JP2008094835A - Intermediate of acid generator of chemical amplification type resist composition - Google Patents
Intermediate of acid generator of chemical amplification type resist composition Download PDFInfo
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- JP2008094835A JP2008094835A JP2007235108A JP2007235108A JP2008094835A JP 2008094835 A JP2008094835 A JP 2008094835A JP 2007235108 A JP2007235108 A JP 2007235108A JP 2007235108 A JP2007235108 A JP 2007235108A JP 2008094835 A JP2008094835 A JP 2008094835A
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- 239000002253 acid Substances 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 title description 13
- 239000000126 substance Substances 0.000 title description 7
- 230000003321 amplification Effects 0.000 title 1
- 238000003199 nucleic acid amplification method Methods 0.000 title 1
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012953 triphenylsulfonium Substances 0.000 abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 fluorosulfonyl compound Chemical class 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YIHXQSQQJBEAKK-UHFFFAOYSA-N 2,2-difluoro-2-fluorosulfonylacetyl fluoride Chemical compound FC(=O)C(F)(F)S(F)(=O)=O YIHXQSQQJBEAKK-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- TZBDEVBNMSLVKT-UHFFFAOYSA-N idramantone Chemical compound C1C(C2)CC3CC1(O)CC2C3=O TZBDEVBNMSLVKT-UHFFFAOYSA-N 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- COSGFOOQKFTWSM-UHFFFAOYSA-N (4-oxo-1-adamantyl) 2,2-difluoro-2-fluorosulfonylacetate Chemical compound C1C(C2)CC3CC1(OC(=O)C(F)(F)S(F)(=O)=O)CC2C3=O COSGFOOQKFTWSM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- DFRBRISULGDINA-UHFFFAOYSA-N C(C)N(CC)CC.O=C1C2CC3(CC(CC1C3)C2)OC(=O)C(S(=O)(=O)O)(F)F Chemical compound C(C)N(CC)CC.O=C1C2CC3(CC(CC1C3)C2)OC(=O)C(S(=O)(=O)O)(F)F DFRBRISULGDINA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- XSQIGJCTPAJWQT-UHFFFAOYSA-M sodium;1,1-difluoro-2-hydroxy-2-oxoethanesulfonate Chemical compound [Na+].OS(=O)(=O)C(F)(F)C([O-])=O XSQIGJCTPAJWQT-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 0 *C1(CC2CC(C3)C1)CC3C2=O Chemical compound *C1(CC2CC(C3)C1)CC3C2=O 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 229960003805 amantadine Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GQJCAQADCPTHKN-UHFFFAOYSA-N methyl 2,2-difluoro-2-fluorosulfonylacetate Chemical compound COC(=O)C(F)(F)S(F)(=O)=O GQJCAQADCPTHKN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- ZFEAYIKULRXTAR-UHFFFAOYSA-M triphenylsulfanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 ZFEAYIKULRXTAR-UHFFFAOYSA-M 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、半導体の微細加工に用いられる化学増幅型レジスト組成物に使用される、化学増幅型レジスト組成物に含有される酸発生剤の中間体に関する。 The present invention relates to an acid generator intermediate contained in a chemically amplified resist composition used in a chemically amplified resist composition used for fine processing of semiconductors.
リソグラフィ技術を用いた半導体の微細加工に用いられる化学増幅型レジスト組成物は、露光により酸を発生する化合物からなる酸発生剤を含有してなる。
半導体の微細加工においては、高い解像度で良好なパターン形状のパターンを形成することが望ましく、化学増幅型レジスト組成物としては、良好なパターン形状を有するパターンを作製することができ、高い解像度を示すものが求められている。
A chemically amplified resist composition used for fine processing of a semiconductor using a lithography technique contains an acid generator composed of a compound that generates an acid upon exposure.
In microfabrication of semiconductors, it is desirable to form a pattern with a good pattern shape at a high resolution, and as a chemically amplified resist composition, a pattern having a good pattern shape can be produced and exhibits a high resolution. Things are sought.
高い解像度を示す化学増幅型レジスト組成物を与える酸発生剤用の塩として、最近、トリフェニルスルホニウム 1−アダマンタンメトキシカルボニルジフルオロメタンスルホナート(塩)等の式(X)で示される塩が提案されており(例えば、特許文献1参照。)、これらの塩をより簡便に製造する方法が求められていた。 Recently, salts represented by the formula (X) such as triphenylsulfonium 1-adamantanemethoxycarbonyldifluoromethanesulfonate (salt) have been proposed as a salt for an acid generator that gives a chemically amplified resist composition exhibiting high resolution. (For example, refer to Patent Document 1), and a method for producing these salts more simply has been demanded.
(式(X)中、Q1およびQ2は互いに独立にフッ素原子又は炭素数1〜6のペルフルオロアルキル基を表し、Rは炭素数2〜30の置換されていてもよい炭化水素基を表し、P1〜P3は、互いに独立に、水素原子、水酸基、炭素数1〜12のアルキル基又は炭素数1〜12のアルコキシ基を表し、該アルキル基及び該アルコキシ基は、直鎖でも分岐していてもよい。) (In formula (X), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and R represents a C 2-30 optionally substituted hydrocarbon group. , P 1 to P 3 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group may be linear or branched. You may do it.)
前記トリフェニルスルホニウム 1−アダマンタンメトキシカルボニルジフルオロメタンスルホナート(塩)は、1−アダマンタンメトキシカルボニルジフルオロメタンスルホン酸ナトリウムを中間体とし、該中間体とトリフェニルスルホニウム クロリドを反応させる製造方法により従来製造されており、1−アダマンタンメトキシカルボニルジフルオロメタンスルホン酸ナトリウムはジフルオロ(フルオロスルホニル)酢酸メチルエステルを水酸化ナトリウムで加水分解し、塩酸でジフルオロスルホ酢酸 ナトリウム塩を得た後、高温下でアルコールと脱水エステル化する方法により製造されていた。このジフルオロスルホ酢酸 ナトリウム塩は、その製造時に副生するフッ化水素がその取り出し工程及び高温下でのエステル化反応で設備を腐食させるため、設備の材料にはハステロイなどの高価な材料が必要であるという問題があった。 Triphenylsulfonium 1-adamantanemethoxycarbonyldifluoromethanesulfonate (salt) is conventionally produced by a production method in which sodium 1-adamantanemethoxycarbonyldifluoromethanesulfonate is used as an intermediate and the intermediate is reacted with triphenylsulfonium chloride. 1-adamantane methoxycarbonyl difluoromethane sulfonate is obtained by hydrolyzing difluoro (fluorosulfonyl) acetic acid methyl ester with sodium hydroxide to obtain sodium difluorosulfoacetate with hydrochloric acid, and then dehydrating alcohol and alcohol at high temperature. It was manufactured by the method to convert. This difluorosulfoacetate sodium salt corrodes the equipment by the hydrogen fluoride produced as a by-product during its production and the esterification reaction under high temperature, and therefore expensive materials such as Hastelloy are required for the equipment. There was a problem that there was.
本発明の目的は、式(X)で示される塩の製造に用いることができる中間体であり、製造にあたり設備を腐食させることが少なく簡便に製造することができる中間体およびその製造方法を提供することにある。 An object of the present invention is an intermediate that can be used in the production of the salt represented by the formula (X), and provides an intermediate that can be easily produced with little corrosion of equipment during production, and a method for producing the same. There is to do.
そこで本発明者らは、上記課題を解決するために式(X)で示される塩の製造に用いることができる中間体およびその製造方法について鋭意検討した結果、設備を腐食させることが少ないマイルドな条件下で合成可能であり、式(X)で示される塩の製造に用いることができる中間体となる塩およびその製造方法を見出し、本発明を完成させるに至った。 Therefore, as a result of intensive studies on an intermediate that can be used in the production of the salt represented by the formula (X) and a method for producing the same in order to solve the above-described problems, the present inventors have obtained a mild reaction that hardly corrodes equipment. The present invention has been completed by finding an intermediate salt that can be synthesized under the conditions and can be used for the production of the salt represented by the formula (X) and a production method thereof.
すなわち本発明は、式(I)で示されることを特徴とする塩を提供する。
(式(I)中、Q1およびQ2は互いに独立にフッ素原子又は炭素数1〜6のペルフルオロアルキル基を表し、Rは炭素数2〜30の置換されていてもよい炭化水素基を表し、A+はアンモニウムイオンを表す。)
That is, the present invention provides a salt represented by the formula (I).
(In formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and R represents a C 2-30 optionally substituted hydrocarbon group. A + represents an ammonium ion.)
また本発明は、式(III)で示されるアルコールと、
(式(III)中、Rは前記と同じ意味を表す。)
式(IV)で示される化合物を脱酸剤の存在下に反応させて式(XX)で示される化合物を得た後、式(XX)で示される化合物をアミン水で加水分解することを特徴とする式(I)で示される塩の製造方法を提供する。
(式(IV)中、Q1およびQ2は前記と同じ意味を表す。)
(式(XX)中、Q1、Q2およびRは前記と同じ意味を表す。)
The present invention also provides an alcohol represented by the formula (III),
(In formula (III), R represents the same meaning as described above.)
The compound represented by formula (IV) is reacted in the presence of a deoxidizing agent to obtain a compound represented by formula (XX), and then the compound represented by formula (XX) is hydrolyzed with amine water. A method for producing a salt represented by the formula (I) is provided.
(In formula (IV), Q 1 and Q 2 represent the same meaning as described above.)
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)
また本発明は、式(XX)で示される化合物を提供する。
(式(XX)中、Q1、Q2およびRは前記と同じ意味を表す。)
The present invention also provides a compound represented by formula (XX).
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)
また本発明は、式(III)で示されるアルコールと、式(IV)で示される化合物を脱酸剤の存在下で反応させることを特徴とする式(XX)で示される化合物の製造方法を提供する。 The present invention also provides a process for producing a compound represented by formula (XX), which comprises reacting an alcohol represented by formula (III) with a compound represented by formula (IV) in the presence of a deoxidizing agent. provide.
また本発明は、式(III)で示されるアルコールと、
(式(III)中、Rは前記と同じ意味を表す。)
式(V)で示される化合物を反応させた後、アミン水で加水分解することを特徴とする式(I)で示される塩の製造方法を提供する。
(式(V)中、Q1およびQ2は前記と同じ意味を表す。)
The present invention also provides an alcohol represented by the formula (III),
(In formula (III), R represents the same meaning as described above.)
Provided is a method for producing a salt represented by the formula (I), wherein the compound represented by the formula (V) is reacted and then hydrolyzed with an amine water.
(In formula (V), Q 1 and Q 2 represent the same meaning as described above.)
また本発明は、式(III)で示されるアルコールと、
(式(III)中、Rは前記と同じ意味を表す。)
式(IV)で示される化合物を反応させた後、脱酸剤の存在下で反応させることを特徴とする式(XX)で示されるフルオロスルホニル化合物の製造方法を提供する。
(式(XX)中、Rは前記と同じ意味を表す。)
The present invention also provides an alcohol represented by the formula (III),
(In formula (III), R represents the same meaning as described above.)
Provided is a method for producing a fluorosulfonyl compound represented by the formula (XX), which comprises reacting a compound represented by the formula (IV) and then reacting in the presence of a deoxidizing agent.
(In formula (XX), R represents the same meaning as described above.)
本発明の塩は、製造にあたり設備を腐食させることが少なく簡便に製造することができ、本発明の塩は高い解像度を示す化学増幅型レジスト組成物を与える酸発生剤用の塩を製造するための中間体として用いることができるので、本発明は工業的に極めて有用である。 The salt of the present invention can be easily produced with little corrosion on equipment during production, and the salt of the present invention produces a salt for an acid generator that gives a chemically amplified resist composition exhibiting high resolution. Therefore, the present invention is extremely useful industrially.
本発明の塩は、式(I)で示されることを特徴とする。
ここで、式(I)中、Q1およびQ2は互いに独立にフッ素原子又は炭素数1〜6のペルフルオロアルキル基を表し、Rは炭素数2〜30の置換されていてもよい炭化水素基(酸素原子、窒素原子、硫黄原子が含まれていてもよい。)を表し、A+はアンモニウムイオンを表す。
Q1およびQ2としてはそれぞれ独立にフッ素原子または−CF3である場合が好ましく、ともにフッ素原子である場合がさらに好ましい。
The salt of the present invention is represented by the formula (I).
Here, in formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group, and R is a C 2-30 optionally substituted hydrocarbon group. (An oxygen atom, a nitrogen atom, and a sulfur atom may be contained), and A + represents an ammonium ion.
Q 1 and Q 2 are preferably each independently a fluorine atom or —CF 3 , more preferably a fluorine atom.
式(I)におけるアンモニウムイオンA+としては、下記式で示されるアンモニウムイオンが好ましい。
(式(XI)中、Z1、Z2およびZ3はそれぞれ独立に水素原子、炭素数1〜6のアルキル基、炭素数1〜6のアルコキシアルキル基、炭素数3〜12のシクロアルキル基、置換されていてもよいフェニル基、置換されていてもよい炭素数7〜12のアラルキル基、置換されていてもよいナフチル基、置換されていてもよい炭素数5〜10のへテロ芳香族基、またはZ1とZ2およびZ3の少なくとも二つ以上でヘテロ原子を含んでも良い環を表す。)
As the ammonium ion A + in the formula (I), an ammonium ion represented by the following formula is preferable.
(In the formula (XI), Z 1 , Z 2 and Z 3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. , An optionally substituted phenyl group, an optionally substituted aralkyl group having 7 to 12 carbon atoms, an optionally substituted naphthyl group, an optionally substituted heteroaromatic group having 5 to 10 carbon atoms A group or a ring which may contain a hetero atom in at least two of Z 1 , Z 2 and Z 3. )
式(XI)で示されるアンモニウムイオンとしては、下記式で示されるアンモニウムイオンが挙げられる。
Examples of ammonium ions represented by the formula (XI) include ammonium ions represented by the following formula.
式(XI)で示されるカチオンの中でもZ1、Z2およびZ3が互いに同一であり、水素原子、炭素数1〜3のアルキル基およびフェニル基のいずれかである場合がより好ましく、式(XII)で示されるカチオンである場合が最も好ましい。
Among the cations represented by the formula (XI), it is more preferable that Z 1 , Z 2 and Z 3 are the same as each other and are any one of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and a phenyl group. Most preferred is the cation represented by XII).
式(I)におけるRとしては、環(環としては、単環でも多環でもよく、二重結合を含んでいても芳香環でもよい。)を含んでいてもよい炭素数2〜30の炭化水素で、Rに含まれる炭素原子はその一部が酸素原子で置換されていてもよく、カルボニル基を形成していてもよい炭化水素の1価の残基などが挙げられ、いずれも炭素数1〜6のアルキル基、炭素数1〜6のアルコキシ基、炭素数1〜4のペルフルオロアルキル基、炭素数1〜6のヒドロキシアルキル基、水酸基又はシアノ基の一つ以上を置換基として含んでいてもよい(Rの炭素数には置換基の炭素数、炭素原子と置換した酸素原子の数も含まれる。)。 R in formula (I) is a carbon atom having 2 to 30 carbon atoms which may contain a ring (the ring may be monocyclic or polycyclic and may contain a double bond or an aromatic ring). Hydrogen is a carbon atom contained in R, part of which may be substituted with an oxygen atom, and examples thereof include a monovalent residue of a hydrocarbon which may form a carbonyl group, all of which have a carbon number One or more of a 1-6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group, or a cyano group is included as a substituent. (The number of carbon atoms in R includes the number of carbon atoms in the substituent and the number of oxygen atoms substituted with carbon atoms.)
式(I)で示される塩のアニオン部の具体例としては、下記式で示されるアニオンが挙げられる。
Specific examples of the anion moiety of the salt represented by the formula (I) include anions represented by the following formula.
式(I)で示される塩としては、Rが式(VI)で示される基である場合が、式(I)で示される塩が優れた解像度及びパターン形状を示す化学増幅型レジスト組成物を与える酸発生剤の中間体となることから好ましい。
環Xは環Xの一部を形成するように記載された二つの炭素原子とともに形成する炭素数3〜30の、=Oと結合している単環式または多環式炭化水素基を表す。
The salt represented by the formula (I) is a chemically amplified resist composition in which the salt represented by the formula (I) exhibits excellent resolution and pattern shape when R is a group represented by the formula (VI). Since it becomes the intermediate body of the acid generator to give, it is preferable.
Ring X represents a monocyclic or polycyclic hydrocarbon group bonded to ═O having 3 to 30 carbon atoms formed with two carbon atoms described so as to form part of ring X.
中でも、本発明の式(I)で示される塩としては、Rが
で示される基の場合である式(II)で示される塩が、優れた解像度及びパターン形状を示す化学増幅型レジスト組成物を与える酸発生剤の中間体となることからさらに好ましい。
(式(II)中、Q1、Q2およびA+は前記と同じ意味を表す。)
Among them, as the salt represented by the formula (I) of the present invention, R is
The salt represented by the formula (II), which is a group represented by the formula (II), is more preferable because it is an intermediate of an acid generator that provides a chemically amplified resist composition exhibiting excellent resolution and pattern shape.
(In formula (II), Q 1 , Q 2 and A + represent the same meaning as described above.)
式(I)で示される塩は、式(III)で示されるアルコールと、
(式(III)中、Rは前記と同じ意味を表す。)
式(IV)で示される化合物とを、
(式(IV)中、Q1およびQ2は前記と同じ意味を表す。)
例えば、クロロホルム等の不活性溶媒中にて、脱酸剤の存在下に0℃〜80℃程度の温度範囲、好ましくは0℃〜40℃の温度範囲にて攪拌して反応させ、式(XX)で示される化合物を得た後、
(式(XX)中、Q1、Q2およびRは前記と同じ意味を表す。)
例えば、クロロホルム等の不活性溶媒中、アミン水と、0℃〜80℃程度の温度範囲、好ましくは0℃〜40℃の温度範囲にて攪拌して加水分解させて製造することができる。脱酸剤としては、ジエチルアニリン、トリエチルアミン、ピリジンのような有機塩基あるいは、水酸化ナトリウム、水酸化カリウム、炭酸カリウム、炭酸水素ナトリウムのような無機塩基あるいは、それらの混合物が挙げられる。好ましくは、トリエチルアミンのような有機塩基が挙げられる。脱酸剤は水溶液として用いることも可能である。脱酸剤の使用量としては、式(IV)で示されるジフルオロ化合物1モルに対して、0.5モル〜5モル程度で、好ましくは、1モル〜2モル程度である。アミン水に用いるアミンとしては、アンモニア、メチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン、シクロヘキシルメチルアミン、アダマンチルアミン、アニリン、ジエチルアニリン、ピリジン、ピペリジン、モルホリンなどの有機アミンが挙げられるが、好ましくは低級トリアルキルアミンが挙げられ、より好ましくはトリエチルアミンが挙げられる。アミンの使用量としては、式(IV)で示されるジフルオロ化合物1モルに対して、0.01モル〜3モル程度で、好ましくは、0.1モル〜1モル程度である。
The salt of formula (I) is an alcohol of formula (III)
(In formula (III), R represents the same meaning as described above.)
A compound of formula (IV)
(In formula (IV), Q 1 and Q 2 represent the same meaning as described above.)
For example, in an inert solvent such as chloroform, the reaction is carried out with stirring in the temperature range of about 0 ° C. to 80 ° C., preferably in the temperature range of 0 ° C. to 40 ° C. in the presence of a deoxidizing agent, and the formula (XX After obtaining the compound represented by
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)
For example, it can be produced by stirring and hydrolyzing in an inert solvent such as chloroform with amine water in a temperature range of about 0 ° C. to 80 ° C., preferably in a temperature range of 0 ° C. to 40 ° C. Examples of the deoxidizer include organic bases such as diethylaniline, triethylamine, and pyridine, inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium hydrogen carbonate, or mixtures thereof. Preferably, an organic base such as triethylamine is used. The deoxidizer can also be used as an aqueous solution. The amount of the deoxidizing agent used is about 0.5 mol to 5 mol, preferably about 1 mol to 2 mol, with respect to 1 mol of the difluoro compound represented by the formula (IV). Examples of amines used in the amine water include organic amines such as ammonia, methylamine, diethylamine, trimethylamine, triethylamine, cyclohexylmethylamine, adamantylamine, aniline, diethylaniline, pyridine, piperidine, morpholine, but preferably lower trialkyl. An amine is mentioned, More preferably, a triethylamine is mentioned. The amount of the amine used is about 0.01 mol to 3 mol, preferably about 0.1 mol to 1 mol, with respect to 1 mol of the difluoro compound represented by the formula (IV).
式(IV)の化合物の使用量としては、通常、式(III)で示されるアルコール1モルに対して、0.5〜2モル程度である。該塩(I)は再結晶で取り出してもよいし、水洗して精製してもよい。 The amount of the compound of the formula (IV) used is usually about 0.5 to 2 mol with respect to 1 mol of the alcohol represented by the formula (III). The salt (I) may be taken out by recrystallization or may be purified by washing with water.
また、式(I)で示される塩の製造方法の別法として、式(III)で示されるアルコールと、
(式(III)中、Rは前記と同じ意味を表す。)
式(V)で示される化合物とを、
(式(V)中、Q1およびQ2は前記と同じ意味を表す。)
例えば、クロロホルム等の不活性溶媒中にて、脱酸剤の存在下に0℃〜80℃程度の温度範囲、好ましくは0℃〜40℃の温度範囲にて攪拌して反応させた後、例えば、クロロホルム等の不活性溶媒中、アミン水と、0℃〜80℃程度の温度範囲、好ましくは0℃〜40℃の温度範囲にて攪拌して反応させて式(I)で示される塩を得る方法も本発明者らは見出した。
As another method for producing the salt represented by formula (I), an alcohol represented by formula (III);
(In formula (III), R represents the same meaning as described above.)
A compound represented by the formula (V):
(In formula (V), Q 1 and Q 2 represent the same meaning as described above.)
For example, after reacting in an inert solvent such as chloroform with stirring in the temperature range of about 0 ° C. to 80 ° C., preferably in the temperature range of 0 ° C. to 40 ° C. in the presence of a deoxidizer, A salt represented by the formula (I) by stirring and reacting with amine water in an inert solvent such as chloroform, in a temperature range of about 0 ° C to 80 ° C, preferably in a temperature range of 0 ° C to 40 ° C. The inventors have also found a method to obtain.
式(V)の化合物の使用量としては、通常、式(III)で示されるアルコール1モルに対して、0.5〜2モル程度である。該塩(I)は再結晶で取り出してもよいし、水洗して精製してもよい。 The amount of the compound of the formula (V) used is usually about 0.5 to 2 mol with respect to 1 mol of the alcohol represented by the formula (III). The salt (I) may be taken out by recrystallization or may be purified by washing with water.
なお、Q1およびQ2としてはそれぞれ独立にフッ素原子または−CF3である場合が好ましく、ともにフッ素原子である場合がさらに好ましい。 Q 1 and Q 2 are preferably each independently a fluorine atom or —CF 3 , more preferably a fluorine atom.
次に実施例を挙げて、本発明をさらに具体的に説明するが、本発明はこれらの実施例によってなんら限定されるものではない。
実施例中、含有量ないし使用量を表す%及び部は、特記ないかぎり重量基準である。また、化合物の構造はNMR(日本電子製JNM−FX90Q型またはVarian製Gemini−200型)、質量分析(日本電子製JMS−700型)で確認した。
EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.
In Examples,% and parts representing the content or amount used are based on weight unless otherwise specified. The structure of the compound was confirmed by NMR (JNM JFX-FX90Q type or Varian Gemini 200 type) and mass spectrometry (JEOL JMS-700 type).
(1)テトラフルオロβ−サルトンの合成
1LのSUS304製耐圧オートクレイブにSO3347g(4.33mol)を入れ、空間部をN2置換した後にテトラフルオロエチレンを圧入した。発熱反応が開始したのを確認後、内温を40〜50℃、圧力0.2〜0.4MPaに調節しながらテトラフルオロエチレンの吸収がなくなるまで圧入を継続した。テトラフルオロエチレンを448g(4.48mol)圧入停止後、室温まで冷却し生成物として779gの無色液体を得た。得られた液体は、19F−NMR測定によりテトラフルオロβ−サルトンであることを確認した。
(1) Synthesis of tetrafluoro β-sultone
In a 1 L SUS304 pressure-resistant autoclave, 347 g (4.33 mol) of SO 3 was put, and after the space portion was substituted with N 2, tetrafluoroethylene was press-fitted. After confirming that the exothermic reaction had started, the press-fitting was continued until the absorption of tetrafluoroethylene disappeared while adjusting the internal temperature to 40 to 50 ° C. and the pressure to 0.2 to 0.4 MPa. After stopping the press-fitting of 448 g (4.48 mol) of tetrafluoroethylene, the mixture was cooled to room temperature to obtain 779 g of a colorless liquid as a product. The obtained liquid was confirmed to be tetrafluoro β-sultone by 19 F-NMR measurement.
19F−NMR(CDCl3、内部標準物質CFCl3):δ(ppm)−99.7(t,CF2SO2);−89.8(t,CF2O) 19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -99.7 (t, CF 2 SO 2 ); -89.8 (t, CF 2 O)
(2)2−(フルオロスルホニル)ジフルオロアセチルフルオリドの合成
撹拌機、滴下漏斗、温度計を備えた100mL四つ口フラスコに、トリエチルアミン6.00g(0.06mol)を投入し0℃に冷却した。滴下漏斗よりテトラフルオロβ−サルトン121.79g(0.68mol)を0〜5℃に維持しながら滴下し、投入後反応液を室温に戻した後1時間撹拌を継続した。得られた液体を常圧下30℃で蒸留精製しテトラフルオロβ−サルトンの異性体である2−(フルオロスルホニル)ジフルオロアセチルフルオリド109.61g(0.61mol)を得た。
(2) Synthesis of 2- (fluorosulfonyl) difluoroacetyl fluoride
To a 100 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 6.00 g (0.06 mol) of triethylamine was added and cooled to 0 ° C. From the dropping funnel, 121.79 g (0.68 mol) of tetrafluoro β-sultone was added dropwise while maintaining the temperature at 0 to 5 ° C. After the addition, the reaction solution was returned to room temperature and stirred for 1 hour. The obtained liquid was purified by distillation at 30 ° C. under normal pressure to obtain 109.61 g (0.61 mol) of 2- (fluorosulfonyl) difluoroacetyl fluoride which is an isomer of tetrafluoro β-sultone.
19F−NMR(CDCl3、内部標準物質CFCl3):δ(ppm)−104.4(dd,CF2)、24.8(td,COF)、43.0(td,SO2F) 19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -104.4 (dd, CF 2 ), 24.8 (td, COF), 43.0 (td, SO 2 F)
(3)4−オキソアダマンタン−1−イル−オキシカルボニル(ジフルオロ)メタンスルホニルフルオリドの合成
撹拌機、滴下漏斗、温度計を備えた200mL四つ口フラスコに、5−ヒドロキシ−2−アダマンタノン5.00g(0.03mol)、トリエチルアミン3.65g(0.04mol)、クロロホルム58.44gを投入した。滴下漏斗より上記2−(フルオロスルホニル)ジフルオロアセチルフルオライド5.96g(0.03mol)を20〜35℃に維持しながら滴下し、投入後反応液を室温付近において1時間撹拌を継続した。この反応液に水37gを加えて有機層を分離した。この水洗操作を更に2回実施した後、有機層を濃縮して反応混合物10.72gを得た。この反応混合物は、展開液にヘキサン:酢酸エチル=5:1(体積比)を用いた5.05gのシリカゲルカラムで精製した。溶媒を減圧下で除去後、6.66g(0.02mol)の目的とするエステルが収率68.1%で得られた。得られた液体は、19F−NMR測定することにより、目的とするエステルであることを確認した。
(3) Synthesis of 4-oxoadamantan-1-yl-oxycarbonyl (difluoro) methanesulfonyl fluoride
In a 200 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5.00 g (0.03 mol) of 5-hydroxy-2-adamantanone, 3.65 g (0.04 mol) of triethylamine, and 58.44 g of chloroform were added. I put it in. From the dropping funnel, 5.96 g (0.03 mol) of 2- (fluorosulfonyl) difluoroacetyl fluoride was added dropwise while maintaining at 20 to 35 ° C. After the addition, the reaction solution was continuously stirred at around room temperature for 1 hour. To this reaction solution, 37 g of water was added to separate the organic layer. This washing operation was further performed twice, and then the organic layer was concentrated to obtain 10.72 g of a reaction mixture. This reaction mixture was purified by a 5.05 g silica gel column using hexane: ethyl acetate = 5: 1 (volume ratio) as a developing solution. After removal of the solvent under reduced pressure, 6.66 g (0.02 mol) of the desired ester was obtained in 68.1% yield. The obtained liquid was confirmed to be the target ester by 19 F-NMR measurement.
19F−NMR(CDCl3、内部標準物質CFCl3):δ(ppm)−103.6(d,CF2)、40.7(t,SO2F) 19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -103.6 (d, CF 2 ), 40.7 (t, SO 2 F)
同様にして、目的物を精製単離しないで次工程につなぐ合成を行った。
撹拌機、滴下漏斗、温度計を備えた200mL四つ口フラスコに、5−ヒドロキシ−2−アダマンタノン5.00g(0.03mol)、トリエチルアミン3.65g(0.04mol)、クロロホルム58.44gを投入した。滴下漏斗より上記2−(フルオロスルホニル)ジフルオロアセチルフルオリド5.96g(0.03mol)を20〜35℃に維持しながら滴下し、投入後反応液を室温付近において1時間撹拌を継続した。得られた液体を19F−NMR測定することにより、目的とするエステルが生成したことを確認した。
Similarly, the synthesis | combination which connected the following process was performed, without purifying and isolating the target object.
In a 200 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5.00 g (0.03 mol) of 5-hydroxy-2-adamantanone, 3.65 g (0.04 mol) of triethylamine, and 58.44 g of chloroform were added. I put it in. 5.96 g (0.03 mol) of 2- (fluorosulfonyl) difluoroacetyl fluoride was dropped from the dropping funnel while maintaining at 20 to 35 ° C., and after the addition, the reaction solution was continuously stirred at around room temperature for 1 hour. The obtained liquid was measured by 19 F-NMR to confirm that the target ester was produced.
19F−NMR(CDCl3、内部標準物質CFCl3):δ(ppm)−103.6(d,CF2)、40.7(t,SO2F) 19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -103.6 (d, CF 2 ), 40.7 (t, SO 2 F)
(4)4−オキソアダマンタン−1−イル−オキシカルボニル(ジフルオロ)メタンスルホン酸 トリエチルアミン塩の合成
撹拌機、温度計を備えた300mL四つ口フラスコに上記で得られた液体を全量投入し、さらに水7.61g、トリエチルアミン10.66g(0.11mol)を液温20〜35℃に維持しながら投入した。投入後反応液を室温付近において1時間撹拌を継続した。19F−NMR測定により原料消失を確認後、反応液を水42gで2回洗浄し得られた有機層を濃縮することで目的のアンモニウム塩を11.52g(収率は、90%)得た。
(4) Synthesis of 4-oxoadamantan-1-yl-oxycarbonyl (difluoro) methanesulfonic acid triethylamine salt
A 300 mL four-necked flask equipped with a stirrer and a thermometer was charged with the whole amount of the liquid obtained above, and further 7.61 g of water and 10.66 g (0.11 mol) of triethylamine were maintained at a liquid temperature of 20 to 35 ° C. While throwing. After the addition, stirring was continued for 1 hour at around room temperature. After confirming disappearance of the raw material by 19 F-NMR measurement, the reaction solution was washed twice with 42 g of water, and the organic layer obtained was concentrated to obtain 11.52 g (yield: 90%) of the target ammonium salt. .
1H−NMR(DMSO−d6、内部標準物質DMSO):δ(ppm)1.79−2.01(c,4H)、2.21−2.53(c,9H)
19F−NMR(CDCl3、内部標準物質CFCl3):δ(ppm)−110.8(s,CF2)
1 H-NMR (DMSO-d 6 , internal standard substance DMSO): δ (ppm) 1.79-2.01 (c, 4H), 2.21-2.53 (c, 9H)
19 F-NMR (CDCl 3 , internal standard substance CFCl 3 ): δ (ppm) -110.8 (s, CF 2 )
(5)4−オキソアダマンタン−1−イル−オキシカルボニル(ジフルオロ)メタンスルホニルフルオリドの合成
撹拌機、滴下漏斗、温度計を備えた100mL四つ口フラスコに、5−ヒドロキシ−2−アダマンタノン5.00g(0.03mol)、トリエチルアミン3.37g(0.03mol)、クロロホルム56.58gを投入した。滴下漏斗より上記(1)で得られたテトラフルオロβ−サルトン5.42g(0.03mol)を20〜35℃に維持しながら滴下し、投入後反応液を室温付近において1時間撹拌を継続した。得られた液体を19F−NMR測定することにより、目的化合物であるエステル体が生成した事を確認した。
(5) Synthesis of 4-oxoadamantan-1-yl-oxycarbonyl (difluoro) methanesulfonyl fluoride
In a 100 mL four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5.00 g (0.03 mol) of 5-hydroxy-2-adamantanone, 3.37 g (0.03 mol) of triethylamine, and 56.58 g of chloroform were added. I put it in. From the dropping funnel, 5.42 g (0.03 mol) of tetrafluoro β-sultone obtained in (1) above was added dropwise while maintaining the temperature at 20 to 35 ° C. After the addition, the reaction solution was continuously stirred at around room temperature for 1 hour. . By measuring 19 F-NMR of the obtained liquid, it was confirmed that the ester compound as the target compound was produced.
(6)4−オキソアダマンタン−1−イル−オキシカルボニル(ジフルオロ)メタンスルホン酸 トリエチルアミン塩の合成
撹拌機、温度計を備えた100mL四つ口フラスコに上記で得られた液体15.01gを投入し、さらに水1.00g、トリエチルアミン1.00g(0.01mol)を液温20〜35℃に維持しながら投入した。投入後反応液を室温付近において2時間撹拌を継続した。19F−NMR測定により原料消失を確認後、反応液を分層し得られた有機層を濃縮することでアンモニウム塩2.46g(収率は、90%)を得た。
(6) Synthesis of 4-oxoadamantan-1-yl-oxycarbonyl (difluoro) methanesulfonic acid triethylamine salt
A 100 mL four-necked flask equipped with a stirrer and a thermometer was charged with 15.01 g of the liquid obtained above, and further 1.00 g of water and 1.00 g (0.01 mol) of triethylamine were brought to a liquid temperature of 20 to 35 ° C. It was thrown in while maintaining. After the addition, the reaction solution was continuously stirred at around room temperature for 2 hours. After confirming disappearance of the raw material by 19 F-NMR measurement, the organic layer obtained by separating the reaction solution was concentrated to obtain 2.46 g (yield: 90%) of the ammonium salt.
本発明の塩は、優れた解像度及びパターン形状を与える化学増幅型ポジ型レジスト組成物用の酸発生剤の中間体として好適に用いられ、中でも、ArFやKrFなどのエキシマレーザーリソグラフィならびにArF液浸露光リソグラフィに好適な高い解像度を示す化学増幅型ポジ型レジスト組成物用の酸発生剤の中間体として用いることができる。 The salt of the present invention is suitably used as an intermediate of an acid generator for a chemically amplified positive resist composition that gives excellent resolution and pattern shape. Among them, excimer laser lithography such as ArF and KrF, and ArF immersion It can be used as an intermediate of an acid generator for a chemically amplified positive resist composition showing high resolution suitable for exposure lithography.
Claims (9)
(式(I)中、Q1、Q2は互いに独立にフッ素原子又は炭素数1〜6のペルフルオロアルキル基を表し、Rは炭素数2〜30の置換されていてもよい炭化水素基を表し、A+はアンモニウムイオンを表す。) A salt represented by the formula (I):
(In the formula (I), Q 1, Q 2 represents independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, R represents a hydrocarbon group which may be substituted having 2 to 30 carbon atoms A + represents an ammonium ion.)
(式(II)中、Q1、Q2およびA+は前記と同じ意味を表す。) The salt according to any one of claims 1 to 3, wherein the salt represented by the formula (I) is a salt represented by the formula (II).
(In formula (II), Q 1 , Q 2 and A + represent the same meaning as described above.)
(式(XI)中、Z1、Z2およびZ3は、互いに独立に水素原子、炭素数1〜6のアルキル基、炭素数1〜6のアルコキシアルキル基、炭素数3〜12のシクロアルキル基、置換されていてもよいフェニル基、置換されていてもよい炭素数7〜12のアラルキル基、置換されていてもよいナフチル基、置換されていてもよい炭素数5〜10のへテロ芳香族基、またはZ1、Z2およびZ3の少なくとも二つ以上でヘテロ原子を含んでもよい環を表す。) The salt according to any one of claims 1 to 4, wherein A + is an ammonium ion represented by the general formula (XI).
(In the formula (XI), Z 1 , Z 2 and Z 3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or a cycloalkyl having 3 to 12 carbon atoms. Group, an optionally substituted phenyl group, an optionally substituted aralkyl group having 7 to 12 carbon atoms, an optionally substituted naphthyl group, an optionally substituted heteroaromatic group having 5 to 10 carbon atoms Represents a group or a ring which may contain a hetero atom in at least two of Z 1 , Z 2 and Z 3. )
(式(III)中、Rは前記と同じ意味を表す。)
式(IV)
(式(IV)中、Q1およびQ2は前記と同じ意味を表す。)
で示される化合物を脱酸剤の存在下で反応させて式(XX)で示される化合物を得た後、
(式(XX)中、Q1、Q2およびRは前記と同じ意味を表す。)
式(XX)で示される化合物をアミン水で加水分解することを特徴とする請求項1記載の式(I)で示される塩の製造方法。 An alcohol represented by the formula (III);
(In formula (III), R represents the same meaning as described above.)
Formula (IV)
(In formula (IV), Q 1 and Q 2 represent the same meaning as described above.)
After reacting the compound represented by formula (XX) in the presence of a deoxidizing agent,
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)
The method for producing a salt represented by the formula (I) according to claim 1, wherein the compound represented by the formula (XX) is hydrolyzed with amine water.
(式(XX)中、Q1、Q2およびRは前記と同じ意味を表す。) A compound represented by the formula (XX)
(In formula (XX), Q 1 , Q 2 and R represent the same meaning as described above.)
(式(III)中、Rは前記と同じ意味を表す。)
式(V)で示される化合物を反応させた後、アミン水で加水分解することを特徴とする請求項1記載の式(I)で示される塩の製造方法。
(式(V)中、Q1およびQ2は前記と同じ意味を表す。) An alcohol represented by the formula (III);
(In formula (III), R represents the same meaning as described above.)
The method for producing a salt represented by the formula (I) according to claim 1, wherein the compound represented by the formula (V) is reacted and then hydrolyzed with amine water.
(In formula (V), Q 1 and Q 2 represent the same meaning as described above.)
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