TMSC1 triarylsulfonium salt in the presence of silane
- this method is preferred as a method for synthesizing a sulfo-dum salt in which the three aromatic rings of the cation moiety are the same, and is a diaryl sulfoxide (where two aromatic rings have the same structure (structure a).
- the combination of the three aromatic rings of the sulfo-pium salt obtained by the method is as follows: Not only the target substance (i.e., a compound in which two of the three aromatic rings have the structure a and the remainder has the structure b), but also two kinds of by-products (i.e., three aromatic Compounds in which all of the rings have structure a or compounds in which one of Z and the three aromatic rings has structure a and the remaining two have structure b] have the following problems.
- Patent Document 1 Japanese Patent No. 3163615
- Non-patent literature l B.S.Wildi, S.W.Taylor and H.A.Portratz, Journal of the American Chemical Society, Vol. 73, ⁇ . 1965 (1951)
- Non-Patent Document 2 J ⁇ . Dektar and N.P.Hacker, Journal of the American Chemical Society, Vol. 112, No. 16, p. 6004 (1990)
- Non-Patent Document 3 G.H.Wiegand and W.E.McEwen, The Journal of Organic chemistry, Vol. 33, No. 7, p. 2671 (1968)
- Patent Document 5 J.V.Crivello and J.H.W.Lam, The Journal of Organic Chemistry, Vol. 43, No. 15, p. 3055 (1978)
- Patent Document 6 Kenneth K. Andersen and Nicholas E. Papanikolaou, Tetrahedron Letters, No. 45, p. 5445 (1966)
- the present invention has been made in view of the above situation, and is a triarylsulfonium salt in which only one of the three aromatic rings in the cation moiety has a different structure (hereinafter referred to as the present invention). It is an object of the present invention to provide a method which can efficiently produce triarylsulfonium salt) at a high yield without producing by-products.
- the present invention has been made for the purpose of solving the above problems, and has a general formula [1]
- R 1 represents a hydrogen atom, a halogen atom, an alkyl group, Haroaruki Le group having 1 one 4 carbon atoms, an alkoxy group, Ashiru group, hydroxy group, an amino group, a nitro group or a Shiano group Diaryl sulfoxide represented by
- R 1 represents a hydrogen atom, a halogen atom, an alkyl group, Haroaruki Le group having 1 one 4 carbon atoms, an alkoxy group, Ashiru group, hydroxy group, an amino group, a nitro group or a Shiano group Diaryl sulfoxide represented by
- R has a substituent selected from a halogen atom, an alkyl group, a haloalkyl group having 14 to 14 carbon atoms, an alkoxy group, an alkylthio group, an N-alkyl group and a group. And the substituent is different from R 1 in the general formula [1], and X represents a halogen atom.
- the method for producing a triarylsulfonium salt of the present invention has an advantage over conventional methods by using an activator having a high affinity for an oxygen atom in an amount of at least the amount used so far.
- an activator having a high affinity for an oxygen atom for example, severe conditions at high temperatures (for example, heating reflux operation, melting reaction, etc.), generation of sulfurous acid gas, discharge of a large amount of aluminum waste liquid, and three aromatic rings of the same cation moiety as the same sulfo-pum
- the desired sulfonium salt can be produced efficiently and in high yield without problems such as synthesis of salt alone and inclusion of by-products as impurities.
- Such an effect is caused by greatly increasing the amount of the activator having a high affinity for an oxygen atom used in the present invention, and it cannot be predicted at all.
- examples of the halogen atom represented by R 1 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
- the alkyl group represented by [0023] R 1, linear, branched one, the Yogu through normal, 1 one 12 carbon atoms or cyclic preferably include those of 1 one 6, specifically Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butynole group, n-pentynole group, isopentinol group, sec-pentynole group, tert-pentinole, neopentyl, 2-methylbutyl, 1-ethylpropyl, n-hexyl, iso- Hexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 1-ethylbutyl group, n-heptyl group, iso
- Methyl group dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, eodomethyl group, jodomethyl group, triodomethyl group, pentafluoroethyl group, pentachloroethyl group, pentabromoethyl group Tyl group, pentoxide ethyl group, heptafluoropropyl group, heptachloropropyl group, heptabromopropyl group, heptaodopro Group, nona full O b butyl group, nonafluorobutyl chlorobutyl group, Bruno Naburomobuchiru group, Nonayodobuchiru group and the like.
- the alkoxy group represented by R 1 may be any of linear, branched or cyclic and usually has 118, preferably 116 carbon atoms.
- acyl group represented by R 1 examples include those derived from a carboxylic acid having usually 11 to 16 carbon atoms. Specific examples include a formyl group, an acetyl group, a propioyl group, a butyryl group, Isobutyryl group, valeryl group, isovaleryl group, bivaloyl group, hexanoyl group, heptanoyl group, otatanyl group, nonanoyl group, decanoyl group, pendecanoyl group, lauroyl group
- those derived from aliphatic carboxylic acids such as myristoyl group, palmitoyl group and cyclohexylcarbon group, and those derived from aromatic carboxylic acids such as benzoyl group, naphthoyl group and toluoyl group.
- the aryl group of the aryl group may be selected from those having a substituent selected from the group usually having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. , A naphthyl group, an anthryl group, a phenanthryl group and the like.
- halogen atom selected from a halogen atom, an alkyl group, a haloalkyl group having 14 to 14 carbon atoms, an alkoxy group, an alkylthio group, an N-alkyl group and a group represented by R
- examples of the halogen atom, alkyl group, haloalkyl group having 14 to 14 carbon atoms and alkoxy group as the substituent of the aryl group include those substituents represented by R 1 in the general formula [1]. And the like.
- R a substituent represented by R, selected from a halogen atom, an alkyl group, a haloalkyl group having 14 to 14 carbon atoms, an alkoxy group, an alkylthio group, an N-alkyl group and a group.
- the alkylthio group mentioned as a substituent of the aryl group may have a substituent represented by the above R! /
- the oxygen atom of the alkoxy group mentioned as the substituent of the aryl group may be a sulfur atom.
- Atoms and may be straight-chain, branched or cyclic and usually have 18 to 18 carbon atoms, preferably 116 carbon atoms, and specifically, for example, methylthio group , Ethylthio, n_propylthio, isopro Pyrthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, isopentylthio, sec-pentylthio, tert-pentylthio, neopentylthio, 2 -Methylbutylthio, 1-ethylpropylthio, n-hexylthio, isohexylthio, sec-hexylthio, tert-hexylthio, neohexylthio, 2-methylpentylthio, 3 -Methylpentylthio, 1,
- R Having a substituent represented by R, selected from a halogen atom, an alkyl group, a haloalkyl group having 14 to 14 carbon atoms, an alkoxy group, an alkylthio group, an N-alkyl group and a group.
- the N-alkylcarbamoyl group mentioned as a substituent of the aryl group may, for example, be a group obtained by partially substituting a hydrogen atom of a rubamoyl group with an alkyl group having 16 carbon atoms.
- Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Among them, for example, a fluorine atom and a chlorine atom are preferred, and a fluorine atom is more preferred. .
- R in formula [2] and R in formula [2] may be a phenyl group.
- R 2 represents an alkyl group, an aryl group, an aralkyl group or a camphor group which may have a halogen atom
- M represents a metalloid atom, and n is 4 or 6
- M represents a metalloid atom, and n is 4 or 6
- examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, for example, a chlorine atom and a bromine atom are preferable. In particular, a bromine atom is more preferred.
- the alkyl group of the alkyl group optionally having a halogen atom represented by R 2 may be any of a straight-chain, branched or cyclic alkyl group.
- the aryl group of the aryl group represented by R 2 having a halogen atom may be, for example, one having 6 to 16 carbon atoms, preferably 6 to 14 carbon atoms. Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group and the like.
- a halogen atom, even I as the Ararukiru group Ararukiru group, usually a carbon number 7 15, preferably include those of carbon number 7-10, specifically For example, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, 1-methyl-3-phenylpropyl group, phenylpentyl group, phenylhexyl group, phenylheptyl group Group, a phenyl group, a phenyl group and the like.
- the alkyl group, aryl group and aralkyl group represented by R 2 having a halogen atom may be a part of a hydrogen atom in the above-mentioned alkyl group, aryl group and aralkyl group Alternatively, those in which all are substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like) can be given.
- a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like
- all hydrogen atoms are substituted with halogen atoms, or usually 110, preferably 1-16, hydrogen atoms are substituted with halogen atoms.
- halogen atoms or usually 110, preferably 1-16, hydrogen atoms are substituted with halogen atoms.
- those in which all hydrogen atoms are replaced by halogen atoms are preferable.
- aryl group there can be mentioned one in which 115, preferably 3 to 5 hydrogen atoms in the ring are replaced by a halogen atom. Those in which an atom is substituted with a halogen atom are preferred.
- aralkyl group those in which a hydrogen atom in the alkyl group portion and a hydrogen atom in the Z or aryl group portion have been substituted with halogen atoms can be mentioned. Hydrogen atoms are substituted, and aryl groups are substituted with 115, preferably 5 hydrogen atoms in the ring.
- the alkyl group, aryl group or aralkyl group represented by R 2 which has a halogen atom may be substituted by an alkyl group, an aryl group or an aralkyl group which may further have a substituent other than the halogen atom.
- the group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
- C14 alkyl groups such as tyl, sec-butyl, tert-butyl, etc., for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl Group, dibromomethyl group, tribromomethyl group, iodomethyl group, iodomethyl group, toriodomethyl group, trifluoroethyl group, trichloroethyl group, tribromoethyl group, triodoethyl group, pentafluoroethyl group, pentachloroethyl group, penta Bromoethyl group, pentaodoethyl group, heptafluorop Mouth pill group, heptachloropropyl group, heptabromopropyl group, heptaodopropyl group, nonafluorobutyl group, no
- examples of the semimetal atom represented by M include a boron atom, a silicon atom, a phosphorus atom, an arsenic atom, and an antimony atom.
- phosphorus atom, arsenic atom, antimony atom and the like are preferable, and for example, boron atom, phosphorus atom and the like are more preferable.
- Examples of the activator having a high affinity for oxygen used in the present invention include halogenotriorganosilane, triorganophosphine, and triorganophosphate. More specifically, for example, Chlorotrimethylsilane, chlorotriethylsilane, chlorodimethylcyclohexynolesilane, chlorodimethylisopropylsilane, chlorodimethyl-tert-butylsilane, chlorodimethyl 2- (2,3-dimethyl) butylsilane, chlorotriisopropylsilane, bromate Halogenotrialkylsilanes such as motrimethylsilane and halogenotriorganosilanes such as chlorodimethylphenylsilane, for example, triphenylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tricyclo He
- diaryl sulfoxide represented by the general formula [1] include, for example, diphenyl sulfoxide, bis (4-methylphenyl) sulfoxide, bis (3-methylphenyl) sulfoxide, bis ( 2-methylphenyl) sulfoxide, bis (4-methoxyphenyl) sulfoxide, bis (3-methoxyphenyl) sulfoxide, bis (2-methoxyphenyl) sulfoxide, bis (4-tert-butylphenyl) sulfoxide , Bis (4-trifluoromethylphenyl) sulfoxide, bis (4-fluorophenyl) sulfoxide, bis (4-chlorophenol) sulfoxide, dinaphthylsulfoxide, bis (hydroxyphenyl) Sulfoxide and the like.
- aryl Grignard reagent represented by the general formula [2] include, for example, phenylmagnesium bromide, 4-methylphenylmagnesium bromide, 3-methylphenylmagnesium bromide, bromobenzene 2-Methylphenylmagnesium, 4-tert-butylphenylmagnesium bromide, 4-cyclohexylphenylmagnesium bromide, 4-methoxyphenylmagnesium bromide, 3-methoxyphenylmagnesium bromide, 3-methoxyphenylmagnesium bromide 4-n-butoxyphenylmagnesium bromide 2-n-butoxyphenylmagnesium bromide 4-tert-butoxyphenylmagnesium bromide, 4-cyclohexyloxymagnesium bromide, 4-methylthiopheneyl bromide Magnesium, 2,4,6-trimethylfelmagnesium, 3,5-dimethyl-4-meth
- hydrohalic acid represented by the general formula [5] or a salt thereof include, for example, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and salts thereof (for example, lithium salt, sodium salt, potassium salt, rubidium salt, silver salt, cesium salt, etc.), among which, for example, hydrochloric acid, hydrobromic acid, etc. are preferred, and among them, hydrogen bromide is preferred. Acids are more preferred.
- sulfonic acid represented by the general formula [6] or a salt thereof include, for example, methansnolephonic acid, ethanesnolephonic acid, pronosnolefonic acid, butansnolefonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid , Octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, pendecanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid, tetradecanesulfonic acid, pentadecanesulfonic acid, hexadecanesulfonic acid, heptadecanesulfonic acid, octadecanesulfonic acid Alkylsulfonic acids such as nonadecanesulfonic acid, icosansulfonic acid, hen
- 2.4.6-Alkyl aromatic sulfonic acids such as tris (trimethyl) benzenesulfonic acid and 2,4,6-tris (isopropyl) benzenesulfonic acid, for example, 2-trifluoromethylbenzenesulfonic acid, 2-trichloromethylbenzene Sulfonic acid, 2-tribromomethylbenzenesulfonic acid, 2-triodomethylbenzenesulfonic acid, 3-trifluoromethylbenzenesulfonic acid, 3-trichloromethylbenzenesulfonic acid, 3-tribromomethylbenzenesulfonic acid , 3-Trimethylmethylbenzenesulfonic acid, 4-Trifluoromethylbenzenesulfonic acid, 4-Trichloromethyl Butylbenzenesulfonic acid, 4-tribromomethylbenzenesulfonic acid, 4-triodomethylbenzenesulfonic acid, 2,6-bis (trifluoromethyl) benzen
- Preferred specific examples of the inorganic strong acid represented by the general formula [7] or a salt thereof include, for example, tetrafluoroboronic acid, tetrafluoroaluminic acid, tetrafluoroferric acid, tetrafluorogallic acid, and hexafluorophosphoric acid.
- the triarylsulfonium salt represented by the general formula [4] is more specifically, for example, represented by the general formula [8]
- sulfonium salt represented by the general formula [8] include, for example, 4-methylphenyldiphenylsulfo-dimethylbromide, 3-methylphenyldibromo- Noresnorefonium bromide, 2-methinoleph-noresife-norresnorefonium bromide, 4-tert-butylphenyl-l-diphenyl-sulfo-pam bromide, 4-cyclohexylfe-noresifeninolesnorrenom Bromide, 4-Methoxypheninoresifeninoresnorefonium Bromide, 3-Methoxyphenyldisulfide-sulfo-pam bromide, 4-n-butoxyphen Ninoresifene-norresnorefonium bromide, 2-n-butoxyphenolenophene -Noresnor
- sulfonium salt (sulfonate) represented by the general formula [9] include, for example, 4-methylphenyldisulfide-dimethyltrifluoromethanesulfonate, 4-methylphenyldiphenylsulfonic acid.
- Nonafluorobutanesulfonate 4-methylphenoresphene-norresnorefonium, norfenoleohexanesnorefonate, 4-methinolefe-ludifir-sulfo-dum perfluorooctanesulfonate, 4-methylphene -Lujifenenoresnorenofenome p-tonorenesorenorhonate, 4-methinolepheninoresifeninoresnorenonium pentafnorolenobenzeneshonolenate, 4-methinolefe-noresife-noresnorenonium p-Trifluoromethylbenzenesulfonate, 3-methylphenyldiphenylsulfo-dum trifluoromethanes To the mouth of rufonate, 3-methylphenol-disulfide-sulfo-pum nonafluorobutanesnorephonate, 3-metidine
- sulfonium salt strong inorganic salt represented by the general formula [10] include, for example, 4-methylphenyldiphenylsulfo-pam park mouthrate, 4-methylphenyldiphenylsulfo- ⁇ Tetrafluoroborate, 4-methylphenyldisulfide-sulfo-dimethylhexafenoleophosphate, 4-methinorefue-norezifue-norresnorefonidium hexafluorofluoroarsenate, 4-methylphenyldiphenyl-sulfo- Pum hexafluoro antimonate, 4-methylphenyldiphenylsulfo-dimethyltetraphenolate, 4-methylphenyldiphenyl-sulfo-dimethyltetrakis ⁇ 3,5-bis (trifluoromethyl) phenyl ⁇ borate, 4-methylphenyldiphenylsulfo-pam park mouthrate
- the sulfo-dum salt represented by the general formula [4] can be produced, for example, as follows.
- the diaryl sulfoxide represented by the general formula [1] is dissolved in an appropriate solvent, and an activator having a high affinity for an oxygen atom (hereinafter referred to as an activator according to the present invention).
- an activator according to the present invention an activator having a high affinity for an oxygen atom
- an aryl Grignard reagent represented by the general formula [2] is prepared in accordance with a conventional method, and a homogeneous solution of the diaryl sulfoxide and the activator according to the present invention prepared above is mixed at 78-50 ° C. Then, stir and react for 0.1-2 hours.
- the resulting reaction solution is reacted with a strong acid represented by the general formula [3] or a salt thereof at 0 to 50 ° C., whereby a triarylsulfon-dimethyl salt represented by the general formula [4] is obtained. can get.
- diaryl sulfoxide represented by the general formula [1] a commercially available product may be used, or a conventional method (for example, Ber., 21, 1844 (1890), J. Chem. Soc. (C), 2424 (1969), Synlett, 2003 (13), p2029, etc.).
- aryl Grignard reagent represented by the general formula [2] a commercially available product may be used, or a reagent appropriately produced by a conventional method may be used.
- the amount of the activator used according to the present invention also varies depending on the type of the diaryl sulfoxide represented by the general formula [1], the aryl Grignard reagent represented by the general formula [2], and the solvent used.
- the lower limit is preferably 3, 4, and 4.5 equivalents
- the upper limit is preferably 7.5, 7, and 6 equivalents to the diaryl sulfoxide.
- the lower limit is preferred in order, 1.2, 1.6, 1.8 equivalents
- the upper limit is preferred in order, 3, 2. 8, 2.4 equivalents.
- the amount of the aryl grignard reagent represented by the general formula [2] is different depending on the type of the diaryl sulfoxide represented by the general formula [1] used and the type of the solvent. 1.0 to 10 equivalents, preferably 2.0 to 5.0 equivalents.
- reaction solvent to be used examples include ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, tert-butyl methyl ether, and cyclopentyl methyl ether, such as methylene chloride and odor.
- ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, tert-butyl methyl ether, and cyclopentyl methyl ether, such as methylene chloride and odor.
- halogenated hydrocarbons such as methylene, 1,2-dichloroethane, and chloroform
- aromatic hydrocarbons such as benzene, toluene, and xylene.
- those of the halogen salts are further subjected to a conventional method (for example, see WO02Z092559). Is dissolved in alcohols such as methanol, ethanol, isopropanol, etc., treated with silver oxide, and 1.0-5.0 moles of various acids are added. The resulting silver halide is filtered off, and then the alcohols are distilled off.
- alcohols such as methanol, ethanol, isopropanol, etc.
- an organic solvent such as methylene chloride, 1,2-dichloroethane, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and methyl ethyl ketone is used.
- Post-treatment after the reaction may be performed according to a post-treatment method usually performed in this field.
- the process for producing a triarylsulfonium salt of the present invention can be carried out by using the activator according to the present invention in an amount that is greater than the amount used so far. Severe conditions at high temperature (for example, heating reflux operation, melting reaction, etc.), generation of sulfurous acid gas, discharge of a large amount of aluminum waste liquid, synthesis of only sulfo-pium salt with the same three aromatic rings in the cation part,
- the triarylsulfonium salt according to the present invention can be produced efficiently and in high yield without problems such as the inclusion of by-products as impurities.
- the triarylsulfonium salt according to the present invention can be reacted with a compound derived from the target aeon according to a conventional method to thereby convert the triaryl to the desired counterone.
- Sulfo-pam salts can be easily produced.
- the triarylsulfonium salt produced by the method of the present invention has an extremely low by-product content, when this is used as an acid generator, for example, the profile of ultrafine patterns or Effects such as improvement of the roughness of the side wall and formation of a good pattern with a small edge roughness in a rectangular shape can be expected.
- Example 3 The same procedure as in Example 1 was carried out, except that the specific aryl chloride shown in Table 13 was used instead of the 4-bromotoluene used in Example 1 as the aryl chloride. Got. The results are shown in Table 3.
- Example 4 Same as Example 1 except that bromobenzene was used instead of 4-bromotoluene used in Example 1 as aryl halide, and the prescribed sulfoxides shown in Tables 4 and 5 were used as sulfoxides instead of diphenylsulfoxide. And the desired product was obtained. The results are shown in Table 4.
- Example 2 The same operation as in Example 1 was carried out, except that the equivalent (5 equiv.) Of TMSC1 used in Example 1 was used as shown below, to give 4-methylphenyldiphenylsulfonium bromide as the target substance. Obtained.
- Table 5 shows the yields of the obtained target product, triphenylsulfonium bromide (by-product 1) and bis (4-methylphenyl) phenylsulfonium-bromobromide (by-product 2).
- the method for producing a triarylsulfonium salt of the present invention has an advantage over conventional methods by using an activator having a high affinity for an oxygen atom in an amount of at least an amount conventionally used. For example, severe conditions at high temperatures (for example, heating reflux operation, melting reaction, etc.), generation of sulfurous acid gas, discharge of a large amount of aluminum waste liquid, and three aromatic rings of the cation part are the same.
- the desired sulfonium salt can be produced efficiently and in high yield without problems such as synthesis of rufodium salt alone and inclusion of by-products as impurities. Such an effect is caused by significantly increasing the amount of the activator having a high affinity for an oxygen atom used in the present invention, and cannot be predicted at all. Met.
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JP2005514735A JP4622858B2 (ja) | 2003-10-21 | 2004-10-04 | トリアリールスルホニウム塩の製造法 |
US10/576,299 US7642368B2 (en) | 2003-10-21 | 2004-10-04 | Process for producing triarylsulfonium salt |
EP04792015.2A EP1676835B1 (en) | 2003-10-21 | 2004-10-04 | Process for producing triarylsulfonium salt |
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Cited By (4)
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JP2014234348A (ja) * | 2013-05-31 | 2014-12-15 | サンアプロ株式会社 | スルホニウム塩および光酸発生剤 |
US9244347B2 (en) | 2013-05-31 | 2016-01-26 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, compound, polymeric compound and method of forming resist pattern |
WO2018003470A1 (ja) * | 2016-06-29 | 2018-01-04 | サンアプロ株式会社 | スルホニウム塩、光酸発生剤、光硬化性組成物、及びその硬化体 |
WO2020073822A1 (zh) | 2018-10-09 | 2020-04-16 | 常州强力先端电子材料有限公司 | 三苯基硫鎓盐化合物及其应用 |
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WO2010066380A1 (en) * | 2008-12-12 | 2010-06-17 | Bayer Schering Pharma Aktiengesellschaft | Triaryl-sulphonium compounds, kit and methods for labeling positron emitting isotopes |
JP5387181B2 (ja) * | 2009-07-08 | 2014-01-15 | 信越化学工業株式会社 | スルホニウム塩、レジスト材料及びパターン形成方法 |
WO2016102157A1 (en) * | 2014-12-23 | 2016-06-30 | Asml Netherlands B.V. | Lithographic patterning process and resists to use therein |
JP6586303B2 (ja) * | 2015-06-26 | 2019-10-02 | 東京応化工業株式会社 | ポジ型レジスト組成物、レジストパターン形成方法、及び光反応性クエンチャー |
JP6708382B2 (ja) * | 2015-09-03 | 2020-06-10 | サンアプロ株式会社 | 硬化性組成物及びそれを用いた硬化体 |
CN110015942B (zh) * | 2019-04-26 | 2021-12-24 | 浙江师范大学 | 一种无金属催化直接合成联芳烃化合物的方法 |
JP7484846B2 (ja) * | 2020-09-28 | 2024-05-16 | 信越化学工業株式会社 | 分子レジスト組成物及びパターン形成方法 |
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- 2004-10-04 US US10/576,299 patent/US7642368B2/en not_active Expired - Fee Related
- 2004-10-04 EP EP04792015.2A patent/EP1676835B1/en not_active Not-in-force
- 2004-10-04 WO PCT/JP2004/014604 patent/WO2005037778A1/ja active Application Filing
- 2004-10-04 KR KR1020067009943A patent/KR101042659B1/ko active IP Right Grant
- 2004-10-04 CN CNB2004800309486A patent/CN100381421C/zh not_active Expired - Fee Related
- 2004-10-04 JP JP2005514735A patent/JP4622858B2/ja not_active Expired - Fee Related
- 2004-10-13 TW TW093130975A patent/TWI318979B/zh not_active IP Right Cessation
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JP2014234348A (ja) * | 2013-05-31 | 2014-12-15 | サンアプロ株式会社 | スルホニウム塩および光酸発生剤 |
US9045398B2 (en) | 2013-05-31 | 2015-06-02 | San-Apro Limited | Sulfonium salt and photo-acid generator |
US9244347B2 (en) | 2013-05-31 | 2016-01-26 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition, compound, polymeric compound and method of forming resist pattern |
WO2018003470A1 (ja) * | 2016-06-29 | 2018-01-04 | サンアプロ株式会社 | スルホニウム塩、光酸発生剤、光硬化性組成物、及びその硬化体 |
JPWO2018003470A1 (ja) * | 2016-06-29 | 2019-04-25 | サンアプロ株式会社 | スルホニウム塩、光酸発生剤、光硬化性組成物、及びその硬化体 |
US10683266B2 (en) | 2016-06-29 | 2020-06-16 | San Apro Ltd. | Sulfonium salt, photoacid generator, photocurable composition, and cured product thereof |
WO2020073822A1 (zh) | 2018-10-09 | 2020-04-16 | 常州强力先端电子材料有限公司 | 三苯基硫鎓盐化合物及其应用 |
EP4198019A1 (en) | 2018-10-09 | 2023-06-21 | Changzhou Tronly Advanced Electronic Materials Co., Ltd. | Triphenylphosphonium salt compound, and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
CN100381421C (zh) | 2008-04-16 |
KR101042659B1 (ko) | 2011-06-20 |
KR20060123180A (ko) | 2006-12-01 |
JPWO2005037778A1 (ja) | 2006-12-28 |
EP1676835A4 (en) | 2007-01-17 |
US7642368B2 (en) | 2010-01-05 |
TW200517396A (en) | 2005-06-01 |
CN1871212A (zh) | 2006-11-29 |
TWI318979B (en) | 2010-01-01 |
EP1676835A1 (en) | 2006-07-05 |
EP1676835B1 (en) | 2014-12-10 |
US20070083060A1 (en) | 2007-04-12 |
JP4622858B2 (ja) | 2011-02-02 |
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