TW200947126A - Novel compound and method of producing the same, acid generator, resist composition and method of forming resist - Google Patents

Novel compound and method of producing the same, acid generator, resist composition and method of forming resist Download PDF

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TW200947126A
TW200947126A TW097149505A TW97149505A TW200947126A TW 200947126 A TW200947126 A TW 200947126A TW 097149505 A TW097149505 A TW 097149505A TW 97149505 A TW97149505 A TW 97149505A TW 200947126 A TW200947126 A TW 200947126A
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group
compound
acid
represented
substituent
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TW097149505A
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TWI407256B (en
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Hideo Hada
Yoshiyuki Utsumi
Keita Ishiduka
Kensuke Matsuzawa
Fumitake Kaneko
Kyoko Ohshita
Hiroaki Shimizu
Yasuhiro Yoshii
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Tokyo Ohka Kogyo Co Ltd
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Priority claimed from JP2007331163A external-priority patent/JP5484671B2/en
Priority claimed from JP2008056880A external-priority patent/JP5186249B2/en
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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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/0285—Silver salts, e.g. a latent silver salt image
    • 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
    • G03F7/06—Silver salts
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Materials For Photolithography (AREA)

Abstract

A resist composition including a base component (A) which exhibits changed solubility in an alkali developing solution under action of acid and an acid-generator component (B) which generates acid upon exposure, the acid-generator component (B) including an acid generator (B1) consisting of a compound represented by general formula (b1-1) shown below: [Chemical Formula 1] wherein Rx represents a hydrocarbon group which may have a substituent exclusive of a nitrogen atom; each of Q2 and Q3 independently represents a single bond or a divalent linkage group; Y1 represents an alkylene group of 1 to 4 carbon atoms or a fluorinated alkyl group; and Z+ represents an organic cation exclusive of an ion represented by general formula general formula (w-1).

Description

200947126 九、發明說明 【發明所屬之技術領域】 本發明爲有關作爲光阻組成物用之酸產生劑之有用的 新穎化合物及其製造方法、酸產生劑、光阻組成物及光阻 圖型之形成方法，與可作爲光阻組成物之酸產生劑使用之 化合物中間體的有用的新穎化合物及其製造方法。 本案爲基於2007年12月21日於日本申請之特願 φ 20 07 -330891號、2 007年12月21日於日本申請之特願 2007 — 331163號，及2008年3月6日於日本申請之特願 2008 — 056880號爲基礎主張優先權，本發明係援用該内 容。 【先前技術】 微影蝕刻技術中，例如於基板上形成由光阻材料所得 之光阻膜，並對於前述光阻膜，以光、電子線等放射線進 〇 行選擇性曝光，經施以顯影處理，使前述光阻膜形成具有 特定形狀之光阻圖型之方式進行。經曝光之部份變化爲具 有溶解於顯影液之特性的光阻材料稱爲正型，經曝光之部 份變化爲具有不溶解於顯影液之特性的光阻材料稱爲負型 〇 近年來，於半導體元件或液晶顯示元件之製造中，伴 隨微影蝕刻技術之進步而急速的推向圖型之微細化。 微細化之方法，一般而言，爲將曝光光源予以短波長 化之方式進行。具體而言爲，以往爲使用g線、i線爲代 200947126 表之紫外線。但現在則開始使用KrF準分子雷射、或ArF 準分子雷射以進行半導體元件之量產。又，對於前述準分 子雷射具有更短波長之F2準分子雷射、電子線、EUV( 極紫外線）或X線等亦已開始進行硏究。200947126 IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to a novel novel compound useful as an acid generator for a photoresist composition, a method for producing the same, an acid generator, a photoresist composition, and a photoresist pattern. A novel method of forming a compound and a compound intermediate which can be used as an acid generator of a photoresist composition and a method for producing the same. This application is based on the special request of φ 20 07 -330891, which was applied for in Japan on December 21, 2007, and the Japanese Patent Application No. 2007-331163, which was applied for in Japan on December 21, 2007, and applied for in Japan on March 6, 2008. Priority is claimed on the basis of 2008-056880, which is hereby incorporated by reference. [Prior Art] In the lithography technique, for example, a photoresist film obtained from a photoresist material is formed on a substrate, and for the photoresist film, selective exposure is performed by radiation such as light or electron lines, and development is performed. The treatment is performed in such a manner that the photoresist film is formed into a photoresist pattern having a specific shape. The exposed portion is changed to have a photoresist material having a property of being dissolved in a developing solution, and the exposed portion is changed to have a property of not dissolving in the developing solution. In the manufacture of a semiconductor element or a liquid crystal display element, the micro-image etching technique has been rapidly advanced to refine the pattern. The method of miniaturization is generally carried out in such a manner as to shorten the wavelength of the exposure light source. Specifically, in the past, the g-ray and the i-line were used as the ultraviolet rays of the 200947126 table. However, KrF excimer lasers or ArF excimer lasers are now being used for mass production of semiconductor components. Further, F2 excimer lasers, electron beams, EUV (extreme ultraviolet rays) or X-rays having shorter wavelengths for the aforementioned quasi-molecular lasers have also been studied.

伴隨曝光光源之短波長化，則尋求一種對於曝光光源 之感度，可重現具有微細尺寸的圖型之解析性等可提高微 影蝕刻特性的光阻材料。可滿足前述要求之光阻材料，已 知例如含有經由酸之作用而對鹼顯影液之溶解性產生變化 Q 之基材成份，與經由曝光而發生酸之酸產生劑成份之化學 增幅型光阻。 以往，該些化學增幅型光阻之基材成份主要爲使用樹 脂，一般例如使用聚羥基苯乙烯（PHS )或其羥基之一部 份被酸解離性溶解抑制基所保護之樹脂等之PHS系樹脂 、（甲基）丙烯酸酯所衍生之共聚物或羧基之一部份被酸 解離性溶解抑制基所保護之樹脂等。 又，「（甲基）丙嫌酸醋（acrylic acid ester)」係 〇 指α位鍵結有氫原子之丙烯酸酯，與該α位鍵結甲基之甲 基丙烯酸酯之一或二者之意。「（甲基）丙烯酸酯（ acrylate )」係指〇：位鍵結有氫原子之丙烯酸酯，與該α 位鍵結甲基之甲基丙烯酸酯之一或二者之意。「（甲基） 丙烯酸」係指α位鍵結有氫原子之丙烯酸，與該α位鍵結 甲基之甲基丙烯酸之一或二者之意。 化學增幅型光阻中所使用之酸產生劑’目前已有各種 各樣之物質被提出，已知例如碘鑰鹽或锍鹽等鎗鹽系酸產 -8 - 200947126 生劑（例如請參考專利文獻1 )。 〔專利文獻1〕特開2003—241385號公報 【發明內容】 上述鐵鹽系酸產生劑，目前，一般多使用陰離子部（ 酸）具有全氟烷基磺酸離子之酸產生劑。 但是’該些鑰鹽系酸產生劑，於其構造上，因對鹼顯 D 影液具有低親和性，又，光阻膜内之分布不易形成均勻， 故對解析性等之微影蝕刻特性會有產生不良影響之疑慮。 又，上述陰離子部之全氟烷基鏈，因可抑制曝光後之 酸的擴散’故就長遠而言爲較佳，但碳數6〜10之全氟烷 基鏈爲具有難分解性。因此、於考慮生物蓄積性之使用安 全，以使用碳數4以下之全氟烷基磺酸離子，例如九氟丁 烷磺酸離子等。 因此，對於作爲光阻組成物用之酸產生劑，要求具有 〇 更有用之陰離子部的鑰鹽系化合物，同時，尋求一種於製 造該化合物之有用的中間體。 本發明，即爲鑒於上述情事所提出者，即以提出作爲 光阻組成物用之酸產生劑使用之新穎化合物及其製造方法 、酸產生劑、光阻組成物及光阻圖型之形成方法，及適合 作爲合成光阻組成物用之酸產生劑使用之化合物時之中間 體的新穎化合物及其製造方法爲目的。 〔解決問題之手段〕 -9 - 200947126 爲達上述之目的，本發明係採用以下之構成。 即，本發明之第一之態樣爲，一種光阻組成物’其爲 含有經由酸之作用而對鹼顯影液之溶解性產生變化之基材 成份（A)，及經由曝光而發生酸之酸產生劑成份（B) 之光阻組成物，其特徵爲， 前述酸產生劑成份（B)爲含有下述通式（bl — 1)所 表示之化合物所形成之酸產生劑（B1)，With the short wavelength of the exposure light source, a sensitivity to the exposure light source is sought, and a photoresist material which can improve the lithographic etching characteristics such as the resolution of a pattern having a fine size can be reproduced. A photoresist material which satisfies the above requirements is known, for example, a substrate component containing a change Q in the solubility of an alkali developer via an action of an acid, and a chemically amplified photoresist having an acid generator component which generates an acid via exposure. . Conventionally, the base material of the chemically amplified photoresists is mainly a resin, and generally, for example, a PHS system using a polyhydroxystyrene (PHS) or a resin whose part of a hydroxyl group is protected by an acid dissociable dissolution inhibiting group is used. A resin, a copolymer derived from (meth) acrylate, or a resin partially protected by an acid dissociable dissolution inhibiting group. Further, "(acrylic acid ester)" means an acrylate having a hydrogen atom bonded to the α-position, and one or both of the methyl methacrylate bonded to the α-position. meaning. "(Meth)acrylate" means an acrylate in which a hydrogen atom is bonded to a terminal, and one or both of a methyl methacrylate bonded to the α-position. "(Meth)acrylic acid" means an acrylic acid having a hydrogen atom bonded to the α-position, and one or both of the methacrylic acid having a methyl group bonded to the α-position. A variety of substances have been proposed for the acid generator used in chemically amplified photoresists. For example, a gun salt acid such as iodine salt or barium salt is known to be produced. (For example, please refer to the patent. Literature 1). [Patent Document 1] JP-A-2003-241385 SUMMARY OF THE INVENTION In the above-mentioned iron salt-based acid generator, an acid generator having an anion moiety (acid) having a perfluoroalkylsulfonate ion is generally used. However, these key salt-based acid generators have low affinity for alkali-based D-shading liquids, and the distribution in the photoresist film is not easily formed uniformly. Therefore, lithographic etching characteristics for resolution and the like are obtained. There will be doubts about adverse effects. Further, the perfluoroalkyl chain of the anion portion is preferable because it can suppress the diffusion of the acid after exposure, but the perfluoroalkyl chain having a carbon number of 6 to 10 is inferior in decomposability. Therefore, in consideration of the safety of use of bioaccumulation, a perfluoroalkylsulfonic acid ion having a carbon number of 4 or less, for example, a nonafluorobutanesulfonic acid ion or the like is used. Therefore, a key salt compound having a more useful anion moiety is required as the acid generator for the photoresist composition, and a useful intermediate for producing the compound is sought. The present invention is a novel compound which is proposed as an acid generator for a photoresist composition, a method for producing the same, an acid generator, a photoresist composition, and a pattern for forming a photoresist pattern, which are proposed in view of the above circumstances. And a novel compound suitable as an intermediate in the case of using a compound for use as an acid generator for a photoresist composition, and a method for producing the same. [Means for Solving the Problem] -9 - 200947126 In order to achieve the above object, the present invention adopts the following constitution. That is, the first aspect of the present invention is a photoresist composition which is a substrate component (A) which contains a change in solubility to an alkali developer via an action of an acid, and an acid which occurs via exposure. The photoresist composition of the acid generator component (B), characterized in that the acid generator component (B) is an acid generator (B1) formed by a compound represented by the following formula (bl-1).

【化1】【化1】

Rx—Q3—Ο—Q2一·V1一S〇3 Z -(bi-t) 〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；Y1爲碳 數1〜4之伸烷基或氟化伸烷基；Z +爲有機陽離子（但下 述通式（w — 1)所表示之離子除外）〕。 【化2】Rx—Q3—Ο—Q2—V1—S〇3 Z—(bi-t) wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 are independent single bonds or a divalent bond group; Y1 is an alkylene group having a carbon number of 1 to 4 or a fluorinated alkyl group; and Z + is an organic cation (except for the ion represented by the following formula (w-1)). [Chemical 2]

··· (W— 1〉··· (W-1)

〔式中，R3〜R6分別爲獨立表示氫原子，或可具有 取代基之烴基，R3〜R6中之至少1個爲前述烴基，R3〜 R6中之至少2個可分別鍵結形成環亦可〕。 本發明之第二之態樣爲，一種光阻圖型之形成方法， 其特徵爲包含，於支撐體上，使用前述第一之態樣之光阻 組成物形成光阻膜之步驟，使前述光阻膜曝光之步驟，及 使前述光阻膜鹼顯影以形成光阻圖型之步驟。 本發明之第三之態樣爲，下述通式（b 1 - 1 )所表示 -10- 200947126 之化合物（以下，亦稱爲化合物（bl—l))。 【化3】 R " Q ~~0—-q2—γ1—S〇3 Z …(bl-1) 〔式中’ RX爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基：Υι爲碳 數1〜4之伸烷基或氟化伸烷基；Ζ+爲有機陽離子（但下 述通式（w— 1)所表示之離子除外）〕。 〇 r 【化4】 R3 R6—ll—R4 R® *· (w— 1) 〔式中，R3〜R6分別爲獨立表示氫原子，或可具有 取代基之烴基，R3〜R6中之至少1個爲前述烴基，R3〜 R6中之至少2個可分別鍵結形成環亦可〕。 本發明之第四之態樣爲，一種化合物之製造方法（以 © 下’亦稱爲化合物（bl—l)之製造方法），其特徵爲包 含’使下述通式（b0— 〇所表示之化合物（bO-Ι)，與 下述通式（b0 — 〇2 )所表示之化合物（b0 - 02 )反應，以 製得下述通式（bl—l)所表示之化合物（bl-Ι)之步驟 【化5】 Q3--〇一Q2—Y1—S05 W4 2 A -.(b〇~〇2)Wherein R3 to R6 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent; at least one of R3 to R6 is the hydrocarbon group, and at least two of R3 to R6 may be bonded to form a ring, respectively. ]. A second aspect of the present invention is a method for forming a photoresist pattern, comprising the steps of: forming a photoresist film on the support using the photoresist composition of the first aspect; The step of exposing the photoresist film and the step of alkali developing the photoresist film to form a photoresist pattern. The third aspect of the present invention is a compound represented by the following formula (b 1 - 1 ) of -10-200947126 (hereinafter also referred to as a compound (bl-1)). [Chemical 3] R " Q ~~0—-q2—γ1—S〇3 Z ((b-1) [wherein RX is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 respectively An independent single bond or a divalent bond group: Υι is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; Ζ+ is an organic cation (but represented by the following formula (w-1) Except ion)). 〇r [Chemical Formula 4] R3 R6—ll—R4 R® *· (w-1) wherein R 3 to R 6 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, and at least 1 of R 3 to R 6 One of the above hydrocarbon groups, at least two of R3 to R6 may be bonded to form a ring, respectively. A fourth aspect of the present invention is a method for producing a compound (hereinafter referred to as a method for producing a compound (bl-1), which is characterized by comprising 'the following formula (b0-〇) The compound (bO-indole) is reacted with a compound represented by the following formula (b0 - 〇2) (b0 - 02) to obtain a compound represented by the following formula (bl-1) (bl-Ι) ) Steps [Chemical 5] Q3--〇一Q2—Y1—S05 W4 2 A -.(b〇~〇2)

Hx—Q3—0—Q2~~V1—"SO3 2+ .,.( -11 - 4 200947126 〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；γΐ爲碳 數1〜4之伸烷基或氟化伸烷基；W +爲鹼金屬離子或下述 通式（w — 1)所表示之離子；Ζ+爲有機陽離子（但下述 通式（w-1)所表示之離子除外）；Α·爲非親核性陰離子 【化6】Hx—Q3—0—Q2~~V1—"SO3 2+ .,.( -11 - 4 200947126 [wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 are independent a single bond or a divalent bond group; γ ΐ is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; and W + is an alkali metal ion or an ion represented by the following formula (w-1); Ζ+ is an organic cation (except for the ion represented by the following formula (w-1); Α· is a non-nucleophilic anion [Chemical 6]

…（w— 1)...(w-1)

〔式中，R3〜R6分別爲獨立表示氫原子，或可具有 取代基之烴基，R3〜R6中之至少1個爲前述烴基，R3〜 R6中之至少2個可分別鍵結形成環亦可〕。 本發明之第五之態樣爲，一種酸產生劑，其特徵爲， 由前述第三之態樣之化合物所形成者。 本發明之第六之態樣爲，一種下述通式（b0— 1)所 表示之化合物（以下，亦稱爲化合物（b〇— 1)) ， ^ 【化7】Wherein R3 to R6 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent; at least one of R3 to R6 is the hydrocarbon group, and at least two of R3 to R6 may be bonded to form a ring, respectively. ]. According to a fifth aspect of the invention, there is provided an acid generator characterized by the compound of the third aspect. The sixth aspect of the present invention is a compound represented by the following formula (b0-1) (hereinafter, also referred to as a compound (b〇-1)), ^ [Chemical 7]

Rx一Q3—Ο—Q2-Y1-SO3 R6--^|||— 肖 …(bO-·1) 〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；Y1爲碳 數1〜4之伸烷基或氟化伸烷基；R3〜R6分別爲獨立表示 -12- 200947126 氫原子’或可具有取代基之烴基，R3〜R6中之至少1個 爲前述烴基’ R3〜R6中之至少2個可分別鍵結形成環亦 可〕。 本發明之第七之態樣爲，一種化合物之製造方法（以 下，亦稱爲化合物（b0— 1)之製造方法（丨）），其特徵 爲包含，使下述通式（1 一 11)所表示之化合物（1 一 11) ，與下述通式（1 一 12)所表示之化合物（1— 12)，與胺 φ 或銨鹽反應以製得下述通式（b0— 1)所表示之化合物（ b〇 - 1 )之步驟， 【化8】 HO—Q2-Y1—SO; Μ+ ·(11”Rx-Q3—Ο—Q2-Y1-SO3 R6--^|||— 肖...(bO-·1) [wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 respectively Is a single bond or a divalent bond group; Y1 is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; and R3 to R6 are independently represented by a -12-200947126 hydrogen atom or may have a substituent At least one of R3 to R6 is a hydrocarbon group, and at least two of the hydrocarbon groups 'R3 to R6 may be bonded to form a ring, respectively. According to a seventh aspect of the present invention, there is provided a method for producing a compound (hereinafter also referred to as a method for producing a compound (b0-1), which comprises the following formula (1-11) The compound (1-11) represented by the formula (1-11) represented by the following formula (1-12) is reacted with an amine φ or an ammonium salt to obtain a compound of the following formula (b0-1) The step of expressing the compound ( b〇-1), [Chemical 8] HO—Q2-Y1—SO; Μ+ ·(11”

Rx--Q3—X21 …〈1-12) fRx--Q3—X21 ...<1-12) f

Rx—Q3-0一Q2—Y1—SO3 R6」^一 白 ··· (bO — 1) 〇 〔式中’ Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；Y1爲碳 數1〜4之伸烷基或氟化伸烷基；R3〜r6分別爲獨立表示 氫原子，或可具有取代基之烴基，R3〜R6中之至少1個 爲前述烴基’ R3〜R6中之至少2個可分別鍵結形成環亦 可；X21爲鹵素原子；M +爲鹼金屬離子〕。 本發明之第八之態樣爲，一種化合物之製造方法（以 下，亦稱爲化合物（bO — 1)之製造方法（2)),其特徵 爲包含’使下述通式（1— 21)所表示之化合物（1—21) -13- 200947126 ，與下述通式（1—12)所表示之化合物（1 一 12)，與胺 或銨鹽反應以製得下述通式（bO-l)所表示之化合物（ b0 — 1 )之步驟， 【化9】Rx—Q3-0—Q2—Y1—SO3 R6”^一白··· (bO — 1) 〇 [wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 are independent a single bond or a divalent bond group; Y1 is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; and R3 to r6 are each independently a hydrogen atom, or a hydrocarbon group which may have a substituent, R3 to R6 At least one of the hydrocarbon groups 'R3 to R6 may be bonded to form a ring, respectively; X21 is a halogen atom; and M + is an alkali metal ion. The eighth aspect of the present invention is a method for producing a compound (hereinafter, also referred to as a method for producing a compound (bO-1) (2)), which is characterized by comprising 'the following formula (1-21) The compound (1-21)-13-200947126 and the compound (1-12) represented by the following formula (1-12) are reacted with an amine or an ammonium salt to obtain the following formula (bO-). l) the step of the compound (b0-1) indicated, [Chemical 9]

R4' HO—Q2—Y1~S〇3 …（1-21) Rx—Q3—0—Q2—Y1—SO3R4' HO—Q2—Y1~S〇3 ...(1-21) Rx—Q3—0—Q2—Y1—SO3

…（bO —1〉...(bO-1)

Rx一Q3—X21 ...(1-12〉Rx-Q3—X21 ...(1-12>

〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基：Q2及Q3分別爲獨立之單鍵或2價之鍵結基；Y1爲碳 數1〜4之伸烷基或氟化伸烷基；R3〜R6分別爲獨立表示 氫原子，或可具有取代基之烴基，R3〜R6中之至少1個 爲前述烴基，R3〜R6中之至少2個可分別鍵結形成環亦 可；R3'〜R6’分別爲獨立表示氫原子，或可具有取代基之 烴基’ Rv〜R6'中之至少1個爲前述烴基’ R3·〜R6’中之至 少2個可分別鍵結形成環亦可：X21爲鹵素原子〕。 本發明之第九之態樣爲，下述通式（1—21)所表示 之化合物（1 一 2 1 )。 -14- 200947126 【化1 0】 H〇—Q2~Y1—SO3 Rpil—R4_ R5' -(1-21) 〔式中，Q2爲單鍵或2價之鍵結基；y1爲碳數1〜4 之伸烷基或氟化伸烷基；R3'〜R6'分別爲獨立表示氫原子 ’或可具有取代基之烴基，R3‘〜R6'中之至少1個爲前述 烴基’ 〜R6’中之至少2個可分別鍵結形成環亦可〕。 本發明之第十之態樣爲，一種化合物之製造方法（以 下’亦稱爲化合物（1 一 21)之製造方法），其特徵爲包 含，使下述通式（1—11)所表示之化合物（1 一 11)，與 錢鹽反應以製得下述通式（1 - 21)所表示之化合物（1 -2 1 )之步驟， 【化1 1】 ❹ H0—Q2—Y1-S〇-3 M+。一川Wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom): Q2 and Q3 are each a single bond or a divalent bond group; Y1 is an alkyl group having 1 to 4 carbon atoms or fluorinated The alkyl group; R3 to R6 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent; at least one of R3 to R6 is the hydrocarbon group, and at least two of R3 to R6 may be bonded to each other to form a ring. And R3' to R6' are each independently represent a hydrogen atom, or at least one of the hydrocarbon groups 'Rv to R6' which may have a substituent is at least two of the above hydrocarbon groups 'R3 to R6' may be bonded to each other to form a ring Also: X21 is a halogen atom]. The ninth aspect of the present invention is a compound (1 - 2 1 ) represented by the following formula (1-21). -14- 200947126 [Chemical 1 0] H〇—Q2~Y1—SO3 Rpil—R4_ R5′ -(1-21) [wherein Q2 is a single bond or a divalent bond group; y1 is a carbon number of 1~ 4 alkyl or fluorinated alkyl; R3' to R6' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and at least one of R3' to R6' is in the aforementioned hydrocarbon group '~R6' At least two of them may be bonded to each other to form a ring. According to a tenth aspect of the present invention, there is provided a method for producing a compound (hereinafter also referred to as a method for producing a compound (1-21), which comprises the following formula (1-11); a compound (1-11) which is reacted with a money salt to obtain a compound (1 - 2 1 ) represented by the following formula (1-21), [Chem. 1 1] ❹ H0-Q2-Y1-S〇 -3 M+. Yichuan

Rs， HO—Q2—Y1—SO3 R6，~tN—R4' I, R5 …(1-21) 〔式中，Q2爲單鍵或2價之鍵結基；Y1爲碳數1〜4 之伸烷基或氟化伸烷基；R3’〜R6’分別爲獨立表示氫原子 ’或可具有取代基之烴基，R3'〜R6'中之至少1個爲前述 烴基，R3’〜R6’中之至少2個可分別鍵結形成環亦可；M + 爲鹼金屬離子〕。 -15- 200947126 本發明之第十一之態樣爲，一種化合物之製造方法（ 以下’亦稱爲化合物（1一 14)之製造方法），其特徵爲 包含’使下述通式（1-13)所表示之化合物（1— I3), 與銨鹽反應以製得下述通式（1-14)所表示之化合物（1 —1 4 )之步驟， 【化1 2】 ΟRs, HO—Q2—Y1—SO3 R6,~tN—R4′ I, R5 (11-2) [wherein Q2 is a single bond or a divalent bond group; Y1 is a carbon number of 1 to 4 An alkyl group or a fluorinated alkyl group; R3' to R6' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and at least one of R3' to R6' is the aforementioned hydrocarbon group, and R3' to R6' At least two may be bonded to each other to form a ring; M + is an alkali metal ion]. -15- 200947126 The eleventh aspect of the present invention is a method for producing a compound (hereinafter, also referred to as a method for producing a compound (1-14)), which comprises the following formula (1) 13) a step of reacting the compound (1-I3) represented by the compound with an ammonium salt to obtain a compound (1 - 14) represented by the following formula (1-14), [Chemical Formula 1] Ο

Rc一Q4-Ο -Y1—SO3 ΜRc-Q4-Ο -Y1-SO3 Μ

Rc_q4_〇. ΟII -c- -Y1-S〇i R6*-±N- -R4’ (1-14) 〔式中，Re爲可具有取代基（但氮原子除外）之烴 基；Q4爲單鍵或2價之鍵結基爲0或liY1爲碳數1 〜4之伸烷基或氟化伸烷基；R3_〜R6’分別爲獨立表示氫 原子，或可具有取代基之烴基，R3_〜R6’中之至少1個爲 前述烴基，R3'〜R6’中之至少2個可分別鍵結形成環亦可 ;M +爲鹼金屬離子〕。 本說明書及申請專利範圍中，「脂肪族」’係爲相對 於芳香族之相對槪念，定義爲不具有芳香族性之基、化合 物等之意。 「伸烷基」’於無特別限定下，爲包含直鏈狀、支鏈 狀及環狀之2價之飽和烴基之物。 「烷基」，於無特別限定下，爲包含直鏈狀、支鏈狀 及環狀之1價之飽和烴基之物。「低級烷基」爲碳原子數 -16- 200947126 1〜5之烷基。 「結構單位」係指構成樹脂成份（聚合物）之單體單 位（monomer單位）之意。 「曝光」爲包含放射線之全般照射之槪念。 〔發明之效果〕 本發明爲提供一種作爲光阻組成物用之酸產生劑使用 Q 之新穎化合物及其製造方法、酸產生劑、光阻組成物及光 阻圖型之形成方法，及適合作爲合成光阻組成物用之酸產 生劑之有用化合物時之中間體的新穎化合物及其製造方法 爲目的。 〔實施發明之最佳形態〕 《化合物（b0 — 1 )》 首先，將對本發明之第六之態樣之化合物（b0 — 1 ) 〇 進行說明。 本發明之第六之態樣之化合物（bo - 1 )係爲上述通 式（b〇 — 1)所表示之化合物。 式（bO — 1 )中，Rx之烴基，可爲芳香族烴基或脂肪 族烴基皆可。Rc_q4_〇. ΟII -c- -Y1-S〇i R6*-±N- -R4' (1-14) [In the formula, Re is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q4 is a single The bond or the divalent bond group is 0 or liY1 is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; and R3_~R6' are independently a hydrogen atom or a hydrocarbon group which may have a substituent, R3_~ At least one of R6' is the hydrocarbon group, and at least two of R3' to R6' may be bonded to form a ring, respectively; M + is an alkali metal ion. In the scope of the present specification and the patent application, "aliphatic" is a relative complication with respect to aromatics, and is defined as a group having no aromatic group, a compound or the like. The "alkylene group" is a compound containing a linear, branched, and cyclic divalent saturated hydrocarbon group, unless otherwise specified. The "alkyl group" is a one having a linear, branched, and cyclic monovalent saturated hydrocarbon group, unless otherwise specified. The "lower alkyl group" is an alkyl group having a carbon number of -16 to 200947126 1 to 5. "Structural unit" means the unit of monomer (monomer unit) constituting the resin component (polymer). "Exposure" is a tribute to the full illumination of radiation. [Effects of the Invention] The present invention provides a novel compound using Q as an acid generator for a photoresist composition, a method for producing the same, an acid generator, a photoresist composition, and a method for forming a photoresist pattern, and is suitable as a method for forming A novel compound of an intermediate when a useful compound of an acid generator for a photoresist composition is synthesized and a method for producing the same are for the purpose. [Best Mode for Carrying Out the Invention] "Compound (b0-1)" First, a compound (b0-1) of the sixth aspect of the present invention will be described. The compound (bo-1) of the sixth aspect of the present invention is a compound represented by the above formula (b〇-1). In the formula (bO-1), the hydrocarbon group of Rx may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

Rx中之芳香族烴基，爲具有芳香環之烴基，該芳香 族烴基之碳數以3〜30爲佳，以5〜30爲較佳，以5〜20 爲更佳’以6〜1 5爲最佳，以6〜1 2爲特佳。但，該碳數 中，係指不含取代基中之碳數者。 -17- 200947126 芳香族烴基，具體而言’例如，苯基、聯苯基（ biphenyl)基、莽基（fluorenyl)基、萘基、恵基（ anthryl )基、啡繞啉基等之芳香族烴環去除1個氫原子所 得之芳基、苯甲基、苯乙基、1_萘基甲基、2 一萘基甲基 、i一萘基乙基、2-萘基乙基等之芳基烷基等。前述芳基 烷基中之烷基鏈的碳數’以1〜4爲佳，以1〜2爲更佳’ 以1爲最佳。 該芳香族烴基，可具有取代基。例如構成該芳香族烴 © 基所具有之芳香環的碳原子之一部份被雜原子所取代亦可 ，鍵結於該芳香族烴基所具有之芳香環的氫原子被取代基 所取代者亦可。 前者之例如，構成前述芳基之環的碳原子之一部份被 氧原子、硫原子等之雜原子（但氮原子除外）所取代之雜 芳基、構成前述芳基烷基中之芳香族烴環之碳原子的一部 份被前述雜原子所取代之雜芳基烷基等。 後者之例如，芳香族烴基之取代基例如，烷基、烷氧 基、鹵素原子、鹵化烷基、羥基、氧原子（=〇)等。 作爲前述芳香族烴基之取代基的烷基，以碳數1〜5 之烷基爲佳，又以甲基、乙基、丙基、η — 丁基、tert-丁 基爲最佳。 作爲前述芳香族烴基之取代基的烷氧基，以碳數1〜 5之烷氧基爲佳，又以甲氧基、乙氧基、η—丙氧基、iso 〜丙氧基、η- 丁氧基、tert — 丁氧基爲佳，甲氧基、乙氧 基爲最佳。 -18- 200947126 作爲前述芳香族烴基之取代基的鹵素原子，例如 子、氯原子、溴原子、碘原子等，又以氟原子爲佳。 作爲前述芳香族烴基之取代基的鹵化院基，例如 院基之氫原子的一部份或全部被前述鹵素原子所取代 等。The aromatic hydrocarbon group in Rx is a hydrocarbon group having an aromatic ring, and the carbon number of the aromatic hydrocarbon group is preferably from 3 to 30, preferably from 5 to 30, more preferably from 5 to 20, and from 6 to 15 The best, with 6~1 2 is especially good. However, in the carbon number, it means that the carbon number in the substituent is not contained. -17- 200947126 An aromatic hydrocarbon group, specifically, for example, an aromatic group such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group or a morphyl group. An aromatic group, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, an i-naphthylethyl group or a 2-naphthylethyl group obtained by removing one hydrogen atom from a hydrocarbon ring. Alkyl group and the like. The carbon number of the alkyl chain in the above arylalkyl group is preferably from 1 to 4, more preferably from 1 to 2, and most preferably from 1. The aromatic hydrocarbon group may have a substituent. For example, a part of a carbon atom constituting an aromatic ring of the aromatic hydrocarbon group may be substituted by a hetero atom, and a hydrogen atom bonded to an aromatic ring of the aromatic hydrocarbon group may be substituted by a substituent. can. In the former, for example, a heteroaryl group in which a part of a carbon atom constituting the ring of the aryl group is substituted with a hetero atom such as an oxygen atom or a sulfur atom (excluding a nitrogen atom) constitutes an aromatic group in the arylalkyl group. A heteroarylalkyl group in which a part of a carbon atom of a hydrocarbon ring is substituted with the aforementioned hetero atom. In the latter, for example, a substituent of the aromatic hydrocarbon group is, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (=〇), or the like. The alkyl group as a substituent of the aromatic hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, a η-butyl group or a tert-butyl group. The alkoxy group as a substituent of the above aromatic hydrocarbon group is preferably an alkoxy group having 1 to 5 carbon atoms, and further a methoxy group, an ethoxy group, a η-propoxy group, an iso-propoxy group, and a η- Butoxy, tert-butoxy is preferred, and methoxy and ethoxy are preferred. -18- 200947126 The halogen atom as a substituent of the aromatic hydrocarbon group, for example, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. The halogenated group which is a substituent of the above aromatic hydrocarbon group, for example, a part or all of a hydrogen atom of a hospital group is substituted by the above halogen atom.

Rx中之脂肪族烴基，可爲飽和脂肪族烴基亦可 爲不飽和脂肪族烴基亦可。又，脂肪族烴基，可爲直 Q 、支鏈狀、環狀中任一者皆可。The aliphatic hydrocarbon group in Rx may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be any of a straight Q, a branched chain, and a cyclic group.

Rx中，脂肪族烴基可爲構成該脂肪族烴基之碳 的一部份被含有雜原子（但氮原子除外）之取代基所 者亦可，或構成當該脂肪族烴基之氫原子的一部份或 被含有雜原子（但氮原子除外）之取代基所取代者亦 Rx中之「雜原子」，只要爲碳原子、氫原子及 子以外之原子時，並未有特別限定，例如可爲鹵素原 氧原子、硫原子等。鹵素原子，例如氟原子、氯原子 Q 原子、溴原子等。 含有雜原子（但氮原子除外）之取代基，可僅由 雜原子所形成者亦可，或含有前述雜原子以外之基或 之基亦可。 取代碳原子之一部份之取代基，具體而言，例如 0 —、一 C(— 0) — 〇— 、一 c( = o)— 、一 〇 — C(= Ο) — 〇 一 S—、— s( = 0)2—、一 s( = o)2 — 〇-等。脂肪族烴基 狀之情形，該些取代基可包含於環構造中亦可。 取代氫原子之一部份或全部之取代基，具體而言 氟原 前述 之基 ，可 鏈狀 原子 取代 全部 可。 氮原 子、 、碘 前述 原子 爲環 ，例 -19- 200947126 如，院氧基、鹵素原子、鹵化院基、羥基、氧原子（=〇 )等。 前述烷氧基’以碳數1〜5之烷氧基爲佳，又以甲氧 基、乙氧基、η —丙氧基、iso —丙氧基' n — 丁氧基、tert -丁氧基爲佳，以甲氧基、乙氧基爲最佳。 前述鹵素原子，例如氟原子、氯原子、溴原子、碘原 子等，又以氟原子爲佳。 前述鹵化烷基爲’碳數1〜5之烷基，例如甲基、乙 φ 基、丙基、η-丁基' tert — 丁基等之烷基中之氫原子的一 部份或全部被前述鹵素原子所取代之基等。 脂肪族烴基，以直鏈狀或支鏈狀之飽和烴基、直鏈狀 或支鏈狀之1價之不飽和烴基，或環狀之脂肪族烴基（脂 肪族環式基）爲佳。 直鏈狀之飽和烴基（烷基），以碳數爲1〜20者爲佳 ，以1〜1 5者爲更佳，以1〜1 〇爲最佳。具體而言，例如 ，甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、 〇 壬基、癸基、十一烷基、十二烷基、十三烷基、異十三烷 基、十四烷基、十五烷基、十六烷基、異十六烷基、十七 烷基、十八烷基、十九烷基、二十烷基、異二十烷基（ henicosyl)、二十二烷基等。 支鏈狀之飽和烴基（烷基），以碳數爲3〜20者爲佳 ，以3〜1 5者爲更佳，以3〜1 〇者爲最佳。具體而言，例 如，1 一甲基乙基、1 一甲基丙基、2 —甲基丙基、1 一甲基 丁基、2—甲基丁基、3 —甲基丁基、1—乙基丁基、2—乙 -20- 200947126 基丁基、1 一甲基戊基、2 —甲基戊基、3 —甲基戊基、4一 甲基戊基等。 不飽和烴基，以碳數爲2〜10者爲佳，以2〜5爲較 佳’以2〜4爲更佳，以3爲最佳。直鏈狀之1價不飽和 烴基’例如、乙烯基、丙烯基（烯丙基）、丁烯基等。支 鏈狀之1價不飽和烴基，例如，1一甲基丙烯基、2_甲基 丙烯基等。 不飽和烴基，於上述之內容中，特別是以丙烯基爲佳 〇 脂肪族環式基，可爲單環式基亦可、多環式基亦可。 其碳數以3〜30者爲佳，以5〜30者爲較佳，以5〜20爲 更佳，以6〜15者爲最佳，以6〜12爲特佳。 具體而言，例如，單環鏈烷去除1個以上之氫原子之 基；雙環鏈烷、三環鏈烷、四環鏈烷等之多環鏈烷去除1 個以上之氫原子之基等。更具體而言，例如，環戊烷、環 己烷等之單環鏈烷去除1個以上之氫原子之基；例如金剛 烷、降冰片烷、異冰片烷、三環癸院、四環十二烷等之多 環鏈烷去除1個以上之氫原子之基等。 脂肪族環式基，其環構造中未含有含雜原子之取代基 之情形，脂肪族環式基以多環式基爲佳’以多環鏈院去除 1個以上之氫原子之基爲佳’以金剛院去除I個以上之氫 原子之基爲最佳。 脂肪族環式基’其環構造中含有含雜原子之取代基之 情形，含有該雜原子之取代基以一 〇一、_c(=0)—〇—、 -21 - 200947126 一 s_、_S( = 0)2、一 S( = 〇)2 — 〇 —爲佳。該脂肪族環式基 之具體例，例如下述式（L丨）〜（L5) 、（s丨）〜（S4) 等。 【化1 3】In Rx, the aliphatic hydrocarbon group may be a part of a carbon constituting the aliphatic hydrocarbon group which is substituted with a hetero atom (except for a nitrogen atom), or may constitute a hydrogen atom of the aliphatic hydrocarbon group. The "hetero atom" in Rx, which is substituted by a substituent containing a hetero atom (excluding a nitrogen atom), is not particularly limited as long as it is an atom other than a carbon atom, a hydrogen atom or a sub. A halogen atom, an oxygen atom, or the like. A halogen atom such as a fluorine atom, a chlorine atom Q atom, a bromine atom or the like. The substituent containing a hetero atom (excluding a nitrogen atom) may be formed only by a hetero atom or may contain a group other than the above hetero atom. Substituting a substituent of a part of a carbon atom, specifically, for example, 0—, a C(—0)—〇—, a c(=o)—, a 〇—C(=Ο)—〇一S— , — s( = 0)2—, one s( = o)2 — 〇-, etc. In the case of an aliphatic hydrocarbon group, the substituents may be included in the ring structure. Substituting a part or all of a substituent of a hydrogen atom, specifically, the above-mentioned group of a fluorocarbon may be substituted by a chain atom. Nitrogen atom, iodine The above atom is a ring, for example, -19- 200947126, such as a oxy group, a halogen atom, a halogenated compound, a hydroxyl group, an oxygen atom (=〇), and the like. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, and further a methoxy group, an ethoxy group, a η-propoxy group, an iso-propoxy group, a n-butoxy group, and a tert-butoxy group. The base is preferred, and the methoxy group and the ethoxy group are the most preferable. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. The halogenated alkyl group is an alkyl group having a carbon number of 1 to 5, and a part or all of a hydrogen atom in an alkyl group such as a methyl group, an ethyl group, a propyl group, a η-butyl 'tert-butyl group or the like is The group substituted by the aforementioned halogen atom or the like. The aliphatic hydrocarbon group is preferably a linear or branched saturated hydrocarbon group, a linear or branched monovalent unsaturated hydrocarbon group, or a cyclic aliphatic hydrocarbon group (aliphatic cyclic group). The linear saturated hydrocarbon group (alkyl group) is preferably one having a carbon number of from 1 to 20, more preferably from 1 to 155%, and most preferably from 1 to 1 Torr. Specifically, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl , isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heterodi Henicosyl, behenyl or the like. The branched saturated hydrocarbon group (alkyl group) is preferably a carbon number of 3 to 20, more preferably 3 to 15, and most preferably 3 to 1. Specifically, for example, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1- Ethyl butyl, 2-ethyl-20-200947126 butyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like. The unsaturated hydrocarbon group is preferably a carbon number of 2 to 10, more preferably 2 to 5, more preferably 2 to 4, and most preferably 3 or less. The linear monovalent unsaturated hydrocarbon group 'e.g., a vinyl group, a propenyl group (allyl group), a butenyl group or the like. A branched monovalent unsaturated hydrocarbon group, for example, a 1-methylpropenyl group, a 2-methylpropenyl group or the like. In the above, the unsaturated hydrocarbon group is preferably a propylene group or an aliphatic ring group, and may be a monocyclic group or a polycyclic group. The carbon number is preferably from 3 to 30, preferably from 5 to 30, more preferably from 5 to 20, most preferably from 6 to 15, and particularly preferably from 6 to 12. Specifically, for example, a monocyclic alkane is removed from one or more hydrogen atoms; and a polycyclic alkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane is removed from one or more hydrogen atoms. More specifically, for example, a monocyclic alkane such as cyclopentane or cyclohexane removes a group of one or more hydrogen atoms; for example, adamantane, norbornane, isobornane, tricyclic brothel, tetracyclic ten A polycyclic alkane such as dioxane removes a group of one or more hydrogen atoms. In the case of an aliphatic cyclic group, the ring structure does not contain a substituent containing a hetero atom, and the aliphatic ring group is preferably a polycyclic group. It is preferred to remove one or more hydrogen atoms in a polycyclic chain. It is best to remove more than one hydrogen atom from King Kong. The aliphatic cyclic group "in the case where the ring structure contains a substituent containing a hetero atom, and the substituent containing the hetero atom is mono-, _c (=0) - 〇 -, -21 - 200947126 - s_, _S ( = 0) 2, one S ( = 〇) 2 - 〇 - is better. Specific examples of the aliphatic cyclic group include, for example, the following formulae (L丨) to (L5), (s丨) to (S4), and the like. 【化1 3】

(SD (S2) (S3) (S4)(SD (S2) (S3) (S4)

〔式中，Q”爲碳數1〜5之伸烷基、一 〇-、一 S—、 —o—R94—或—s-R95—，R94及R95分別爲獨立之碳數1 〜5之伸烷基，Π1爲〇或1之整數〕°[wherein Q" is an alkylene group having a carbon number of 1 to 5, an anthracene-, an S-, an -o-R94- or a -s-R95-, and R94 and R95 are independent carbon numbers of 1 to 5, respectively. Alkyl, Π1 is 〇 or an integer of 1]°

Q”中之伸烷基’例如與前述Rl之伸院基爲相同之內 容。 R94及R95中之伸烷基，例如與前述R1之伸烷基爲相 同之內容。 該些脂肪族環式基中’鍵結於構成環構造之碳原子的 氫原子之一部份可被取代基所取代者亦可。該取代基’例 如烷基、烷氧基、鹵素原子、鹵化烷基、羥基、氧原子（ =Ο )等。 前述烷基以碳數1〜5之烷基爲佳，以甲基、乙基、 丙基、η— 丁基、tert — 丁基爲最佳。 -22- 200947126 前述烷氧基、鹵素原子分別爲與前述氫原子之一部份 或全部被取代所列舉之取代基爲相同之內容。 本發明中，Rx以可具有取代基之直鏈狀之烷基，或 可具有取代基之環式基爲佳。該環式基，可爲具有取代基 之芳香族烴基，或可具有取代基之脂肪族環式基皆可，又 以可具有取代基之脂肪族環式基爲更佳。 前述芳香族烴基以可具有取代基之萘基，或可具有取 Q 代基之苯基爲佳。 可具有取代基之脂肪族環式基，以可具有取代基之多 環式之脂肪族環式基爲佳。該多環式之脂肪族環式基，以 前述多環鏈烷去除1個以上之氫原子之基、前述（L2)〜 (L5 ) 、 （ S3 )〜（S4 )等爲隹，其中又以金剛烷基爲 佳。 Q2及Q3分別爲獨立之單鍵或2價之鍵結基。 2價之鍵結基，例如，伸烷基、含雜原子之基（以下 Q ，稱爲含雜原子之鍵結基）等。 含雜原子之鍵結基中之「雜原子」，係指碳原子及氫 原子以外之原子，例如氧原子、硫原子、氮原子等。 2價鍵結基之伸烷基，可爲直鏈狀者亦可，支鏈狀者 亦可。該伸烷基之碳數，以1〜12爲佳，以1〜5爲更佳 ，以1〜3爲最佳。 該伸烷基，具體而言，例如，伸甲基〔一 CH2—〕； 一 CH(CΗ3)_、一 CH(CH2CH3)_、一 C(CH3)2—、 -C(CH3)(CH2CH3)- ' - C(CH3)(CH2CH2CH3)- ' -23- 200947126 -c(ch2ch3)2-等之烷基伸甲基；伸乙基〔一 ch2ch2 — 〕；一CH(CH3)CH2-、一 CH(CH3)CH(CH3)—、 _C(CH3)2CH2-、一ch(ch2ch3)ch2—等之院基伸乙基； 三伸甲基（η—伸丙基）〔一 CH2CH2CH2—〕； -CH(CH3)CH2CH2—、-CH2CH(CH3)CH2—等之烷基三伸 甲基；四伸甲基〔一CH2CH2CH2CH2—〕; -CH(CH3)CH2CH2CH2 —、— CH2CH(CH3)CH2CH2 -等之 烷基四伸甲基；五伸甲基〔一CH2CH2CH2CH2CH2 —〕等 0 〇 含雜原子之鍵結基，例如氧原子（醚鍵結；一〇—） 、硫原子（硫醚鍵結；一 S— ) 、一 NH—鍵結（H可被烷 基、醯基等之取代基所取代）、酯鍵結（―C( = 0) — 0 — )、醯胺鍵結（—c( = 0)— NH —)、羰基（-c( = 0) —)The alkylene group in Q" is, for example, the same as the above-mentioned Rl. The alkylene group in R94 and R95 is, for example, the same as the alkylene group of the above R1. The aliphatic cyclic group A part of a hydrogen atom bonded to a carbon atom constituting a ring structure may be substituted by a substituent such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or an oxygen group. Atom (=Ο), etc. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, preferably methyl, ethyl, propyl, η-butyl or tert-butyl. -22- 200947126 The alkoxy group and the halogen atom are the same as those exemplified as a part or the whole of the above-mentioned hydrogen atom. In the present invention, Rx may be a linear alkyl group which may have a substituent, or may be The cyclic group having a substituent is preferred. The cyclic group may be an aromatic hydrocarbon group having a substituent, or an aliphatic cyclic group which may have a substituent, and an aliphatic ring group which may have a substituent More preferably. The aforementioned aromatic hydrocarbon group may be a naphthyl group which may have a substituent, or may have a Q generation The phenyl group is preferably an aliphatic cyclic group which may have a substituent, and is preferably a polycyclic aliphatic ring group which may have a substituent. The polycyclic aliphatic ring group has the aforementioned polycyclic ring The alkane removes one or more hydrogen atom groups, and the above (L2) to (L5), (S3) to (S4), etc. are ruthenium, and adamantyl group is preferred. Q2 and Q3 are independent single bonds, respectively. Or a divalent bond group. A 2-valent bond group, for example, an alkyl group, a hetero atom-containing group (hereinafter Q, a hetero atom-containing bond group), etc., a hetero atom-containing bond group The "hetero atom" means an atom other than a carbon atom or a hydrogen atom, such as an oxygen atom, a sulfur atom, or a nitrogen atom. The alkyl group of the divalent bond group may be a linear one or a branched one. The carbon number of the alkyl group is preferably from 1 to 12, more preferably from 1 to 5, and most preferably from 1 to 3. The alkylene group, specifically, for example, a methyl group [-CH2-]; a CH(CΗ3)_, a CH(CH2CH3)_, a C(CH3)2-, -C(CH3)(CH2CH3) - '-C(CH3)(CH2CH2CH3)-' -23- 200947126 -c(ch2ch3)2-alkyl alkyl group; methyl group [1 ch2ch2 —]; a CH(CH3)CH2-, a CH ( CH3)CH(CH3)-, _C(CH3)2CH2-, a ch(ch2ch3)ch2-, etc., a pendant alkyl group; a trimethyl group (η-extended propyl) [-CH2CH2CH2-]; -CH(CH3 Alkyltrimethylidene of CH2CH2-, -CH2CH(CH3)CH2-, etc.; tetramethyl-[CH2CH2CH2CH2-]; -CH(CH3)CH2CH2CH2-, -CH2CH(CH3)CH2CH2-, etc. Methyl group; pentamethyl group [-CH2CH2CH2CH2CH2-], etc. 0 〇 containing a hetero atom bonding group, such as an oxygen atom (ether bond; a 〇-), a sulfur atom (thioether bond; a S-), An NH-bond (H can be substituted by a substituent such as an alkyl group, a thiol group, etc.), an ester bond (-C(= 0) — 0 — ), a guanamine bond (—c( = 0)—NH —), carbonyl (-c( = 0) —)

、碳酸酯鍵結（―o — c( = o) - ο-)等之非烴系之含雜原 子之鍵結基；該非烴系之含雜原子之鍵結基與前述伸烷基 之組合等。該組合，例如，一 R91 - 0 —、- R92 — Ο — Q C( = 0) -、一 C( = 0) — 0 一 R93—(式中，R” 分別爲 獨立之伸烷基）等或該些組合等。前述式中，R91〜R93之 伸烷基’例如與上述2價鍵結基所列舉之伸烷基爲相同之 內容。 Q2’以羯基、單鍵、—R92— 〇— C( = 0) —爲佳。 Q3，以單鍵、伸烷基、羰基爲佳。 特別是Q2爲羰基，且Q3爲單鍵、Q2爲單鍵，且Q3 爲伸烷基，或Q2爲一 R92— 0—C( = 0)-，且Q3爲羰基者 -24- 200947126 爲佳。 式（bO—l)中，Y1爲碳數1〜4之伸烷基或氟化伸 烷基。 Υ1之伸烷基，例如與前述2價鍵結基所列舉之伸烷 基中，碳數爲1〜4者爲相同之內容。氟化伸烷基，例如 該伸烷基之氫原子之一部份或全部被氟原子所取代之基等a non-hydrocarbon-containing hetero atom-bonding group such as a carbonate bond (-o - c( = o) - ο-); a combination of the non-hydrocarbon-containing hetero atom-containing bonding group and the aforementioned alkylene group Wait. The combination, for example, a R91 - 0 -, - R92 - Ο - QC (= 0) -, a C (= 0) - 0 - R93 - (wherein, R" are independent alkyl groups, etc.) In the above formula, the alkylene group of R91 to R93 is, for example, the same as the alkylene group exemplified for the above-mentioned divalent bonding group. Q2' is a fluorenyl group, a single bond, and -R92- 〇- C ( = 0) - preferably. Q3, preferably a single bond, an alkyl group, a carbonyl group. Especially Q2 is a carbonyl group, and Q3 is a single bond, Q2 is a single bond, and Q3 is an alkylene group, or Q2 is A R92-0-C(=0)-, and Q3 is a carbonyl group -24-200947126 is preferred. In the formula (bO-1), Y1 is an alkylene group having a carbon number of 1 to 4 or a fluorinated alkyl group. The alkylene group of hydrazine 1 is, for example, the same as the alkylene group exemplified for the above-mentioned divalent bonding group, and the carbon number is 1 to 4. The fluorinated alkyl group, for example, one of the hydrogen atoms of the alkylene group a group or the like partially or completely replaced by a fluorine atom

Υ1，具體而 W ’ 例如—CF2—、一 CF2CF2—、 -cf2cf2cf2-、一 cf(cf3)cf2-、一 cf(cf2cf3)—、 —C(CF3)2-、- CF2CF2CF2CF2 -、- CF(CF3)CF2CF2 -、 -CF2CF(CF3)CF2 -、一 CF(CF3)CF(CF3) —、 —C(CF3)2CF2-、- CF(CF2CF3)CF2 -、一 cf(cf2cf2cf3) —、-C(CF3)(CF2CF3) - ； - CHF-、一 CH2CF2—、 -CH2CH2CF2 -、一 CH2CF2CF2—、- CH(CF3)CH2 -、 -CH(CF2CF3) -、- C(CH3)(CF3) -、一 CH2CH2CH2CF2-、一CH2CH2CF2CF2—、- CH(CF3)CH2CH2 -、 -CH2CH(CF3)CH2 -、一 ch(cf3)ch(cf3)—、 —C(CF3)2CH2— ; — CH2—、一 CH2CH2—、— CH2CH2CH2 -、一CH(CH3)CH2 -、一 CH(CH2CH3)—、一 C(CH3)2 —、 -CH2CH2CH2CH2- ' - CH(CH3)CH2CH2- ' -ch2ch(ch3)ch2 —、一 ch(ch3)ch(ch3) —、 -C(CH3)2CH2-、一 ch(ch2ch3)ch2-、 -CH(CH2CH2CH3)—、一 c(ch3)(ch2ch3)-等。 Y1以氟化伸烷基爲佳，特別是以鄰接之硫原子所鍵 -25- 200947126 結之碳原子經氟化所得之氟化伸烷基爲佳。該些氟化伸烷 基，例如一CF2-、一 CF2CF2-、- CF2CF2CF2 -、 -CF(CF3)CF2 -、- CF2CF2CF2CF2 -、- CF(CF3)CF2CF2 —、-CF2CF(CF3)CF2 -、- CF(CF3)CF(CF3)-、 —C(CF3)2CF2—、一 CF(CF2CF3)CF2— ； - CH2CF2 -、 -CH2CH2CF2- ' - CH2CF2CF2- ; - CH2CH2CH2CF2-、 -ch2ch2cf2cf2-、一 CH2CF2CF2CF2-等。 其中又以一 CF2 -、- CF2CF2 -、- CF2CF2CF2 -， Λ 或一 CH2CF2CF2—爲佳，以-cf2-、- CF2CF2-或 —cf2cf2cf2 -爲更佳，以—cf2 —爲最佳。 式（bO—l)中，R3〜R6分別爲獨立之氫原子，或可 具有取代基之烴基，R3〜R6中之至少1個爲前述烴基。 R3〜R6中之烴基，係與前述Rx爲相同之內容。 該烴基，可爲脂肪族烴基亦可，芳香族烴基亦可。該 烴基爲脂肪族烴基之情形，該脂肪族烴基，特別是以可具 有取代基之碳數1〜12之烷基爲佳。 〇 該烴基所可具有之取代基，例如與前述Rx之烴基所 可具有之取代基所列舉之基爲相同之內容，特別是以羥基 爲佳。又，含氮原子之取代基，例如可具有氮原子、氰基 (~CN)、胺基（―NH2)、醯胺基（―NH—C( = 〇)—) 等。 R3〜R6之中，至少1個爲前述烴基，又以2或3個 爲前述烴基爲佳。 R3〜R6中之至少2個亦可分別鍵結形成環。例如， -26- 200947126 R3〜R6中之2個亦可鍵結形成1個環、R3〜R6中之3個 亦可鍵結形成1個環、R3〜R6中之各2個亦可分別鍵結 形成2個環。 R3〜R6中之至少2個分別鍵結，與式中之氮原子共 同形成環（包含作爲雜原子之氮原子的雜環），其可爲脂 肪族雜環，或芳香族雜環亦可。又，該雜環可爲單環式者 ，或多環式者亦可。 0 式（b0 - 1 )中之陽離子部（N+ ( R3 ) ( R4 ) ( R5 ) (R6 ))之具體例，例如胺所衍生之銨離子等。 其中，「胺所衍生之銨離子」，係指胺之氮原子上鍵 結氫原子而形成陽離子者，胺之氮原子上再鍵結1個取代 基之四級銨離子。 衍生上述銨離子之胺，可爲脂肪族胺，或芳香族胺亦 可 〇 脂肪族胺，特別是以氨nh3之氫原子中之至少1個 〇 被碳數12以下之烷基或羥基烷基所取代之胺（烷基胺或 烷基醇胺）或環式胺爲佳。 烷基胺及烷基醇胺之具體例，如η-己基胺、n —庚 基胺、η-辛基胺、η-壬基胺、η—癸基胺等之單烷基胺 :二乙基胺、二—η —丙基胺、二一 η —庚基胺、二—η — 辛基胺、二環己基胺等之二烷基胺；三甲基胺 '三乙基胺 、三—η —丙基胺、三_η — 丁基胺、三_η—己基胺、三 一 η—戊基胺、二—η —庚基胺、二—η —辛基胺、三—η — 壬基胺、三—η —癸基胺、三- η—十二烷基胺等之三烷基 -27- 200947126 胺；二乙醇胺、三乙醇胺、二異丙醇胺、三異丙醇胺、二 一 η—辛醇胺、三一 η —辛醇胺等之烷基醇胺等。 環式胺’例如，含有雜原子之氮原子的雜環化合物等 。該雜環化合物，可爲單環式化合物（脂肪族單環式胺） 或多環式化合物（脂肪族多環式胺）皆可。 脂肪族單環式胺，具體而言，例如，哌啶、哌嗪等。 脂肪族多環式胺，以碳數爲6〜10者爲佳，具體而言 ’例如’ 1，5 —二氮雜雙環〔4.3.0〕— 5 -壬烯、1,8 —二 ❿ 氮雜雙環〔5.4.0〕一 7—十一烯、六甲基四胺、1，4 一二氮 雜雙環〔2.2.2〕辛烷等。 芳香族胺，例如苯胺、耻啶、4 -二甲基胺基吡啶（ DMAP )、吡咯、吲哚、吡唑、咪唑等。 四級銨離子，例如四甲基銨離子、四乙基銨離子、四 丁基銨離子等。 本發明中，式（b0— 1)中之陽離子部（N+(R3) (R4)( R5) ( R6))，特別是以R3〜R6中，至少1個爲烷基’且 〇 至少1個爲氫原子者爲佳。 其中又以R3〜R6中之3個爲烷基，且剩餘之1個爲 氫原子者（三烷基銨離子），或R3〜R6中之2個爲烷基 ，且剩餘之1個爲氫原子者（二烷基銨離子）爲佳。 三烷基銨離子或二烷基銨離子中之烷基，分別爲獨立 ’且以碳數爲1〜10者爲佳，以1〜8者爲更佳，以1〜5 爲最佳。具體而言，例如，甲基、乙基、丙基、丁基、戊 基、己基、庚基、辛基、壬基'癸基等。其中又以乙基爲 -28- 200947126 最佳。 本發明中，化合物（bo — 1 )，以下述通式（b0— 1 — 1 )所表示者爲佳，特別是以下述通式（b0 — 1 — 1 1 )或（ b〇 — 1 — 12 )所表示者爲佳。 【化1 4】 RX__q3 一 〇_ ΟII ◊Υ1, specifically W', for example, CF2, CF2CF2, -cf2cf2cf2-, cf(cf3)cf2-, cf(cf2cf3)-, -C(CF3)2-, -CF2CF2CF2CF2-, -CF(CF3 ) CF2CF2 -, -CF2CF(CF3)CF2 -, a CF(CF3)CF(CF3) -, -C(CF3)2CF2-, -CF(CF2CF3)CF2 -, a cf(cf2cf2cf3) -, -C(CF3 )(CF2CF3) - ; - CHF-, -CH2CF2 -, -CH2CH2CF2 -, -CH2CF2CF2 -, -CH(CF3)CH2 -, -CH(CF2CF3) -, -C(CH3)(CF3) -, -CH2CH2CH2CF2- , a CH2CH2CF2CF2—, —CH(CF3)CH2CH2 -, -CH2CH(CF3)CH2 -, a ch(cf3)ch(cf3)-, -C(CF3)2CH2—; —CH2—, a CH2CH2—, —CH2CH2CH2 -, a CH(CH3)CH2-, a CH(CH2CH3)-, a C(CH3)2-, -CH2CH2CH2CH2-'-CH(CH3)CH2CH2-'-ch2ch(ch3)ch2-, a ch(ch3) Ch(ch3) —, —C(CH3)2CH2-, one ch(ch2ch3)ch2-, —CH(CH2CH2CH3)—, one c(ch3)(ch2ch3)-, and the like. Y1 is preferably a fluorinated alkyl group, and particularly preferably a fluorinated alkyl group obtained by fluorinating a carbon atom of a bond of -25-200947126. The fluorinated alkyl groups, such as a CF2-, a CF2CF2-, -CF2CF2CF2-, -CF(CF3)CF2-, -CF2CF2CF2CF2-, -CF(CF3)CF2CF2-, -CF2CF(CF3)CF2-,- CF(CF3)CF(CF3)-, -C(CF3)2CF2-, a CF(CF2CF3)CF2-; - CH2CF2 -, -CH2CH2CF2-' - CH2CF2CF2-; - CH2CH2CH2CF2-, -ch2ch2cf2cf2-, one CH2CF2CF2CF2-, etc. . Further, a CF2 -, - CF2CF2 -, - CF2CF2CF2 -, Λ or a CH2CF2CF2 - is preferred, and -cf2-, -CF2CF2- or -cf2cf2cf2 - is more preferred, and -cf2 is preferred. In the formula (bO-1), R3 to R6 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and at least one of R3 to R6 is the aforementioned hydrocarbon group. The hydrocarbon group in R3 to R6 is the same as the above Rx. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In the case where the hydrocarbon group is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group is particularly preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent. The substituent which the hydrocarbon group may have, for example, the same as those exemplified for the substituent which the hydrocarbon group of the above Rx may have, particularly preferably a hydroxyl group. Further, the substituent containing a nitrogen atom may have, for example, a nitrogen atom, a cyano group (~CN), an amine group (-NH2), or a guanamine group (-NH-C(= 〇)-). At least one of R3 to R6 is the hydrocarbon group, and 2 or 3 of the above hydrocarbon groups are preferred. At least two of R3 to R6 may also be bonded to each other to form a ring. For example, -26-200947126 two of R3 to R6 may be bonded to form one ring, and three of R3 to R6 may be bonded to form one ring, and each of R3 to R6 may be separately selected. The knot forms two loops. At least two of R3 to R6 are bonded to each other, and form a ring (including a hetero ring as a nitrogen atom of a hetero atom) together with a nitrogen atom in the formula, which may be an aliphatic heterocyclic ring or an aromatic heterocyclic ring. Further, the heterocyclic ring may be a monocyclic one or a polycyclic one. Specific examples of the cation moiety (N+(R3)(R4)(R5)(R6)) in the formula (b0-1), such as an ammonium ion derived from an amine. Here, the "ammonium ion derived from an amine" refers to a quaternary ammonium ion in which a nitrogen atom of an amine is bonded to a hydrogen atom to form a cation, and a nitrogen atom of the amine is further bonded to one substituent. The amine derived from the above ammonium ion may be an aliphatic amine, or an aromatic amine may be an aliphatic amine, particularly an alkyl group or a hydroxyalkyl group having at least one of hydrogen atoms of ammonia nh3 and having a carbon number of 12 or less. The substituted amine (alkylamine or alkylolamine) or cyclic amine is preferred. Specific examples of alkylamines and alkylolamines, such as η-hexylamine, n-heptylamine, η-octylamine, η-decylamine, η-decylamine, and the like, monoalkylamines: diethyl a dialkylamine such as a base amine, a di-n-propylamine, a di-n-heptylamine, a di-n-octylamine or a dicyclohexylamine; a trimethylamine 'triethylamine, a tri- Η-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, di-n-heptylamine, di-n-octylamine, tri-n- 壬a trialkyl -27- 200947126 amine such as a base amine, a tri-n-decylamine or a tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, and An alkyl alcohol amine such as η-octanolamine or tris-n-octanolamine. The cyclic amine 'for example, a heterocyclic compound containing a nitrogen atom of a hetero atom or the like. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine). The aliphatic monocyclic amine, specifically, for example, piperidine, piperazine or the like. The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, specifically, 'for example, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-dioxane nitrogen Heterobicyclo[5.4.0]-7-undecene, hexamethyltetramine, 1,4-diazabicyclo[2.2.2]octane, and the like. Aromatic amines such as aniline, dioxin, 4-dimethylaminopyridine (DMAP), pyrrole, hydrazine, pyrazole, imidazole, and the like. A quaternary ammonium ion such as tetramethylammonium ion, tetraethylammonium ion, tetrabutylammonium ion or the like. In the present invention, the cation moiety (N+(R3)(R4)(R5)(R6)) in the formula (b0-1), particularly at least one of R3 to R6, is an alkyl group and at least one of 〇 It is better for hydrogen atoms. Wherein three of R3 to R6 are alkyl groups, and the remaining one is a hydrogen atom (trialkylammonium ion), or two of R3 to R6 are alkyl groups, and the remaining one is hydrogen. Atoms (dialkylammonium ions) are preferred. The alkyl group in the trialkylammonium ion or the dialkylammonium ion is independently ' and preferably has a carbon number of 1 to 10, more preferably 1 to 8, and most preferably 1 to 5. Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluorenyl group, and the like. Among them, the ethyl group is -28-200947126. In the present invention, the compound (bo-1) is preferably represented by the following formula (b0-1 - 1), particularly in the following formula (b0 - 1 - 1 1 ) or (b〇 - 1 - 12) ) is better. [化1 4] RX__q3 一 〇 _ Ο II ◊

-Y1—S〇3-Y1—S〇3

（bO— 1 — 1) 〔式中，1^、（53、丫1、113〜116分別爲與前述通式（ 匕0—1)中之1^、（53、丫1、113〜116爲相同之內容，11爲〇 或1〕。 【化1 5】 Ο 0(bO-1 - 1) [wherein, 1^, (53, 丫1, 113~116 are respectively 1^, (53, 丫1, 113~116) in the above formula (匕0-1) For the same content, 11 is 〇 or 1]. [Chemical 1 5] Ο 0

Jl II , _Jl II , _

Rb—C——Ο——R1—Ο——C—Y1—S03Rb—C——Ο——R1—Ο——C—Y1—S03

·· (bO~1 11) Ο DC 4丄丨丨 Rc—Q4-〇——C- η -Y1—S〇3 R6—Ν- R4 〔式中，〜R6分別爲前述通式（b0— 1—1 )中之η、Y1、R3〜R6爲相同之內容，R1爲伸烷基，Rb 及Re爲分別獨立之可具有取代基（但氮原子除外）之烴 基，Q4爲單鍵或伸烷基〕。 式（b0 — 1 — 1 1 )中，Rb例如與前述Rx爲相同之內 容，又以可具有取代基之直鏈狀或支鏈狀之飽和烴基、可 -29 - 200947126 具有取代基之碳數脂肪族環式基，或可具有取代基之芳香 族烴基爲佳。其中又以直鏈狀之飽和烴基，或可具有取代 基之脂肪族環式基爲佳。 R1之伸烷基以直鏈狀或支鏈狀之伸烷基爲佳，該伸 烷基之碳數以1〜12爲佳，以1〜5爲更佳，以1〜3爲最 佳。具體例如，與上述2價之鍵結基所列舉之伸烷基爲相 同之內容。 式（bO — 1 — 12 )中，Rc例如與前述Rx爲相同之內 容，又以可具有取代基之脂肪族環式基，或可具有取代基 之芳香族烴基爲佳。其中又以該環構造中含有含雜原子之 取代基的脂肪族環式基爲佳。 Q4之伸烷基’例如與上述2價之鍵結基所列舉之伸 烷基爲相同之內容。 η以1爲佳。 化合物（b0 — 1 )，特別是以下述通式（b〇_ i 一 21 ) 〜（bO-1—22) 、（bO-1—31)〜（b0 - 1-35)所表 示之化合物爲佳。 【化1 6】··(bO~1 11) Ο DC 4丄丨丨Rc—Q4-〇——C- η -Y1—S〇3 R6—Ν- R4 [wherein, R6 is the above formula (b0-1) -1) wherein η, Y1, R3 to R6 are the same, R1 is an alkylene group, and Rb and Re are each independently a hydrocarbon group which may have a substituent (except for a nitrogen atom), and Q4 is a single bond or a stretched alkyl group. base〕. In the formula (b0 - 1 - 1 1 ), Rb is, for example, the same as the above Rx, and is a linear or branched saturated hydrocarbon group which may have a substituent, and a carbon number which may have a substituent of -29 - 200947126 An aliphatic cyclic group or an aromatic hydrocarbon group which may have a substituent is preferred. Further, it is preferably a linear saturated hydrocarbon group or an aliphatic cyclic group which may have a substituent. The alkyl group of R1 is preferably a linear or branched alkyl group. The carbon number of the alkyl group is preferably from 1 to 12, more preferably from 1 to 5, most preferably from 1 to 3. Specifically, for example, the alkylene group exemplified as the above-mentioned divalent bond group is the same. In the formula (bO - 1 - 12), Rc is, for example, the same as the above Rx, and is preferably an aliphatic cyclic group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent. Among them, an aliphatic cyclic group having a substituent containing a hetero atom in the ring structure is preferred. The alkylene group of Q4 is, for example, the same as the alkylene group exemplified for the above-mentioned divalent bond group. η is preferably 1. The compound (b0-1), particularly the compound represented by the following formula (b〇_i-21)~(bO-1-22), (bO-1-31)~(b0-1-35) is good. 【化1 6】

IIII

Η—Ν—CeH2e+iΗ—Ν—CeH2e+i

CfH2fn ίκπ—1 — 21)CfH2fn ίκπ—1 — 21)

200947126 〔式中，d、e、f分別爲獨立之1〜10之整數，】 之整數，ql〜q2分別爲獨立之1〜5之整數’ rl 之整數，g爲1〜20之整數’R爲取代基〕。 〇 ❹ 【化1 7】200947126 [wherein, d, e, and f are independent integers of 1 to 10, respectively], integers, ql to q2 are integers of integers 1 to 5, respectively, integers of rl, and g is an integer of 1 to 20 'R As a substituent]. 〇 ❹ 【化1 7】

(bO — 1 (R7)w5 Ο- (CH2)v5- 9dH2d+1 O II c- -(CF2)rs〇3(bO — 1 (R7)w5 Ο- (CH2)v5- 9dH2d+1 O II c- -(CF2)rs〇3

nS H——CeH2e+1 CfH^inS H——CeH2e+1 CfH^i

.(b〇 — V 〔式中，Q，，、d、e、f、P分別爲前述爲相同之 ，nl〜n3分別爲獨立之〇或1 ’ Vl〜V5分別爲獨立之 3之整數，wl〜w5分別爲獨乂之〇〜3之整數，R爲 基〕。 R7之取代基，係與前述RX中’可具有脂肪族烴 -31) -32) -33) -34) •35) 內容 0〜 取代 基之 -31 - 200947126 取代基、可具有芳香族烴基之取代基所列舉者爲相同之內 容。 R7所附之符號（r 1、w 1〜w5 )爲2以上之整數之情 形，當該化合物中之複數的R7可分別爲相同或相異皆可 〇 本發明之化合物（bo - 1)爲新穎化合物。 本發明之化合物（bo - 1 )，可作爲合成光阻組成物 用之酸產生劑的有用化合物（特別是本發明之第三之態樣 的化合物（bl—l))時之中間體。 本發明之化合物（b0 — 1 )，例如可以後述本發明之 第七之態樣之化合物（b0 — 1 )之製造方法（！），或本發 明之第八之態樣之化合物（bO-Ι)之製造方法（2)予以 製造。 《化合物（b0_l)之製造方法（1)》 其次，將對本發明之第七之態樣之化合物（b0 — i ) 之製造方法（1)進行說明。 本發明之化合物（bO— 1)之製造方法（1)，爲包含 使下述通式（1 - 11)所表示之化合物（1—U),與下述 通式（1一 12)所表不之化合物（1— 12)，與胺或銨鹽反 應之方式而製得下述通式（b0- 1 )所表示之化合物（b0 一 1 )之步驟。 -32- 200947126 【化1 8】 HO—Q2—Y1—SO3 M+ …(ι — 11)(b〇- V [wherein, Q,,, d, e, f, and P are the same as described above, respectively, nl~n3 are independent or 1 'Vl~V5 are independent integers of 3, respectively. Wl~w5 are the integers of 乂3, respectively, and R is a group. The substituent of R7, which may have an aliphatic hydrocarbon-31 with the aforementioned RX, -32) -33) -34) • 35) Content 0 to Substituent -31 - 200947126 The substituents and the substituents which may have an aromatic hydrocarbon group are the same. Where the symbol (r 1 , w 1 to w5 ) attached to R7 is an integer of 2 or more, when the plural R 7 in the compound may be the same or different, the compound (bo - 1) of the present invention may be Novel compounds. The compound (bo - 1 ) of the present invention can be used as an intermediate of a useful compound for synthesizing an acid generator for a photoresist composition (particularly, a compound of the third aspect of the invention (bl-1)). The compound (b0-1) of the present invention may, for example, be a method for producing a compound (b0-1) of the seventh aspect of the present invention (!), or a compound of the eighth aspect of the present invention (bO-Ι) The manufacturing method (2) is manufactured. <<Manufacturing Method (1) of Compound (b0-1)>> Next, a method (1) for producing a compound (b0-i) of the seventh aspect of the present invention will be described. The method (1) for producing the compound (bO-1) of the present invention includes the compound (1-U) represented by the following formula (1-11) and the following formula (1-12). The step of the compound (b0-1) represented by the following formula (b0-1) is carried out by reacting a compound (1-12) with an amine or an ammonium salt. -32- 200947126 【化1 8】 HO—Q2—Y1—SO3 M+ ...(ι — 11)

Rx一Q3一X21 …d-ι 2) R3 - 」Rx-Q3-X21 ...d-ι 2) R3 - ”

Rx - Q3 - O—Q2-Y1-S03 R^ljJ—R4 R® …(bO-1) 〔式中，Rx、Q2、Q3、Y1、R3〜R6分別爲前述通式 O (bO— 1)中之1?/、（)2、03、丫1、113〜116爲相同之內容 :X21爲鹵素原子；M +爲鹼金屬離子〕。 式（1— 11)中，M+爲鈉離子、鉀離子 '鋰離子等。 化合物（1 - Π)，可使用市售之化合物，或合成者 亦可。 例如化合物（1— 11)爲，式（1一 11)中之Q2爲幾 基之化合物（以下，亦稱爲化合物（1一 11一 1))之情形 時’爲包含使下述通式（0 - 1)所表示之化合物（0 一 1) 於鹼之存在下加熱、中和以製得下述通式（0一 2)所表示 之化合物（〇 — 2 )之步驟（以下，亦稱爲鹽形成步驟）， 與 使前述化合物（〇— 2)於酸強度較化合物（1—Rx - Q3 - O-Q2-Y1-S03 R^ljJ-R4 R® (bO-1) [wherein, Rx, Q2, Q3, Y1, R3 to R6 are the above-mentioned general formula O (bO-1) Among them, 1?, (2, 03, 丫1, 113~116 are the same contents: X21 is a halogen atom; M + is an alkali metal ion). In the formula (1-11), M+ is a sodium ion, a potassium ion 'lithium ion, or the like. The compound (1-anthracene) may be a commercially available compound or a synthetic compound. For example, the compound (1-11) is a compound of the formula (1-11) in which Q2 is a group (hereinafter, also referred to as a compound (1-11)). 0 - 1) A compound (0-1) which is heated and neutralized in the presence of a base to obtain a compound represented by the following formula (0-2) (〇-2) (hereinafter, also referred to as For the salt formation step), and to make the aforementioned compound (〇-2) in acid strength compared to the compound (1—

)爲更尚之酸的存在下進行加熱’以製得化合物（1_U —1)之步驟（以下，十 /亦稱爲羧酸化步驟）之方法等。 -33- 200947126 【化1 9】 Ο …（0 — 1) M …(Ο —2) 01 II ,A method in which a compound (1_U-1) is produced by heating in the presence of a more acidic acid (hereinafter, a ten/also referred to as a carboxylation step). -33- 200947126 【化1 9】 Ο ...(0 — 1) M ...(Ο —2) 01 II ,

R01—Ο一C一'Y1—S02F ο + . II ,. Μ Ο——C—~Υ1—S〇3 HO— IU— S〇i M+ ，·（1 一 11 一 1 ) ❺ 〔式中，Rei爲烷基，Υ1、Μ +爲與前述爲相同之內容 ]° rm之烷基，以直鏈狀或支鏈狀之烷基爲佳，具體而 言，例如，甲基 '乙基、丙基、異丙基、η — 丁基、異丁 基、tert—丁基、戊基、異戊基、新戊基等。其中又以碳 數1〜4之烷基爲佳，以甲基爲最佳。 化合物（〇 - 1)可使用市售之物質。R01—Ο一C一'Y1—S02F ο + . II ,. Μ Ο——C—~Υ1—S〇3 HO— IU—S〇i M+ ,·(1-11 1 1 ) ❺ 〔 Rei is an alkyl group, and Υ1, Μ+ are the same as described above. The alkyl group of rm is preferably a linear or branched alkyl group, specifically, for example, methyl 'ethyl, ethyl Base, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and the like. Among them, an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is preferred. A commercially available substance can be used as the compound (〇-1).

鹽形成步驟，例如，可將化合物（0 — 1 )溶解於溶劑 中，於該溶液中添加鹼，經加熱之方式實施。 溶劑’只要可溶解化合物（0 — 1 )者即可，例如水、 四氫呋喃等。 鹼，可使用對應於式（0— 2)中之Μ的鹼，該鹼例 如氫氧化鈉、氫氧化鉀、氫氧化鋰等鹼金屬氫氧化物等。 鹼之使用量，相對於化合物（0 - 1 ) 1莫耳，以使用 1〜5莫耳爲佳，以2〜4莫耳爲更佳。 加熱溫度，以20〜120°C左右爲佳，以50〜l〇〇°C左 右爲更佳。加熱時間，依加熱溫度等而有所不同，通常以 0.5〜1 2小時爲佳，以1〜5小時爲更佳。 -34- 200947126 前述加熱後之中和’可以於前述加熱後之反應液中添 加鹽酸、硫酸、p -甲苯磺酸等酸之方式實施。 此時，中和，以使添加酸後之反應液的pH ( 25 °C ) 達6〜8之方式進行實施爲佳。又，中和時之反應液的溫 度，以20〜3 0°C者爲佳，以23〜27t爲更佳。 反應結束後，可將反應液中之化合物（〇 - 2)單離、 精製。單離、精製，可利用以往公知之方法等，例如單獨 0 使用任一濃縮、溶劑萃取、蒸餾、結晶化、再結晶、色層 分析等，或將2種以上組合使用皆可。 羧酸化步驟中，爲將前述鹽形成步驟所得之化合物（ 0 - 2)，於酸強度較化合物（1 一 11 一 1)爲更高之酸的存 在下進行加熱而製得該化合物（1一 11 一 1)。 「酸強度較化合物（1— 11 一 1)爲更高之酸（以下， 亦僅稱爲強酸）」，係指相較於化合物（1 — 1 1 一 1 )中之 —COOH，其PKa ( 25°C )之値較小之酸之意。使用該強 Q 酸時，可使化合物（0—2)中之一 COO-M +形成—COOH， 而得到化合物（1 — 1 1 一 1 )。 強酸’可由公知之酸之中，適當選擇相較於前述化合 物（1— 11— 1)中之- COOH的pKa爲更小之pKa的酸使 用即可。化合物（1一11 一 1)中之—COOH之pKa，可使 用公知之滴定法方式計算。 強酸’具體而言，例如，芳基磺酸、烷基磺酸等之磺 酸、硫酸、鹽酸等。芳基磺酸，例如p一甲苯磺酸等。烷 基磺酸’例如甲烷磺酸或三氟甲烷磺酸等。強酸，就對有 -35- 200947126 機溶劑之溶解性或精製之容易性等觀點，特別是以p〜甲 苯磺酸爲佳。 羧酸化步驟’例如可將化合物（〇 — 2 )溶解於溶劑中 ’添加強酸進行加熱之方式實施。 溶劑，只要可溶解化合物（0 — 2)者即可，例如乙腾 、甲基乙基酮等。 強酸之使用量，相對於化合物（0— 2) 1莫耳，以使 用0.5〜3莫耳爲佳，以1〜2莫耳爲更佳。 ❹ 加熱溫度，以20〜150°C左右爲佳，以50〜12(TC左 右爲更佳。加熱時間，依加熱溫度等而有所不同，通常以 0.5〜1 2小時爲佳，以1〜5小時爲更佳。 反應結束後，可將反應液中之化合物（1 一 11— 1)單 離、精製亦可。單離、精製，可利用以往公知之方法，例 如可單獨使用任一濃縮、溶劑萃取、蒸餾、結晶化、再結 晶、色層分析等，或將2種以上組合使用亦可。 又，例如爲化合物（1一11)，與式（1—U)中之 φ Q2爲—R1 — 0 — C( = 0)—(式中，R1係與前述R92相同般 ，爲伸烷基）基之化合物（以下，亦稱爲化合物（1一 11 一 2 ))之情形，爲包含使下述通式（0 - 3 )所表示之化 合物（〇 — 3 )，與前述化合物（1 一 1 1 一 1 )反應以製得化 合物（1 一 11 一 2)之步驟的方法等。 -36- 200947126 【化2 0】 HO一R1—Ο一R2 …(0-3) Ο HO—C—Y1一SO3 Μ ...(-I_-j 1 _D Ο II , - + HO—R1—Ο一C—Υ1—S〇3 Μ …（卜”一幻 〔式中，R1爲伸烷基；R2爲可具有取代基爲芳香族 0 基之脂肪族基、Υ1爲碳數1〜4之伸烷基或氟化伸烷基； Μ +爲鹼金屬離子〕。 使化合物（〇 - 3)與化合物（1— 11— 1)反應之方法 ，並未有特別限定，例如可於溶劑中使化合物（〇 - 3 )與 化合物（1 一 11 一 1)混合、溶解、加熱之方式實施。 溶劑，例如甲苯、二氯苯、1,2 _二氯乙烷、1，3 —二 氯丙烷等。 加熱溫度（反應溫度），以20〜140°C左右爲佳，以 Q 60〜130°c左右爲更佳。加熱時間，依加熱溫度等而有所 相異，通常，以1〜72小時爲佳，6〜48小時爲更佳。 上述反應，可於酸性觸媒之存在下進行。酸性觸媒， 並未有特別限定，例如，芳基磺酸、烷基磺酸等之磺酸、 硫酸、鹽酸等。芳基磺酸，例如p -甲苯磺酸等。烷基觸 酸，例如甲烷磺酸或三氟甲烷磺酸等。該些可單獨使用1 種’或將2種以上合倂使用亦可。酸性觸媒，就對有機溶 劑之溶解性或Ιί製之容易性等觀點，特別是以p -甲苯觸 酸爲佳。 -37- 200947126 酸性觸媒之使用量，相對於化合物（1—11—1) 1莫 耳，以0.1〜2莫耳爲佳，以0.1〜1莫耳爲更佳。 反應結束後，可將反應液中之化合物（1 一 11-2)單 離、精製亦可。單離、精製，可利用以往公知之方法，例 如單獨使用任一濃縮、溶劑萃取、蒸餾、結晶化、再結晶 、色層分析等，或將2種以上組合使用亦可。 式（1— I2)中，X21之鹵素原子，例如溴原子、氯原 子、碘原子、氟原子等，就具有優良反應性等觀點，以使 用溴原子或氯原子爲佳。 化合物（1一 12)，可使用市售之化合物。 胺或鉸鹽，可使用對應於式（b0 - 1)中之陽離子部 (N + (R3)(R4)(R5)(R6))之內容。該胺之具體例，分別爲 前述之衍生銨離子之胺所列舉之烷基胺、二烷基胺、三烷 基胺、芳香族胺等。銨鹽之具體例如，氫氧化四甲基銨、 氫氧化四乙基銨、氫氧化四丁基銨等之四級銨鹽等。 使化合物（ι-ll)與化合物（1一 12)與胺或銨鹽反 應之方法，並未有特別限定，例如，於反應溶劑中，使化 合物（1一 11) ’與化合物（1 一 12)，與胺或銨鹽接觸之 方法等。該方法中，例如，於溶解有化合物（1 一 11)之 反應溶劑所得之溶液中，添加化合物（1 - 12)與胺或四 級銨化合物之方式實施。 反應溶劑，只要可溶解化合物（1 一 1 1 )及化合物（1 一 1 2 )之溶劑即可，具體而言’例如，四氫呋喃（T H F ) 、丙酮、二甲基甲醯胺（DMF )、二甲基乙醯胺、二甲基 200947126 亞諷（DMSO )、乙腈等。 化合物（1 - 1 2 )之添加量，相對於化合物（1 _丨i ) ，以約1〜3當量爲佳，以1〜2當量爲更佳。 胺或四級錢化合物之添加量，相對於化合物（1 一 ^ J )’以約1〜3當量爲佳，以i〜2當量爲更佳。 反應溫度’以一 20〜40°C爲佳，以〇〜30°C爲更佳。 反應時間，依化合物（1 — 1 1 )及化合物（1 — 1 2 )之反應 0 性或反應溫度等而有所不同，通常以1〜1 2 0小時爲佳， 以1〜4 8小時爲更佳。 反應結束後，可將反應液中之化合物（bO-l)單離 、精製。單離、精製’可利用以往公知之方法，例如可單 獨使用任一洗淨、濃縮、溶劑萃取、蒸餾、結晶化、再結 晶、色層分析等，或將2種以上組合使用皆可。 本發明中’化合物（b0— 1)具有陽離子部之N+(r3 )(R4) (R5) (R6)，因其不易溶解於水，故可以水洗 〇 方式進行精製。 所得化合物（bo - 1)之構造，可使用1H —核磁共振 (NMR)圖譜法、13C—NMR圖譜法、19f— NMR圖譜法 、紅外線吸收（IR )圖譜法、質量分析（Ms )法、元素 分析法、X線結晶繞射法等一般性有機分析法進行確認。 《化合物（b0— 1)之製造方法（2)、化合物（1 一 21 ) &gt; 其次，將對本發明之第八之態樣之化合物（b 0 _ 1 ) -39- 200947126 之製造方法（2)，及本發明之第九之態樣之化合物（1 -2 1 )進行說明。 本發明之化合物（bO—Ι)之製造方法（2)，爲包含 使下述通式（1 一 21)所表示之化合物（1一 21)，與下述 通式（1— 12)所表示之化合物（1-12)，與胺或錢鹽反 應以製得下述通式（b0- 1 )所表示之化合物（bO— 1 )之 步驟。 【化2 1】 -N—R4' HO—Q2—Y1—SO&quot; RX—Q3—·X21 ...(1-12) R3 RX 一 q3—〇—〇2_γ1_δ〇- R6^t,!j 一R4 (bO-1)The salt forming step, for example, can be carried out by dissolving the compound (0-1) in a solvent, adding a base to the solution, and heating. The solvent 'suffisable as long as it can dissolve the compound (0-1), such as water, tetrahydrofuran or the like. As the base, a base corresponding to ruthenium in the formula (0-2) such as an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide can be used. The amount of the base to be used is preferably 1 to 5 moles, more preferably 2 to 4 moles, relative to the compound (0 - 1 ) 1 mole. The heating temperature is preferably about 20 to 120 ° C, preferably about 50 to l ° ° C. The heating time varies depending on the heating temperature, etc., and is usually preferably 0.5 to 12 hours, more preferably 1 to 5 hours. -34- 200947126 The above-mentioned heating and neutralization can be carried out by adding an acid such as hydrochloric acid, sulfuric acid or p-toluenesulfonic acid to the reaction liquid after the heating. In this case, it is preferred to carry out the neutralization so that the pH (25 ° C) of the reaction liquid after the addition of the acid is 6 to 8. Further, the temperature of the reaction liquid at the time of neutralization is preferably from 20 to 30 ° C, more preferably from 23 to 27 t. After completion of the reaction, the compound (〇-2) in the reaction mixture can be isolated and purified. For the separation and purification, a conventionally known method or the like can be used. For example, any concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like may be used alone or in combination of two or more. In the carboxylation step, the compound (0-2) obtained by the above salt formation step is heated in the presence of an acid having a higher acid strength than the compound (1-11) to obtain the compound (1). 11 a 1). "Acid acid is higher in acid than compound (1-11-1) (hereinafter, also referred to as "strong acid"), which means PKa (compared to -COOH in compound (1 - 1 1 - 1)" 25 ° C) means less acid. When the strong Q acid is used, one of the compounds (0-2), COO-M + , can be formed into -COOH to give a compound (1 - 1 1 - 1 ). The strong acid' may be appropriately selected from the known acids, and is preferably used in comparison with the acid having a pKa of -COOH in the above compound (1-11-1) being a smaller pKa. The pKa of -COOH in the compound (1-11) can be calculated by a known titration method. The strong acid' is specifically, for example, a sulfonic acid such as an arylsulfonic acid or an alkylsulfonic acid, sulfuric acid, hydrochloric acid or the like. An aryl sulfonic acid such as p-toluenesulfonic acid or the like. An alkyl sulfonic acid such as methanesulfonic acid or trifluoromethanesulfonic acid or the like. For the strong acid, it is preferable to use p-toluenesulfonic acid as a viewpoint of solubility or reproducibility of the solvent of -35-200947126. The carboxylation step can be carried out, for example, by dissolving the compound (〇-2) in a solvent and adding a strong acid to heat. The solvent may be any one as long as it can dissolve the compound (0-2), such as ethene or methyl ethyl ketone. The amount of strong acid used is preferably from 0.5 to 3 moles, more preferably from 1 to 2 moles, relative to the compound (0-2) 1 mole.加热 Heating temperature is preferably about 20~150°C, preferably 50~12 (TC is better. Heating time varies depending on heating temperature, etc., usually 0.5~1 2 hours, preferably 1~ After the completion of the reaction, the compound (1-11-1) in the reaction mixture may be isolated or purified. It may be isolated or purified, and a conventionally known method may be used. For example, any concentration may be used alone. And solvent extraction, distillation, crystallization, recrystallization, chromatography, etc., or two or more types may be used in combination. Further, for example, compound (1-11), and φ Q2 in formula (1-U) are - R1 - 0 - C( = 0) - (wherein, R1 is the same as the above R92, which is an alkylene group) (hereinafter, also referred to as a compound (1-11)), A method comprising the step of reacting a compound represented by the following formula (0-3) (〇-3) with the above compound (1-11 1 1) to obtain a compound (1-11 2), and the like. -36- 200947126 [Chemical 2 0] HO-R1—Ο一R2 ...(0-3) Ο HO—C—Y1—SO3 Μ ...(-I_-j 1 _D Ο II , - + HO—R1— Ο一C —Υ1—S〇3 Μ ...(卜”一幻 [wherein R1 is an alkylene group; R2 is an aliphatic group which may have an aromatic group of a substituent, and Υ1 is an alkylene group having a carbon number of 1 to 4; Or a fluorinated alkyl group; Μ + is an alkali metal ion. The method for reacting the compound (〇-3) with the compound (1-11-1) is not particularly limited, and for example, the compound can be used in a solvent. - 3) It is carried out by mixing, dissolving and heating the compound (1-11). Solvents such as toluene, dichlorobenzene, 1,2-dichloroethane, 1,3-dichloropropane, etc. Heating temperature (reaction temperature), preferably about 20 to 140 ° C, more preferably about Q 60 to 130 ° C. The heating time varies depending on the heating temperature, etc., usually, it is preferably from 1 to 72 hours. 6 to 48 hours is more preferable. The above reaction can be carried out in the presence of an acidic catalyst. The acidic catalyst is not particularly limited, and examples thereof include sulfonic acid, sulfuric acid, and hydrochloric acid such as arylsulfonic acid and alkylsulfonic acid. Etyl. aryl sulfonic acid, such as p-toluenesulfonic acid, etc. alkylic acid, such as methanesulfonic acid or trifluoromethanesulfonic acid, etc. One type may be used in combination of two or more types. The acidic catalyst is preferably p-toluene acid in view of solubility in an organic solvent or ease of preparation. -37- 200947126 The amount of the catalyst used is preferably 0.1 to 2 moles, more preferably 0.1 to 1 mole, relative to the compound (1-11-1) 1 mole. After the reaction, the compound in the reaction solution can be used. (1 - 11-2) It is also possible to separate and refine. For the separation and purification, a conventionally known method can be used. For example, any one of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like may be used alone or in combination of two or more. In the formula (1-I2), a halogen atom of X21, for example, a bromine atom, a chlorine atom, an iodine atom or a fluorine atom, has excellent reactivity, and a bromine atom or a chlorine atom is preferably used. As the compound (1-12), a commercially available compound can be used. As the amine or the hinge salt, the content corresponding to the cationic moiety (N + (R3) (R4) (R5) (R6)) in the formula (b0-1) can be used. Specific examples of the amine are alkylamines, dialkylamines, trialkylamines, aromatic amines and the like which are exemplified by the above-mentioned amine-derived amine. Specific examples of the ammonium salt include a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide. The method of reacting the compound (I-ll) with the compound (1-12) with an amine or an ammonium salt is not particularly limited. For example, in the reaction solvent, the compound (1-11) is compounded with the compound (1-12). ), a method of contacting with an amine or an ammonium salt, and the like. In the method, for example, a compound (1-12) is added to a solution obtained by dissolving a reaction solvent of the compound (1-11) with an amine or a quaternary ammonium compound. The reaction solvent may be any solvent which can dissolve the compound (1-11) and the compound (1-12), specifically, for example, tetrahydrofuran (THF), acetone, dimethylformamide (DMF), Methylacetamide, dimethyl 200947126, DMSO, acetonitrile, etc. The amount of the compound (1 - 1 2 ) to be added is preferably from about 1 to 3 equivalents, more preferably from 1 to 2 equivalents, based on the compound (1 _丨i). The amount of the amine or quaternary acid compound to be added is preferably from about 1 to 3 equivalents, more preferably from i to 2 equivalents, based on the compound (1 - J ). The reaction temperature is preferably from 20 to 40 ° C, more preferably from 〇 30 ° C. The reaction time varies depending on the reaction property of the compound (1 - 1 1 ) and the compound (1 - 1 2 ), the reaction temperature, etc., and is usually preferably 1 to 120 hours, and 1 to 48 hours. Better. After completion of the reaction, the compound (bO-1) in the reaction mixture can be isolated and purified. For the separation and purification, a conventionally known method can be used. For example, any one of washing, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like can be used alone or in combination of two or more. In the present invention, the compound (b0-1) has N+(r3)(R4)(R5)(R6) in the cation portion, and since it is not easily dissolved in water, it can be purified by washing with water. The structure of the obtained compound (bo-1) can be 1H-nuclear magnetic resonance (NMR) pattern, 13C-NMR spectrum method, 19f-NMR spectrum method, infrared absorption (IR) pattern method, mass analysis (Ms) method, element General organic analysis methods such as analytical methods and X-ray crystal diffraction methods are used for confirmation. <<Method for Producing Compound (b0-1), Compound (1-21) &gt; Next, a method for producing the compound of the eighth aspect of the present invention (b 0 _ 1 ) -39- 200947126 (2) And the compound (1 - 2 1 ) of the ninth aspect of the invention will be described. The method (2) for producing the compound (bO-oxime) of the present invention comprises the compound (1-21) represented by the following formula (1-21) and represented by the following formula (1-12) The compound (1-12) is reacted with an amine or a money salt to obtain a compound (bO-1) represented by the following formula (b0-1). [化2 1] -N-R4' HO-Q2—Y1—SO&quot; RX—Q3—·X21 (1-12) R3 RX a q3—〇—〇2_γ1_δ〇- R6^t, !j R4 (bO-1)

〔式中，Rx、Q2、Q3、Y1、R3〜R6分別爲前述通式 (bO— 1 )中之Rx、Q2、Q3、γι、R3〜r6爲相同之內容 ;R3’〜R6’分別爲獨立之氫原子’或可具有取代基之烴基 ，R3’〜R6’中之至少丨個爲前述烴基，R3’〜R6’中之至少 2個可分別鍵結形成環；X2 1爲鹵素原子〕。 式（1 — 21 )中，R3’〜R6’分別與前述R3〜R6爲相同 之內容。 本製造方法（2)中，式（1— 21)中之陽離子部（N + (R ) (R’） （R5，） （R6’）） ’ 與式（b〇—l)中之陽 離子部（N+ ( R3 ) ( R4 ) ( R5 ) ( ))，可爲相同或相 -40- 200947126 異皆可’就考慮步驟之簡素化等，以相同者爲佳。 使化合物（1 - 21)與化合物與胺或銨鹽反 應之步驟’可於則述製造方法（1)中，除使化合物（1 一 11)以化合物（1- 21)替代使用以外，皆依前述製造方 法（1 )之相同方法實施。 本製造方法（2)中’作爲起始物質使用之化合物（1 —21) ’爲新穎之化合物。 〇 化合物（1 — 2 1 )，例如可依後述化合物（1 — 2 1 )之 製造方法進行製造。 《化合物（1— 21)之製造方法》 其次’將說明本發明之第十之態樣之化合物（1 _ 2 t )之製造方法。 本發明之化合物（1_21)之製造方法，爲包含使下 述通式（1 一 11)所表示之化合*(1—u)，與銨鹽反應 Ο 以製得下述通式（1— 21)所表示之化合物（1— 21)之步 驟。 【化2 2】 HO—Q2_yi_s〇-3 m+[wherein, Rx, Q2, Q3, Y1, and R3 to R6 are the same contents of Rx, Q2, Q3, γι, and R3 to r6 in the above formula (bO-1); respectively; R3' to R6' are respectively a separate hydrogen atom' or a hydrocarbon group which may have a substituent, at least one of R3' to R6' is the aforementioned hydrocarbon group, and at least two of R3' to R6' may each be bonded to form a ring; X2 1 is a halogen atom] . In the formula (1-21), R3' to R6' are the same as those of the above R3 to R6. In the production method (2), the cation portion (N + (R ) (R') (R5,) (R6')) ' in the formula (1-21) and the cation portion in the formula (b〇-1) (N+ ( R3 ) ( R4 ) ( R5 ) ( )), can be the same or phase -40-200947126. All of them can be considered as the simplification of the steps, etc., the same is preferred. The step of reacting the compound (1-21) with the compound and the amine or the ammonium salt can be carried out in the production method (1) except that the compound (1-11) is used instead of the compound (1-21). The same method as the above production method (1) is carried out. The compound (1-21) used as the starting material in the production method (2) is a novel compound. The hydrazine compound (1 - 2 1 ) can be produced, for example, according to the production method of the compound (1 - 2 1 ) described later. <<Method for Producing Compound (1-21)>> Next, a method for producing the compound (1 _ 2 t) of the tenth aspect of the present invention will be described. The method for producing the compound (1-21) of the present invention comprises reacting an ammonium salt with a compound represented by the following formula (1-11) and reacting with an ammonium salt to obtain the following formula (1-21). The step of the compound (1-21) indicated. [化2 2] HO—Q2_yi_s〇-3 m+

HO—-Q2—γΐ—S〇3 R8—N——R4·HO—Q2—γΐ—S〇3 R8—N—R4·

…（1-21) 式中，Q2、γ1、r3’〜r6’、M +分別爲與前述爲相同之 內容。 -41 - 200947126 銨鹽，例如上述之烷基胺、二烷基胺、三烷基胺，及 芳香族胺之鹽酸鹽或溴酸鹽等。 使化合物（1一 11)與銨鹽之反應，可使用與以往公 知之鹽取代方法爲相同之方法實施。例如，使化合物（1 一 11)，與銨鹽溶解於水、二氯甲烷、乙腈、甲醇、氯仿 等溶劑，經攪拌等使其進行反應。 反應溫度，以〇 °C〜1 5 0 °c左右爲佳，以〇 °C〜1 00 °c 左右爲更佳。反應時間，依化合物（1 一 11)及銨鹽之反 應性或反應溫度等而有所不同，通常以0.5〜10小時爲佳 ，以1〜5小時爲更佳。 反應結束後，可將反應液中之化合物（1 - 2 1 )單離 、精製。單離、精製，可利用以往公知之方法，例如可單 獨使用任一濃縮、溶劑萃取、蒸餾、結晶化、再結晶、色 層分析等，或將2種以上組合使用皆可。 所得化合物（1一 21)之構造，可使用1H -核磁共振 (NMR)圖譜法、13C—NMR圖譜法、19F—NMR圖譜法 '紅外線吸收（IR)圖譜法、質量分析（MS)法、元素 分析法、X線結晶繞射法等一般性有機分析法進行確認。 《化合物（1-14)之製造方法》 其次，將對本發明之第十一之態樣之化合物（1 一 14 )之製造方法進行說明。 本發明之化合物（1- 14)之製造方法，爲包含使下 述通式（1—13)所表示之化合物（1—13)，與銨鹽反應 -42- 200947126 以製得下述通式（i-W)所表示之化合物（1一 14)之步 驟。 【化2 3】 RC 一 q4 一 〇 RC 一 q4—〇.(1-21) In the formula, Q2, γ1, r3'~r6', and M + are the same as described above. -41 - 200947126 Ammonium salt, for example, the above alkylamine, dialkylamine, trialkylamine, and hydrochloride or bromate of an aromatic amine. The reaction of the compound (1-11) with an ammonium salt can be carried out by the same method as the conventionally known salt substitution method. For example, the compound (1-11) and the ammonium salt are dissolved in a solvent such as water, dichloromethane, acetonitrile, methanol or chloroform, and the mixture is stirred or the like to carry out a reaction. The reaction temperature is preferably about 〇 ° C to 150 ° C, preferably about 〇 ° C to 100 ° C. The reaction time varies depending on the reactivity of the compound (1-11) and the ammonium salt, the reaction temperature, etc., and is usually preferably 0.5 to 10 hours, more preferably 1 to 5 hours. After completion of the reaction, the compound (1 - 2 1 ) in the reaction mixture can be isolated and purified. For the separation and purification, a conventionally known method can be used. For example, any concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like can be used alone or in combination of two or more. The structure of the obtained compound (1-21) can be 1H-nuclear magnetic resonance (NMR) spectroscopy, 13C-NMR spectroscopy, 19F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), and elements. General organic analysis methods such as analytical methods and X-ray crystal diffraction methods are used for confirmation. <<Method for Producing Compound (1-14)>> Next, a method for producing the compound (1-14) of the eleventh aspect of the present invention will be described. The method for producing the compound (1-14) of the present invention comprises reacting a compound (1-13) represented by the following formula (1-13) with an ammonium salt - 42-200947126 to obtain the following formula (iW) The step of the compound (1-14) represented. [Chemical 2 3] RC a q4 a RC RC a q4 - 〇.

Ο -cfY1—so; MH οII -c- --(1-13) R3' ❹ -Y1—S〇3 RS'-^N一R4· 〔式中’ Re爲可具有取代基（但氮原子除外）之烴 基’ Q4爲單鍵或2價之鍵結基；η爲〇或1; Y1爲碳數1 〜4之伸烷基或氟化伸烷基；R3,〜R6,分別爲獨立之氫原 子，或可具有取代基之烴基，R3,〜R6,中之至少1個爲前 述烴基’ R3’〜R6,中之至少2個可分別鍵結形成環；Μ +爲 鹼金屬離子〕。 式中’ Rc、、n、Y1、R3,〜R6’、Μ +分別爲與前述 爲相同之內容。 銨鹽’例如上述之烷基胺、二烷基胺、三烷基胺，及 芳香族胺之鹽酸鹽或溴酸鹽等。 化合物（1 一 13)與銨鹽之反應，可使用與以往公知 之鹽取代方法爲相同之方法實施。例如，使化合物（1 一 13)與銨鹽溶解於水、二氯甲烷、乙腈、甲醇、氯仿等之 溶劑中，以攪拌等使其進行反應。 反應溫度，以0 °C〜1 5 (TC左右爲佳，以0 °c〜1 0 0 °c 左右爲更佳。反應時間依化合物（1- 13)及銨鹽之反應 -43- 200947126 性或反應溫度等而有所不同，通常以〇 · 5〜1 〇小時爲佳’ 以1〜5小時爲更佳。 反應結束後，可將反應液中之化合物（1-14)單離 、精製。單離、精製，可利用以往公知之方法，例如可單 獨使用任一洗淨、濃縮、溶劑萃取、蒸餾、結晶化、再結 晶、色層分析等，或2種以上組合使用皆可。 本發明中，因化合物（1-14)具有陽離子部之Ν+( R3’） （ R4’） （ R5’） （ R6’），因其不易溶解於水，故可 @ 以水洗方式進行精製。 所得化合物（1 — 1 4 )之構造，可使用1 Η —核磁共振 (NMR)圖譜法、13C — NMR圖譜法、19F—NMR圖譜法 、紅外線吸收（IR )圖譜法、質量分析（MS )法、元素 分析法、X線結晶繞射法等一般性有機分析法進行確認。 《化合物（bO — 1 )之用途》 如上所述般，本發明之化合物（b0 - 1 )爲新穎化合 © 物’其爲適合作爲光阻組成物用之酸產生劑的有用化合物 、特別是適合作爲合成本發明之第三之態樣之化合物（b 1 一 1 )之際的中間體。 即，化合物（bO—Ι)以鹽取代，化合物（bO— 1)之 陽離子部（N+(R3) (R4) (R5) (R6))以適當之陽離 子部’例如锍離子、碘鑰離子等有機陽離子取代所得之化 合物’可經由曝光而產生酸（磺酸）。該化合物，適合作 爲光阻組成物用之酸產生劑。 -44 - 200947126 本發明之化合物（b0 _ 1 )，極適合作爲製造前述經 鹽取代之酸產生劑的有用化合物之際的中間體。即，陽離 子部爲N+ ( R3 ) ( R4 ) ( R5 ) ( R6 )時，該化合物經由 水洗而容易精製，而可期待提高最終產物之純度。例如陽 離子部爲鹼金屬離子時，經由水洗進行精製時，將因該化 合物產生溶解而不易精製。 又，本發明之化合物（b0 — 1)經鹽取代而製造之化 0 合物，除可被利用作爲酸產生劑以外，使用該化合物作爲 酸產生劑添加於光阻組成物所得之光阻組成物，可提高其 微影蝕刻特性，例如可提高形成光阻圖型之際的解析性、 遮罩重現性（例如遮罩線性等）或曝光量（EL )寬容度 、光阻圖型形狀、焦點景深寬度（DOF)等。 EL寬容度，係指改變曝光量下進行曝光之際，以相 對於標靶尺寸之偏差在特定範圍內時之尺寸可形成光阻圖 型之曝光量之範圍，即，可得到忠實反應遮罩圖型之光阻 〇 圖型時之曝光量範圍，EL寬容度，其數値越大時，伴隨 曝光量變動所產生之圖型尺寸的變化量越小，就提升製程 之寬容度上爲較佳。 可得到上述效果之理由，推測爲以下內容。即，前述 化合物（b0 — 1)經由鹽取代所製造之化合物，其陰離子 部中具有「Y1 — S03·」之骨架鍵結有Rx— Q3—0— Q2-之 構造。因此，與以往作爲陰離子使用之氟化烷基磺酸離子 相比較時，具有極性更高，具有立體性之高體積密度之龐 大構造。因具有高極性，故推測其可經由分子間之相互作 -45- 200947126 用，或經該龐大之立體構造，而與九氟丁烷磺酸酯等以往 之酸產生劑的陰離子部相比較時，於光阻膜内可以化學性 或物理性方式抑制該陰離子部（酸）之擴散。因此，可抑 制曝光域所發生之酸擴散至未曝光區域，其結果，可提升 未曝光區域與曝光區中對鹼顯影液之溶解性差（溶解反差 )，因而推測可提高解析性或提升光阻圖型之形狀。Ο -cfY1—so; MH οII -c- --(1-13) R3' ❹ -Y1—S〇3 RS'-^N-R4· [wherein Re is a substituent (except for a nitrogen atom) The hydrocarbon group 'Q4 is a single bond or a divalent bond group; η is 〇 or 1; Y1 is an alkyl or fluorinated alkyl group having a carbon number of 1 to 4; and R3, R6 are independently hydrogen The atom, or a hydrocarbon group which may have a substituent, at least one of R3, R6, is a hydrocarbon group 'R3' to R6, at least two of which may be bonded to each other to form a ring; Μ+ is an alkali metal ion]. In the formula, 'Rc, n, Y1, R3, R6', and Μ+ are the same as described above. The ammonium salt is, for example, the above-mentioned alkylamine, dialkylamine, trialkylamine, and hydrochloride or bromate of an aromatic amine. The reaction of the compound (1-13) with an ammonium salt can be carried out by the same method as the conventionally known salt substitution method. For example, the compound (1-13) and the ammonium salt are dissolved in a solvent such as water, dichloromethane, acetonitrile, methanol or chloroform, and the mixture is stirred or the like to carry out a reaction. The reaction temperature is preferably from 0 ° C to 1 5 (about TC, more preferably from 0 ° c to 1 0 ° ° C. The reaction time depends on the reaction of the compound (1-3) and the ammonium salt -43- 200947126 Or the reaction temperature may be different, and it is usually preferably 〇 5 to 1 〇 hours. It is preferably 1 to 5 hours. After the reaction is completed, the compound (1-14) in the reaction solution can be separated and refined. For the separation and purification, a conventionally known method can be used, and for example, any one of washing, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like can be used alone or in combination of two or more. In the invention, since the compound (1-14) has ruthenium + (R3') (R4') (R5') (R6') in the cation portion, since it is not easily dissolved in water, it can be purified by water washing. The structure of the compound (1 - 14) can be measured by 1 Η - nuclear magnetic resonance (NMR) spectroscopy, 13C - NMR spectroscopy, 19F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), It is confirmed by general organic analysis methods such as elemental analysis and X-ray crystal diffraction. Use of bO-1) As described above, the compound (b0-1) of the present invention is a novel compound which is a useful compound suitable as an acid generator for a photoresist composition, and is particularly suitable as a synthetic product. An intermediate of the third aspect of the invention (b 1 - 1 ). That is, the compound (bO-oxime) is substituted with a salt, and the cationic moiety of the compound (bO-1) (N+(R3) (R4) (R5) (R6)) An acid (sulfonic acid) can be produced by exposure with an appropriate cationic moiety, such as a compound obtained by substituting an organic cation such as a cerium ion or an iodine ion. The compound is suitable as a photoresist composition. Acid generator. -44 - 200947126 The compound (b0 _ 1 ) of the present invention is extremely suitable as an intermediate for producing a useful compound of the above salt-substituted acid generator. That is, the cation portion is N+ ( R3 ) ( R4 (R5) (R6), the compound is easily purified by washing with water, and it is expected to improve the purity of the final product. For example, when the cation portion is an alkali metal ion, when it is purified by washing with water, the compound is dissolved and is not easily refined. . A compound obtained by substituting a salt of the compound (b0-1) of the present invention, which can be used as an acid generator, and a photoresist composition obtained by adding the compound as an acid generator to a photoresist composition. It can improve its lithography etching characteristics, such as improving the resolution of the photoresist pattern, mask reproducibility (such as mask linearity, etc.) or exposure (EL) latitude, photoresist pattern shape, Focus depth of field (DOF), etc. EL latitude refers to the range of exposure amount that can form a resist pattern when the exposure is within a certain range with respect to the target size when the exposure is changed. That is, the exposure amount range and the EL latitude when the photoresist pattern of the faithful response mask pattern is obtained can be obtained, and the larger the number of 値, the smaller the amount of change in the pattern size caused by the variation of the exposure amount, It is better to improve the tolerance of the process. The reason why the above effects can be obtained is presumed to be as follows. Namely, the compound (b0-1) is a compound produced by substituting a salt, and the anion portion has a structure in which a skeleton of "Y1 - S03·" is bonded to Rx - Q3 - 0 - Q2-. Therefore, when compared with the conventional fluorinated alkylsulfonic acid ion used as an anion, it has a structure having a higher polarity and a high volume density of stericity. Because of its high polarity, it is presumed that it can be used by the inter-molecular interaction -45-200947126, or by the bulky three-dimensional structure, compared with the anion portion of a conventional acid generator such as nonafluorobutane sulfonate. The diffusion of the anion (acid) can be inhibited chemically or physically in the photoresist film. Therefore, it is possible to suppress the diffusion of the acid generated in the exposure region to the unexposed region, and as a result, the solubility in the unexposed region and the exposed region to the alkali developer can be improved (dissolution contrast), and thus it is presumed that the resolution or the light resistance can be improved. The shape of the pattern.

又，Y1之可具有取代基之伸烷基或可具有取代基之 氟化伸烷基之烷基鏈，例如相對於碳數6〜10之全氟烷基 Q 鏈具有難分解性，而顯示出良好之分解性，對於提升考慮 生物蓄積性之使用性上，可得到更好之效果。 本發明之化合物（b0 - 1 )作爲中間體所製造之，作 爲光阻組成物用之酸產生劑之有用化合物之一例示，例如 後述本發明之化合物（bl— 1)等。 《化合物（b 1 - 1 )》Further, an alkyl chain of a fluorinated alkyl group which may have a substituent or an alkyl group which may have a substituent, and, for example, a hardly decomposable one with respect to a perfluoroalkyl Q chain having a carbon number of 6 to 10, A good decomposability is obtained, and a better effect can be obtained for improving the usability of considering bioaccumulation. The compound (b0-1) of the present invention is produced as an intermediate, and is exemplified as one of useful compounds of the acid generator for a photoresist composition, for example, the compound (bl-1) of the present invention described later. Compound (b 1 - 1 )

其次，將對本發明之第三之態樣之化合物（b 1 - 1 ) Q 進行說明。化合物（bl-1)，爲適合作爲本發明之第一 之態樣之光阻組成物之酸產生劑使用之化合物。 式（bl — 1 )中，Rx、Y1、Q2及Q3分別爲前述通式 (b0 — 1 )中之Rx、Y1、Q2及Q3爲相同之內容。 Z+之有機陽離子，只要爲前述通式（w- 1)所表示 之離子以外時，則無特別之限制，其可適當使用以往作爲 鑰鹽系酸產生劑之陽離子部的已知陽離子。該陽離子部中 ，又以Z+之有機陽離子爲锍離子或碘鑰離子爲佳，特別 -46- 200947126 是以锍離子爲佳。 具體而言，例如’其可使適當使用下述通式（b’一1 )、(b5 - 2 ) 、（b— 5)或（b — 6)所表示之陽離子部 【化2 4】 R2·二辛 + …(b，-1) 〉+ .音2) © R3&quot; R6.· 〔式中，R1，’〜R3”、R5”〜R6”，各自獨立表示芳基或 烷基；尺1”〜！^3”中，任意2個可相互鍵結並與式中之硫原 子共同形成環亦可；R1”〜R3”中至少1個爲芳基’ r5〜 R6’’中至少1個爲芳基〕。Next, the compound (b 1 - 1 ) Q of the third aspect of the present invention will be described. The compound (bl-1) is a compound which is suitable for use as an acid generator of the photoresist composition of the first aspect of the invention. In the formula (bl-1), Rx, Y1, Q2 and Q3 are the same contents of Rx, Y1, Q2 and Q3 in the above formula (b0-1). The organic cation of Z+ is not particularly limited as long as it is other than the ion represented by the above formula (w-1), and a known cation which is a cationic portion of a conventional key acid generator can be suitably used. In the cation portion, the organic cation of Z+ is preferably ruthenium ion or iodine ion, and particularly -46-200947126 is preferably ruthenium ion. Specifically, for example, 'the cation portion represented by the following general formula (b'-1), (b5-2), (b-5) or (b-6) can be suitably used. ·二辛+ ...(b,-1) 〉+.2) © R3&quot; R6.· [wherein, R1, '~R3", R5"~R6", each independently represents an aryl group or an alkyl group; 1"~! In ^3", any two of them may be bonded to each other and form a ring together with a sulfur atom in the formula; at least one of R1" to R3" is an aryl group, and at least one of R5 to R6'' is an aryl group. ].

【化2 5][Chem. 2 5]

〔式中，r4〇爲氫原子或烷基，R41爲烷基、乙酸基 、羧基，磲羥烷基，R42〜r46爲各自獨立之烷基、乙醯基 、烷氧基、羧基，或羥烷基；n〇〜ns爲各自獨立之〇〜3 之整數、但，nQ+ni爲5以下，n6爲0〜2之整數〕。 -47- 200947126 式（b'— 1)中’ R1’’〜R3’’爲各自獨立之芳基或烷基。 R1”〜R3”中，任意2個可相互鍵結並與式中之硫原子共同 形成環亦可。 又，Ri”〜R3”中’至少1個爲芳基。R1”〜R3”中以2 個以上爲芳基爲佳，又以R1’’〜R3’’全部爲芳基者爲最佳。 R1”〜R3’’之芳基，並未有特別限制，例如爲碳數6〜 20之無取代之芳基，且該無取代之芳基之氫原子的一部 份或全部可被烷基、烷氧基 '烷氧基烷基氧基、烷氧基羰 烷基氧基、鹵素原子、羥基等所取代之取代芳基、-（ R4') — C( = 0)— R5’等。R4’爲碳數1〜5之伸烷基。RS爲 芳基。R5’之芳基，例如與前述R1&quot;〜R3&quot;之芳基爲相同之 內容。 無取代之芳基，就可廉價合成等觀點，以使用碳數6 〜1〇之芳基爲佳。具體而言，例如苯基、萘基等。 取代芳基中之烷基，以碳數1〜5之烷基爲佳，又以 甲基、乙基、丙基、n_ 丁基、tert — 丁基爲最佳。 取代芳基中之烷氧基，以碳數1〜5之烷氧基爲佳， 又以甲氧基、乙氧基、η —丙氧基、iso —丙氧基、η— 丁 氧基、tert— 丁氧基爲最佳。 取代芳基中之鹵素原子，以氟原子爲佳。 取代芳基中之烷氧烷基氧基，例如，通式：一 〇一 C(R47)(R48)— 0—R49〔式中，R47、R48爲各自獨立之氫原 子或直鏈狀或支鏈狀之烷基’ R49爲烷基〕所表示之基。 R47、R48中’烷基之碳數較佳爲1〜5，其可爲直鏈 200947126 狀、支鏈狀中任一者皆可，以乙基、甲基爲佳，以甲基爲 最佳。 R47、R48，以至少一者爲氫原子爲佳。特別是以一方 爲氫原子，另一方爲氫原子或甲基爲更佳。 R49之烷基，較佳爲碳數1〜15，其可爲直鏈狀、支 鏈狀或環狀中任一者皆可。 R49中之直鏈狀、支鏈狀之烷基，以碳數爲1〜5者爲 0 爲佳，例如，甲基、乙基、丙基、η — 丁基、tert — 丁基等 〇 R49中之環狀之烷基，以碳數4〜15爲佳，以碳數4 〜12爲更佳，以碳數5〜10爲最佳。具體而言，其爲可 被碳數1〜5之烷基、氟原子或氟化烷基所取代，或未被 取代亦可之單環鏈烷、二環鏈烷、三環鏈烷、四環鏈烷等 多環鏈烷去除1個以上之氫原子之基等。單環鏈烷，例如 環戊烷、環己烷等。多環鏈烷，例如金剛烷、降冰片烷、 Q 異冰片烷、三環癸烷、四環十二烷等。其中又以金剛烷去 除1個以上之氫原子之基爲佳。 取代芳基中之烷氧羰基烷基氧基，例如，通式：_〇 —R5° — C( = 0)— 0 — R51〔式中，R50爲直鏈狀或支鏈狀之 伸烷基，R51爲三級烷基〕所表示之基。 R5C)中之直鏈狀、支鏈狀之伸烷基，以碳數爲1〜5者 爲爲佳，例如，伸甲基、伸乙基、三伸甲基、四伸甲基、 1，1—二甲基伸乙基等。 R51中之二級院基，爲2—甲基—2_金剛院基、2 — -49- 200947126 乙基—2—金剛烷基、1 一甲基—1—環戊基、1 一乙基一 1 一環戊基、1—甲基一1—環己基、1 一乙基—1—環己基、 1— (1—金剛院基）—1—甲基乙基、1一 ( 1 —金剛院基 )—1 一甲基丙基、1— (1 一金剛烷基）-1—甲基丁基、 1- (1 一金剛烷基）—1一甲基戊基；1— (1—環戊基） 一 1—甲基乙基、1_ (1一環戊基）一1—甲基丙基、1一 (1—環戊基）—1_甲基丁基、1一（1 一環戊基）一 1 — 甲基戊基；1一 （1—環己基）一1—甲基乙基、1一（1— © 環己基）一 1一甲基丙基、1- (1—環己基）—1一甲基丁 基、1— (1—環己基）一1 一甲基戊基、tert— 丁基、tert 一戊基、tert —己基等。 R1”〜R3”之芳基，以分別表示苯基或萘基爲佳。 r 1 ”〜R3&quot;之烷基，並未有特別限制，例如碳數1〜1 0 之直鏈狀、支鏈狀或環狀之烷基等。就具有優良解析性等 觀點，以碳數1〜5爲佳。具體而言，例如甲基、乙基、n 一丙基、異丙基、η—丁基、異丁基、n_戊基、環戊基、 © 己基、環己基、壬基、癸基等，其中，就具有優良解析性 ，或可廉價合成等觀點，可列舉甲基等。 R1，，〜R3，，中，任意2個可相互鍵結並與式中之硫原子 共同形成環之情形，以包含硫原子形成3〜1〇貢環爲彳圭’ 又以形成5〜7員環爲更佳。 R1&quot;〜R3，，中，任意2個相互鍵結並與式中之硫原子共 同形成環之情形，殘餘之1個，以芳基爲佳。前述芳基’ 與前述R1&quot;〜R3&quot;之芳基爲相同之內容。 -50- 200947126 式（b，- 1)所表示之陽離子部的具體之例示如’三 苯基毓、（3,5-二甲基苯基）一苯基鏑、（4— (2_金 剛院氧基甲基氧基）一3,5-二甲基苯基）二苯基锍、（4 一（2 —金剛烷氧基甲基氧基）苯基）二苯基鏑、（4—( tert- 丁氧羰甲基氧基）苯基）二苯基銃、（4— (tert — 丁氧羰甲基氧基）一 3,5 —二甲基苯基）二苯基毓、（4 一 (2—甲基_2_金剛烷基氧代羰基甲基氧基）苯基）二苯 〇 基鏑、（4— (2 -甲基一2 —金剛烷基氧代羰基甲基氧基 )—3,5—二甲基苯基）二苯基锍、三（4 一甲基苯基）锍 、二甲基（4 —羥基萘基）锍、單苯基二甲基锍、二苯基 單甲基鏑、（4 一甲基苯基）二苯基銃、（4 一甲氧基苯基 )二苯基銃、三（4 — tert-丁基）苯基銃、二苯基（1 一 (4 —甲氧基）萘基）鏑、二（1_萘基）苯基鏡、1—苯 基四氫噻吩鑰、1 一（4 一甲基苯基）四氫噻吩鑰、1_ ( 3，5 —二甲基_4 —羥基苯基）四氫噻吩鎗、1— (4 一甲氧 〇 基萘一丨―基）四氫噻吩鑰、1 一（4 一乙氧基萘—1一基） 四氫噻吩鑷、1— (4 一 η— 丁氧萘一 1 一基）四氫噻吩鎗、 1—苯基四氫噻喃鎗、1_ (4 一羥基苯基）四氫噻喃鎗、1 一（3,5 —二甲基_4 一羥基苯基）四氫噻喃鎗、(4 一 甲基苯基）四氫噻喃鎗等。 式（b'— 2)中，R5&quot;及R6&quot;爲各自獨立之芳基或烷基 。R5&quot;及R6&quot;中，至少1個表示芳基。又以R5&quot;及R6”二者 爲方基者爲佳。 R5&quot;及R6”之芳基係與R1”〜R3&quot;之芳基爲相同之內容 -51 - 200947126 R5&quot;及R6”之烷基係與R1”〜R3”之烷基爲相同之內容 〇 其中，又以R5”及R6&quot;二者同時爲苯基爲最佳。 式（b'- 2)所表示之陽離子部之具體之例示如，二 苯基碘鍚、雙（4 — tert - 丁基苯基）碘鎗等。 通式（b— 5)及（b— 6)之R4°〜R46中’烷基以碳 數1〜5之烷基爲佳，其中又以直鏈或支鏈狀之烷基爲更 0 佳，以甲基、乙基、丙基、異丙基、η - 丁基，或tert — 丁基爲最佳。 烷氧基，以碳數1〜5之烷氧基爲佳’其中又以直鏈 或支鏈狀之烷氧基爲更佳，以甲氧基、乙氧基爲最佳。 羥烷基，以上述烷基中之一個或複數個氫原子被羥基 所取代之基爲佳，例如羥甲基、羥乙基、羥丙基等。 附於OR4()之符號nG爲2以上之整數之情形’複數之 OR40”分別爲相同或相異皆可。 〇 附於RU〜R46之符號ηι〜IU爲2以上之整數之情形 ’複數之R41〜R46分別爲相同或相異皆可。 n〇，較佳爲0或1。 n i，較佳爲0〜2。 n2及n3’較佳爲各自獨立之0或丨’更佳爲0。 n4，較佳爲0〜2，更佳爲〇或卜 n5，較佳爲0或1，更佳爲0 ° n6，較佳爲〇或1。 -52- 200947126 Z+，以式（b· — 1 )或（b — 5 )所表示之陽離子部爲 佳，特別是以下述式（b，~l— i)〜（b'—l—l〇) 、（b 一 5 - 1)〜（b— 5 — 4)所表示之陽離子部爲佳，以式（ b，一 1— 1)〜（^一1_8)所表示之陽離子部等三苯基骨 架之陽離子部，或（b'— 1- 1〇)所表示之陽離子部爲更 佳。 式（b，一 1 一 9)〜（b’一 1— 10)中，R8、R9 爲各自 獨立之可具有取代基之苯基、萘基或碳數1〜5之烷基、 院氧基，或經基°較丨圭爲可具有&quot;取代基之·苯基° 11爲1〜3之整數’以1或2爲最佳。 〇 -53- 200947126Wherein r4 is a hydrogen atom or an alkyl group, R41 is an alkyl group, an acetoxy group, a carboxyl group, a hydroxyalkyl group, and R42 to r46 are each independently an alkyl group, an ethyl group, an alkoxy group, a carboxyl group, or a hydroxy group. The alkyl group; n 〇 ns are integers of 〇 3 3, respectively, but nQ+ni is 5 or less, and n6 is an integer of 0 to 2). -47- 200947126 In the formula (b'-1), 'R1'' to R3'' are each independently an aryl group or an alkyl group. In R1" to R3", any two of them may be bonded to each other and may form a ring together with a sulfur atom in the formula. Further, at least one of Ri" to R3" is an aryl group. It is preferable that two or more of R1" to R3" are aryl groups, and all of R1'' to R3'' are aryl groups. The aryl group of R1" to R3'' is not particularly limited, and is, for example, an unsubstituted aryl group having 6 to 20 carbon atoms, and a part or all of the hydrogen atom of the unsubstituted aryl group may be alkyl group. a substituted aryl group substituted with an alkoxy 'alkoxyalkyloxy group, an alkoxycarbonylalkyloxy group, a halogen atom, a hydroxyl group or the like, -( R4') - C(=0)-R5', and the like. R4' is an alkylene group having a carbon number of 1 to 5. RS is an aryl group. The aryl group of R5' is, for example, the same as the above-mentioned aryl group of R1&quot;~R3&quot;. Unsubstituted aryl group can be synthesized inexpensively. From the viewpoint of using an aryl group having a carbon number of 6 to 1 Å, specifically, for example, a phenyl group, a naphthyl group, etc. The alkyl group in the substituted aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and Methyl, ethyl, propyl, n-butyl, tert-butyl is preferred. The alkoxy group in the substituted aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group. Ethoxy, η-propoxy, iso-propoxy, η-butoxy, tert-butoxy are preferred. The halogen atom in the substituted aryl group is preferably a fluorine atom. Alkoxyalkyloxy group, For example, the formula: mono-C (R47) (R48) - 0 - R49 [wherein, R47, R48 are each independently a hydrogen atom or a linear or branched alkyl group 'R49 is an alkyl group" In the case of R47 and R48, the carbon number of the 'alkyl group is preferably from 1 to 5, which may be any of a linear chain of 200947126 and a branched chain, preferably an ethyl group or a methyl group. Preferably, R47 and R48 are at least one hydrogen atom, and particularly preferably one is a hydrogen atom and the other is a hydrogen atom or a methyl group. The alkyl group of R49 is preferably a carbon number of 1. ～15, which may be linear, branched or cyclic. The linear or branched alkyl group in R49 preferably has a carbon number of 1 to 5, preferably 0. For example, a methyl group, a methyl group, an ethyl group, a propyl group, a η-butyl group, a tert-butyl group, or the like, a cyclic alkyl group in the group R49, preferably having a carbon number of 4 to 15 and a carbon number of 4 to 12, more preferably It is most preferably a carbon number of 5 to 10. Specifically, it is a monocyclic alkane which may be substituted by an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, or may be unsubstituted. Polycyclic alkanes such as cycloalkanes, tricycloalkanes, tetracycloalkanes, etc. a group of one or more hydrogen atoms, etc. Monocyclic alkane, such as cyclopentane, cyclohexane, etc. Polycyclic alkane, such as adamantane, norbornane, Q isobornane, tricyclodecane, tetra Cyclododecane, etc., wherein a group in which one or more hydrogen atoms are removed by adamantane is preferred. The alkoxycarbonylalkyloxy group in the substituted aryl group, for example, the formula: _〇-R5° - C( = 0) — 0 — R51 (wherein R50 is a linear or branched alkyl group, and R51 is a tertiary alkyl group). The linear or branched alkylene in R5C) The base is preferably one having a carbon number of from 1 to 5, for example, a methyl group, an ethyl group, a methyl group, a methyl group, a methyl group, a 1,1-dimethyl group and the like. The second-grade courtyard base in R51 is 2-methyl- 2_金刚院基, 2 — 49- 200947126 ethyl-2-adamantyl, 1-methyl-1-cyclopentyl, 1-ethyl 1-1 cyclopentyl, 1-methyl- 1 -cyclohexyl, 1-ethyl-1-cyclohexyl, 1-(1-golden base)-1-methylethyl, 1 (1 - King Kong Institute Base)-1 monomethylpropyl, 1-(1-adamantyl)-1-methylbutyl, 1-(1-adamantyl)-l-methylpentyl; 1—(1-ring Butyl) 1-methylethyl, 1-(1-cyclopentyl)-1-methylpropyl, 1-(1-cyclopentyl)-1-methylbutyl, 1-mono(1-cyclopentyl) ) 1-methyl-pentyl; 1-(1-cyclohexyl)-1-methylethyl, 1-(1--cyclohexyl)-l-methylpropyl, 1-(1-cyclohexyl) 1-monomethylbutyl, 1-(1-cyclohexyl)-1-methylpentyl, tert-butyl, tert-pentyl, tert-hexyl, and the like. The aryl group of R1" to R3" preferably represents a phenyl group or a naphthyl group, respectively. The alkyl group of r 1 " to R3" is not particularly limited, and is, for example, a linear, branched or cyclic alkyl group having a carbon number of 1 to 10, etc., and has excellent resolution and the like, and has a carbon number. 1 to 5 is preferred. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, n-pentyl, cyclopentyl, hexyl, cyclohexyl, Examples of the sulfhydryl group, the fluorenyl group, and the like, which have excellent analytical properties or can be inexpensively synthesized, etc., may be exemplified by a methyl group, etc. R1,, R3, or any of the two may be bonded to each other and to the sulfur in the formula. In the case where atoms form a ring together, a sulfur atom is formed to form a 3~1 〇 gong ring for the 彳 ' ' and it is better to form a 5~7 member ring. R1&quot;~R3,,,,,,,,,,,,,, Where the sulfur atoms in the formula together form a ring, the remaining one is preferably an aryl group. The above aryl group is the same as the above-mentioned R1&quot;~R3&quot; aryl group. -50- 200947126 Formula (b,- 1) Specific examples of the cationic moiety represented by 'triphenylphosphonium, (3,5-dimethylphenyl)-phenylindole, (4-(2_金刚院oxymethyloxy) a 3,5-dimethylphenyl)diphenylphosphonium, (4-(2-adamantyloxymethyloxy)phenyl)diphenylphosphonium, (4-(tert-butoxycarbonyl) (1,2-(2-methyl) _2_adamantyloxycarbonylmethyloxy)phenyl)diphenylfluorenyl hydrazide, (4-(2-methyl-2-hydroxyadalkyloxycarbonylmethyloxy)-3,5- Dimethylphenyl)diphenylphosphonium, tris(4-methylphenyl)anthracene, dimethyl(4-hydroxynaphthyl)anthracene, monophenyldimethylhydrazine, diphenylmonomethylhydrazine, (4-methylphenyl)diphenylphosphonium, (4-methoxyphenyl)diphenylphosphonium, tris(4-tert-butyl)phenylhydrazine, diphenyl (1 -4 -A Oxy)naphthyl)anthracene, bis(1-naphthyl)phenyl mirror, 1-phenyltetrahydrothiophene, 1 -(4-methylphenyl)tetrahydrothiophene, 1_ (3,5 - 2 Methyl 4-(hydroxyphenyl) tetrahydrothiophene gun, 1-(4-methoxyindolylnaphthalene-yl)tetrahydrothiophene, 1 (4-ethoxynaphthalene) 1-yl) tetrahydrothiophene oxime, 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophene gun, 1-phenyltetrahydrothiophene gun, 1-(4-hydroxyphenyl)tetrahydrothiophene a gun, a mono-(3,5-dimethyl-4-tetrahydroxyphenyl)tetrahydrothiophene gun, a (4-methylphenyl) tetrahydrothiophene gun, etc. In the formula (b'-2), R5&quot; and R6&quot; are independent aryl or alkyl groups. At least one of R5&quot; and R6&quot; represents an aryl group. R5&quot; and R6" are preferred. The aryl group of R5&quot; and R6" is the same as the aryl group of R1"~R3&quot; -51 - 200947126 R5&quot; and the alkyl group of R6" are the same as the alkyl group of R1"~R3" R5" and R6&quot; both are the best for phenyl. Specific examples of the cationic moiety represented by the formula (b'-2) include a diphenyliodonium, a bis(4-tert-butylphenyl) iodine gun, and the like. In the formulae (b-5) and (b-6), in the R4° to R46, the 'alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a linear or branched alkyl group. It is preferably methyl, ethyl, propyl, isopropyl, η-butyl or tert-butyl. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms. Further, a linear or branched alkoxy group is more preferable, and a methoxy group and an ethoxy group are most preferred. The hydroxyalkyl group is preferably a group in which one of the above alkyl groups or a plurality of hydrogen atoms is substituted by a hydroxyl group, such as a methylol group, a hydroxyethyl group, a hydroxypropyl group or the like. The case where the symbol nG attached to OR4() is an integer of 2 or more 'OR40' of the plural number is the same or different. 〇 The symbol ηι~IU attached to RU to R46 is an integer of 2 or more 'plural number R41 to R46 are respectively the same or different. n〇, preferably 0 or 1. ni, preferably 0 to 2. n2 and n3' are preferably each independently 0 or 丨' more preferably 0. N4, preferably 0 to 2, more preferably 〇 or 卜 n5, preferably 0 or 1, more preferably 0 ° n6, preferably 〇 or 1. -52- 200947126 Z+, by formula (b· The cation moiety represented by 1) or (b-5) is preferred, particularly in the following formulas (b, -l-i)~(b'-l-l〇), (b-5-1)~(b) — 5 — 4) The cation moiety represented by the formula is a cation moiety such as a cation moiety represented by the formula (b, 1-1) to (^1_8), or (b' 1- The cation moiety represented by 1 〇) is more preferably. In the formula (b, 1-1-9)~(b'1-10), R8 and R9 are each independently a phenyl group, a naphthyl group which may have a substituent or The alkyl group having a carbon number of 1 to 5, the epoxy group, or the base group may have a &quot; The base of the phenyl group 11 is an integer of 1 to 3', preferably 1 or 2. 〇 -53- 200947126

-54- 200947126-54- 200947126

【化2 7】[化 2 7]

化合物（bl-1)，以下述通式（bl — 之化合物爲佳。 【化2 8】 Ο Ο rX—C—Ο—Ri—Ο—C——S〇3 2 …(bi-1-.1) 〔式中，Rx、Y1及Z +分別與前述通式 Rx、Y1及Z+爲相同之內容；R1爲伸烷基〕 前述通式（bl— 1— 1)中，Rx、Y1及 通式（bl— 1)中之RlY1及Z+爲相同之P R1之伸烷基，可爲直鏈狀、支鏈狀、 皆可，又以直鏈狀或支鏈狀爲佳，以直鏈狀 直鏈狀或支鏈狀之伸烷基的碳數，以1 1〜5爲更佳，以1〜3爲最佳。該伸垸基’ 1 一 1 )所表示 (bl — 1 )中之 〇 Z+分別與前述 J容。 環狀中任一者 爲更佳。 〜1 2爲佳’以 具體而言，例 -55- 200947126 如，伸甲基〔一ch2—〕 ； - ch(ch3) —、一 ch(ch2ch3) -、一c(ch3)2-、一c(ch3)(ch2ch3)-、 —C(CH3)(CH2CH2CH3)—、— C(CH2CH3)2 —等之院基伸甲 基；伸乙基〔一 CH2CH2—〕； 一 CH(CH3)CH2-、 -ch(ch3)ch(ch3)—、一c(ch3)2ch2—' -CH(CH2CH3)CH2-等之烷基伸乙基；三伸甲基（η—伸 丙基）〔—CH2CH2CH2—〕； - CH(CH3)CH2CH2 - ' 一 CH2CH(CH3)CH2-等之烷基三伸甲基；四伸甲基〔 一 CH2CH2CH2CH2 -〕； 一 CH(CH3)CH2CH2CH2 —、 一 CH2CH(CH3)CH2CH2-等之烷基四伸甲基；五伸甲基〔 -CH2CH2CH2CH2CH2 —〕等。該些之中，又以伸甲基、 伸乙基或η -伸丙基爲佳，特別是以伸乙基爲佳。 化合物（bl-Ι)，特別是以下述通式（bl — 1— 11) 〜（bl— 1— 13)所表示之化合物爲佳。 【化2 9】The compound (bl-1) is preferably a compound of the following formula (bl). [Chem. 2 8] Ο Ο rX-C-Ο-Ri-Ο-C-S〇3 2 ... (bi-1-. 1) wherein Rx, Y1 and Z + are the same as the above-mentioned general formulas Rx, Y1 and Z+; R1 is an alkylene group; in the above formula (bl-1 to 1), Rx, Y1 and RlY1 and Z+ in the formula (bl-1) are the same alkylene group of P R1 , and may be linear or branched, and may be linear or branched, preferably in a linear form. The carbon number of the linear or branched alkyl group is preferably from 1 to 5, more preferably from 1 to 3. The exoskelein '1 to 1) is represented by (bl - 1) 〇Z+ is respectively associated with the aforementioned J. Any of the rings is preferred. ~1 2 is better 'specifically, example -55- 200947126, for example, stretch methyl (a ch2 -); - ch (ch3) -, a ch (ch2ch3) -, a c (ch3) 2-, one C(ch3)(ch2ch3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc., a pendant methyl group; an ethyl group [CH2CH2—]; a CH(CH3)CH2-, -ch(ch3)ch(ch3)-, a c(ch3)2ch2-'-CH(CH2CH3)CH2-, etc. alkyl-extended ethyl; tri-methyl(η-propyl)[-CH2CH2CH2-—; - CH(CH3)CH2CH2 - 'A CH2CH(CH3)CH2-, etc. alkyl tri-methyl; tetramethyl [CH2CH2CH2CH2 -]; a CH(CH3)CH2CH2CH2 -, a CH2CH(CH3)CH2CH2-, etc. The alkyl tetramethyl group; the pentamethyl group [-CH2CH2CH2CH2CH2-], and the like. Among them, methyl, ethyl or η-propyl groups are preferred, and ethyl is particularly preferred. The compound (bl-Ι) is particularly preferably a compound represented by the following formula (bl - 1 - 11) - (bl - 1 - 13). [化2 9]

Ο 〇II II C—0-(CH2〉q「0-C—(CF2)rS03 z+Ο 〇 II II C—0-(CH2>q “0-C—(CF2)rS03 z+

(bl -1 -11) Ο Ο II \\ _ ^29+1¾ C Ο ~*(CH2)q2~Ο一C-(CF2)p~S〇3 Ζ+(bl -1 -11) Ο Ο II \\ _ ^29+13⁄4 C Ο ~*(CH2)q2~Ο一C-(CF2)p~S〇3 Ζ+

-(bl-1 -12) ·· (bl — 1 — 1 3) 〔式中，Z +係與前述爲相同之內容，p爲1〜3之整 數’ ql〜q3分別爲獨立之1〜12之整數，rl爲〇〜3之整 -56- 200947126 數，g爲1〜20之整數，R7爲取代基〕。 R7之取代基，係與前述Rx中，可具有脂肪族烴基之 取代基所列舉者爲相同之內容。 附於R7之符號（r 1 )爲2以上之整數之情形，當該 化合物中之複數之R7分別可爲相同或相異皆可。 P以1或2爲佳。 ql〜q3分別爲獨立之1〜5者爲佳，又以1〜3者爲 ❹ 更佳。 rl以0〜2之整數者爲佳，又以0或1者爲更佳。 g以1〜1 5者爲佳，又以1〜1 0者爲更佳。 本發明之化合物（bl-l)爲新穎化合物。 本發明之化合物（bl-Ι)，適合作爲化學增幅型光 阻組成物用之酸產生劑，而可作爲添加於化學增幅型光阻 組成物之酸產生劑使用。 本發明之化合物（b 1 - 1 )之製造方法並未有特別限 〇 定，例如可以後述本發明之化合物（b 1 - 1)之製造方法 進行製造。 《化合物（b 1 — 1 )之製造方法》 其次，將對本發明之第四之態樣之化合物（bl - 1) 之製造方法進行說明。 本發明之第四之態樣之化合物（b 1 - 1 )之製造方法 ’爲包含使下述通式（bO—l)所表示之化合物（b0— 1) ，與下述通式（bO— 02)所表示之化合物（bO— 02)反應 -57- 200947126 而製得化合物（bl— 1)之步驟。 【化3 0】-(bl-1 -12) ·· (bl - 1 - 1 3) [wherein, Z + is the same as the above, p is an integer of 1 to 3 'ql~q3 are independent 1~12 The integer, rl is 〇~3 of the whole -56-200947126 number, g is an integer from 1 to 20, and R7 is a substituent]. The substituent of R7 is the same as those exemplified as the substituent which may have an aliphatic hydrocarbon group in the above Rx. In the case where the symbol (r 1 ) attached to R7 is an integer of 2 or more, the plural R7 in the compound may be the same or different, respectively. P is preferably 1 or 2. It is better that ql~q3 are independent 1~5, and 1~3 is better. It is preferable that rl is an integer of 0 to 2, and 0 or 1 is more preferable. g is preferably 1 to 1 5, and more preferably 1 to 1 0. The compound (bl-1) of the present invention is a novel compound. The compound (bl-Ι) of the present invention is suitably used as an acid generator for a chemically amplified resist composition, and can be used as an acid generator added to a chemically amplified resist composition. The method for producing the compound (b 1 - 1 ) of the present invention is not particularly limited, and for example, it can be produced by a method for producing the compound (b 1 - 1) of the present invention described later. <<Method for Producing Compound (b 1-1)>> Next, a method for producing the compound (bl-1) of the fourth aspect of the present invention will be described. The method for producing the compound (b 1 - 1 ) of the fourth aspect of the present invention is a compound (b0-1) represented by the following formula (bO-1), and the following formula (bO- 02) The compound (b02) is represented by the reaction -57-200947126 to obtain the compound (bl-1). [化3 0]

Rx—。3—Ο—Q2—V1一S03 W+ …奴卜” 2 A …滅Rx—. 3—Ο—Q2—V1—S03 W+ ... slaves” 2 A ...

Rx—Q3—Ο—Q2—Y1一S〇s 2h .'個―ηRx—Q3—Ο—Q2—Y1—S〇s 2h .’

〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立爲單鍵或2價之鍵結基；γ1爲碳 數1〜4之伸烷基或氟化伸烷基；W+爲鹼金屬離子或下述 通式（w- 1.)所表示之離子；Z+爲有機陽離子（但下述 通式（w—l)所表示之離子除外）；A·爲非親核性陰離子 ]° 【化3 1】Wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 are each a single bond or a divalent bond group; γ1 is an alkyl group having 1 to 4 carbon atoms or fluorinated An alkyl group; W+ is an alkali metal ion or an ion represented by the following formula (w-1); Z+ is an organic cation (except for the ion represented by the following formula (w-1); Non-nucleophilic anion]° [Chemical 3 1]

(W—1)(W-1)

〔式中，R3〜R6分別爲獨立之氫原子，或可具有取 代基之烴基’ R3〜R6中之至少1個爲前述烴基，R3〜R6 中之至少2個可分別鍵結形成環亦可〕。 式中，Rx、Q2、Q3、γ1、z+分別爲與前述通式（Μ —1 )中之Rx、Q2、Q3、Υ1、Z+爲相同之內容。 W+爲鹼金屬離子或前述通式（w_i)所表示之離子 (以下’亦稱爲取代銨離子）。 W+中’鹼金屬離子例如鈉離子、鉀離子、鋰離子等 -58- 200947126 式（w— 1 )中，R3〜R6分別爲與前述通 中之R3〜R6爲相同之內容。 A_爲非親核性陰離子。 該非親核性離子，例如溴離子、氯離子_ 、可得到酸性度低於化合物（b 0 — 1 )之酸二 、AsF6·、SbF6_、PF6·或 CI04·等。 Ο 中之酸性度低於化合物（b〇 — 1 )之捏 如p—甲苯磺酸離子、甲烷磺酸離子、苯磺画 甲烷磺酸離子等之磺酸離子。 本發明之第四之態樣之化合物（b 1 - 1 ) 中，以化合物（b0 - 1)爲下述通式（b0— 0 化合物（b0—01)，化合物（bl— 1)爲下述 一 1)所表示之化合物（bl—1_1)爲最佳。 【化3 2】 © f f[wherein R3 to R6 are each independently a hydrogen atom, or a hydrocarbon group which may have a substituent: at least one of R3 to R6 is the hydrocarbon group, and at least two of R3 to R6 may be bonded to form a ring, respectively. ]. In the formula, Rx, Q2, Q3, γ1, and z+ are the same as those of Rx, Q2, Q3, Υ1, and Z+ in the above formula (Μ-1). W+ is an alkali metal ion or an ion represented by the above formula (w_i) (hereinafter referred to as a substituted ammonium ion). In the W+ medium, an alkali metal ion such as a sodium ion, a potassium ion, a lithium ion or the like -58- 200947126 In the formula (w-1), R3 to R6 are the same as those in the above-mentioned R3 to R6. A_ is a non-nucleophilic anion. The non-nucleophilic ion, such as bromide ion or chloride ion, can give acidity II, AsF6·, SbF6_, PF6· or CI04· having a lower acidity than the compound (b 0-1). The acidity in Ο is lower than that of the compound (b〇-1) such as p-toluenesulfonate, methanesulfonate, benzenesulfonate, methanesulfonate or the like. In the compound (b 1 - 1 ) of the fourth aspect of the present invention, the compound (b0-1) is a compound of the following formula (b0-0 compound (b0-01), and the compound (bl-1) is as follows The compound (bl-1_1) represented by a 1) is optimal. [化3 2] © f f

Rx-—C一〇一R1-—〇—CY1—S03 W …(b0_0” 〇一R1—。一C—Y1 — so3 Z+ …(b1_ 卜 Ί) 〔式中，Rx、Υ1及W +與前述通式（b0_ 、Y1及W +爲相同之內容；Rb與rX爲相同二 前述通式（bl— 1)中之Z +爲相同之內容·’ R (b0— 1— 11)中之R1爲相同之內容〕。 前述化合物（b〇 - 01) ’例如’可使下δ 式（b 0 — 1 ) I之鹵素離子 匕離子、bf4· ?之離子，例 隻離子、三氟 之製造方法 1 )所表示；^ 通式（bl \ iRx-—C—〇 R1-—〇—CY1—S03 W ((b0_0” 〇一 R1—.1—C—Y1 — so3 Z+ ((b1_ 卜Ί) [wherein, Rx, Υ1, and W+ are as described above The general formulas (b0_, Y1, and W+ are the same; Rb and rX are the same; Z + in the above formula (bl-1) is the same content. R1 in R (b0-11-11) is The same thing]. The above compound (b〇-01) 'for example, can make the lower δ formula (b 0 - 1 ) I halogen ion 匕 ion, bf4 · ion, for example, only ion, trifluoro production method 1 Said; ^ general formula (bl \ i

1 )中之 內容；z+與 與前述通式 通式（1 \ 3 -59- 200947126 )所表示之化合物（1 一 3) ’與下述通式（2—D所表示 之化合物（2— 1)反應予以合成。 【化3 3】 Ο 4 II _ +1) content; z+ and the compound represented by the above formula (1 \ 3 -59- 200947126 ) (1 - 3) ' and the compound represented by the following formula (2 - D (2 - 1) The reaction is synthesized. [Chemical 3 3] Ο 4 II _ +

HO—R1-〇—C—Y1—S〇3 W+ …(卜 〇 3) χ IIHO—R1-〇—C—Y1—S〇3 W+ ...(卜 〇 3) χ II

Rx—C—X22 ...(2—1) 〔式中，Rx、Ri、Y1、W+分別爲前述爲相同之內容 ，χ22爲鹵素原子〕。 Θ 又22之_素原子’例如溴原子、氯原子'碘原子、氟 原子等’就具有優良反應性等觀點，以溴原子或氯原子爲 佳，以氣原子爲最佳。 化合物（1 一 3 )、（ 2 — 1 )可分別使用市售之化合物 ，或合成者亦可。 例如化合物（1 一 3 )中之W+爲鹼金屬離子之情形， 該化合物（下述通式（1 一 3’）所表示之化合物（1_3，） )之較佳合成方法，例如包含使下述通式（丨一1)所表示 屬 之化合物（1一 1)，與下述通式（丨一 2)所表示之化合物 (1 — 2 )反應以製得化合物（丨一 3，）之步驟之方法等。 【化3 4】 HO—R1—〇—R2 …（1 —，) Ο HO—Rx - C - X22 (2 - 1) wherein Rx, Ri, Y1, and W+ are the same as described above, and χ22 is a halogen atom. Further, a sulfonium atom or a chlorine atom is preferred, and a gas atom is preferred. As the compound (1 - 3 ) or ( 2 - 1 ), a commercially available compound may be used, or a synthesizer may be used. For example, in the case where the W+ in the compound (1 - 3 ) is an alkali metal ion, a preferred synthesis method of the compound (the compound (1 - 3,)) represented by the following formula (1 - 3') includes, for example, the following A step of reacting a compound (1-1) represented by the formula (丨-1) with a compound (1-2) represented by the following formula (丨2) to obtain a compound (丨-1) Method and so on. [化3 4] HO—R1—〇—R2 ...(1 —,) Ο HO—

…（1 —2) HO—R1-〇—C—Y1—s〇~ Μ+ ...(τ-3·) 爲可 〔式中’ R1、Y1分別爲前述爲相同之內容，R2 -60- 200947126 具有芳香族基爲取代基之脂肪族基，M +爲鹼金屬離子〕 〇 M+，係與前述W +所列舉之鹼金屬離子爲相同之內容 〇 R2爲可具有作爲取代基之芳香族基的脂肪族基。 該脂肪族基，可爲飽和脂肪族基或不飽和脂肪族基皆 可。又，脂肪族基，可爲直鏈狀、支鏈狀、環狀中任一者 0 ，或該些組合皆可。 脂肪族基，可爲僅由碳原子及氫原子所形成之脂肪族 烴基’構成該脂肪族烴基之碳原子的一部份被含有雜原子 之取代基所取代之基亦可，構成該脂肪族烴基之氫原子的 一部份或全部被含有雜原子之取代基所取代之基亦可。 前述雜原子，只要爲碳原子及氫原子以外之原子時， 並未有特別限定’例如鹵素原子、氧原子、硫原子、氮原 子等。鹵素原子’例如氟原子、氯原子、碘原子、溴原子 ❹ 等。 含有雜原子之取代基’可爲僅由雜原子所形成之取代 基，或含有雜原子以外之基或原子之基亦可。 取代碳原子之一部份之取代基，具體而言，例如， —0—、— C( = 0) — Ο —、— C( = 0) —、_〇 — c( = 〇) — ο — 、—C( = 0)— ΝΗ—、— ΝΗ— (Η可被烷基、醯基等取代基 所取代）、—S_、一 S( = 〇)2—、— S( = 0)2— 〇 —等。脂肪 族基爲含有環式基之情形，該些取代基可包含於該環式基 之環構造中。 -61 - 200947126 取代氫原子之一部份或全部之取代基，具體而言，例 如’烷氧基、鹵素原子、歯化烷基、羥基、氧原子（=〇) 、—COOR96、— 0C( = 0)R97、氰基等。 前述烷氧基，以碳數1〜5之烷氧基爲佳，以甲氧基 、乙氧基、η —丙氧基、iso—丙氧基、η — 丁氧基、tert — 丁氧基爲較佳，以甲氧基、乙氧基爲最佳。 前述鹵素原子，例如氟原子、氯原子、溴原子、碘原 子等，又以氟原子爲佳。 © 前述鹵化烷基爲碳數1〜5之烷基，例如甲基、乙基 、丙基、η— 丁基、tert- 丁基等之院基之氫原子之一部份 或全部被前述鹵素原子所取代之基等。 R96及R97分別爲獨立之氫原子或爲碳數1〜15之直 鏈狀、支鏈狀或環狀之烷基。 R96及R97中之烷基爲直鏈狀或支鏈狀之情形，其碳 數以1〜10者爲佳，以1〜5者爲更佳’以1或2者爲最 佳。具體而言，例如’與後述之直鏈狀或支鏈狀之1價之 0 飽和烴基爲相同之內容。 R96及R97中之烷基爲環狀之情形，該環可爲單環或 多環皆可。其碳數以3〜15者爲佳’以4〜12爲更佳’以 5〜1〇爲最佳。具體而言，例如，與後述之環狀之1價之 飽和烴基爲相同之內容° 脂肪族烴基，以碳數1〜30之直鏈狀或支鏈狀之飽和 烴基、碳數2〜1〇之直鏈狀或支鏈狀之1價之不飽和烴基 ，或爲碳數3〜30之環狀之脂肪族;烴基（0旨肪族環式基） -62- 200947126 爲佳。 直鏈狀之飽和烴基，以碳數1〜20者 者爲更佳，以1〜10者爲最佳。具體而言 乙基、丙基、丁基、戊基、己基、庚基、 基、十一烷基、十二烷基、十三烷基、異 烷基、十五烷基、十六烷基、異十六烷基 八烷基、十九烷基、二十烷基、異二十烷 〇 等。 支鏈狀之飽和烴基，以碳數3〜20者 者爲更佳，以3〜10者爲最佳。具體而| 基乙基、1 一甲基丙基、2_甲基丙基、1-甲基丁基、3_甲基丁基、1_乙基丁基、 —甲基戊基、2 -甲基戊基、3 —甲基戊· 等。 不飽和烴基，以碳數2〜5者爲佳，》 〇 ，以3爲最佳。直鏈狀之1價不飽和烴基 、丙烯基（烯丙基）、丁烯基等。支鏈狀 基，例如、1一甲基丙稀基、2 —甲基丙嫌 不飽和烴基，於上述例示中，特別是 脂肪族環式基，可爲單環式基或多環 數以3〜3 0者爲佳，以5〜3 0者爲較佳， 佳，以6〜15者爲最佳，以6〜12者爲特 例如，單環鏈烷去除1個以上之氫原子之 三環鏈烷、四環鏈烷等之多環鏈烷去除1 ‘爲佳，以1〜1 5 ’例如，甲基、 辛基、壬基、癸 十三烷基、十四 、十七烷基、十 基、二十二烷基 爲佳，以3〜1 5 Ϊ，例如，1一甲 -甲基丁基、2 — 2—乙基丁基、1 g、4—甲基戊基 又2〜4者爲較佳 ，例如、乙烯基 之1價不飽和烴 基等。 以丙烯基爲佳。 式基皆可。其碳 以5〜20者爲更 佳。具體而言， 基；雙環鏈烷、 個以上之氫原子 -63- 200947126 之基等。更具體而言，例如，環戊烷、環己烷等之單環鏈 烷去除1個以上之氫原子之基；金剛烷、降冰片烷、異冰 片烷、三環癸烷、四環十二烷等之多環鏈烷去除1個以上 之氫原子之基等。 R2中，前述脂肪族基爲可具有取代基之芳香族基者 亦可。 芳香族基例如，由苯基、聯苯基（biphenyl )基、莽 基（fluorenyl )基、萘基、蒽基（anthryl )基、啡基等之 _ 芳香族烴之環去除1個氫原子所得之芳基；構成該些芳基 之環的碳原子之一部份被氧原子、硫原子、氮原子等雜原 子所取代之雜芳基等。 該些芳香族基，可具有碳數1〜10之烷基、鹵化烷基 、烷氧基、羥基、鹵素原子等之取代基。該取代基中之烷 基或鹵化烷基，以碳數1〜8者爲佳，以碳數1〜4者爲更 佳。又，該鹵化烷基，以氟化烷基者爲佳。該鹵素原子例 如氟原子、氯原子、碘原子、溴原子等，又以氟原子爲佳 〇 〇 又，化合物（1— 1)中之R2爲芳香族基時，即，鄰 接於R2之氧原子未介由脂肪族基而直接鍵結於芳香環時 ，因未進行化合物（1 一 1)與化合物（1 一 2)之反應，故 未能得到化合物（1 一 3 )。 化合物（1 一 1) 、（1— 2)可分別使用市售之化合物 ，或利用公知之手法進行合成亦可。 例如化合物（1—2)，包含使下述通式（〇—1)所表 -64- 200947126 示之化合物（0-1)於鹼之存在下加熱、中和，而製得下 述通式（〇— 2)所表示之化合物（〇— 2)之步驟（以下， 亦稱爲鹽形成步驟），與 使前述化合物（0 - 2)於酸強度較化合物（1_2)之 酸強度爲更高之酸的存在下進行加熱，而製得化合物（1 - 2)之步驟（以下，亦稱爲羧酸化步驟）之方法等。 【化3 5】...(1 - 2) HO—R1-〇—C—Y1—s〇~ Μ+ ...(τ-3·) is [wherein R1 and Y1 are the same as the above, R2 -60 - 200947126 An aliphatic group having an aromatic group as a substituent, M + is an alkali metal ion] 〇M+, which is the same as the above-mentioned alkali metal ion of W + 〇 R 2 is an aromatic group which may have a substituent The base of the aliphatic group. The aliphatic group may be a saturated aliphatic group or an unsaturated aliphatic group. Further, the aliphatic group may be any of a linear chain, a branched chain, and a ring, or may be any combination. The aliphatic group may be an aliphatic hydrocarbon group formed only of a carbon atom and a hydrogen atom. A part of a carbon atom constituting the aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom, and the aliphatic group may be formed. A part or all of a hydrogen atom of a hydrocarbon group may be substituted by a substituent containing a hetero atom. When the hetero atom is an atom other than a carbon atom or a hydrogen atom, it is not particularly limited, for example, a halogen atom, an oxygen atom, a sulfur atom or a nitrogen atom. The halogen atom 'e.g., a fluorine atom, a chlorine atom, an iodine atom, a bromine atom or the like. The substituent "containing a hetero atom" may be a substituent formed only of a hetero atom, or a group containing a group other than a hetero atom or an atom. Substituting a substituent of a part of a carbon atom, specifically, for example, -0-, -C(= 0) - Ο -, - C( = 0) -, _〇 - c( = 〇) - ο - , —C( = 0)—ΝΗ—, —ΝΗ—(Η can be replaced by a substituent such as an alkyl group or a fluorenyl group), —S_, an S(=〇)2—, —S( = 0)2— Hey—wait. The aliphatic group is in the case of a cyclic group, and the substituents may be included in the ring structure of the ring group. -61 - 200947126 Substituting a part or all of a substituent of a hydrogen atom, specifically, for example, 'alkoxy group, halogen atom, alkyl group, hydroxyl group, oxygen atom (=〇), -COOR96, -0C( = 0) R97, cyano and the like. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, and is a methoxy group, an ethoxy group, a η-propoxy group, an iso-propoxy group, a η-butoxy group, or a tert-butoxy group. Preferably, methoxy group and ethoxy group are preferred. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. © The above-mentioned halogenated alkyl group is an alkyl group having 1 to 5 carbon atoms, and some or all of the hydrogen atoms of the hospital base such as methyl, ethyl, propyl, η-butyl, tert-butyl or the like are partially or partially halogenated. The base replaced by an atom, etc. R96 and R97 are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. In the case where the alkyl group in R96 and R97 is linear or branched, the carbon number is preferably from 1 to 10, more preferably from 1 to 5, and most preferably from 1 or 2. Specifically, for example, it is the same as the linear or branched monovalent zero-saturated hydrocarbon group described later. In the case where the alkyl group in R96 and R97 is cyclic, the ring may be monocyclic or polycyclic. The carbon number is preferably from 3 to 15 and is preferably from 4 to 12, with 5 to 1 being the best. Specifically, for example, it is the same as the cyclic monovalent saturated hydrocarbon group described later. The aliphatic hydrocarbon group is a linear or branched saturated hydrocarbon group having a carbon number of 1 to 30, and the carbon number is 2 to 1 Å. The linear or branched monovalent unsaturated hydrocarbon group is preferably a cyclic aliphatic group having a carbon number of 3 to 30; and the hydrocarbon group (0 is a aliphatic ring group) is preferably -62 to 200947126. The linear saturated hydrocarbon group is preferably one having a carbon number of from 1 to 20, and most preferably from 1 to 10. Specifically ethyl, propyl, butyl, pentyl, hexyl, heptyl, decyl, undecyl, dodecyl, tridecyl, isoalkyl, pentadecyl, hexadecyl , isohexadecyl octadecyl, nonadecyl, eicosyl, isoicosane and the like. The branched saturated hydrocarbon group is preferably a carbon number of 3 to 20, and preferably 3 to 10. Specifically, ethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 3-methylbutyl, 1-ethylbutyl, methylpentyl, 2- Methyl amyl, 3-methylpentane, etc. The unsaturated hydrocarbon group is preferably a carbon number of 2 to 5, and 〇 is preferably 3. A linear monovalent unsaturated hydrocarbon group, a propenyl group (allyl group), a butenyl group or the like. a branched group, for example, a 1-methylpropyl group, a 2-methylpropane unsaturated hydrocarbon group, and in the above examples, particularly an aliphatic ring group, may be a monocyclic group or a polycyclic number of 3 Preferably, it is preferably from 3 to 30, preferably from 6 to 15, and from 6 to 12, for example, three or more hydrogen atoms are removed from the monocyclic alkane. The polycyclic alkane of a cycloalkane, a tetracycloalkane or the like is preferably removed by 1 ', preferably 1 to 1 5 ', for example, methyl, octyl, decyl, decyltridecyl, tetradecyl, heptadecyl More preferably, deca- or t-dialkyl, and 3 to 15 Ϊ, for example, 1-methyl-methyl butyl, 2- 2 -ethylbutyl, 1 g, 4-methylpentyl and 2 It is preferable that it is ～4, for example, a monovalent unsaturated hydrocarbon group of a vinyl group. The propylene group is preferred. The formula can be used. The carbon is preferably 5 to 20 carbon atoms. Specifically, a biscycloalkane, a hydrogen atom of at least -63-200947126, and the like. More specifically, for example, a monocyclic alkane such as cyclopentane or cyclohexane removes a group of one or more hydrogen atoms; adamantane, norbornane, isobornane, tricyclodecane, tetracyclic twelve A polycyclic alkane such as an alkane is removed from a group of one or more hydrogen atoms. In R2, the aliphatic group may be an aromatic group which may have a substituent. The aromatic group is, for example, obtained by removing one hydrogen atom from a ring of an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthyl group or a morphyl group. The aryl group; a heteroaryl group in which a part of a carbon atom constituting the ring of the aryl group is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. These aromatic groups may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkoxy group, a hydroxyl group or a halogen atom. The alkyl group or the halogenated alkyl group in the substituent is preferably a carbon number of 1 to 8, and more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is preferably a fluorinated alkyl group. The halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom is preferably a fluorine atom. When R 2 in the compound (1-1) is an aromatic group, that is, an oxygen atom adjacent to R 2 . When the aromatic ring is not bonded directly to the aromatic ring, the compound (1 - 1) is not obtained because the compound (1 - 1) is not reacted with the compound (1 - 2). The compounds (1 to 1) and (1-2) may each be used as a commercially available compound or may be synthesized by a known method. For example, the compound (1-2) contains a compound (0-1) represented by the following formula (〇-1) in the presence of a base in the presence of a base, and the following formula is obtained. (〇-2) The step of the compound (〇-2) (hereinafter, also referred to as a salt formation step), and the acid strength of the compound (1-2) is higher than that of the compound (0-2) A method of obtaining a compound (1-2) (hereinafter, also referred to as a carboxylation step) by heating in the presence of an acid. [化3 5]

Ο 01 II , R01—Ο—C—Y1—S02FΟ 01 II , R01—Ο—C—Y1—S02F

-(0-1) M ..-(0-2) HO—C—Y1—SO3 M+ 式中，Rei爲烷基，Y1、M +與前述爲相同之內容〕 R1*1之烷基，以直鏈狀或支鏈狀之烷基爲佳，具體而 言，例如，甲基、乙基、丙基、異丙基、η— 丁基、異丁 基、tert - 丁基、戊基、異戊基、新戊基等。其中又以碳 數1〜4之烷基爲佳，以甲基爲最佳。 化合物（〇 — 1 )，可使用市售之化合物。 鹽形成步驟，例如，可使化合物（〇 - 1 )溶解於溶劑 中，於該溶液中添加鹼，再予加熱之方式實施。 溶劑，只要可溶解化合物（〇 — 1 )之物質即可，例如 水、四氫呋喃等。 鹼，可使用對應於式（〇_2)中之Μ的鹼，該鹼例 -65- 200947126 如，氫氧化鈉、氫氧化鉀、氫氧化鋰等之鹼金屬氫氧化物 等。 鹼之使用量，相對於化合物（〇 - 1) 1莫耳，以1〜5 莫耳爲佳，以2〜4莫耳爲更佳。 加熱溫度，以20〜120°C左右爲佳，以50〜100°C左 右爲更佳。加熱時間，依加熱溫度等而有所不同，通常以 0.5〜1 2小時爲佳，以1〜5小時爲更佳。 前述加熱後之中和，可於前述加熱後之反應液中添加 0 鹽酸、硫酸、P-甲苯磺酸等之酸之方式實施。 此時，中和，以使添加酸後之反應液的pH ( 25 °C ) 達6〜8之方式實施爲佳。又，中和時之反應液的溫度， 以20〜30 °C者爲佳，以23〜27 °C爲更佳。 反應結束後，可將反應液中之化合物（〇_2)單離、 精製。單離、精製，可利用以往公知之方法，例如單獨使 用任一種濃縮、溶劑萃取、蒸餾、結晶化、再結晶、色層 分析等，或將2種以上組合使用亦可。 0 羧酸化步驟中，爲將前述鹽形成步驟所得之化合物（ 〇 — 2)，於酸強度較化合物（1 一 2)之酸強度爲高之酸的 存在下進行加熱而製得該化合物（1 - 2)。 「酸強度較化合物（1 一 2)之酸強度爲高之酸（以下 ，亦僅稱爲強酸）」，係指相較於化合物（1 一 2 )中之一 COOH，其pKa ( 25〇C )之値較小之酸之意。使用該強酸 時，可使化合物（〇 — 2 )中之一 COCTM +形成一 COOH，而 得到化合物（1 — 2 )。 -66- 200947126 強酸，可由公知之酸之中，適當的選擇使用pKa値較 前述化合物（1-2)中之一 COOH的pKa爲小之酸。化合 物（1— 2)中之一 COOH的pKa，可使用公知之滴定法計 算。 強酸，具體而言，例如，芳基擴酸、院基磺酸等之擴 酸、硫酸、鹽酸等。芳基磺酸，例如P -甲苯磺酸等。烷 基磺酸，例如甲烷磺酸或三氟甲烷磺酸等。強酸，就對有 0 機溶劑之溶解性或精製之容易性等觀點，特別是以P-甲 苯磺酸爲佳。 羧酸化步驟，例如使化合物（〇- 2)溶解於溶劑中， 添加強酸後進行加熱之方式實施。 溶劑，只要可溶解化合物（0 — 2 )之溶劑即可，例如 乙腈、甲基乙基酮等。 強酸之使用量，相對於化合物（0 — 2 ) 1莫耳，以 0.5〜3莫耳爲佳，以1〜2莫耳爲更佳。 Q 加熱溫度，以20〜150 °c左右爲佳，以50〜120 °C左 右爲更佳。加熱時間，依加熱溫度等而有所不同，通常以 0.5〜1 2小時爲佳，以1〜5小時爲更佳。 反應結束後’可將反應液中之化合物（1一 2)單離、 精製。單離、精製，可利用以往公知之方法，例如單獨使 用任一種濃縮、溶劑萃取、蒸餾、結晶化、再結晶、色層 分析等，或將2種以上組合使用皆可。 又’化合物（1 一 3)中之W+爲前述取代銨離子之情 形，該化合物（下述通式（1— 3”）所表示之化合物（1 一 -67- 200947126 3&quot;)) ’例如可使前述化合物（1—3，）與銨鹽反應之方 式製造。 【化3 6】 〇 R3 HO—R1—〇—C—Y1—SO3 R6-^—r4 R5 …(1-3”） 〔式中’ Rx、R1、Y1、R3〜r6分別爲與前述爲相同-(0-1) M ..-(0-2) HO—C—Y1—SO3 M+ wherein Rei is an alkyl group, and Y1 and M+ are the same as those described above] R1*1 alkyl group, A linear or branched alkyl group is preferred, specifically, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, iso Amyl, neopentyl and the like. Among them, an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group is preferred. For the compound (〇-1), a commercially available compound can be used. In the salt formation step, for example, the compound (〇 - 1 ) can be dissolved in a solvent, and a base is added to the solution, followed by heating. The solvent may be any one which dissolves the compound (〇-1), such as water, tetrahydrofuran or the like. As the base, a base corresponding to ruthenium in the formula (?_2) such as an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide can be used. The amount of the base to be used is preferably 1 to 5 moles, more preferably 2 to 4 moles, relative to the compound (〇 - 1) 1 mole. The heating temperature is preferably about 20 to 120 ° C, preferably about 50 to 100 ° C. The heating time varies depending on the heating temperature, etc., and is usually preferably 0.5 to 12 hours, more preferably 1 to 5 hours. The neutralization after heating may be carried out by adding an acid such as hydrochloric acid, sulfuric acid or P-toluenesulfonic acid to the reaction liquid after the heating. In this case, the neutralization is preferably carried out so that the pH (25 ° C) of the reaction liquid after the addition of the acid is 6 to 8. Further, the temperature of the reaction liquid at the time of neutralization is preferably from 20 to 30 ° C, more preferably from 23 to 27 ° C. After completion of the reaction, the compound (〇_2) in the reaction mixture can be isolated and purified. For the separation and purification, a conventionally known method can be used, for example, any one of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like, or two or more types may be used in combination. In the carboxylation step, the compound (〇-2) obtained by the above salt formation step is heated in the presence of an acid having a higher acid strength than the compound (1-2), and the compound (1) is obtained. - 2). "Acid with a higher acid strength than the compound (1 to 2) (hereinafter, also referred to as a strong acid only)" means a pKa (25 〇C) compared to one of the compounds (1 to 2). ) The meaning of the smaller acid. When the strong acid is used, one of the compounds (〇-2), COCTM + , can be formed into a COOH to give a compound (1-2). -66- 200947126 A strong acid may be selected from known acids, and a pKa of one of the above compounds (1-2) is used as a small acid. The pKa of one of the compounds (1-2) can be calculated by a known titration method. The strong acid is specifically, for example, an aryl acid-expanding acid, an acid-based sulfonic acid or the like, sulfuric acid, hydrochloric acid or the like. An aryl sulfonic acid such as P-toluenesulfonic acid or the like. An alkyl sulfonic acid such as methanesulfonic acid or trifluoromethanesulfonic acid or the like. The strong acid is particularly preferably P-toluenesulfonic acid from the viewpoints of solubility in a solvent or purification of a solvent. The carboxylation step is carried out, for example, by dissolving the compound (〇-2) in a solvent, adding a strong acid, and heating. The solvent may be any solvent which dissolves the compound (0-2), for example, acetonitrile, methyl ethyl ketone or the like. The amount of strong acid used is preferably 0.5 to 3 moles, more preferably 1 to 2 moles, relative to the compound (0 - 2 ) 1 mole. Q Heating temperature is preferably about 20 to 150 ° C, preferably about 50 to 120 ° C. The heating time varies depending on the heating temperature, etc., and is usually preferably 0.5 to 12 hours, more preferably 1 to 5 hours. After completion of the reaction, the compound (1-2) in the reaction mixture can be isolated and purified. For the separation and purification, a conventionally known method can be used, and for example, any one of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like can be used alone or in combination of two or more. Further, in the case where the W+ in the compound (1 - 3) is the above-mentioned substituted ammonium ion, the compound (1 - 67 - 200947126 3 &quot;)) of the compound (the following formula (1-3)) can be, for example, The above compound (1-3) is produced by reacting with an ammonium salt. [Chemical 3 6] 〇R3 HO-R1—〇—C—Y1—SO3 R6-^—r4 R5 (1-3”) 'Rx, R1, Y1, R3~r6 are the same as the above

之內容〕。 此時所使用之銨鹽’例如上述之烷基胺、二烷基胺、 三烷基胺，及芳香族胺之鹽酸鹽或溴酸鹽等。 反應，例如，可使化合物（1 一 3')，與銨鹽溶解於 水、二氯甲烷、乙腈、甲醇、氯仿等之溶劑，以攪拌等進 行反應。Content]. The ammonium salt used in this case is, for example, the above-mentioned alkylamine, dialkylamine, trialkylamine, and hydrochloride or bromate of an aromatic amine. For the reaction, for example, the compound (1 - 3') and the ammonium salt can be dissolved in a solvent such as water, dichloromethane, acetonitrile, methanol, chloroform or the like, and the reaction is carried out by stirring or the like.

反應溫度’以〇 °C〜1 5 0 °c左右爲佳，以〇它〜1 〇 〇。〇 左右爲更佳。反應時間’依化合物（1—3，）、錢鹽之反 應性或反應溫度等而有所不同’通常以〇 . 5〜1 〇小時爲佳 ，以1〜5小時爲更佳。 使化合物（1一 3)與化合物（2一 1)反應之方法，並 未有特別限定’例如’於反應溶劑中，使化合物（丨_ 3 ) 與化合物（2 — 1)接觸之方法等。該方法，例如，於驗之 存在下’使化合物（1 - 3)溶解於反應溶劑所得之溶液中 ，添加化合物（2 —丨）之方式實施。 反應溶劑，只要可溶解原料之化合物一 及化合 物（2 — 1 )之溶劑即可’具體而言，例如，四氫呋喃（ -68- 200947126 THF)、丙酮、二甲基甲醯胺（DMF)、二甲基乙醯胺、 二甲基亞颯（DMSO)、乙腈等。 鹼’例如三乙基胺、4 一二甲基胺基吡啶（DMAP)、 吡啶等之有機鹼；氫化鈉、K2C03、Cs2C03等無機鹼等。 化合物（2-1)之添加量，相對於化合物（1-3)， 以約1〜3當量爲佳，以1〜2當量爲更佳。 反應溫度’以一20〜40 °C爲佳，以0〜30。(：爲更佳。 0 反應時間’依化合物（1 — 3 )及化合物（2 — 1 )之反應性 或反應溫度等而有所不同，通常，以1〜1 2 0小時爲佳， 以1〜4 8小時爲更佳。 又，化合物（b〇- 01)中之W+爲前述取代銨離子之 情形，該化合物（下述通式（b 0 — 0 1')所表示之化合物 (b0 — 0 1'))，例如’可使前述化合物（1 — 3 ')，與前 述化合物（2 - 1) ’與胺或銨鹽同時反應之方法進行製造The reaction temperature is preferably about 〇 ° C to 150 ° C, so that it is ~1 〇 〇.左右 Left and right is better. The reaction time ' differs depending on the reactivity of the compound (1-3), the salt of the money, the reaction temperature, etc., and is usually preferably 〇5~1 〇hour, more preferably 1 to 5 hours. The method of reacting the compound (1-3) with the compound (2-1) is not particularly limited, for example, a method of bringing the compound (?3) into contact with the compound (2-1) in a reaction solvent. This method is carried out, for example, in the presence of a compound (1-3) in which a compound (1-3) is dissolved in a reaction solvent. The reaction solvent is as long as it can dissolve the solvent of the compound 1 and the compound (2-1), specifically, for example, tetrahydrofuran (-68-200947126 THF), acetone, dimethylformamide (DMF), Methylacetamide, dimethyl hydrazine (DMSO), acetonitrile, and the like. The base 'e.g., an organic base such as triethylamine, 4-dimethylaminopyridine (DMAP) or pyridine; an inorganic base such as sodium hydride or K2C03 or Cs2C03. The amount of the compound (2-1) to be added is preferably about 1 to 3 equivalents, more preferably 1 to 2 equivalents based on the compound (1-3). The reaction temperature is preferably from 20 to 40 ° C, and from 0 to 30. (: is more preferable. 0 reaction time ' differs depending on the reactivity of the compound (1 - 3) and the compound (2 - 1), the reaction temperature, etc., usually, it is preferably 1 to 120 hours, and 1 Further, in the case where the W+ in the compound (b〇-01) is the above-mentioned substituted ammonium ion, the compound (the compound represented by the following formula (b 0 - 0 1 ') (b0 - 0 1 ')), for example, can be produced by a method in which the aforementioned compound (1 - 3 ') can be simultaneously reacted with the above compound (2 - 1) ' with an amine or an ammonium salt.

【化3 7】 Ο II , + HO—R1—Ο—c—Y1—S03 M+ ...(卜3，） Ο[化3 7] Ο II , + HO—R1—Ο—c—Y1—S03 M+ ... (卜3,) Ο

Rx-C—X22 -(2-1) O O r3Rx-C—X22 -(2-1) O O r3

Rx—C一O一R1—Ο—C—~Y1—s〇3 R6—li一R4 ··，（bO—01 ’） 〔式中’ Rx、R1、Y1、w+、X22分別爲與前述爲相同 之內容〕。 前述化合物（1—3，），與前述化合物（2 - 1)，與 -69- 由佳 可較 } 爲 1 而 1-造 b 製 /IV 行 物進 合豐 化間 ’ 中 中之 法子 方離 造銨 製代 之取 明述 發前 本有 ’ 具 此部 因子 1*·三 難 陽 200947126 胺或敍鹽之反應，可依前述化合物（1 - 3)與前述化合物 (2 — 1)反應爲相同之情形下進行反應。 此時所使用之胺，例如上述之烷基胺、二烷基胺、三 烷基胺，及芳香族胺等，銨鹽，例如氫氧化四甲基銨、氫 氧化四乙基銨、氫氧化四丁基銨等之氫氧化四烷基銨等（ 四烷基銨中之烷基，分別獨立爲碳數1〜4之烷基）。 上述製造方法中，前述化合物（1 一 3&quot;)、化合物（ bO—ΟΓ)等之取代銨鹽，對於製造本發明之化合物（bl 一 1 )之際，極適合作爲中間體使用。即，陽離子部爲N + (R3) (R4) (R5) (R6)時，當該化合物容易經由水洗 而精製，而可期待最終產物純度之提升。例如陽離子部爲 鹼金屬離子時，經由水洗之精製方式，將因該化合物產生 溶解而不易精製。 化合物（b0-01)，與化合物（b0 — 〇2)之反應，可 依以往公知之鹽取代方法爲相同之方式實施。例如，使化 合物（b0— 01)，與化合物（b0 - 02)溶解於水、二氯甲 烷、乙腈、甲醇、氯仿等之溶劑中，以攪拌等使其進行反 應。 反應溫度，以0°C〜150°c左右爲佳，以〇°C〜100°C 左右爲更佳。反應時間，依化合物（b0 — 01)及化合物（ bo - 02 )之反應性或反應溫度等而有所不同，通常以0.5Rx—C—O—R1—Ο—C—~Y1—s〇3 R6—li—R4 ··, (bO—01 ') [wherein Rx, R1, Y1, w+, and X22 are The same content]. The foregoing compound (1-3), and the aforementioned compound (2-1), and -69- are better than 1 and 1 is made into a system/IV. The ammonium-forming system is prepared by the reaction of the above-mentioned compound (1 - 3) with the aforementioned compound (2 - 1). The reaction is carried out under the same conditions. The amine used at this time, for example, the above alkylamine, dialkylamine, trialkylamine, and aromatic amine, ammonium salt, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydrogen hydroxide A tetraalkylammonium hydroxide or the like such as tetrabutylammonium or the like (the alkyl group in the tetraalkylammonium, each independently being an alkyl group having 1 to 4 carbon atoms). In the above production method, the substituted ammonium salt such as the above compound (1 - 3 &quot;) or the compound (bO-oxime) is preferably used as an intermediate when producing the compound (bl-1) of the present invention. That is, when the cation moiety is N + (R3) (R4) (R5) (R6), when the compound is easily purified by washing with water, the purity of the final product can be expected to be improved. For example, when the cation portion is an alkali metal ion, the compound is dissolved by water washing, and the compound is dissolved and is not easily purified. The reaction of the compound (b0-01) with the compound (b0 - 〇2) can be carried out in the same manner as in the conventionally known salt substitution method. For example, the compound (b0-01) and the compound (b0-02) are dissolved in a solvent such as water, methylene chloride, acetonitrile, methanol or chloroform, and the mixture is reacted by stirring or the like. The reaction temperature is preferably from about 0 ° C to about 150 ° C, more preferably from about 〇 ° C to about 100 ° C. The reaction time varies depending on the reactivity of the compound (b0-01) and the compound (bo-02), the reaction temperature, etc., usually 0.5.

-70- 200947126 〜1 〇小時爲佳，以1〜5小時爲更佳。 反應結束後，可將反應液中之化合物（bl - 1)單離 、精製。單離、精製，可利用以往公知之方法，例如單獨 使用任一種濃縮、溶劑萃取、蒸餾、結晶化、再結晶、色 層分析等，或將2種以上組合使用皆可。 所得化合物（b 1 - 1 )之構造，可使用1 η —核磁共振 (NMR)圖譜法、13C— NMR圖譜法、19F~NMR圖譜法 〇 、紅外線吸收（IR )圖譜法、質量分析（MS )法、元素 分析法、X線結晶繞射法等一般性有機分析法進行確認。 《酸產生劑》 本發明之第五之態樣之酸產生劑，爲由前述本發明之 化合物（b 1 - 1 )所形成者。 該酸產生劑，適合作爲化學增幅型光阻組成物用之酸 產生劑，例如適合作爲後述本發明之第一之態樣之光阻組 〇 成物的酸產生劑成份（B)。 該酸產生劑，以前述通式（bl-1— 1)所表示之化合 物爲最佳。 《光阻組成物》 其次，將對本發明之第一之態樣之光阻組成物進行說 明。 本發明之第一之態樣之光阻組成物，爲含有經由酸之 作用而對鹼顯影液之溶解性產生變化之基材成份（A)( -71 - 200947126 以下，亦稱爲（A)成份），及經由曝光而發生酸之酸產 生劑成份（B )(以下，亦稱爲（B )成份）。 使用該光阻組成物所形成之光阻膜，於光阻圖型形成 時進行選擇性曝光時，會使得（B)成份產生酸，並經由 該酸使（A )成份對鹼顯影液之溶解性產生變化。其結果 ，將可使該光阻膜之曝光部對鹼顯影液之溶解性產生變化 之同時，未曝光部則對鹼顯影液之溶解性並未產生變化下 ，經由鹼顯影，正型之情形時爲曝光部，於負型之情形時 則未曝光部發生溶解而去除，而形成光阻圖型。 本發明之光阻組成物，可爲負型光阻組成物亦可，或 爲正型光阻組成物亦可。 &lt; (A )成份&gt; (A)成份，通常可將作爲化學增幅型光阻用之基材 成份使用之有機化合物，以1種單獨，或2種以上混合使 用。 ❹ 其中’ 「基材成份」係指具有膜形成能之有機化合物 ，較佳爲使用分子量爲500以上之有機化合物。該有機化 合物之分子量爲5 00以上時，可提高膜形成能，且容易形 成奈米左右之光阻圖型。 前述分子量爲5 00以上之有機化合物，可大致區分爲 分子量爲500以上、未達2000之低分子量之有機化合物 (以下，亦稱爲低分子化合物），與分子量爲2000以上 之高分子量之樹脂（高分子材料）。前述低分子化合物， -72- 200947126 通常爲使用於非聚合物。樹脂（聚合物、共聚物）之情形 中’ 「分子量」爲使用GPC (凝膠滲透色層分析法）之聚 苯乙烯換算之質量平均分子量。以下，僅稱爲「樹脂」之 情形中，係指分子量爲2000以上之樹脂之意。 (A)成份，可使用經由酸之作用使鹼溶解性產生變 化之樹脂，或使用經由酸之作用使鹼溶解性產生變化之低 分子材料。 〇 本發明之光阻組成物爲負型光阻組成物時，（A)成 份可使用對鹼顯影液具有可溶性之基材成份，或對該負型 光阻組成物添加交聯劑。 該負型光阻組成物，經由曝光使（B)成份產生酸時 ’經由該酸之作用於基材成份與交聯劑之間產生交聯，而 變化爲鹼顯影液爲難溶性。因此，於光阻圖型之形成中， 對塗佈該負型光阻組成物於基板上所得之光阻膜進行選擇 性曝光時，可使曝光部轉變爲對鹼顯影液爲難溶性的同時 〇 ，未曝光部仍爲對鹼顯影液爲可溶性之未變化下，經由鹼 顯影而形成光阻圖型。 負型光阻組成物之（A )成份，通常，爲使用對鹼顯 影液爲可溶性之樹脂（以下，亦稱爲鹼可溶性樹脂）。 鹼可溶性樹脂，以具有由ci -（羥烷基）丙烯酸、或 α -(羥烷基）丙烯酸之低級烷基酯所選出之至少一個所 衍生之單位的樹脂，可形成具有較少膨潤之良好光阻圖型 ，而爲較佳。又，α -（羥烷基）丙烯酸，爲鍵結於羧基 之α位之碳原子鍵結氫原子所得之丙烯酸，與該α位之碳 -73- 200947126 原子鍵結羥烷基（較佳爲碳數1〜5之羥烷基）所鍵結之 α -羥烷基丙烯酸之一或二者之意。 交聯劑，例如，通常使用具有羥甲基或烷氧甲基之甘 脲等之胺基系交聯劑時，可形成具有較少膨潤之良好光阻 圖型，而爲較佳。交聯劑之添加量，相對於鹼可溶性樹脂 100質量份，以1〜50質量份爲佳。 本發明之光阻組成物爲正型光阻組成物時，（A )成 份可使用經由酸之作用而增大對鹼顯影液之溶解性的基材 @ 成份。即，該（A )成份，於曝光前對鹼顯影液爲難溶性 ，經由曝光使前述（B)成份產生酸時，經由該酸之作用 而增大對鹼顯影液之溶解性，因此，於光阻圖型形成時， 對將該正型光阻組成物塗佈於基板上所得之光阻膜進行選 擇性曝光時，曝光部由對鹼顯影液爲難溶性轉變爲可溶性 的同時，未曝光部則爲鹼難溶性之未變化之狀態，經由鹼 顯影而可形成光阻圖型。 本發明之光阻組成物中，（A )成份以經由酸之作用 0 而增大對鹼顯影液之溶解性的基材成份爲佳。即，本發明 之光阻組成物以正型光阻組成物爲佳。 該（A)成份，可爲經由酸之作用而增大對鹼顯影液 之溶解性的樹脂成份（A1 )(以下，亦稱爲（A1 )成份 )爲佳，或經由酸之作用而增大對鹼顯影液之溶解性的低 分子化合物（A2 )(以下，亦稱爲（A2 )成份）亦可， 或其之之混合物亦可。其中又以該（A)成份以含有（A1 )成份者爲佳。 -74- 200947126 〔（A 1 )成份〕 (A 1 )成份，通常爲使用作爲化學增幅型光阻用之 基材成份之樹脂成份（基礎樹脂），其可單獨1種，或將 2種以上混合使用亦可。 本態樣中，（A 1 )成份，以含有丙烯酸酯所衍生之 結構單位爲佳。 0 其中’本說明書與申請專利範圍中，「丙烯酸酯所衍 生之結構單位」係指丙烯酸酯之乙烯性雙鍵經開裂所構成 之結構單位之意。 「丙烯酸酯」，係指α位之碳原子除鍵結有氫原子之 丙烯酸酯以外’亦包含α位之碳原子鍵結有取代基（氫原 子以外之原子或基）之化合物之槪念。取代基，例如低級 烷基、鹵化低級烷基等。 又，丙烯酸酯所衍生之結構單位之α位（α位之碳原 〇 子）’於未有特別限定下，係指鍵結於羰基之碳原子。 丙烯酸酯中，0：位取代基之低級烷基，具體而言，例 如甲基、乙基、丙基、異丙基、η— 丁基、異丁基、tert — 丁基、戊基、異戊基、新戊基等低級之直鏈狀或支鏈狀之 院基等。 又，鹵化低級烷基，具體而言，以上述「α位取代基 之低級烷基」中之氫原子的一部份或全部被鹵素原子取代 所得之基等。該鹵素原子，例如氟原子、氯原子、溴原子 、碘原子等，特別是以氟原子爲佳。 -75- 200947126 本發明中，丙烯酸酯之α位所鍵結者，以氫原子、低 級烷基或鹵化低級烷基爲佳，又以氫原子、低級烷基或氟 化低級烷基爲更佳，就工業上容易取得等觀點，以氫原子 或甲基爲最佳。 (A 1 )成份，特別是以具有含有酸解離性溶解抑制 基之丙烯酸酯所衍生之結構單位（al )爲佳。 又，（A1 )成份，除結構單位（al )以外，以再具有 含有含內酯之環式基的丙烯酸酯所衍生之結構單位（a2) 爲佳。 (A1)成份’除結構單位（al)以外，或結構單位（ al )及（a2 )以外，以再具有含有含極性基之脂肪族烴基 之丙烯酸酯所衍生之結構單位（a3 )爲佳。 •結構單位（al ) 結構單位（a 1 )中之酸解離性溶解抑制基，只要爲解 離前使（A 1 )成份全體具有鹼不溶性之鹼溶解抑制性的 同時，經由酸之解離後使此（A1)成份全體增大對鹼顯 影液之溶解性之基即可，其可使用目前爲止被提案作爲化 學增幅型光阻組成物用基礎樹脂之酸解離性溶解抑制基之 物。一般而言，已知者例如可與（甲基）丙烯酸中之羧基 形成環狀或鏈狀之三級烷基酯之基，或烷氧烷基等縮醛型 酸解離性溶解抑制基等。 其中，「三級烷基酯」，例如羧基之氫原子被鏈狀或 環狀之烷基取代而形成酯，使該羰氧基（一 C(O) — 〇 -） 200947126 末端之氧原子，鍵結於前述鏈狀或環狀之烷基之三級碳原 子所得之結構。前述三級烷基酯中，經由酸之作用時，即 可切斷氧原子與三級碳原子之間的鍵結。 又，前述鏈狀或環狀之烷基可具有取代基。 以下，經由羧基與三級烷基酯所構成之具有酸解離性 之基，方便上將其稱爲「三級烷基酯型酸解離性溶解抑制 基」。 0 三級烷基酯型酸解離性溶解抑制基，例如脂肪族支鏈 狀酸解離性溶解抑制基、含有脂肪族環式基之酸解離性溶 解抑制基等。 「脂肪族支鏈狀」係指不具有芳香族性之支鏈狀結構 之意。 「脂肪族支鏈狀酸解離性溶解抑制基」之結構，並未 限定爲由碳與氫所形成之基（烴基），但以烴基爲佳。又 ，「烴基」可爲飽和或不飽和者皆可，一般以飽和爲佳。 Q 脂肪族支鏈狀酸解離性溶解抑制基以碳數4〜8之三 級烷基爲佳，具體而言，例如tert — 丁基、tert—戊基、 tert —庚基等。 「脂肪族環式基」係指不具有芳香族性之單環式基或 多環式基。 結構單位（al)中之「脂肪族環式基」，其可具有取 代基或未取有取代基皆可。取代基例如碳數1〜5之低級 烷基、氟原子、被氟原子取代之碳數1〜5之氟化低級烷 基、氧原子（=0 )等。 -77- 200947126 「脂肪族環式基」中去除取代基之基本的環結構，並 未限定由碳與氫所構成之基（烴基），但以烴基爲佳。又 ，「烴基」可爲飽和或不飽和者皆可，一般又以飽和爲佳 。「脂肪族環式基」以多環式基爲較佳。 脂肪族環式基之具體例，例如可被低級烷基、氟原子 或氟化烷基所取代者，或未取代亦可之由單環鏈烷、二環 鏈烷、三環鏈烷、四環鏈烷等多環鏈烷中去除1個以上氫 原子所得之基等。更具體而言，例如由環戊烷、環己烷等 單環鏈烷或，金剛烷、降冰片烷、異降冰片烷、三環癸烷 、四環十二烷等多環鏈烷中去除1個以上氫原子所得之基 等。 含有脂肪族環式基之酸解離性溶解抑制基，例如於環 狀之烷基的環骨架上具有三級碳原子之基等，具體而言， 例如2 —甲基—2_金剛烷基，或2—乙基_2_金剛烷基 等。或例如下述通式（al” 一 1)〜（al”— 6)所示結構單 位中，鍵結於羰氧基（—C(0)-0—)之氧原子之基般， 具有金剛烷基、環己基、環戊基、降冰片烷基、三環癸烷 基、四環十二烷基等之脂肪族環式基，及與其鍵結之具有 三級碳原子之支鏈狀伸烷基之基等。 200947126 【化3 8】-70- 200947126 ~1 〇 hours is better, with 1~5 hours as better. After completion of the reaction, the compound (bl - 1) in the reaction mixture can be isolated and purified. For the separation and purification, a conventionally known method can be used. For example, any one of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like may be used alone or in combination of two or more. The structure of the obtained compound (b 1 - 1 ) can be measured by 1 η - nuclear magnetic resonance (NMR) spectroscopy, 13C-NMR spectroscopy, 19F NMR spectroscopy, infrared absorption (IR) spectroscopy, mass analysis (MS) General organic analysis methods such as methods, elemental analysis, and X-ray crystal diffraction are confirmed. <<Acid generator>> The acid generator of the fifth aspect of the invention is formed from the aforementioned compound (b 1 - 1 ) of the present invention. The acid generator is suitably used as an acid generator for a chemically amplified photoresist composition, and is, for example, an acid generator component (B) suitable as a photoresist composition of the first aspect of the present invention. The acid generator is preferably a compound represented by the above formula (bl-1-1). <<Photoresist Composition>> Next, the photoresist composition of the first aspect of the present invention will be described. The photoresist composition of the first aspect of the present invention is a substrate component (A) containing a change in solubility to an alkali developer via an action of an acid (-71 - 200947126 or lower, also referred to as (A) Ingredient), and an acid generator component (B) (hereinafter, also referred to as (B) component) which generates acid by exposure. When the photoresist film formed by the photoresist composition is selectively exposed during the formation of the photoresist pattern, the (B) component is caused to generate an acid, and the (A) component is dissolved in the alkali developing solution via the acid. Sex changes. As a result, the solubility of the exposed portion of the resist film to the alkali developing solution can be changed, and the unexposed portion does not change the solubility of the alkali developing solution. The time is the exposure portion, and in the case of the negative type, the unexposed portion is dissolved and removed to form a photoresist pattern. The photoresist composition of the present invention may be a negative photoresist composition or a positive photoresist composition. &lt;(A) Component&gt; (A) The organic compound to be used as a substrate component for a chemically amplified photoresist can be used singly or in combination of two or more kinds. ❹ Wherein 'substrate component' means an organic compound having a film forming ability, and preferably an organic compound having a molecular weight of 500 or more. When the molecular weight of the organic compound is 500 or more, the film formation energy can be improved, and a photoresist pattern of about nanometers can be easily formed. The organic compound having a molecular weight of 500 or more can be roughly classified into an organic compound having a molecular weight of 500 or more and a low molecular weight of less than 2,000 (hereinafter also referred to as a low molecular compound), and a high molecular weight resin having a molecular weight of 2,000 or more ( Polymer Materials). The aforementioned low molecular compound, -72-200947126, is generally used for non-polymers. In the case of a resin (polymer, copolymer), 'molecular weight' is a mass average molecular weight in terms of polystyrene converted by GPC (gel permeation chromatography). Hereinafter, the term "resin" alone means a resin having a molecular weight of 2,000 or more. As the component (A), a resin which changes the solubility of the alkali by the action of an acid or a low molecular material which changes the solubility of the alkali by the action of an acid can be used. 〇 When the photoresist composition of the present invention is a negative photoresist composition, a component of the substrate which is soluble in the alkali developer may be used as the component (A), or a crosslinking agent may be added to the negative resist composition. When the negative resist composition is caused to cause an acid to be generated in the component (B) by exposure, cross-linking occurs between the substrate component and the crosslinking agent by the action of the acid, and the alkali developing solution is insoluble. Therefore, in the formation of the photoresist pattern, when the photoresist film coated on the substrate is selectively exposed by the negative photoresist composition, the exposed portion can be converted to be insoluble to the alkali developer. The unexposed portion was formed into a photoresist pattern by alkali development without being changed to be soluble in the alkali developing solution. The component (A) of the negative resist composition is usually a resin which is soluble in an alkali developing solution (hereinafter also referred to as an alkali-soluble resin). The alkali-soluble resin, which is a resin having a unit derived from at least one selected from the group consisting of ci-(hydroxyalkyl)acrylic acid or a lower alkyl ester of α-(hydroxyalkyl)acrylic acid, can form a good swelling with less swelling. The photoresist pattern is preferred. Further, α-(hydroxyalkyl)acrylic acid is an acrylic acid obtained by bonding a hydrogen atom bonded to a carbon atom at the α-position of a carboxyl group, and a hydroxyalkyl group bonded to the carbon-73-200947126 atom at the α-position (preferably One or both of the α-hydroxyalkylacrylic acid bonded to the hydroxyalkyl group having 1 to 5 carbon atoms. The crosslinking agent, for example, when an amine-based crosslinking agent having a methylol group or an alkoxymethyl group of glycolide or the like is usually used, a good photoresist pattern having less swelling is formed, and is preferable. The amount of the crosslinking agent to be added is preferably 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin. When the photoresist composition of the present invention is a positive photoresist composition, the substrate (component) which increases the solubility to the alkali developer via the action of an acid can be used as the component (A). In other words, the component (A) is poorly soluble in the alkali developing solution before exposure, and when the component (B) is acidified by exposure, the solubility in the alkali developing solution is increased by the action of the acid. When the resist pattern is formed, when the resist film obtained by applying the positive resist composition on the substrate is selectively exposed, the exposed portion is converted from soluble to soluble in the alkali developing solution, and the unexposed portion is formed. In the state in which the alkali is poorly soluble, a photoresist pattern can be formed by alkali development. In the photoresist composition of the present invention, the component (A) is preferably a component of the substrate which increases the solubility in the alkali developer by the action of the acid. That is, the photoresist composition of the present invention is preferably a positive photoresist composition. The component (A) may be a resin component (A1) (hereinafter, also referred to as (A1) component) which increases solubility in an alkali developer via an action of an acid, or may be increased by an action of an acid. The low molecular compound (A2) (hereinafter also referred to as (A2) component) which is soluble in the alkali developer may be used, or a mixture thereof may be used. Among them, the component (A) is preferably a component containing (A1). -74- 200947126 [(A 1 ) component] (A 1 ) is usually a resin component (base resin) which is used as a substrate component for chemically amplified photoresist, and may be used alone or in combination of two or more. Mixed use is also possible. In this aspect, the (A 1 ) component is preferably a structural unit derived from an acrylate. 0 In the specification and the scope of the patent application, "the structural unit derived from acrylate" means the structural unit constituted by the cracking of the ethylenic double bond of the acrylate. The "acrylate" refers to a compound in which a carbon atom at the α-position is a acrylate having a hydrogen atom bonded thereto, and a compound having a carbon atom bonded to the α-position (atom or a group other than a hydrogen atom) is also contained. The substituent is, for example, a lower alkyl group, a halogenated lower alkyl group or the like. Further, the α-position (carbon atom of the α-position) of the structural unit derived from the acrylate is not specifically limited, and means a carbon atom bonded to a carbonyl group. In the acrylate, the lower alkyl group of the 0: substituent, specifically, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, iso Low-grade linear or branched hospital bases such as amyl and neopentyl. Further, the halogenated lower alkyl group is specifically a group obtained by substituting a part or all of a hydrogen atom in the above-mentioned "lower alkyl group of the α-substituted group" with a halogen atom. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. -75- 200947126 In the present invention, the α-position of the acrylate is preferably a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and more preferably a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group. It is preferable to use a hydrogen atom or a methyl group from the viewpoint of easy industrial availability. The component (A 1 ) is particularly preferably a structural unit (al ) derived from an acrylate having an acid-dissociable dissolution inhibiting group. Further, the component (A1) is preferably a structural unit (a2) derived from an acrylate having a cyclic group containing a lactone, in addition to the structural unit (al). The component (A1) is preferably a structural unit (a3) derived from an acrylate having a polar group-containing aliphatic hydrocarbon group, in addition to the structural unit (al) or structural units (al) and (a2). • Structural unit (al) The acid dissociable dissolution inhibiting group in the structural unit (a 1 ) is such that, as long as the (A 1 ) component has an alkali-insoluble alkali dissolution inhibiting property before dissociation, the acid is dissociated. (A1) It is sufficient to increase the solubility in the alkali developing solution as a whole, and it is possible to use an acid dissociable dissolution inhibiting group which has been proposed as a base resin for a chemically amplified resist composition. In general, for example, a carboxyl group in (meth)acrylic acid may form a cyclic or chain tertiary alkyl ester group, or an acetal acid dissociable dissolution inhibiting group such as an alkoxyalkyl group. Wherein, "trialkyl ester", for example, a hydrogen atom of a carboxyl group is substituted with a chain or a cyclic alkyl group to form an ester such that the carbonyloxy group (mono C(O) - 〇-) is an oxygen atom at the end of 200947126, A structure obtained by bonding to a tertiary carbon atom of the aforementioned chain or cyclic alkyl group. In the above tertiary alkyl ester, the bond between the oxygen atom and the tertiary carbon atom can be interrupted by the action of an acid. Further, the aforementioned chain or cyclic alkyl group may have a substituent. Hereinafter, the acid dissociable group composed of a carboxyl group and a tertiary alkyl ester is conveniently referred to as a "triester alkyl ester type acid dissociable dissolution inhibiting group". The tertiary alkyl ester type acid dissociable dissolution inhibiting group is, for example, an aliphatic branched acid dissociable dissolution inhibiting group, or an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group. "Aliphatic branched" means a branched structure having no aromaticity. The structure of the "aliphatic branched acid dissociable dissolution inhibiting group" is not limited to a group (hydrocarbon group) formed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is generally preferred to saturate. The Q-group branched fatty acid dissociable dissolution inhibiting group is preferably a C 3 to 8 alkyl group, and specifically, for example, tert-butyl, tert-pentyl, tert-heptyl or the like. The "aliphatic cyclic group" means a monocyclic or polycyclic group having no aromaticity. The "aliphatic cyclic group" in the structural unit (al) may have a substituent or may not have a substituent. The substituent is, for example, a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, or an oxygen atom (=0). -77- 200947126 The "aliphatic cyclic group" removes the basic ring structure of the substituent, and does not limit the group (hydrocarbon group) composed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and generally it is preferably saturated. The "aliphatic cyclic group" is preferably a polycyclic group. Specific examples of the aliphatic cyclic group, for example, may be substituted by a lower alkyl group, a fluorine atom or a fluorinated alkyl group, or may be unsubstituted, or may be a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetra. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a cycloalkane. More specifically, for example, it is removed from a monocyclic alkane such as cyclopentane or cyclohexane or a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. A group obtained by one or more hydrogen atoms. An acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, for example, a group having a tertiary carbon atom on a ring skeleton of a cyclic alkyl group, and the like, specifically, for example, a 2-methyl-2-adamantyl group, Or 2-ethyl 2 - adamantyl and the like. Or, for example, in the structural unit represented by the following general formula (al"-1) to (al"-6), the bond is bonded to the oxygen atom of the carbonyloxy group (-C(0)-0-), and has a diamond An aliphatic cyclic group such as an alkyl group, a cyclohexyl group, a cyclopentyl group, a norbornyl group, a tricyclodecyl group, a tetracyclododecyl group, or the like, and a branched chain having a tertiary carbon atom bonded thereto Alkyl group and the like. 200947126 【化3 8】

〔式中，R爲氫原子、低級烷基或鹵化低級烷基之意 :R15、R16爲烷基（可爲直鏈、支鏈狀皆可，較佳爲碳數 1 〜5 )〕。 通式（al”一 1 )〜（al” — 6 )中，R之低級烷基或鹵 化低級烷基，例如與上述可鍵結於丙烯酸酯之α位之低級 烷基或鹵化低級烷基爲相同之內容。 「縮醛型酸解離性溶解抑制基」一般爲鍵結於取代羧 基、羥基等之鹼可溶性基末端之氫原子的氧原子上。因此 ，經由曝光產生酸時，經由該酸之作用，而切斷縮醛型酸 解離性溶解抑制基與該縮醛型酸解離性溶解抑制基所鍵結 之氧原子之間的鍵結。 縮醛型酸解離性溶解抑制基，例如，下述通式（pi) 所示之基等。 【化3 9】 -C— O^CH^y (p 1) -79- 200947126 〔式中、R1’，R2’各自獨立表示氫原子或低級烷基，n 爲〇〜3之整數，Y爲低級烷基或脂肪族環式基〕。 上述式中，η以0〜2之整數爲佳，以0或1爲更佳 ，以〇爲最佳。 R1’、R2’之低級烷基，例如與上述R之低級烷基爲相 同之內容，又以甲基或乙基爲佳，以甲基爲最佳。 本發明中，以R1’、R2’中至少1個爲氫原子爲佳。即 ，酸解離性溶解抑制基（Ρ 1 )以下述通式（Ρ 1 — 1 )所示 之基爲佳。 【化4 0】Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group: R15 and R16 are an alkyl group (may be linear or branched, preferably having a carbon number of 1 to 5). In the formula (al"-1)~(al"-6), a lower alkyl group or a halogenated lower alkyl group of R, for example, a lower alkyl group or a halogenated lower alkyl group which may be bonded to the α-position of the acrylate as described above. The same content. The "acetal type acid dissociable dissolution inhibiting group" is generally bonded to an oxygen atom which is substituted with a hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or a hydroxyl group. Therefore, when an acid is generated by exposure, the bond between the acetal type acid dissociable dissolution inhibiting group and the oxygen atom to which the acetal type acid dissociable dissolution inhibiting group is bonded is cut by the action of the acid. The acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (pi). [Chem. 3 9] -C—O^CH^y (p 1) -79- 200947126 [wherein, R1', R2' each independently represent a hydrogen atom or a lower alkyl group, n is an integer of 〇~3, and Y is Lower alkyl or aliphatic cyclic group]. In the above formula, η is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 〇. The lower alkyl group of R1' and R2' is, for example, the same as the lower alkyl group of the above R, and preferably a methyl group or an ethyl group, and a methyl group is most preferable. In the present invention, it is preferred that at least one of R1' and R2' is a hydrogen atom. Namely, the acid dissociable dissolution inhibiting group (Ρ 1 ) is preferably a group represented by the following formula (Ρ 1-1 ). [化4 0]

〇4。七丫 …（Ρ 1 — 1) 〔式中、R1’、η、Υ係與上述內容爲相同之內容〕。 Υ之低級烷基，例如與上述R之低級烷基爲相同之內 容。 Υ之脂肪族環式基，例如可由以往於ArF光阻等之中 ，被多次提案之單環或多環式脂肪族環式基之中適當地選 擇使用，例如與上述「脂肪族環式基」爲相同之內容。 又，縮醛型酸解離性溶解抑制基，例如下述通式（P2 )所示之基等。 【化4 1】 R17 —C—Ο—R18 R18 200947126 〔式中、R17、R18各自獨立表示直鏈狀或支鏈狀之烷 基或氫原子’ R19爲直鏈狀、支鏈狀或環狀之烷基，或 R17與R19各自獨立表示直鏈狀或支鏈狀之伸烷基，R17之 末端與R19之末端鍵結形成環亦可〕。 R17、R18中，烷基之碳數較佳爲1〜15，其可爲直鏈 狀或支鏈狀皆可，又以乙基、甲基爲佳，以甲基爲最佳。 特別萆以R17、R18中之任一者爲氫原子，另一者爲 ^ 甲基爲最佳。 R19爲直鏈狀、支鏈狀或環狀之烷基時，碳數較佳爲 1〜15，其可爲直鏈狀、支鏈狀或環狀中任一者皆可。 R19爲直鏈狀或支鏈狀時，碳數以1〜5爲佳，又以乙 基、甲基爲更佳，以乙基爲最佳。 R19爲環狀時，以碳數4〜15爲佳，以碳數4〜12爲 更佳，以碳數5〜10爲最佳。具體而言，其可被氟原子或 氟化烷基取代，或未被取代皆可之單環鏈烷、二環鏈烷、 〇 三環鏈烷、四環鏈烷等多環鏈烷中去除1個以上氫原子之 基等。具體而言，例如環戊烷、環己烷等單環鏈烷，或金 剛烷、降冰片烷、異降冰片烷、三環癸烷、四環十二烷等 多環鏈烷中去除1個以上氫原子之基等。其中又以金剛烷 去除1個以上氫原子所得之基爲佳。 又，上述式中，R17與R19各自獨立表示直鏈狀或支 鏈狀之伸烷基（較佳爲碳數1〜5之伸烷基），且R19之 末端可與R17之末端鍵結亦可。 此時，R17與R19，與鍵結於R19之氧原子，與該氧原 -81 - 200947126 子與鍵結於R17之碳原子形成環式基。該環式基，以4〜7 員環爲佳，以4〜6員環爲更佳。該環式基之具體例’例 如四氫吡喃基、四氫呋喃基等。 結構單位（al)，以使用由下述通式（al— 0—1)所 示結構單位，與下述通式（al - 0 - 2)所示結構單位所成 群中所選出之1種以上爲佳。 【化4 2】〇 4.七丫 ...(Ρ 1 - 1) [wherein, R1', η, Υ are the same as the above). The lower alkyl group of hydrazine is, for example, the same as the lower alkyl group of the above R. The aliphatic cyclic group of hydrazine can be appropriately selected from among the monocyclic or polycyclic aliphatic cyclic groups which have been proposed many times in the conventional ArF photoresist, for example, and the above-mentioned "aliphatic ring type". The base is the same content. Further, the acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (P2). [Chemical 4 1] R17 —C—Ο—R18 R18 200947126 [wherein, R17 and R18 each independently represent a linear or branched alkyl group or a hydrogen atom. R19 is linear, branched or cyclic. The alkyl group, or R17 and R19 each independently represents a linear or branched alkyl group, and the terminal of R17 is bonded to the end of R19 to form a ring. In R17 and R18, the alkyl group preferably has 1 to 15 carbon atoms, and may be linear or branched, preferably ethyl or methyl, and most preferably methyl. In particular, either one of R17 and R18 is a hydrogen atom, and the other is preferably a methyl group. When R19 is a linear, branched or cyclic alkyl group, the number of carbon atoms is preferably from 1 to 15, and it may be any of a linear chain, a branched chain or a cyclic chain. When R19 is linear or branched, the carbon number is preferably from 1 to 5, more preferably ethyl or methyl, and most preferably ethyl. When R19 is a ring, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, it may be substituted by a fluorine atom or a fluorinated alkyl group, or may be removed from a polycyclic alkane such as a monocyclic alkane, a bicycloalkane, an anthracene tricycloalkane or a tetracycloalkane which is not substituted. One or more hydrogen atom groups or the like. Specifically, for example, a monocyclic alkane such as cyclopentane or cyclohexane or a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane is removed. The base of the above hydrogen atom or the like. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferred. Further, in the above formula, R17 and R19 each independently represent a linear or branched alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and the end of R19 may be bonded to the end of R17. can. At this time, R17 and R19, and the oxygen atom bonded to R19, form a cyclic group with the oxygen group -81 - 200947126 and the carbon atom bonded to R17. The ring base is preferably a 4 to 7 member ring, and a 4 to 6 member ring is preferred. Specific examples of the cyclic group are, for example, a tetrahydropyranyl group or a tetrahydrofuranyl group. The structural unit (al) is one selected from the group consisting of the structural unit represented by the following general formula (al-0-1) and the structural unit represented by the following general formula (al - 0 - 2) The above is better. [化4 2]

〔式中，R爲氫原子、鹵素原子、低級焼基或鹵化低 級烷基；X1爲酸解離性溶解抑制基〕° 【化4 3】Wherein R is a hydrogen atom, a halogen atom, a lower sulfhydryl group or a halogenated lower alkyl group; and X1 is an acid dissociable dissolution inhibiting group] ° [Chem. 4 3]

〔式中，R爲氫原子、低級院基或鹵化低級院基；X2 爲酸解離性溶解抑制基；Y2爲丨申院基或脂肪族環式基或 具有醚鍵結之2價之鍵結基〕° 通式（a i — 1 )中，R之低級烷基或鹵化低級烷基 -82- 200947126 ，係與上述可鍵結於丙烯酸酯之α位之低級烷基、鹵化低 級烷基爲相同之內容。 X1，只要爲酸解離性溶解抑制基時則未有特別限定， 例如可爲三級烷基酯型酸解離性溶解抑制基、縮醛型酸解 離性溶解抑制基等，又以三級烷基酯型酸解離性溶解抑制 基爲佳。 通式（al— 0-2)中，R具有與上述相同之內容。 0 X2則與式（al— 0-1)中之X1爲相同之內容。 Y2爲伸烷基或脂肪族環式基或具有醚鍵結之2價之 鍵結基。 Y2爲伸烷基時，較佳爲碳數1〜1 0之伸烷基，又以 碳數1〜6者爲佳，以碳數1〜4者爲更佳，以碳數1〜3 者爲最佳。 Y2爲脂肪族環式基時，較佳爲2價之脂肪族環式基 ，該脂肪族環式基除使用去除2個以上氫原子所得之基以 〇 外，其他皆與前述「脂肪族環式基」之說明中所使用者爲 相同之內容。 Y2爲2價之脂肪族環式基時，以由環戊烷、環己烷 、降冰片烷、異冰片烷、金剛烷、三環癸烷、四環十二烷 去除二個以上氫原子所得之基爲特佳。 Y2爲具有醚鍵結之2價鍵結基之情形，以—Ya— 〇 — Yb_所表示之基爲佳。 前述-Ya-〇-Yb —所表示之基中，Ya爲可具有取代 基之碳數2以上之2價之烴基。烴基，可爲脂肪族烴基或 -83- 200947126 芳香族烴基皆可。較佳爲脂肪族烴基。脂肪族烴基，可爲 直鏈狀或支鏈狀之脂肪族烴基，構造中含有環之脂肪族烴 基等。具體而言，例如與Y2爲2價之脂肪族環式基之情 形，或Y2爲伸烷基之情形所列舉之內容中’碳數爲2以 上之基爲相同之內容。又，Ya可具有取代基，該取代基 中，Ya爲鏈狀之脂肪族烴基之情形，例如氟原子 '氟原 子所取代之碳數1〜5之氟化低級烷基、氧原子（=0)[wherein, R is a hydrogen atom, a lower-grade or a halogenated lower-grade courtyard; X2 is an acid-dissociable dissolution-inhibiting group; and Y2 is a thiophene-based or aliphatic ring-based group or a 2-valent bond having an ether bond; In the formula (ai-1), the lower alkyl group of R or the halogenated lower alkyl group -82- 200947126 is the same as the lower alkyl group or the halogenated lower alkyl group which may be bonded to the α position of the acrylate. The content. X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and may be, for example, a tertiary alkyl ester type acid dissociable dissolution inhibiting group or an acetal type acid dissociating dissolution inhibiting group, and a tertiary alkyl group. The ester type acid dissociable dissolution inhibiting group is preferred. In the general formula (al-0-2), R has the same content as described above. 0 X2 is the same as X1 in the formula (al-0-1). Y2 is an alkylene or aliphatic cyclic group or a divalent bond group having an ether bond. When Y2 is an alkylene group, it is preferably an alkylene group having a carbon number of 1 to 10, and preferably a carbon number of 1 to 6, preferably a carbon number of 1 to 4, and a carbon number of 1 to 3. For the best. When Y2 is an aliphatic cyclic group, it is preferably a divalent aliphatic cyclic group, and the aliphatic cyclic group is the same as the above-mentioned "aliphatic ring" except that a base obtained by removing two or more hydrogen atoms is used. The user in the description of the formula is the same content. When Y2 is a divalent aliphatic cyclic group, two or more hydrogen atoms are removed by cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane or tetracyclododecane. The basis is especially good. Y2 is a case of a divalent bond group having an ether bond, and a group represented by -Ya - 〇 - Yb_ is preferred. In the group represented by the above-mentioned -Ya-〇-Yb-, Ya is a hydrocarbon group having a carbon number of 2 or more which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an -83-200947126 aromatic hydrocarbon group. It is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be a linear or branched aliphatic hydrocarbon group, and the structure may contain a cyclic aliphatic hydrocarbon group or the like. Specifically, for example, the case where Y2 is a divalent aliphatic cyclic group or the case where Y2 is an alkylene group is the same as the case where the carbon number is 2 or more. Further, Ya may have a substituent in which Ya is a chain-like aliphatic hydrocarbon group, for example, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom 'fluorine atom, and an oxygen atom (=0) )

等，Ya爲構造中含有環之脂肪族烴基之情形，係與上述 Q 之「脂肪族環式基」中之取代基爲相同之內容。In the case where Ya is an aliphatic hydrocarbon group having a ring in the structure, it is the same as the substituent in the "aliphatic cyclic group" of the above Q.

Ya，較佳者以直鏈狀之脂肪族烴基爲佳，以直鏈狀之 伸烷基爲更佳，以碳數2〜5之直鏈狀之伸烷基爲最佳， 以伸乙基爲特佳。Ya is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkyl group, and a linear alkyl group having a carbon number of 2 to 5 is preferred. It is especially good.

Yb爲可具有取代基之碳數1以上之2價烴基。Yb中 之烴基，係與前述Ya所列舉爲相同之碳數2以上之2價 烴基，及可具有取代基之伸甲基等。伸甲基所可具有之取 代基，例如與前述鏈狀之脂肪族烴基所可具有之取代基所 H 列舉之取代基爲相同之內容。Yb is a divalent hydrocarbon group having 1 or more carbon atoms which may have a substituent. The hydrocarbon group in Yb is a divalent hydrocarbon group having 2 or more carbon atoms which is the same as the above-mentioned Ya, and a methyl group which may have a substituent. The substituent which the methyl group may have, for example, is the same as the substituent of the substituent which the aforementioned aliphatic hydrocarbon group may have.

Yb，以直鏈狀或支鏈狀之脂肪族烴基爲佳，特別是以 伸甲基或烷基伸甲基爲佳。 烷基伸甲基中之烷基，以碳數1〜5之直鏈狀之烷基 爲佳，以碳數1〜3之直鏈狀之烷基爲更佳，以甲基爲最 佳。 結構單位（al)中，更具體而言，例如下述通式（al 一 1 )〜（al — 4 )所示之結構單位。 -84- 200947126 【化4 4】Yb is preferably a linear or branched aliphatic hydrocarbon group, particularly preferably a methyl group or an alkyl group. The alkyl group in the alkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. In the structural unit (al), more specifically, for example, a structural unit represented by the following general formula (al-1) to (al-4). -84- 200947126 【化4 4】

(al — 1) (a 1 —2) (a 1 ~3) (a 1 —4) 〔式中，X ’爲三級烷基酯型酸解離性溶解抑制基；γ 爲碳數1〜5之低級烷基，或脂肪族環式基；η爲〇〜3之 整數；Υ2爲伸烷基或脂肪族環式基或具有醚鍵結之2價 之鍵結基；R具有與上述相同之內容；R1’、R2’各自獨立 表示氫原子或碳數1〜5之低級烷基〕。 式中，X'係與前述X1中所例示之環狀之三級烷基酯 © 型酸解離性溶解抑制基爲相同之內$ °(al - 1) (a 1 - 2) (a 1 ~ 3) (a 1 - 4) [wherein, X ' is a tertiary alkyl ester type acid dissociable dissolution inhibiting group; γ is a carbon number of 1 to 5 a lower alkyl group, or an aliphatic cyclic group; η is an integer of 〇~3; Υ2 is an alkylene group or an aliphatic cyclic group or a divalent bond group having an ether bond; R has the same meaning as above R1' and R2' each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. In the formula, X' is the same as the cyclic tertiary alkyl ester exemplified in the above X1, and the acid dissociable dissolution inhibiting group is the same within the range of $ °

RJ，、R 解抑制基 2'、η、Υ係分別與上述之「縮醒型酸解離性溶 之說明中所列舉之通式（ρ1)中之r1’、r2’、The RJ, R solution inhibiting groups 2', η, and Υ are respectively the "r1" and r2' in the general formula (ρ1) recited in the above description of the awake type acid dissociable solution.

R1'、R η、Y爲相同之內容。 Υ2，例如與上述通式 (al- 0- 2)中之Y2爲相同之 內容。 以下爲上述通式（al (a 1 - 4 )所示之結構單 位之具體例， -85- 200947126 【化4 5】 CH3 -^CH2-㈠ )==V ch3o. 0=R1', R η, and Y are the same content. Υ2, for example, is the same as Y2 in the above formula (al- 0-2). The following is a specific example of the structural unit represented by the above formula (al (a 1 - 4 )), -85- 200947126 [Chemical 4 5] CH3 -^CH2-(一) )==V ch3o. 0=

•CH2—CH)0=A CHg•CH2—CH)0=A CHg

(al-1-1) Ϊ0 CH3 CH3 -^•CH2—?+· -|ch2—c-^- 0==\ CzHs 0==\ CHaCCHabCHa 0、‘ Λ(al-1-1) Ϊ0 CH3 CH3 -^•CH2—?+· -|ch2—c-^- 0==\ CzHs 0==\ CHaCCHabCHa 0, ‘ Λ

(a1-1-3)(a1-1-3)

(a1-W) (a1-1-2)(a1-W) (a1-1-2)

(a1-1-15) (a1_1~16) Ca1-1-t7) % % ❹ -86- 200947126 【化4 6】(a1-1-15) (a1_1~16) Ca1-1-t7) % % ❹ -86- 200947126 [Chem. 4 6]

ch3V) Ό °t&amp;(al-1-21) (al-1-22) (a1-1-23) ch3 -^~CK&lt;2-C-j— —^CH2—CH^&quot; 0=^ ch3 ch3ch3V) Ό °t&amp;(al-1-21) (al-1-22) (a1-1-23) ch3 -^~CK&lt;2-C-j—^CH2—CH^&quot; 0=^ ch3 ch3

(a1*1-24) CH3 I \ -ch2—c —^CH2—CH^— —^CH2—ch|- —|ch2—CH^- 0==1^ CH3/CH3 0==1^ CH3 0==^ ch3 o=\ ch3/ch3 o(a1*1-24) CH3 I \ -ch2—c —^CH2—CH^—^CH2—ch|- —|ch2—CH^- 0==1^ CH3/CH3 0==1^ CH3 0 ==^ ch3 o=\ ch3/ch3 o

CHgj CH3 (a1-1 -25) CHd 0'CHgj CH3 (a1-1 -25) CHd 0'

CH3(a1-1~26) O(al-1-27)CH3(a1-1~26) O(al-1-27)

-C-C

(a1-1-28)(a1-1-28)

-87- 200947126 【化4 7】-87- 200947126 【化4 7】

(al-1-37) (al-1-38) (a1-1-39) (al-1-40)(al-1-37) (al-1-38) (a1-1-39) (al-1-40)

(a1-1-41) (at~1~42) (a1-1-43) (a1-1-44) (a1-1_45) 【化4 8】(a1-1-41) (at~1~42) (a1-1-43) (a1-1-44) (a1-1_45) [Chem. 4 8]

88 200947126 【化4 9】 ch3 ch2-c·)— 〆〇 〇4 ch3 (a1-2-7)88 200947126 【化4 9】ch3 ch2-c·)— 〆〇 〇4 ch3 (a1-2-7)

(a1-2-8) CHS(a1-2-8) CHS

&quot;XKD (cH2-C-f (a1-2-9)&quot;XKD (cH2-C-f (a1-2-9)

J (a1*2&quot;10)J (a1*2&quot;10)

CH3 —{ch2-十妥 0==^ (a1-2-13) :¾ (al-2-11) -(ch2-ch)- (a1~2*14) 〆0CH3 —{ch2- 十妥 0==^ (a1-2-13) :3⁄4 (al-2-11) -(ch2-ch)- (a1~2*14) 〆0

-(chj-ch)-〇=K (a1-2-16) —(ch2-c}- 〇4 〇〜 (al-2-19)-(chj-ch)-〇=K (a1-2-16) —(ch2-c}- 〇4 〇~ (al-2-19)

.0 u r： -fcH2-〒今- (a1-2-17),r：如3十 ° °^°&quot;τΓ] (a1-2-20) (a1-2-12) CH3 —(ch2-c)— (a1-2-15&gt; —(d (a1-2-18) 200947126 【化5 0】.0 ur: -fcH2-〒今- (a1-2-17),r: such as 3°°°^°&quot;τΓ] (a1-2-20) (a1-2-12) CH3 —(ch2- c)—(a1-2-15&gt;—(d (a1-2-18) 200947126 【化5 0】

CHS 、0^/〇 (al-2-21) -^CHj—CH)- 4 « &lt;a1-2-22) -fcH2 CH] -{ch2-c4- ° 〇-^^〇、 (al-2-23) -(cHj-CH)- _^〇Η2_έ]— -fCH,-CH) 〇4- &quot;丫^ 0=O' / (a1-2-25) J (a1-2-26) (a1-2-24) —(CHj-C^- -(CH2-C4- —(cHj-C^—〇=l 〇4 Λ 〇=4, . (a1-2-27)CHS, 0^/〇(al-2-21) -^CHj—CH)- 4 « &lt;a1-2-22) -fcH2 CH] -{ch2-c4- ° 〇-^^〇, (al- 2-23) -(cHj-CH)- _^〇Η2_έ]— -fCH,-CH) 〇4- &quot;丫^ 0=O' / (a1-2-25) J (a1-2-26) (a1-2-24) —(CHj-C^- -(CH2-C4--(cHj-C^-〇=l 〇4 Λ 〇=4, . (a1-2-27)

(a1-2-28) ch3 (a1-2-29) (a1-2-31) 【化5 1(a1-2-28) ch3 (a1-2-29) (a1-2-31) [Chemical 5 1

(a1-2-38) (al-2-39) 200947126 【化5 2】 CHS CH3 --/ -’(a1-2-38) (al-2-39) 200947126 [Chem. 5 2] CHS CH3 --/ -’

C Γ c2h5VC Γ c2h5V

cT0 Yo C2HS-V^j — 上 （2 -^CHj-CH^- -^CH2-Ch)· -(CH2-CH·^· 〇=\ 0=4 0==Λ p 飞 pcT0 Yo C2HS-V^j — upper (2 -^CHj-CH^- -^CH2-Ch)· -(CH2-CH·^· 〇=\ 0=4 0==Λ p fly p

O C2HsO C2Hs

00

OO

&gt;〇&gt;〇

(e 卜3-10) h3c，\ / c2h5- (al-3-11) (al-3-12)(e 卜 3-10) h3c, \ / c2h5- (al-3-11) (al-3-12)

【化5 3】【化5 3】

-91 - 200947126 【化5 4】-91 - 200947126 [Chem. 5 4]

(»1-3-25) (al-3-26) («1-3-27) (al-3-28)(»1-3-25) (al-3-26) («1-3-27) (al-3-28)

(al-3-30)(al-3-30)

(al-3-31) (el-3-32) CHj-CH^-(al-3-31) (el-3-32) CHj-CH^-

(β1-3-3β) -92 200947126 【化5 5】 ch3 ch ^ ^ ^ ^(β1-3-3β) -92 200947126 [Chemical 5 5] ch3 ch ^ ^ ^ ^

Q =〇 &gt;〇 0’ (al-3-37) (al-3-38) (al-3-39) (al-3-40)Q =〇 &gt;〇 0’ (al-3-37) (al-3-38) (al-3-39) (al-3-40)

(al-3-41) (ai'3-42) ο ch3 ch 如;&lt;十如如gH-步如2。_《叶 Ο =0 0 0= (a 卜3*^3) Cat-3-44) 0= 0= 0= (a&lt;-3-45) (et-3-46) Cal-3-47) (a1-3-48) 【化5 6】 ❹ ch3 CHz~?~)~ -|ch2-ch)—(al-3-41) (ai'3-42) ο ch3 ch as; &lt; ten as gH-step as 2. _《叶Ο =0 0 0=(a 卜3*^3) Cat-3-44) 0= 0= 0= (a&lt;-3-45) (et-3-46) Cal-3-47) (a1-3-48) [化5 6] ❹ ch3 CHz~?~)~ -|ch2-ch)-

OO

O 戶〇 &gt;=〇 (at-3-49) (a1-3-50) -93- 200947126 【化5 7】 ch3 -(OHj-CH)- ^CHj-C-)- -fCH2~Ch)· -fCHj-C-fO 〇&gt;=〇(at-3-49) (a1-3-50) -93- 200947126 [Chemical 5 7] ch3 -(OHj-CH)- ^CHj-C-)- -fCH2~Ch) · -fCHj-Cf

oo

o &gt; Qo &gt; Q

O 〇 Q (al-4-1) (el+2) (al-4-5)O 〇 Q (al-4-1) (el+2) (al-4-5)

o- o 〇)O- o 〇)

o 〇&gt; o 〇&gt;o 〇&gt; o 〇&gt;

o 〇&gt; ^ ^ ^ 'Ό (a1~4-e) (at-4^-7) (a1-4*~8) (et -4-9) (a 卜4H0) (a1-4-11) , ch3 ch3 ch3 。o 0 〇 〇 p 0=^_ 0 0 h4〇 ^ 0.o 〇&gt; ^ ^ ^ 'Ό (a1~4-e) (at-4^-7) (a1-4*~8) (et -4-9) (a Bu 4H0) (a1-4-11 ), ch3 ch3 ch3. o 0 〇 〇 p 0=^_ 0 0 h4〇 ^ 0.

.0 o.0 o

PP

) 〇· o o) 〇· o o

o &gt;=0 〇. Qo &gt;=0 〇. Q

ό (•1-4-15) (al-4-Ιβ) 〇)© (al-4-17) -94- 200947126 Ο 【化5 8】ό (•1-4-15) (al-4-Ιβ) 〇)© (al-4-17) -94- 200947126 Ο 【化5 8】

(al-4-18) (·1~4Ί9) (.1-4-20) (al-4-21) (al+22) (·1_4_23) “’+24)(al-4-18) (·1~4Ί9) (.1-4-20) (al-4-21) (al+22) (·1_4_23) “’+24)

結構單位（al)，可單獨使用1種’或將2種以上組 〇 合使用亦可。 上述式中’又以通式（al - 1)所示之結構單位爲佳 。具體而言’以使用由式（al — 1-1)〜（al— 1—6)、 (al— 1— 17)〜（al— 1— 18) 、 ( al — 1— 35)〜（al —1—41)、及（al— 3-49)〜（al— 3— 50)所成群中 所選出之至少1種爲更佳。 又，結構單位（al )特別是以包含式（al — 1 — 1 )〜 (a 1 — 1 — 4 )之結構單位的下述通式（al — 1 — 01)所示 之單位’或包含式（al — 1—35)〜（al — 1— 41)之結構 -95- 200947126 單位的下述通式（al_1 一 〇2)者爲佳。 【化5 9】The structural unit (al) may be used singly or in combination of two or more. In the above formula, 'the structural unit represented by the formula (al - 1) is preferred. Specifically, 'by using the formula (al - 1-1) ~ (al - 1 - 6), (al - 1 - 17) ~ (al - 1 - 18), (al - 1 - 35) ~ (al At least one selected from the group consisting of -1 - 41) and (al - 3 - 49) - (al - 3 - 50) is more preferred. Further, the structural unit (al) is, in particular, a unit ' or a unit of the following general formula (al-1 - 01) containing a structural unit of the formula (al - 1 - 1 ) to (a 1 - 1 - 4 ) The structure of the formula (al - 1 - 35) ~ (al - 1 - 41) - 95 - 200947126 The unit of the following formula (al_1 - 2) is preferred. [化5 9]

〔式中，R爲氫原子、低級烷基或鹵化低級烷基， © R1 1爲低級院基〕。 【化6 0】Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R 1 1 is a lower-grade hospital base. [化60]

〔式中，R爲氫原子、低級烷基或鹵化低級烷基， R12爲低級烷基，h爲1〜3之整數〕。 通式（al_l— 01)中’ R具有與上述相同之內容。 R11之低級烷基係與R所示之低級烷基爲相同之內容 ，又以甲基或乙基爲佳。 通式（al— 1- 02)中，R具有與上述相同之內容。 R12之低級烷基係與前述R所示之低級烷基爲相同之 內容，又以甲基或乙基爲佳’又以乙基爲最佳。h以1或 2爲佳，又以2爲最佳。 -96- 200947126 結構單位（al) ’可單獨使用1種，或將2種以上組 合使用亦可。 (A1 )中’結構單位（a 1 )之比例，相對於構成（ A1 )成份之全體結構單位而言，以1〇〜莫耳％爲佳， 以2 0〜7 0莫耳％爲更佳，以2 5〜5 0莫耳％爲最佳。於下 限値以上時，於作爲光阻組成物時可容易形成圖型，於上 限値以下時，可與其他結構單位達成平衡。 ❹ •結構單位（a2 ) 結構單位（a2) ’爲含有含內酯之環式基之丙烯酸酯 所衍生之結構單位。 其中，含內酯之環式基，爲含有—0—C(0) —結構之 一個環（內酯環）之環式基。並以內酯環作爲一個環單位 進行計數，僅爲內酯環之情形爲單環式基，若尙具有其他 環結構時，無論其結構爲何，皆稱爲多環式基。 Q 結構單位（a2)之內酯環式基，於（A1)成份用於形 成光阻膜之情形中，可有效提高光阻膜對基板之密著性， 並可有效地提高與含有水之顯影液的親和性。 結構單位（a2 )，未有任何限定而可使用任意之單位 〇 具體而言，含內酯之單環式基’例如r — 丁內酯去除 1個氫原子所得之基等。又’含內酯之多環式基’例如由 具有內酯環之二環鏈烷、三環鏈烷、四環鏈烷去除1個氫 原子所得之基等。 -97- 200947126 結構單位（a2)之例示中’更具體而言’例如下述通 (a2 _ 1 )〜（a2 — 5 )所示結構單位等。 【化6 1】Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R12 is a lower alkyl group, and h is an integer of from 1 to 3. The 'R in the general formula (al_1-01) has the same content as described above. The lower alkyl group of R11 is the same as the lower alkyl group represented by R, and a methyl group or an ethyl group is preferred. In the general formula (al - 1- 02), R has the same contents as described above. The lower alkyl group of R12 is the same as the lower alkyl group represented by the above R, and preferably a methyl group or an ethyl group, and an ethyl group is most preferable. h is preferably 1 or 2, and 2 is the best. -96- 200947126 The structural unit (al) ' can be used singly or in combination of two or more. The ratio of 'structural unit (a 1 ) in (A1) is preferably from 1 〇 to mol%, and more preferably from 20 to 70 mol%, relative to the entire structural unit constituting the component (A1). , with 2 5~5 0 mol% as the best. When it is more than the lower limit, it can be easily formed into a pattern when it is used as a photoresist composition. When it is below the upper limit, it can be balanced with other structural units.结构 • Structural unit (a2) The structural unit (a2) ' is a structural unit derived from an acrylate containing a lactone-containing cyclic group. Here, the cyclic group containing a lactone is a cyclic group having a ring (lactone ring) of a structure of -0-C(0). The lactone ring is counted as a ring unit, and the monocyclic group is only a lactone ring. If the ring has other ring structures, it is called a polycyclic group regardless of its structure. The structure of the Q (a2) lactone ring group, in the case where the (A1) component is used to form the photoresist film, the adhesion of the photoresist film to the substrate can be effectively improved, and the water content can be effectively improved. The affinity of the developer. The structural unit (a2) may be any unit without any limitation. Specifically, a monocyclic group containing a lactone, for example, a group obtained by removing one hydrogen atom from er-butyrolactone or the like. Further, the polycyclic group having a lactone is, for example, a group obtained by removing one hydrogen atom from a bicycloalkane having a lactone ring, a tricycloalkane or a tetracycloalkane. -97- 200947126 In the example of the structural unit (a2), 'more specifically', for example, the structural unit shown by the following (a2 _ 1 ) to (a2 - 5). 【化6 1】

[式中，R爲氫原子、低級烷基或鹵化低級烷基，R· 〇 爲氫原子、低級烷基’或碳數1〜5之院氧基或一 COOR&quot; ，前述R&quot;爲氫原子’或碳數1〜15之直鏈狀、支鏈狀或 環狀之烷基，111爲0或1之整數’ A&quot;爲可含有氧原子或硫 原子之碳數1〜5之伸院基' 氧原子或硫原子〕。 通式（a2 - 1)〜（a2— 5)中之R具有與上述結構單 位（al)中之R爲相同之內容。 R’之低級烷基’具有與上述結構單位（al)中之尺的 低級烷基爲相同之內容。 R”爲直鏈狀或支鏈狀之烷基之情形中’以碳數1〜10 爲佳，又以碳數1〜5爲最佳。 R”爲環狀之烷基之情形中，以碳數3〜15爲佳，以碳 數4〜12爲更佳，以碳數5〜10爲最佳。具體而言，例如 可被氟原子或氟化烷基所取代，或未被取代之單環鏈烷、 二環鏈烷、三環鏈烷、四環鏈烷多環鏈烷去除1個以上之 氫原子所得之基等。具體之內容如由環戊烷、環己烷等單 環鏈烷，或金剛烷、降冰片烷、異冰片烷、三環癸烷、四 -98- 200947126 環十二烷等多環鏈烷去除1個以上之氫原子所得之基等。 遜式（a2—l)〜（a2— 5)中，R1於考慮工業上容易 取得等觀點，以使用氫原子爲佳。 A&quot;之可含有氧原子或硫原子之碳數1〜5之伸院基’ 具體而言，例如，伸甲基、伸乙基、n 一伸丙基、異伸丙 基、 Ο 〜Ο — CH2 -、 CH2 〜s _ Ch2 一等。 以下爲前述通式 CHa — 〇 — CΗ2 一 、一 S 一 CΗ2 a2 — 1 ) (a2— 5 )之具體結構單 示 【化S 2】 CH3 &lt;a2小 CH3 Ο ^ch2-ch)- -^ch2-c^· ch2 (a2-1-4&gt; (a2-1-5) &lt;a2-1-6) -99- 200947126 【化6 3】 ch3 ch3如 如2-丫呤七H2-令 + -fCH2-c). 0= Γ 〇4 ：-1) 〇 (a2-2-2) (a2-2-3) 0= 〇_ CH3Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R·〇 is a hydrogen atom, a lower alkyl group or an alkoxy group having a carbon number of 1 to 5 or a COOR&quot;, and the aforementioned R&quot; is a hydrogen atom 'or a linear, branched or cyclic alkyl group having a carbon number of 1 to 15, and 111 is an integer of 0 or 1. 'A&quot; is a carbon number of 1 to 5 which may contain an oxygen atom or a sulfur atom. 'Oxygen or sulfur atom'. R in the general formulae (a2 - 1) to (a2 - 5) has the same content as R in the above structural unit (al). The lower alkyl group of R' has the same content as the lower alkyl group of the above structural unit (al). In the case where R" is a linear or branched alkyl group, it is preferably a carbon number of 1 to 10, and preferably a carbon number of 1 to 5. When R" is a cyclic alkyl group, The carbon number is preferably from 3 to 15, preferably from 4 to 12 carbon atoms, and most preferably from 5 to 10 carbon atoms. Specifically, for example, one or more unsubstituted monocyclic alkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkane polycyclic alkanes may be removed by a fluorine atom or a fluorinated alkyl group. The base obtained by a hydrogen atom or the like. Specific contents are as follows: monocyclic alkane such as cyclopentane or cyclohexane, or polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetra-98-200947126 cyclododecane. A group obtained by one or more hydrogen atoms. In the case of the (a2 - 1) to (a2 - 5), it is preferable to use a hydrogen atom in view of the fact that it is easy to obtain industrially. A&quot; may contain an oxygen atom or a sulfur atom having a carbon number of 1 to 5, specifically, for example, methyl, ethyl, n-propyl, iso-propyl, Ο~Ο-CH2 -, CH2 ~ s _ Ch2 First class. The following is a specific structure of the above-mentioned general formula CHa - 〇 - C Η 2, a S - C Η 2 a2 - 1 ) (a2 - 5). [S2] CH3 &lt; a2 small CH3 Ο ^ch2-ch) - -^ Ch2-c^· ch2 (a2-1-4&gt; (a2-1-5) &lt;a2-1-6) -99- 200947126 [Chem. 6 3] ch3 ch3 as in 2-丫呤七 H2-令+ -fCH2-c). 0= Γ 〇4 :-1) 〇(a2-2-2) (a2-2-3) 0= 〇_ CH3

(a2-2-1) 〇 (a2-2-2) CH3 ch3(a2-2-1) 〇 (a2-2-2) CH3 ch3

O (82-2-4) ch3 -(CHj-C-)- -fcH2-C-)- -(CH2-CH 〇=J^ ch3 0=4^ 〇==\_ f -fcH2-cf0=1 (a2-2-5) 〇O (82-2-4) ch3 -(CHj-C-)- -fcH2-C-)- -(CH2-CH 〇=J^ ch3 0=4^ 〇==\_ f -fcH2-cf0=1 (a2-2-5) 〇

0 (a2-2-7) o CH3·0 (a2-2-7) o CH3·

CT (a2-2-8)CT (a2-2-8)

(a2-2-6)(a2-2-6)

-100- 200947126 【化6 4】-100- 200947126 【化6 4】

(a2-3-10) -101 - 200947126 【化6 5】(a2-3-10) -101 - 200947126 [Chem. 6 5]

-102 - 200947126 【化6 6】 CHa-102 - 200947126 【化6 6】CHa

結構單位（a2)中，以使用由前述通式（a2— 1)〜 Q (a2— 5)所示結構單位所形成之群所選出之至少1種爲 佳，又以由通式（a2 - 1 )〜（a2 — 3 )所示結構單位所成 群中所選出之至少1種爲更佳。其中，又以由化學式（a2 _ 1 — 1) 、( ά2 — 1 — 2 ) 、( a. 2 — 2 — 1) 、（a2 — 2 - 2 ) 、(a 2 — 2 — 9) Λ ( a 2 — 2 — 10) 、( a 2 — 3 一 1) 、（a2 —3— 2) 、（a2— 3— 9)與（a2— 3 - 10)所示結構單位 所成群中所選出之至少1種爲佳。 結構單位（a2 )，可單獨使用1種，或將2種以上組 合使用亦可。 -103- 200947126 (A1)成份中，結構單位（a2)的比例，以對構成（ A 1 )成份之全體結構單位之合計，以5〜6 0莫耳％爲佳， 以1 0〜5 0莫耳％爲較佳，以2 0〜5 〇莫耳％爲最佳。於下 限値以上時’含有結構單位（a2)時可充分達到效果，於 上限値以下時，可得到與其他結構單位之平衡。 •結構單位（a3) 結構單位（a3 )，爲含有含極性基之脂肪族烴基之丙 烯酸酯所衍生之結構單位。 (A1)成份含有結構單位（a3)時，可提高（A1) 成份之親水性’而提高與顯影液之親和性，進而提昇曝光 部之鹼溶解性’而可期待解析度之提升。 極性基’例如羥基、氰基、羧基、烷基中一部份氫原 子被氟原子取代之羥烷基等，又以羥基爲最佳。 脂肪族烴基’例如碳數1〜1 〇之直鏈狀或支鏈狀烴基 (較佳爲伸烷基），或多環式之脂肪族烴基（多環式基） 等。該多環式基’例如可由ArF準分子雷射用光阻組成物 用之樹脂中’由多數提案內容中作適當選擇使用。該多環 式基的碳數爲7〜30較佳。 其中’又以含有羥基、氰基、羧基，或含有烷基中氫 原子之一部份被氟原子取代之羥烷基的脂肪族多環式基之 丙烯酸酯所衍生之結構單位爲更佳。該多環式基，例如由 二環鏈烷、三環鏈烷、四環鏈烷中去除2個以上之氫原子 所得之基等。具體而言，例如由金剛烷、降冰片烷、異降 -104- 200947126 冰片烷、三環癸烷、四環十二烷等多環鏈烷中去除2個以 上氫原子所得之基等。前述多環式基中，又以金剛院去除 2個以上氫原子之基、降冰片烷去除2個以上氫原子之基 、四環十二烷去除2個以上氫原子之基等更適合工業上使 用。 結構單位（a3)中，於含有極性基之脂肪族烴基中之 烴基爲碳數1〜10之直鏈狀或支鏈狀烴基時’以由丙烯酸 之羥乙基酯所衍生之結構單位爲佳’該烴基爲多環式基時 ’例如下式（a3 - 1 )所示結構單位、（a3 — 2 )所示結構 單位、（a3 — 3 )所示結構單位等爲佳。 【化6 7】In the structural unit (a2), at least one selected from the group consisting of the structural units represented by the above formulas (a2-1) to Q(a2-5) is preferred, and the formula (a2 - It is preferable that at least one selected from the group consisting of structural units represented by 1 to (a2 - 3) is preferable. Among them, by the chemical formula (a2 _ 1 - 1), ( ά 2 - 1 - 2 ), ( a. 2 - 2 - 1), (a2 - 2 - 2 ), (a 2 - 2 - 9) Λ ( a 2 - 2 - 10) , ( a 2 - 3 - 1) , (a2 - 3 - 2) , (a2 - 3 - 9) and (a2 - 3 - 10) are selected from the group of structural units At least one of them is preferred. The structural unit (a2) may be used alone or in combination of two or more. -103- 200947126 (A1) The ratio of the structural unit (a2) to the total structural unit of the component (A 1 ) is preferably 5 to 60 mol%, and 1 0 to 50. Molar% is preferred, and 2 0 to 5 〇 mol% is the best. When the lower limit is exceeded, the effect can be sufficiently achieved when the structural unit (a2) is contained, and the balance with other structural units can be obtained when the upper limit is less than or equal to the upper limit. • Structural unit (a3) The structural unit (a3) is a structural unit derived from an acrylate having an aliphatic hydrocarbon group containing a polar group. When the component (A3) contains a structural unit (a3), the hydrophilicity of the component (A1) can be improved, and the affinity with the developer can be improved, and the alkali solubility of the exposed portion can be improved, and the resolution can be expected to be improved. A polar group such as a hydroxyl group, a cyano group, a carboxyl group, a hydroxyalkyl group in which a part of hydrogen atoms in the alkyl group is substituted by a fluorine atom, and the like are preferably a hydroxyl group. The aliphatic hydrocarbon group 'e.e., a linear or branched hydrocarbon group having a carbon number of 1 to 1 Torr (preferably an alkylene group) or a polycyclic aliphatic hydrocarbon group (polycyclic group). The polycyclic group ' can be suitably used, for example, from a resin for a photoresist composition for an ArF excimer laser.' The polycyclic group preferably has a carbon number of from 7 to 30. Further, the structural unit derived from an acrylate having a hydroxyl group, a cyano group, a carboxyl group, or an aliphatic polycyclic group containing a hydroxyalkyl group in which one of hydrogen atoms in the alkyl group is substituted by a fluorine atom is more preferable. The polycyclic group is, for example, a group obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, for example, a group obtained by removing two or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isoborn-104-200947126 norbornane, tricyclodecane or tetracyclododecane. In the polycyclic group, it is more suitable for industrial use to remove two or more hydrogen atoms from the diamond plant, to remove two or more hydrogen atoms from the norbornane, and to remove two or more hydrogen atoms from the tetracyclododecane. use. In the structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group having a polar group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, it is preferable that the structural unit derived from hydroxyethyl acrylate is preferred. When the hydrocarbon group is a polycyclic group, for example, a structural unit represented by the following formula (a3 - 1), a structural unit represented by (a3 - 2), a structural unit represented by (a3 - 3), or the like is preferable. 【化6 7】

〔式中，R具有與前述相同之內容，j爲1〜3之整數 ，让爲1〜3之整數，t’爲1〜3之整數，1爲1〜5之整數 ，s爲1〜3之整數〕。 通式（a3 — 1 )中，j以1或2爲佳，又以1爲更佳。 j爲2之情形中，以羥基鍵結於金剛烷基之3位與5位者 爲更佳。j爲1之情形中，特別是以羥基鍵結於金剛烷基 之3位爲最佳。 -105- 200947126 其中，又以j爲1爲佳’特別是經基鍵結於金剛院基 之3位者爲最佳。 式（a3- 2)中，以k爲1者爲佳。又以氰基鍵結於 降冰片烷基之5位或6位者爲佳。 式（a3 一 3 )中，以t·爲1者爲佳，以1爲1者爲佳 ，以s爲1者爲佳。其以丙烯酸之羧基的末端鍵結2—降 冰片烷基或3-降冰片烷基者爲佳。氟化烷基醇以鍵結於 降冰片烷基之5或6位者爲佳。 結構單位（a3)，可單獨使用1種，或將2種以上組 合使用亦可。 (A1 )成份中，結構單位（a3 )之比例，相對於構成 (A1 )成份之全體結構單位，以5〜50莫耳％爲佳，以5 〜40莫耳％爲更佳，以5〜25莫耳％爲最佳。於下限値以 上時，可充分得到含有結構單位（a3)之效果，於上限値 以下時可得到與其他結構單位之平衡性。 •結構單位（a4 ) (A1)成份，於不損害本發明之效果之範圍中，可 再含有上述結構單位（al)〜（a3)以外之其他結構單位 (a4 )。 結構單位（a4)只要爲未分類於前述結構單位（al) 〜（a3 )以外之結構單位時，並無特別限定。其可使用 ArF準分子雷射用、KrF準分子雷射用（較佳爲ArF準分 子雷射用）等光阻用樹脂所使用之以往已知之多數結構單 -106- 200947126 位。 結構單位（a4 )，例如含有非酸解離性之脂肪族多環 式基的丙烯酸酯所衍生之結構單位等爲佳。該多環式基， 例如爲與前述結構單位（al )時所例示之相同例示內容， 其可使用ArF準分子雷射用、KrF準分子雷射用（較佳爲 ArF準分子雷射用）等光阻組成物之樹脂成份所使用之以 往已知之多數結構單位。 特別是由三環癸烷基、金剛烷基、四環十二烷基、異 降冰片烷基、降冰片烷基所選出之至少1種以上時，以工 業上容易取得而爲較佳。此等多環式基，可被碳數1〜5 之直鏈狀或支鏈狀之烷基取代亦可。 結構單位（a4 )，具體而言，例如下述通式（a4 - 1 )〜（a4 — 5 )所示結構單位等。 【化6 8】[wherein R has the same content as described above, j is an integer of 1 to 3, an integer of 1 to 3, t' is an integer of 1 to 3, 1 is an integer of 1 to 5, and s is 1 to 3 The integer]. In the formula (a3 - 1), j is preferably 1 or 2, and more preferably 1 is used. In the case where j is 2, it is more preferable that the hydroxyl group is bonded to the 3 and 5 positions of the adamantyl group. In the case where j is 1, it is particularly preferable that the hydroxyl group is bonded to the 3 position of the adamantyl group. -105- 200947126 Among them, it is better to use j as the first one, especially the one with the base bond of the King Kong base. In the formula (a3 - 2), it is preferred that k is one. Further, it is preferred that the cyano group is bonded to the 5- or 6-position of the norbornyl group. In the formula (a3 to 3), it is preferable that t is 1 or 1 is preferred, and s is preferably 1. It is preferably a terminal bond 2 - norbornyl group or 3-norbornyl group of a carboxyl group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group. The structural unit (a3) may be used alone or in combination of two or more. In the component (A1), the ratio of the structural unit (a3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and more preferably 5 to 50 mol% of the total structural unit constituting the component (A1). 25% Mo is the best. When the lower limit is 値 or more, the effect of containing the structural unit (a3) can be sufficiently obtained, and when it is less than the upper limit 値, the balance with other structural units can be obtained. • The structural unit (a4) (A1) component may further contain other structural units (a4) other than the structural units (al) to (a3) insofar as the effects of the present invention are not impaired. The structural unit (a4) is not particularly limited as long as it is a structural unit that is not classified into the structural units (al) to (a3). It is possible to use a conventionally known structure of -106-200947126 used for a resist resin such as an ArF excimer laser or a KrF excimer laser (preferably for ArF quasi-laser laser). The structural unit (a4), for example, a structural unit derived from an acrylate having a non-acid dissociable aliphatic polycyclic group is preferred. The polycyclic group is, for example, the same as exemplified in the above structural unit (al), and can be used for ArF excimer laser or KrF excimer laser (preferably for ArF excimer laser). Most of the structural units previously known for use in the resin composition of the photoresist composition. In particular, when at least one selected from the group consisting of a tricyclodecylalkyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is industrially preferable, it is preferably obtained. These polycyclic groups may be substituted by a linear or branched alkyl group having 1 to 5 carbon atoms. The structural unit (a4) is specifically, for example, a structural unit represented by the following general formula (a4 - 1) to (a4 - 5). 【化6 8】

〔式中，R具有與前述相同之內容〕。 (A1)成份中含有前述結構單位（a4)時，（A1) 成份中之結構單位（a4 )之比例，相對於構成（a 1 )成份 之全體結構單位之合計，以含有1〜3 0莫耳％爲佳，又以 含有10〜20莫耳％爲更佳。 -107- 200947126 本發明中，（A1)成份以含有具有結構單位（ (a2)、及（a3)之共聚物爲佳。前述共聚物，例 構單位（al) 、（a2)、及（a3)所得之共聚物， 位（al) 、（a2) 、（a3)及（a4)所得之共聚物 (A1)成份，可將各結構單位所衍生之單體 使用偶氮二異丁腈（AIBN )等自由基聚合引發劑 之自由基聚合等聚合反應而製得。 又，（A1)成份，於上述聚合之際，例如可伤 —CH2— CH2— CH2— C(CF3)2~- oh 等鏈移轉劑’而 導入—C(CF3)2- OH基。如此，可得到導入有烷基 子之一部份被氟原子取代之羥烷基的共聚物，因而 降低缺陷或降低LER ( Line Edge Roughness :線路 有不均勻凹凸）之效果。 (A1)成份之質量平均分子量（Mw)(凝膠 層分析法之聚苯乙烯換算量）並未有特別限定， 2,000〜50,000爲佳，以3,000〜30,000爲更佳，公 〜20,00 0爲最佳。小於此範圍之上限時，作爲光阻 對光阻溶劑可得到充分之溶解性，大於此範圍之下 可得到良好之耐乾蝕刻性或光阻圖型之截面形狀。 又’分散度（Mw/Mn )以1.0〜5.0之範圍爲 1_〇〜3.0爲更佳，以1.2〜2.5爲最佳。又，Μη爲 分子量。 〔（A2)成份〕 a 1 )、 如由結 結構單 等。 ，例如 依公知 t用 HS 於末端 中氫原 可有效 側壁具 滲透色 一般以 I 5,000 使用時 限時， 佳，以 數平均 -108- 200947126 (A2)成份，以分子量爲500以上、未達2000 有上述（A 1 )成份之說明中所例示之酸解離性溶解 基，與親水性基之低分子化合物爲佳。具體而言，具 數之酚骨架之化合物的羥基之氫原子的一部份被上述 離性溶解抑制基所取代之化合物等。 (A2 )成份，例如，已知非化學增幅型之g線或 光阻中之增感劑，或耐熱性提升劑之低分子量酚化合 Q 羥基之氫原子之一部份被上述酸解離性溶解抑制基所 之成份，前述成份可任意使用。 該低分子量酚化合物，例如，雙（4-羥基苯基 烷、雙（2,3,4 _三羥基苯基）甲烷、2— (4 -羥基 )—2-（4· 一羥基苯基）丙烷、2_ (2,3，4 一三羥基 )—2— (2、3'，4'一三羥基苯基）丙烷、三（4 一羥基 )甲烷、雙（4 —羥基—3，5—二甲基苯基）—2 —羥 基甲烷、雙（4 —羥基—2,5 -二甲基苯基）—2 —羥 Q 基甲烷、雙（4 一羥基—3,5 —二甲基苯基）—3,4 — 基苯基甲烷、雙（4 -羥基—2,5 —二甲基苯基） 二羥基苯基甲烷、雙（4 一羥基—3 —甲基苯基） 二羥基苯基甲烷、雙（3 —環己基一4 一羥基一 6—甲 基）一4一羥基苯基甲烷、雙（3 —環己基-4—羥基-甲基苯基）一3,4 —二羥基苯基甲烷、1一〔1_ (4一 苯基）異丙基〕—4—〔1，1 一雙（4 —羥基苯基）乙 苯、酚、m—甲酚、p_甲酚或二甲酚等酚類之甲醛 合物之2、3、4核體等。當然並不限定於此。 之具 抑制 有複 酸解 i線 物的 取代 )甲 苯基 苯基 苯基 基苯 基苯 二羥 1,4 - 丨，4 - 基苯 -6 — 羥基 基〕 水縮 -109- 200947126 酸解離性溶解抑制基並未有特別限定’例如可爲上述 之內容。 (A)成份，可單獨使用1種’或將2種以上合併使 用。 本發明之光阻組成物中，（A)成份之含量，可配合 所欲形成之光阻膜厚度等進行調整即可。 &lt; (B )成份&gt; (B)成份，爲含有前述通式（bl-1)所表示之化合 物所形成之酸產生劑（B 1 )(以下，亦稱爲（B1 )成份 )。該（B1)成份，係與前述本發明之化合物（B1)爲 相同之內容。 (B1)成份，可使用1種或將2種以上混合使用。 又，本發明之光阻組成物中，（B)成份中（B1)成 份之含量，以40質量％以上爲佳，以70質量％以上爲更 佳，亦可爲100質量％。最佳爲100質量％。於該範圍之 下限値以上時，使用本發明之光阻組成物形成光阻圖型之 際，可提高解析性、遮罩重現性、線路寬度不均度（LWR )、圖型形狀、曝光量（EL)寬容度、焦點景深寬度（ DOF )等微影鈾刻特性。 (B)成份中，前述（B1)成份以外之酸產生劑（B2 )(以下亦稱爲（B2)成份）亦可倂用前述（B1)成份 〇 (B2)成份，只要爲前述（B1)成份以外之成份時 -110- 200947126 並未有特別限定，其可使用目前爲止被提案作爲化學增ψ畐 型光阻用之酸產生劑的成份。 前述酸產生劑，目前爲止例如碘鎗鹽或锍鹽等鑷鹽系 酸產生劑，肟磺酸酯系酸產生劑、雙烷基或雙芳基磺醯基 重氮甲烷類、聚（雙磺醯基）重氮甲烷類等重氮甲烷系酸 產生劑、硝基苄磺酸酯類系酸產生劑、亞胺基磺酸酯系酸 產生劑、二楓類系酸產生劑等多種已知化合物。 鎗鹽系酸產生劑，例如可使用下述通式（b _ 1 )或（ b - 2 )所示化合物。 【化6 9】[wherein R has the same content as described above]. When the component (a4) is contained in the component (A1), the ratio of the structural unit (a4) in the component (A1) is 1 to 30% with respect to the total of the structural units constituting the component (a1). The ear % is preferably more preferably 10 to 20 mol%. -107- 200947126 In the present invention, the component (A1) is preferably a copolymer having a structural unit ((a2), and (a3). The copolymer, the constituent units (al), (a2), and (a3) The obtained copolymer, the copolymer (A1) obtained in (al), (a2), (a3) and (a4), can be used as azobisisobutyronitrile (AIBN) for the monomer derived from each structural unit. And a polymerization reaction such as radical polymerization of a radical polymerization initiator, etc. Further, the component (A1) may be, for example, injurious at the time of the polymerization, CH2—CH2—CH2—C(CF3)2~-oh, etc. The chain transfer agent' is introduced into a -C(CF3)2-OH group. Thus, a copolymer into which a hydroxyalkyl group in which one of the alkyl groups is substituted by a fluorine atom can be obtained, thereby reducing defects or reducing LER (Line Edge Roughness: The effect of the unevenness of the line. (A1) The mass average molecular weight (Mw) of the component (the polystyrene conversion amount of the gel layer analysis method) is not particularly limited, and 2,000 to 50,000 is preferable, and 3,000 〜 30,000 is better, and the best is ~20,00 0. Below the upper limit of this range, it can be obtained as a photoresist against photoresist. The solubility of the fraction is larger than the range to obtain a good dry etching resistance or a cross-sectional shape of the photoresist pattern. Further, the degree of dispersion (Mw/Mn) is preferably 1.0 to 5.0 in the range of 1.0 to 5.0. It is preferably 1.2 to 2.5. Further, Μη is a molecular weight. [(A2) component] a 1 ), such as a single structure. For example, it is known that HS is used in the terminal end. Hydrogen is effective. The side wall has a penetrating color. Generally, when the time is 1 5,000, the average number is -108-200947126 (A2), and the molecular weight is 500 or more, less than 2000. The acid dissociable dissolving group exemplified in the description of the above (A 1 ) component is preferably a low molecular compound of a hydrophilic group. Specifically, a compound in which a part of a hydrogen atom of a hydroxyl group of a compound having a phenol skeleton is substituted with a above-mentioned cleavage-suppressing group or the like. (A2) component, for example, a sensitizer in a g-line or photoresist which is known to be a non-chemically amplified type, or a part of a hydrogen atom of a low molecular weight phenolic compound Q hydroxy group of a heat-resistant enhancer is dissolved by the above-mentioned acid dissociation The components of the group are inhibited, and the aforementioned components can be used arbitrarily. The low molecular weight phenol compound, for example, bis(4-hydroxyphenylalkane, bis(2,3,4-trihydroxyphenyl)methane, 2-(4-hydroxy)-2-(4-hydroxyphenyl) Propane, 2_(2,3,4-trihydroxy)-2-(2,3',4'-trihydroxyphenyl)propane, tris(4-hydroxy)methane, bis(4-hydroxy-3,5- Dimethylphenyl)-2-hydroxymethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyl-methane, bis(4-hydroxy-3,5-dimethylbenzene —3,4 —phenylphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)dihydroxyphenylmethane, bis(4-hydroxy-3-methylphenyl)dihydroxybenzene Methane, bis(3-cyclohexyl-4-hydroxy-6-methyl)-tetrahydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-methylphenyl)-3,4-dihydroxy Phenylmethane, 1-[1-(4-phenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethylbenzene, phenol, m-cresol, p-cresol or two 2, 3, 4 nucleus of a phenolic phenolic compound such as cresol, etc. Of course, it is not limited thereto. Substitution of acidolysis i-line) tolylphenylphenylphenyl phenyl dihydroxy 1,4 - fluorene, 4-phenylbenzene-6 - hydroxy group] water shrinkage -109- 200947126 Acid dissociation dissolution inhibitory group There is a particular limitation 'for example, the above may be the content. (A) The components may be used singly or in combination of two or more. In the photoresist composition of the present invention, the content of the component (A) may be adjusted in accordance with the thickness of the photoresist film to be formed. &lt; (B) Component&gt; The component (B) is an acid generator (B 1 ) (hereinafter, also referred to as a component (B1)) which is formed by containing the compound represented by the above formula (bl-1). The component (B1) is the same as the above-mentioned compound (B1) of the present invention. (B1) The components may be used alone or in combination of two or more. Further, in the resist composition of the present invention, the content of the component (B1) in the component (B) is preferably 40% by mass or more, more preferably 70% by mass or more, and may be 100% by mass. The best is 100% by mass. When the photoresist pattern of the present invention is used to form a photoresist pattern at a lower limit of the range, the resolution, mask reproducibility, line width unevenness (LWR), pattern shape, and exposure can be improved. The lithography characteristics such as the amount of (EL) latitude and the depth of field (DOF). In the component (B), the acid generator (B2) other than the above component (B1) (hereinafter also referred to as (B2) component) may also be used as the component (B2) of the above (B1) component, as long as the above (B1) When the ingredients other than the ingredients are -110-200947126, there is no particular limitation, and the ingredients which have been proposed so far as acid generators for chemically amplified photoresists can be used. The acid generator is, for example, an oxime salt-based acid generator such as an iodine salt or a sulfonium salt, an oxime sulfonate-based acid generator, a dialkyl or bisarylsulfonyldiazomethane, or a polysulfonate.醯 base) diazomethane acid generator such as diazomethane, nitrobenzyl sulfonate acid generator, iminosulfonate acid generator, bismuth acid generator, etc. Compound. As the gun salt acid generator, for example, a compound represented by the following formula (b _ 1 ) or ( b - 2 ) can be used. 【化6 9】

〔式中，R1&quot;〜R3&quot;、R5”及R6&quot;，各自獨立爲芳基或烷 基：式（b— 1)中之R1&quot;〜R3&quot;中，任意2個可相互鍵結並 〇 與式中之硫原子共同形成環亦可：R4&quot;爲直鏈狀、支鏈狀 或環狀烷基或氟化烷基；R1&quot;〜R3&quot;中至少1個爲芳基，Rv 〜r6’’中至少1個爲芳基〕。 式（b—l)中，R1&quot;〜R3”各自獨立與前述（b1— 1)中 之R1&quot;〜R3’_爲相同之內容。 R4&quot;爲直鏈狀、支鏈狀或環狀之烷基，或直鏈狀、支 鏈狀或環狀氟化烷基。 前述直鏈狀或支鏈狀之烷基，以碳數1〜10者爲佳， 以碳數1〜8者爲更佳，以碳數1〜4者爲最佳。 -111 - 200947126 前述環狀之烷基，係如前述R1&quot;所示環式基，其以碳 數4〜15者爲佳，以碳數4〜10者爲更佳，以碳數6〜10 者爲最佳。 前述氟化烷基，以碳數1〜10者爲佳，以碳數1〜8 者爲更佳，以碳數1〜4者爲最佳。 又，該氟化烷基之氟化率（烷基中氟原子之比例）較 佳爲1 〇〜1 0 0 %，更佳爲5 0〜1 0 0 %，特別是氫原子全部被 氟原子取代所得氟化烷基（全氟烷基）者，以其酸之強度 更強而爲更佳。 R4&quot;，以直鏈狀或環狀之烷基，或直鏈狀、支鏈狀或 環狀氟化烷基者爲最佳。 式（b-2)中，R5&quot;及R6&quot;各自獨立爲與前述（V — 2 )中之R5&quot;及R6&quot;爲相同之內容。 式（b_2)中之R4”爲與前述（b—l)中之R4&quot;爲相 同之內容。 式（b— 1) 、（b— 2)所示鎗鹽系酸產生劑之具體例 如，二苯基碘鎗之三氟甲烷磺酸酯或九氟丁烷磺酸酯、雙 (4 一 tert—丁基苯基）碘鑰之三氟甲烷磺酸酯或九氟丁烷 磺酸酯、三苯基锍之三氟甲烷磺酸酯、其七氟丙烷磺酸酯 或其九氟丁烷磺酸酯、三（4一甲基苯基）鏑之三氟甲烷 磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯、二甲基 (4-羥基萘基）毓之三氟甲烷磺酸酯、其七氟丙烷磺酸 酯或其九氟丁烷磺酸酯、單苯基二甲基銃之三氟甲烷磺酸 酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯、二苯基單甲 -112- 200947126 基锍之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷 磺酸酯、（4一甲基苯基）二苯基鏑之三氟甲烷磺酸酯、 其七氟丙院磺酸酯或其九氟丁垸擴酸醋、（4一甲氧基苯 基）二苯基锍之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或其 九氟丁烷磺酸酯、三（4一 ter t-丁基）苯基锍之三氟甲烷 磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯、二苯基 (1 一 （4 —甲氧基）萘基）鏑之三氟甲烷磺酸酯、其七氟 0 丙烷磺酸酯或其九氟丁烷磺酸酯、二（1 -萘基）苯基锍 之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸 酯、1 -苯基四氫噻吩鑰之三氟甲烷磺酸酯、其七氟丙烷 磋酸醋或其九氣丁院碌酸醋、1一（4-甲基苯基）四氮嚷 吩鎗之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷 磺酸酯、1 一（3,5 —二甲基_4 —羥苯基）四氫噻吩鎗之 三氟甲院磺酸酯、其七氟丙烷磺酸酯或其九氟丁院擴酸酯 、1— (4 一甲氧基萘一 1 一基）四氫噻吩鑰之三氟甲烷磺 0 酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯、1- (4_ 乙氧基萘- 1 -基）四氫噻吩鎗之三氟甲院擴酸醋、其七 氟丙烷磺酸酯或其九氟丁烷磺酸酯、1— (4- η — 丁氧基 萘-1 -基）四氫噻吩鑰之三氟甲烷磺酸酯、其七氟丙烷 磺酸酯或其九氟丁烷磺酸酯、1-苯基噻喃鎗之三氟甲烷 磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯、1 -（4 一羥苯基）四氫噻喃鑰之三氟甲烷磺酸酯、其七氟丙烷磺 酸酯或其九氟丁烷磺酸酯、1_ (3,5 -二甲基—4 —羥苯 基）四氫噻喃鑰之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或 -113- 200947126 其九氟丁烷磺酸酯、1一（4 一甲基苯基）四氫噻喃鑰之三 氟甲烷磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯等 〇 又，可使用前述鑰鹽之陰離子部被甲烷磺酸酯、n-丙烷磺酸酯、η - 丁烷磺酸酯、η -辛烷磺酸酯所取代之鑰 鹽。 又，可使用前述通式（b—l)或（b— 2)中，陰離子 部被下述式（b- 3)或（b— 4)所示陰離子部取代所得之 鎗鹽系酸產生劑亦可（陽離子部係與前述式（b — 1)或（ b — 2 )相同）。 【化7 0】[wherein R1&quot;~R3&quot;, R5" and R6&quot; are each independently aryl or alkyl: in R1&quot;~R3&quot; in formula (b-1), any two can be bonded to each other and The sulfur atom in the formula may form a ring together: R4&quot; is a linear, branched or cyclic alkyl group or a fluorinated alkyl group; at least one of R1&quot;~R3&quot; is an aryl group, Rv~r6'' At least one of them is an aryl group. In the formula (b-1), R1 &quot;~R3" are each independently the same as R1&quot;~R3'_ in the above (b1 - 1). R4&quot; is a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group. The linear or branched alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. -111 - 200947126 The above cyclic alkyl group is a ring group represented by the above R1 &quot;, preferably having a carbon number of 4 to 15, and more preferably having a carbon number of 4 to 10, and having a carbon number of 6 to 10. The best. The fluorinated alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. Further, the fluorination ratio of the fluorinated alkyl group (the ratio of the fluorine atom in the alkyl group) is preferably from 1 〇 to 100%, more preferably from 50 to 100%, and particularly all of the hydrogen atoms are fluorine atoms. In place of the obtained fluorinated alkyl group (perfluoroalkyl group), it is more preferable because the strength of the acid is stronger. R4&quot; is preferably a linear or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group. In the formula (b-2), R5&quot; and R6&quot; are independently the same as those of R5&quot; and R6&quot; in the above (V-2). R4" in the formula (b_2) is the same as R4&quot; in the above (b-1). Specific examples of the gun salt acid generator represented by the formulas (b-1) and (b-2) are, for example, two. Phenyl iodide trifluoromethanesulfonate or nonafluorobutane sulfonate, bis(4-tert-butylphenyl) iodine trifluoromethanesulfonate or nonafluorobutane sulfonate, three Phenylhydrazine trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tris(4-methylphenyl)phosphonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or Its nonafluorobutane sulfonate, dimethyl (4-hydroxynaphthyl) fluorene trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, monophenyl dimethyl hydrazine Trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl monomethyl-112-200947126-based trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nine Fluorobutanesulfonate, (4-methylphenyl)diphenylphosphonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutanyl acid vinegar, (4-methoxy) Phenyl)diphenyl Trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tris(4-tert-butyl)phenylphosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate Or a nonafluorobutane sulfonate thereof, a triphenylmethanesulfonate of diphenyl(1-(4-methoxy)naphthyl)anthracene, a heptafluoropropane sulfonate thereof or a nonafluorobutane sulfonate thereof Acid ester, tris(1-naphthyl)phenylhydrazine trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-phenyltetrahydrothiophene key trifluoromethanesulfonic acid Ester, its heptafluoropropane acid vinegar or its nine gas Dingyuan acid vinegar, 1-(4-methylphenyl) tetraazepine gun trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane Alkane sulfonate, trifluoromethyl sulfonate of 1-(3,5-dimethyl-4-cyclohydroxy)tetrahydrothiophene gun, heptafluoropropane sulfonate or its nonafluorobutyrate acid ester, 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene-trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, 1-(4-ethoxynaphthalene) - 1 - base) tetrahydrothiophene gun Fluoride vinegar, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(4-η-butoxynaphthalen-1-yl)tetrahydrothiophene-trifluoromethanesulfonate, Its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, triphenylmethanesulfonate of 1-phenyl thiopyran, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1- (4 Hydroxyphenyl) tetrahydrothiamium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrogen Thiatrien trifluoromethanesulfonate, its heptafluoropropane sulfonate or -113- 200947126 its nonafluorobutane sulfonate, 1-(4-methylphenyl)tetrahydrothiofuran trifluoromethanesulfonate The acid ester, the heptafluoropropane sulfonate or the nonafluorobutane sulfonate thereof can be used, and the anion portion of the above-mentioned key salt can be used as a methanesulfonate, n-propane sulfonate or η-butane sulfonate. a key salt substituted with η-octane sulfonate. Further, a gun salt-based acid generator obtained by substituting an anion moiety with an anion moiety represented by the following formula (b-3) or (b-4) in the above formula (b-1) or (b-2) can be used. Alternatively, the cationic moiety may be the same as the above formula (b-1) or (b-2). [化7 0]

〔式中，X&quot;爲至少1個氫原子被氟原子取代之碳數2 〜6之伸烷基；Y”、Z&quot;各自獨立爲至少1個氫原子被氟原 子取代之碳數1〜10之烷基〕。 X”爲至少1個氫原子被氟原子取代之直鏈狀或支鏈狀 伸烷基，該伸烷基之碳數較佳爲2〜6，更佳爲碳數3〜5 ，最佳爲碳數3。 Y&quot;、Z”各自獨立爲至少1個氫原子被氟原子取代之直 鏈狀或支鏈狀烷基，該烷基之碳數較佳爲1〜10，更佳爲 碳數1〜7，最佳爲碳數1〜3。 X&quot;之伸烷基之碳數或Y”、Z&quot;之烷基的碳數於上述範 -114- 200947126 圍內時，基於對光阻溶劑具有優良溶解性等理由，以越小 越好。 又，X&quot;之伸烷基或 γ&quot;、z”之烷基中，被氟原子取代 之氫原子數越多時，酸之強度越強，又，相對於200nm 以下之高能量光線或電子線時，以其可提高透明性而爲較 佳。該伸烷基或烷基中之氟原子之比例，即氟化率，較佳 爲70〜100%，更佳爲90〜100%，最佳爲全部氫原子被氟 0 原子取代之全氟伸烷基或全氟烷基。 又，以具有前述通式（b — 5)或（b— 6)所表示之陽 離子部，與具有前述（B1)成份之陰離子部以外之其他陰 離子部之锍鹽亦可作爲鑰鹽系酸產生劑使用。 前述其他陰離子部，可使用目前爲止被提案作爲鎗鹽 系酸產生劑之陰離子部，例如上述通式（b — 1)或（b — 2 )所表示之鑰鹽系酸產生劑之陰離子部（R4’_S03_)等氟 化烷基磺酸離子；上述通式（b-3)或（b-4)所表示之 G 陰離子部等。其中，又以氟化烷基磺酸離子爲佳，以碳數 1〜4之氟化烷基磺酸離子爲更佳，以碳數1〜4之直鏈狀 之全氟烷基磺酸離子爲最佳。具體例如三氟甲基磺酸離子 、七氟一 η—丙基磺酸離子、九氟一 η - 丁基磺酸離子等。 本說明書中，肟磺酸酯系酸產生劑例如至少具有1個 下述通式（Β-1)所示之基之化合物，其具有經由放射線 照射可產生酸之特性。前述肟磺酸酯系酸產生劑，常用於 化學增幅型正型光阻組成物使用，本發明可任意進行選擇 使用。 -115- 200947126 【化7 1】 ：B-1 ) ——C=N一0一S02—R31 R32 〔式（B— 1)中，R31、R3 2各自獨立爲有機基〕。 R31、R32之有機基爲含有碳原子之基，但其亦可含有 碳原子以外之原子（例如氫原子、氧原子、氮原子、硫原 子、鹵素原子（氟原子、氯原子等）等）。 H31之有機基，以直鏈狀、支鏈狀或環狀烷基或芳基 爲佳。前述烷基、芳基可具有取代基。該取代基並未有任 何限制，例如可爲氟原子、碳數1〜6之直鏈狀、支鏈狀 或環狀烷基等。其中，「具有取代基」係指烷基或芳基之 氫原子中一部份或全部被取代基所取代之意。 烷基以碳數1〜20爲佳，以碳數1〜10爲較佳，以碳 數1〜8爲更佳，以碳數1〜6爲最佳，以碳數1〜4爲特 佳。其中，烷基，特別是以部份或完全被鹵化所得之烷基 (以下，亦稱爲鹵化烷基）爲佳。又，部份鹵化之烷基， 係指氫原子之一部份被鹵素原子所取代之烷基，完全鹵化 之烷基，係指氫原子全部被鹵素原子所取代之烷基之意。 前述鹵素原子，例如氟原子、氯原子、溴原子、碘原子等 ，特別是以氟原子爲佳。即，鹵化烷基以氟化烷基爲佳。 芳基以碳數4〜20者爲佳，以碳數4〜10者爲較佳， 以碳數6〜1 0者爲更佳。芳基特別是以部份或完全被鹵化 所得之芳基爲佳。又，部份鹵化之芳基，係指氫原子之一 部份被鹵素原子所取代之芳基，完全鹵化之芳基，係指氫 -116- 200947126 原子全部被鹵素原子所取代之芳基之意。 R31特別是以不具有取代基之碳數1〜4之院基，或碳 數1〜4之氟化烷基爲佳。 R3 2之有機基，以直鏈狀、支鏈狀或環狀烷基、芳基 或氰基爲佳。R32之烷基、芳基，例如與前述r3i所列舉 之烷基、芳基爲相同之內容。 R32特別是爲氰基、不具有取代基之碳數1〜8之院基 ，或碳數1〜8之氟化烷基爲佳。 肟磺酸酯系酸產生劑，更佳者例如下述通式（B-2) 或（B— 3)所示化合物等。 【化7 2】 -C=! R33 R34-C=N——Ο—S〇2—-R35 〔式（B_2)中，R3 3爲氰基、不具有取代基之烷基 或鹵化烷基；R34爲芳基；R35爲不具有取代基之垸基或 〇 圍化烷基〕。 【化7 3】[wherein, X&quot; is an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom; Y", Z&quot; are each independently a carbon number of 1 to 10 in which at least one hydrogen atom is replaced by a fluorine atom. The alkyl group] X" is a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the carbon number of the alkyl group is preferably 2 to 6, more preferably 3 to 6. 5, the best is carbon number 3. Y&quot;, Z" are each independently a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the alkyl group preferably has a carbon number of from 1 to 10, more preferably a carbon number of from 1 to 7. The most preferred carbon number is 1 to 3. The carbon number of the alkyl group of X&quot; or the carbon number of the Y", Z&quot; alkyl group is in the range of the above-mentioned range -114-200947126, based on excellent solubility to the photoresist solvent. For other reasons, the smaller the better. Further, in the alkyl group of X&quot;alkyl or γ&quot;, z", the greater the number of hydrogen atoms substituted by fluorine atoms, the stronger the strength of the acid, and the higher energy light or electron line with respect to 200 nm or less Preferably, the transparency is improved by the ratio of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, most preferably a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted by a fluorine atom. Further, the cation moiety represented by the above formula (b-5) or (b-6) has the above (B1) The sulfonium salt of the anion portion other than the anion portion of the component may be used as a key salt acid generator. The other anion portion may be an anion portion which has been proposed as a gun salt acid generator, for example, the above formula a fluorinated alkylsulfonate ion such as an anion moiety (R4'_S03_) of the key salt acid generator represented by (b-1) or (b-2); the above formula (b-3) or (b-4) a G anion moiety or the like, wherein a fluorinated alkylsulfonic acid ion is preferred, and a fluorinated alkyl group having a carbon number of 1 to 4 is used. The acid ion is more preferable, and a linear perfluoroalkylsulfonic acid ion having a carbon number of 1 to 4 is preferred. Specifically, for example, a trifluoromethanesulfonate ion, a heptafluoro-n-propylsulfonate ion, and a ninth In the present specification, the oxime sulfonate-based acid generator has, for example, a compound having at least one group represented by the following formula (Β-1), which has a radiation irradiation. The acid-forming property of the above-mentioned sulfonate-based acid generator is generally used for a chemically amplified positive-type photoresist composition, and the present invention can be arbitrarily selected and used. -115- 200947126 [Chem. 7 1] : B-1 ) - C = N - 0 - S02 - R31 R32 [In the formula (B-1), R31 and R3 2 are each independently an organic group]. The organic group of R31 and R32 is a group containing a carbon atom, but it may also contain An atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.), etc.). An organic group of H31, which is a linear, branched or cyclic alkyl group. Or an aryl group is preferred. The aforementioned alkyl group and aryl group may have a substituent. The substituent is not limited at all, for example a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, etc., wherein "having a substituent" means that a part or all of a hydrogen atom of an alkyl group or an aryl group is substituted. Replaced by meaning. The alkyl group is preferably a carbon number of from 1 to 20, preferably a carbon number of from 1 to 10, more preferably a carbon number of from 1 to 8, a carbon number of from 1 to 6, and a carbon number of from 1 to 4. . Among them, the alkyl group is particularly preferably an alkyl group (hereinafter, also referred to as a halogenated alkyl group) obtained by partial or complete halogenation. Further, a partially halogenated alkyl group means an alkyl group in which a part of a hydrogen atom is substituted by a halogen atom, and a completely halogenated alkyl group means an alkyl group in which a hydrogen atom is entirely substituted by a halogen atom. The halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. That is, the halogenated alkyl group is preferably a fluorinated alkyl group. The aryl group is preferably a carbon number of 4 to 20, preferably a carbon number of 4 to 10, and more preferably a carbon number of 6 to 10. The aryl group is particularly preferably an aryl group obtained by partial or complete halogenation. Further, a partially halogenated aryl group refers to an aryl group in which a part of a hydrogen atom is replaced by a halogen atom, and an aryl group which is completely halogenated refers to an aryl group in which hydrogen -116-200947126 atoms are all substituted by a halogen atom. meaning. R31 is particularly preferably a phenyl group having 1 to 4 carbon atoms which does not have a substituent, or a fluorinated alkyl group having 1 to 4 carbon atoms. The organic group of R3 2 is preferably a linear, branched or cyclic alkyl group, an aryl group or a cyano group. The alkyl group and the aryl group of R32 are, for example, the same as those of the alkyl group and the aryl group exemplified in the above r3i. R32 is particularly preferably a cyano group, a substituent having a carbon number of 1 to 8 or a fluorinated alkyl group having 1 to 8 carbon atoms. The oxime sulfonate-based acid generator is more preferably a compound represented by the following formula (B-2) or (B-3). [Chemical 7 2] -C=! R33 R34-C=N——Ο—S〇2—R35 [In the formula (B_2), R3 3 is a cyano group, an alkyl group having no substituent or an alkyl halide; R34 is an aryl group; and R35 is a fluorenyl group or a fluorene-containing alkyl group having no substituent. 【化7 3】

N—Ο—S〇2—R38 〔式（B. — 3)中，R36爲氰基、不具有取代基之院基 或鹵化烷基；R37爲2或3價之芳香族烴基；R38爲不具 有取代基之烷基或鹵化烷基，P”爲2或3〕。 則述式（B— 2)中’ R33之不具有取代基之院基或齒 -117- 200947126 化烷基，以碳數1〜10爲佳，以碳數1〜8爲更佳，以碳 數1〜6爲最佳。 R33以鹵化烷基爲佳，又以氟化烷基爲更佳。 R33中之氟化烷基，其烷基中氫原子以5 0%以上被氟 化者爲佳，更佳爲70%以上，又以90%以上被氟化者爲最 佳。 R34之芳基，例如苯基或聯苯基（biphenyl)、荀基 (fluorenyl )、萘基、蒽基（anthracyl )基、菲基等之芳 香族烴之環去除1個氫原子之基，及構成前述基之環的碳 原子之一部份被氧原子、硫原子、氮原子等雜原子取代所 得之雜芳基等。其中又以芴基爲更佳。 R34之芳基，可具有碳數1〜10之烷基、鹵化烷基、 烷氧基等取代基亦可。該取代基中之烷基或鹵化烷基，以 碳數1〜8爲佳，以碳數1〜4爲更佳。又，該鹵化烷基以 氟化烷基爲更佳。 R35之不具有取代基之烷基或鹵化烷基，以碳數1〜 10爲佳，以碳數1〜8爲更佳，以碳數1〜6爲最佳。 R35以鹵化烷基爲佳，以氟化烷基爲更佳。 R35中之氟化烷基，其烷基之氫原子以5 0%以上被氟 化者爲佳，更佳爲70%以上，又以90%以上被氟化時，可 提高所產生之酸而爲更佳。最佳者則爲氫原子100%被氟 取代之全氟化烷基。 前述式（B- 3)中，R36之不具有取代基之烷基或鹵 化烷基，例如與上述R33所示之不具有取代基之烷基或鹵 -118- 200947126 化烷基爲相同之內容。 R37之2或3價之芳香族烴基，例如由上述R34之芳 基中再去除1或2個氫原子所得之基等。 R3 8之不具有取代基之烷基或鹵化烷基，例如與上述 R3 5所示之不具有取代基之烷基或鹵化烷基爲相同之內容 〇 p &quot;較佳爲2。 q 肟磺酸酯系酸產生劑之具體例’如α_(ρ—甲苯磺 醯氧亞胺基）一苄基氰化物（cyanide) 、α — ( ρ —氯基 苯磺醯氧亞胺基）一节基氰化物、α 一（4 —硝基苯磺醯 氧亞胺基）一苄基氰化物、α_ (4 —硝基一 2 —三氟甲基 苯磺醯氧亞胺基）一苄基氰化物、《 一（苯磺酿氧亞胺基 )_4_氯基苄基氰化物、α_ (苯磺醯氧亞胺基）一 2,4 一二氯基节基氰化物、(苯磺醯氧亞胺基）_2,6_ 二氯基苄基氰化物、α —（苯磺醯氧亞胺基）_4 一甲氧 Q 基苄基氰化物、(2 —氯基苯磺醯氧亞胺基）—4一甲 氧基苄基氰化物、α -（苯磺醯氧亞胺基）一噻嗯一 2 — 基乙腈、α -（4 —十二烷基苯磺醯氧亞胺基）一苄基氰 化物、α —〔 （Ρ —甲苯磺醯氧亞胺基）_4_甲氧基苯基 〕乙腈、α —〔（十二烷基苯磺醯氧亞胺基）一 4一甲氧 基苯基〕乙腈、α -(對甲苯磺醯氧亞胺基）一 4一噻嗯 基氰化物、α -（甲基擴醯氧亞胺基）一 1 一環戊嫌基乙 腈、α —(甲基磺醯氧亞胺基）一 1—環己烯基乙腈、α —(甲基磺醯氧亞胺基）—1 一環庚烯基乙腈、(甲 -119- 200947126 基磺醯氧亞胺基）一 i -環辛烯基乙腈、α 一（三氟甲基 磺醯氧亞胺基）—1-環戊烯基乙腈、α —(三氟甲基磺 醯氧亞胺基）一環己基乙腈、α —（乙基磺醯氧亞胺基） 一乙基乙腈、α —（丙基磺醯氧亞胺基）—丙基乙腈、α —(環己基磺醯氧亞胺基）_環戊基乙腈、α-(環己基 磺醯氧亞胺基）-環己基乙腈、α -(環己基磺醯氧亞胺 基）_1一環戊烯基乙腈、(乙基磺醯氧亞胺基）一 1 —環戊烯基乙腈、(異丙基磺醯氧亞胺基）一 1—環 戊烯基乙腈、α -（η— 丁基磺醯氧亞胺基）—1一環戊烯 基乙腈、(乙基磺醯氧亞胺基）-1 -環己烯基乙腈 、α —(異丙基磺醯氧亞胺基）一 1—環己烯基乙腈、α 一（η— 丁基磺醯氧亞胺基）一1—環己烯基乙腈、α —( 甲基磺醯氧亞胺基）-苯基乙腈、α-(甲基磺醯氧亞胺 基）一Ρ—甲氧基苯基乙腈、α —（三氟甲基磺醯氧亞胺 基）一苯基乙腈、α—(三氟甲基磺醯氧亞胺基）—ρ- 甲氧基苯基乙腈、α —(乙基磺醯氧亞胺基）-Ρ -甲氧 基苯基乙腈、α -（丙基磺醯氧亞胺基）一 ρ -甲基苯基 乙腈、α —（甲基磺醯氧亞胺基）一 ρ -溴基苯基乙腈等 〇 又’特開平9—208554號公報（段落〔〇〇12〕〜〔 〇〇14〕之〔化18〕〜〔化19〕）所揭示之肟磺酸酯系酸 產生劑，國際公開第04/074242號公開公報（65〜85頁之 Example 1〜40)所揭示之肟磺酸酯系酸產生劑亦可配合 需要使用。 -120- 200947126 又，較適當者例如下述所示之化α物等 【化7 4】N—Ο—S〇2—R38 [In the formula (B.-3), R36 is a cyano group, a substituent group or a halogenated alkyl group; R37 is a 2 or 3 valent aromatic hydrocarbon group; R38 is not a substituted alkyl group or a halogenated alkyl group, P" is 2 or 3]. In the formula (B-2), the substituent group of the R33 having no substituent or the tooth -117-200947126 alkyl group, with carbon Preferably, the number is from 1 to 10, more preferably from 1 to 8 carbon atoms, and most preferably from 1 to 6 carbon atoms. R33 is preferably a halogenated alkyl group and more preferably a fluorinated alkyl group. The alkyl group is preferably one in which the hydrogen atom in the alkyl group is fluorinated at 50% or more, more preferably 70% or more, and more preferably 90% or more. The aryl group of R34, such as phenyl or a ring of an aromatic hydrocarbon such as a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group or a phenanthryl group, which removes a hydrogen atom group, and a carbon atom constituting the ring of the aforementioned group. a heteroaryl group obtained by substituting a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, etc., wherein a sulfhydryl group is more preferred. The aryl group of R34 may have an alkyl group having 1 to 10 carbon atoms and an alkyl halide. Substituent such as alkoxy group The alkyl group or the halogenated alkyl group in the substituent is preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is more preferably a fluorinated alkyl group. The alkyl group or the halogenated alkyl group having no substituent is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 6. R35 is preferably a halogenated alkyl group. The fluorinated alkyl group is more preferably a fluorinated alkyl group in R35, wherein the hydrogen atom of the alkyl group is preferably fluorinated at 50% or more, more preferably 70% or more, and more preferably 90% or more. It is more preferable to increase the acid produced. The most preferred one is a perfluorinated alkyl group in which 100% of hydrogen atoms are replaced by fluorine. In the above formula (B-3), an alkyl group having no substituent of R36 or The halogenated alkyl group is, for example, the same as the alkyl group having no substituent or the halogen-118-200947126 alkyl group represented by the above R33. The 2 or 3 valent aromatic hydrocarbon group of R37, for example, the aryl group of the above R34 a group obtained by removing 1 or 2 hydrogen atoms, etc. R3 8 of an alkyl group having no substituent or a halogenated alkyl group, for example, the same as the alkyl group or halogenated alkyl group having no substituent represented by the above R3 5 within 〇p &quot; preferably 2. Specific examples of the oxime sulfonate acid generator such as α_(ρ-toluenesulfonyloxyimido)-benzyl cyanide (cyanide), α - (ρ-chloro Benzosulfonyloxyimido) a cyano cyanide, α-(4-nitrobenzenesulfonyloxyimino)-benzyl cyanide, α_(4-nitro-2-trifluoromethylbenzene Sulfonoxyimino)-benzyl cyanide, "(phenylsulfonyloxyimino)_4-chlorobenzyl cyanide, α_(phenylsulfonyloxyimino)- 2,4-dichloro Base group cyanide, (phenylsulfonyloxyimido)_2,6-dichlorobenzyl cyanide, α-(phenylsulfonyloxyimino)_4-methoxy Q-benzyl benzyl cyanide, (2 -Chlorophenylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(phenylsulfonyloxyimino)-thiazol-2-ylacetonitrile, α-(4-dodecane Benzosulfonyloxyimido)-benzyl cyanide, α-[(Ρ-toluenesulfonyloxyimido)_4-methoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonate) Oxyimido)-4-methoxyphenyl]acetonitrile, α-(p-toluenesulfonate Oxyimido)-4-ylthiocyanate, α-(methylxanthoxyimino)- 1 -cyclopentane acetonitrile, α-(methylsulfonyloxyimino)-1 ring Hexenylacetonitrile, α-(methylsulfonyloxyimino)-1 monocycloheptenylacetonitrile, (methyl-119-200947126 sulfonyloxyimino)-i-cyclooctene acetonitrile, α- (trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-cyclohexylacetonitrile, α-(ethylsulfonyloxyimino) Ethyl acetonitrile, α-(propylsulfonyloxyimino)-propylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclopentylacetonitrile, α-(cyclohexylsulfonate) Amino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimido)_1-cyclopentenylacetonitrile, (ethylsulfonyloxyimido)-1-cyclopentenylacetonitrile, (isopropyl) Sulfomethoxyimido)-1-cyclopentenylacetonitrile, α-(η-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, (ethylsulfonyloxyimino)-1 -cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino) 1-cyclohexenylacetonitrile, α-(η-butylsulfonyloxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-phenylacetonitrile, α -(methylsulfonyloxyimino)-fluorenyl-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonate Imino)-ρ-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-fluorene-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-ρ -methylphenylacetonitrile, α-(methylsulfonyloxyimido)-ρ-bromophenylacetonitrile, etc., JP-A-9-208554 (paragraph [〇〇12]~[ 〇〇14 The oxime sulfonate-based acid generator disclosed in [Chem. 18] to [Chem. 19], and the oxime sulfonic acid disclosed in International Publication No. 04/074242 (Examples 1 to 40 on pages 65 to 85). The ester acid generator can also be used as needed. -120- 200947126 Further, for example, the α substance shown below, etc., etc. [Chem. 7 4]

© 重氮甲烷系酸產生劑中，雙烷基或雙芳基磺醯基重氮 甲烷類之具體例，如雙（異丙基磺醯基）重氮甲烷、雙（ ρ—甲苯磺醯基）重氮甲院、雙（1，1_二甲基乙基磺酸基 )重氮甲烷、雙（環己基磺醯基）重氮甲烷、雙（2，4 一 二甲基苯基磺醯基）重氮甲烷等。 又，亦適合使用特開平11—035551號公報、特開平 〇35552號公報、特開平11— 〇35573號公報所揭示之 重氮甲烷系酸產生劑。 ❹ 又，聚（雙磺醯基）重氮甲烷類，例如特開平u__ 3227 07號公報所揭示之l，3 —雙（苯基磺醯基重氮甲基擴 醯基）丙烷、1，4_雙（苯基磺醯基重氮甲基磺醯基）丁 院' 1，6~雙（苯基磺醯基重氮甲基磺醯基）己院、i 一雙（苯基磺醯基重氮甲基磺醯基）癸烷、1，2 —雙 己基擴酸基重氮甲基擴釀基）乙垸、1，3 一雙（環己基擴 醯基重氮甲基磺醯基）丙烷、1&gt;6一雙（環己基磺酿基重 氮甲基磺醯基）己烷、1,10-雙（環己基磺醯基重氮甲基 磺醯基）癸烷等。 -121 - 200947126 (B2)成份可單獨使用1種前述酸產生劑，或 以上組合使用亦可。 本發明之光阻組成物中，（B )成份之含量’ )成份100質量份爲使用0·5〜30質量份，較佳爲 〜20質量份。於上述範圍時，可充分形成圖型。 到均勻之溶液，與良好之保存安定性。 &lt;任意成份&gt; 本發明之光阻組成物中，爲提升光阻圖型形狀 安定性(post exposure stability of the latent formed by the pattern — wise exposure of the r e s i s )時，以再含有含氮有機化合物（D)(以下亦稱 )成份）爲佳。 此（D)成份，目前已有多種化合物之提案， 使用公知之任意成份，其中又以脂肪族胺、特別是 肪族胺或三級脂肪族胺爲佳。其中，脂肪族胺，爲 個以上之脂肪族基之胺，該脂肪族基以碳數1〜1 2 〇 脂肪族胺，例如氨NH3中之至少1個氫原子 12以下之烷基或羥烷基取代所得之胺（烷基胺或 )或環式胺等。 烷基胺與烷醇胺之具體例如η -己基胺、η-、η —辛基胺、η —壬基胺、η —癸基胺等單烷基胺 基胺、二_η —丙基胺、二—η —庚基胺、二_η — 將2種 對（A 使用1 且可得 、保存 image t layer :爲（D 其亦可 二級脂 具有1 者爲佳 被碳數 烷醇胺 庚基胺 :二乙 辛基胺 -122- 200947126 、二環己基胺等二烷基胺；三甲基胺、三乙基胺、三_n 一丙基胺、三—η — 丁基胺、三—n_戊基胺、三一 η —己 基胺、三一 η—庚基胺、三_η-辛基胺、三一 η —壬基胺 、三一 η-癸基胺、三—η_十二烷基胺等三烷基胺；二乙 醇胺、三乙醇胺、二異丙醇胺、三異丙醇胺、二—η_辛 醇胺、三一 η —辛醇胺等烷醇胺。其中又以碳數5〜10之 烷基鍵結3個氮原子之三烷基胺爲佳，以三- η -戊基胺 0 爲最佳。 環式胺，例如含有作爲雜原子之氮原子的雜環化合物 等。該雜環化合物，可爲單環式之化合物（脂肪族單環式 胺），或多環式之化合物（脂肪族多環式胺）亦可。 脂肪族單環式胺，具體而言，例如哌啶、哌嗪（ piperazine )等。 脂肪族多環式胺，以碳數6〜10者爲佳’具體而言’ 例如1，5—二氮雜二環〔4.3.0〕一 5—壬烯、1，8 —二氮雜 Q 二環〔5.4.0〕一 7 —十一碳烯、六伸甲基四胺、1，4_二氮 雜二環〔2.2.2〕辛烷等。 除上述所列舉之內容以外’亦適合使用硬脂二乙醇胺 〇 此些可單獨使用或將2種以上組合使用皆可。 (D)成份對（A)成份100質量份’一般爲使用 0.01〜5.0質量份之範圍。 本發明之光阻組成物’爲防止感度劣化（Deterioration in sensitivity )，或提升光阻圖型形狀、保存安定性（ 200947126 post exposure stability of the latent image formed by the pattern - wise exposure of the resist layer )等目的上，可 再含有任意成份之有機羧酸與磷之含氧酸及其衍生物所成 之群所選出之至少1種化合物（E)(以下亦稱爲（E) 成份）。 有機羧酸，例如乙酸、丙二酸、檸檬酸、蘋果酸、琥 珀酸、苯甲酸、水楊酸等爲佳。 磷之含氧酸，例如磷酸、膦酸（Phosphonic acid)、 次膦酸（Phosphinic acid )等，其中又以膦酸爲佳。 磷酸之含氧酸衍生物，例如前述含氧酸之氫原子被烴 基取代所得之酯基等，前述烴基，例如碳數1〜5之烷基 ，碳數6〜15之芳基等。 磷酸衍生物例如磷酸二一 n 一丁酯、磷酸二苯酯等磷 酸酯等。 膦酸（Phosphonic acid)衍生物例如膦酸二甲醋、膦 酸一二一 η- 丁酯、苯基膦酸、膦酸二苯酯、膦酸二苄酯 等膦酸酯等。 次膦酸（phosPhinic acid)衍生物例如’苯基次鱗酸 等次膦酸酯。 (E)成份可單獨使用1種，或將2種以上合倂使用 亦可。 (E)成份，以有機酸爲較佳’又以水楊酸爲最佳。 (E )成份對（A )成份1 〇〇質量份而言，一般爲使 用0.01〜5.0質量份之比例。 -124- 200947126 本發明之光阻組成物，可再配合需要適當添加具有混 合性之添加劑’例如可改良光阻膜性能之加成樹脂，提升 塗覆性之界面活性劑、溶解抑制劑、可塑劑、安定劑、著 色劑、光暈防止劑、染料等。 [有機溶劑（S )] 本發明之光阻組成物，可將材料溶解於有機溶劑（S 0 )(以下亦稱爲（S)成份）之方式製造。 (S )成份，只要可溶解所使用之各成份而形成均勻 之溶液即可，例如可由以往作爲化學增幅型光阻溶劑之公 知溶劑中，適當的選擇1種或2種以上使用。 例如T-丁內酯等內酯類，丙酮、甲基乙基酮、環己 酮、甲基一 η—戊酮、甲基異戊酮、2 —庚酮等酮類；乙二 醇、二乙二醇、丙二醇、二丙二醇等多元醇類；乙二醇單 乙酸酯、二乙二醇單乙酸酯、丙二醇單乙酸酯、或二丙二 Q 醇單乙酸酯等具有酯鍵結之化合物；前述多元醇類或前述 具有酯鍵結之化合物的單甲基醚、單乙基醚、單丙基醚、 單丁基醚等單烷基醚或單苯基醚等具有醚鍵結之化合物等 之多元醇類之衍生物〔其中，又以丙二醇單甲基醚乙酸醋 (PGMEA )、丙二醇單甲基醚（PGME)爲佳〕；二噁烷 等環狀醚類；或乳酸甲酯、乳酸乙酯（EL)、乙酸甲醋 、乙酸乙酯、乙酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧 基丙酸甲酯、乙氧基丙酸乙酯等酯類；苯甲醚、乙基苄基 醚、甲酚甲基醚、二苯基醚、二苄基醚、苯乙醚、丁基苯 -125- 200947126 基醚、乙基苯、二乙基苯、戊基苯、異丙基苯、甲苯、二 甲苯、異丙基苯、三甲基苯等芳香族系有機溶劑等。 前述有機溶劑可單獨使用，或以2種以上之混合溶劑 形式使用亦可。 又，其中又以使用由丙二醇單甲基醚乙酸酯（ PGMEA)與丙二醇單甲基醚（PGME )、乳酸乙酯（EL ) 爲佳。 又，亦可使用PGMEA與極性溶劑混合所得之混合溶 劑。其添加比（質量比）可依PGMEA與極性溶劑之相溶 性等作適當之決定即可，較佳爲1: 9〜9: 1，更佳爲2: 8〜8 : 2之範圍。 更具體而言，極性溶劑爲使用乳酸乙酯（EL)時， PGMEA : EL之質量比較佳爲1: 9〜9: 1，更佳爲2: 8〜 8 : 2。極性溶劑爲使用PGME時，PGMEA : PGME之質量 比較佳爲1: 9〜9: 1，更佳爲2: 8〜8: 2，最佳爲3: 7 〜7 : 3。 又，（S )成份中，其他例如使用由PGMEA與EL中 選出之至少1種與7 - 丁內酯所得混合溶劑爲佳。此時， 混合比例中，前者與後者之質量比較佳爲70 : 3 0〜95 : 5 〇 (S)成份之使用量並未有特別限定，一般可配合塗 佈於基板等之濃度，塗膜厚度等作適當的選擇設定，一般 可於光阻組成物中之固體成份濃度爲2〜20質量％，較佳 爲5〜1 5質量％之範圍下使用。 -126 - 200947126 上述本發明之光阻組成物，爲以往所未知之新穎組成 物。 又，含有本發明之化合物（bl - 1)作爲酸產生劑時 ，可提高微影蝕刻特性，例如可提升光阻圖型形成之際的 解析性、遮罩重現性（例如遮罩線性等）或曝光量（EL )寬容度、光阻圖型形狀、焦點景深寬度（D OF )等。 EL寬容度，係指改變曝光量下進行曝光之際，以相 u 對於標靶尺寸之偏差在特定範圍內時之尺寸可形成光阻圖 型之曝光量之範圍，即，可得到忠實反應遮罩圖型之光阻 圖型時之曝光量範圍，EL寬容度，其數値越大時，伴隨 曝光量變動所產生之圖型尺寸的變化量越小，就提升製程 之寬容度上爲較佳。 可得到上述效果之理由，推測爲以下內容。即，前述 化合物（bl-l)，其陰離子部中具有「Y^SOr」之骨 架鍵結有RX — Q3-〇-Q2 —之構造。因此，與以往作爲陰 離子使用之氟化烷基磺酸離子相比較時，具有極性更高， 具有立體性之高體積密度之龐大構造。因具有高極性，故 推測其可經由分子間之相互作用，或經該龐大之立體構造 ，而與九氟丁烷磺酸酯等以往之酸產生劑的陰離子部相比 較時，於光阻膜内可以化學性或物理性方式抑制該陰離子 部（酸）之擴散。因此，可抑制曝光域所發生之酸擴散至 未曝光區域，其結果，可提升未曝光區域與曝光區中對鹼 顯影液之溶解性差（溶解反差），因而推測可提高解析性 或提升光阻圖型之形狀。 -127- 200947126 又，y1之可具有取代基之伸烷基或可具有取代基之 氟化伸烷基之烷基鏈，例如相對於碳數6〜10之全氟烷基 鏈具有難分解性，而顯示出良好之分解性，對於考慮生物 蓄積性之使用性提升上，可得到更好之效果。 《光阻圖型之形成方法》 本發明之第二之態樣之光阻圖型之形成方法，爲包含 使用上述本發明之光阻組成物於支撐體上形成光阻膜之步 驟、使前述光阻膜曝光之步驟、使前述光阻膜鹼顯影以形 成光阻圖型之步驟。 該光阻圖型之形成方法，例如可依下述方式進行。 即，首先，於支撐體上，將上述本發明之光阻組成物 使用旋轉塗佈器等進行塗佈後，於80〜150 °C之溫度條件 下’進行40〜120秒鐘，較佳爲60〜90秒鐘之塗佈後燒 焙（post— apply bake(PAB))，其爲藉由例如 ArF 曝 光裝置等，再利用ArF準分子雷射光介由所期待之遮罩圖 型進行選擇性曝光後，再於8 0〜1 5 0。(：之溫度條件下，進 行40〜120秒鐘，較佳爲60〜90秒鐘之曝光後燒焙（ Post exposure bake’ PEB)。其次，將其使用鹼顯影液， 例如0 · 1〜1 0質量％氫氧化四甲基銨（TM A Η )水溶液進 行鹼顯影處理，較佳爲使用純水進行洗滌後，乾燥。又， 必要時’於上述鹼顯影處理後可進行燒焙處理（後燒焙） 。如此’即可得到忠實反應遮罩圖型之光阻圖型。 支撐體並未有特別限定，其可使用以往公知之物品， -128- 200947126 例如電子零件用之基板’或於其上形成特定配線圖型之物 品等。更具體而言’例如矽晶圓、銅、鉻、鐵、鋁等金屬 製之基板或，玻璃基板等。配線圖型之材料，例如可使用 銅、銘、鎳、金等。 又’支撐體，例如亦可於上述基板上，設置無機系及 /或有機系之膜。無機系之膜，例如無機抗反射膜（無機 BARC )等。有機系之膜，例如有機抗反射膜（有機 ❹ BARC)等。 曝光所使用之波長，並未有特別限定，其可使用ArF 準分子雷射、KrF準分子雷射、F2準分子雷射、EUV (極 紫外線）、VUV (真空紫外線）、EB (電子線）、X線、 軟X線等放射線進行。上述光阻組成物，以對KrF準分 子雷射、ArF準分子雷射、EB或EUV有效，特別是對 ArF準分子雷射爲有效。 光阻膜之曝光，可於空氣或氮等惰性氣體中進行之通 Q 常曝光（乾式曝光），或浸潤式曝光亦可。 浸潤式曝光，如上所述般，係於曝光時，於以往充滿 空氣或氮等惰性氣體之透鏡與晶圓上之光阻膜之間的部份 ，充滿具有折射率較空氣之折射率爲大之溶劑（浸潤式媒 體）的狀態下進行曝光。 更具體而言，浸潤式曝光，爲將上述所得之光阻膜與 曝光裝置之最下位置的透鏡間，充滿具有折射率較空氣之 折射率爲大之溶劑（浸潤式媒體），並於該狀態下，介由 所期待之光阻圖型進行曝光（浸潤式曝光）之方式實施。 -129- 200947126 浸潤式媒體，以具有折射率較空氣之折射率爲大，且 較該浸潤式曝光進行曝光之光阻膜所具有之折射率爲小的 折射率之溶劑爲佳。該溶劑之折射率，只要爲前述範圍内 時，則無特別限制。 具有折射率較空氣之折射率爲大，且較光阻膜之折射 率爲小的折射率之溶劑，例如，水、氟系惰性液體、矽系 溶劑、烴系溶劑等。 氟系惰性液體之具體例如 C3HC12F5、（:4F9OCH3、 C4F9OC2H5、C5H3F7等氟系化合物爲主成份之液體等，又 以沸點爲70〜180 °c者爲佳，以80〜160°c者爲更佳。氟 系惰性液體中，沸點於上述範圍內之物時，於曝光結束後 ，可以簡便之方法去除浸潤式所使用之介質，而爲較佳。 氟系惰性液體，特別是以烷基中之氫原子全部被氟原 子取代所得之全氟烷基化合物爲佳。全氟烷基化合物，具 體而言，例如全氟烷基醚化合物或全氟烷基胺化合物等。 又，更具體而言，前述全氟烷基醚化合物，例如全氟 (2- 丁基一四氫呋喃）（沸點102°C)，前述全氟烷基 胺化合物，例如全氟三丁基胺（沸點1 74°C )等。 【實施方式】 〔實施例〕 其次，將以實施例對本發明作更詳細之說明，但本發 明並不受該些例示所限定。 以下之各例示中，化學式（II )所表示之化合物記載 -130- 200947126 爲「化合物（II)」，其他化學式所表示之化合物亦分別 以相同方式記載。 〔合成例1〕 將化合物（Π) 4.34g (純度·_ 94.1%) 、2—苯甲基 氧代乙醇3.14g、甲苯43.4g混合’添加p —甲苯磺酸一 水合物〇.47g，於1051：下迴流20小時。將反應液過瀘’ 0 濾物中添加己烷20g，進行攪拌。再度過濾，將濾物乾燥 後得化合物（III ) 1 ·4 1 g (產率：43 · 1 % )。 【化7 5】 〇r°^°: HOx^t VNf (II) ⑽ 對所得化合物（III )，以NMR進行分析。 - NMR ( DMSO — d6、400MHz ) ： &lt;5 ( ppm ) =4.74 〇 -4_83(t，lH，OH)、4.18-4.22(t，2H，Ha) ' 3.59 -3.64 ( q，2H，Hb )。 19F - NMR ( DMSO - d6、3 76MHz ) : δ ( ppm )= -106.6 。 由上述結果得知，確認化合物（III)具有下述所示 構造。 -131 - 200947126 【化7 6】Specific examples of dialkyl or bisarylsulfonyldiazomethanes in diazomethane acid generators, such as bis(isopropylsulfonyl)diazomethane, bis(ρ-toluenesulfonyl) Diazo Azide, bis(1,1-dimethylethylsulfonate)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonate) Base) diazomethane and the like. Further, a diazomethane-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Further, poly(disulfonyl)diazomethane, such as 1,3 -bis(phenylsulfonyldiazomethylmethyl)propane, 1,4 disclosed in Japanese Patent Laid-Open Publication No. Hei. _Bis(phenylsulfonyldiazomethylsulfonyl) Dingyuan' 1,6~bis(phenylsulfonyldiazomethylsulfonyl)hexyl, i-double (phenylsulfonyl) Diazomethanesulfonyl)decane, 1,2-dihexylpropionic acid diazomethyl extended base) acetamidine, 1,3 bis(cyclohexylmethane diazomethanesulfonyl) Propane, 1&gt;6-double (cyclohexylsulfonic aciddiazomethylsulfonyl)hexane, 1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl)decane, and the like. -121 - 200947126 (B2) The above-mentioned acid generator may be used alone or in combination of the above. In the photoresist composition of the present invention, 100 parts by mass of the component (B) component is used in an amount of from 0.5 to 30 parts by mass, preferably from 20 to 20 parts by mass. In the above range, the pattern can be sufficiently formed. To a homogeneous solution, with good preservation stability. &lt;arbitrary component&gt; In the photoresist composition of the present invention, in order to enhance the resistive of the latent formed by the pattern-wise exposure of the resis, The compound (D) (hereinafter also referred to as a component) is preferred. As the component (D), there have been proposals for various compounds, and any of the known components is used, and among them, an aliphatic amine, particularly an aliphatic amine or a tertiary aliphatic amine is preferred. Wherein the aliphatic amine is an amine of more than one aliphatic group, and the aliphatic group is an aliphatic amine having a carbon number of 1 to 12 2 , for example, an alkyl group or a hydroxyalkane having at least one hydrogen atom of 12 or less in the NH 3 NH 3 . The resulting amine (alkylamine or) or cyclic amine is substituted. Specific alkylamines and alkanolamines such as η-hexylamine, η-, η-octylamine, η-decylamine, η-decylamine, and the like, monoalkylaminoamines, di-n-propylamines , bis-η-heptylamine, bis-η- will be two pairs (A uses 1 and can be obtained, save image t layer: for (D which can also have a secondary lipid with 1 is better by the carbon number alkanolamine Heptylamine: dialkylamine such as diethyloctylamine-122-200947126, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tris-n-butylamine, Tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, tri-n a trialkylamine such as dodecylamine; an alkanolamine such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine or tris-n-octanolamine. Further, a trialkylamine having three nitrogen atoms bonded to an alkyl group having 5 to 10 carbon atoms is preferred, and tri-n-pentylamine 0 is preferred. The cyclic amine, for example, contains a nitrogen atom as a hetero atom. Heterocyclic compound, etc. The heterocyclic compound may be a single ring A compound of the formula (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine) may also be used. An aliphatic monocyclic amine, specifically, for example, piperidine, piperazine, etc. Aliphatic polycyclic amines, preferably having a carbon number of 6 to 10 'specifically', for example, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diaza Q bicyclo[5.4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, etc. In addition to the contents listed above, It is suitable to use stearyl diethanolamine, and these may be used singly or in combination of two or more kinds. (D) Component (A) component 100 parts by mass 'usually used in the range of 0.01 to 5.0 parts by mass. The resist composition 'for the purpose of preventing deterioration of sensitivity, or improving the shape of the photoresist pattern, and the stability of the resisting image (200947126 post exposure stability of the latent image formed by the pattern - wise exposure of the resist layer), An organic carboxylic acid and phosphorus oxyacid and a derivative thereof which may further contain any component At least one compound (E) (hereinafter also referred to as (E) component) selected from the group. Organic carboxylic acids such as acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid Etc. Phosphorus oxyacids such as phosphoric acid, Phosphonic acid, Phosphinic acid, etc., of which phosphonic acid is preferred. The oxo acid derivative of phosphoric acid, for example, an ester group obtained by substituting a hydrogen atom of the oxo acid with a hydrocarbon group, and the hydrocarbon group is, for example, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 15 carbon atoms. The phosphoric acid derivative is, for example, a phosphate such as di-n-butyl phosphate or diphenyl phosphate. Phosphonic acid derivatives such as phosphonic acid dimethyl vinegar, phosphonic acid 1-2 η-butyl ester, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and the like. A phosphinic acid (phosPhinic acid) derivative such as a phosphinic acid ester such as 'phenyldecanoic acid. (E) The components may be used singly or in combination of two or more. (E) Ingredients, organic acids are preferred ‘and salicylic acid is the best. The component (E) is usually used in an amount of 0.01 to 5.0 parts by mass based on 1 part by mass of the component (A). -124- 200947126 The photoresist composition of the present invention can be further blended with an additive which is suitable for mixing, for example, an additive resin which can improve the properties of the photoresist film, a surfactant for improving coating properties, a dissolution inhibitor, and a plasticizer. Agents, stabilizers, colorants, halo inhibitors, dyes, and the like. [Organic Solvent (S)] The photoresist composition of the present invention can be produced by dissolving a material in an organic solvent (S 0 ) (hereinafter also referred to as a component (S)). The (S) component can be used as long as it can dissolve the components to be used in a uniform manner. For example, one or two or more kinds of the above-mentioned conventional solvents can be used as the chemically amplified resist solvent. For example, lactones such as T-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl η-pentanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, Polyols such as ethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate having ester bonds a compound of the above; a polyether or a monoalkyl ether such as monoethyl ether, monoethyl ether, monopropyl ether or monobutyl ether or a monophenyl ether having an ester bond; a derivative of a polyhydric alcohol such as a compound, wherein propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) is preferred; a cyclic ether such as dioxane; or lactic acid Methyl ester, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate, etc. Anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butylbenzene-125-200947126 alkyl ether, ethylbenzene, Ethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cumene, mesitylene and the like, aromatic organic solvents. These organic solvents may be used singly or in combination of two or more. Further, among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and ethyl lactate (EL) are preferably used. Further, a mixed solvent obtained by mixing PGMEA with a polar solvent can also be used. The addition ratio (mass ratio) may be appropriately determined depending on the compatibility of PGMEA with a polar solvent, etc., and is preferably in the range of 1:9 to 9:1, more preferably 2:8 to 8:2. More specifically, when the polar solvent is ethyl lactate (EL), the mass of PGMEA: EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When the polar solvent is PGME, the mass of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and most preferably 3: 7 to 7: 3. Further, among the components (S), for example, a mixed solvent of at least one selected from PGMEA and EL and 7-butyrolactone is preferably used. In this case, in the mixing ratio, the mass of the former and the latter is preferably 70: 3 0 to 95: 5 The amount of the 〇 (S) component is not particularly limited, and generally it can be applied to a concentration such as a substrate, and a coating film is used. The thickness and the like are appropriately selected and set, and it is generally used in the range of 2 to 20% by mass, preferably 5 to 15% by mass, based on the solid content of the photoresist composition. -126 - 200947126 The above-mentioned photoresist composition of the present invention is a novel composition which has not been known in the past. Further, when the compound (bl-1) of the present invention is contained as an acid generator, the lithographic etching characteristics can be improved, for example, the repellability and mask reproducibility (for example, mask linearity) at the time of formation of the photoresist pattern can be improved. ) or exposure (EL) latitude, photoresist pattern shape, focal depth of field (D OF ), and the like. EL latitude refers to the range of the exposure amount that can form the resist pattern when the deviation of the target size is within a certain range when the exposure is changed under the exposure amount, that is, the faithful reaction can be obtained. The exposure range of the mask pattern type, the EL latitude, the larger the number, the smaller the amount of change in the pattern size caused by the variation of the exposure amount, and the latitude of the process is improved. good. The reason why the above effects can be obtained is presumed to be as follows. That is, the compound (bl-1) has a structure in which the skeleton of "Y^SOr" in the anion portion is bonded to RX - Q3-〇-Q2. Therefore, compared with the conventional fluorinated alkylsulfonic acid ion used as an anion, it has a bulky structure having a higher polarity and a high volume density of three-dimensionality. Because of its high polarity, it is presumed that it can pass through the interaction between molecules or through the bulky three-dimensional structure, compared with the anion portion of a conventional acid generator such as nonafluorobutane sulfonate. The diffusion of the anion (acid) can be inhibited chemically or physically. Therefore, it is possible to suppress the diffusion of the acid generated in the exposure region to the unexposed region, and as a result, the solubility in the unexposed region and the exposed region to the alkali developer can be improved (dissolution contrast), and thus it is presumed that the resolution or the light resistance can be improved. The shape of the pattern. Further, an alkyl chain of a fluorinated alkyl group which may have a substituent or a fluorinated alkyl group which may have a substituent, for example, is difficult to decompose with respect to a perfluoroalkyl chain having a carbon number of 6 to 10 It shows good decomposability, and a better effect can be obtained for improving the usability of bioaccumulation. <<Formation Method of Photoresist Pattern>> The method for forming a photoresist pattern according to a second aspect of the present invention includes the step of forming a photoresist film on a support using the photoresist composition of the present invention described above, and The step of exposing the photoresist film and the step of alkali developing the photoresist film to form a photoresist pattern. The method of forming the photoresist pattern can be carried out, for example, in the following manner. That is, first, the photoresist composition of the present invention is applied onto a support by a spin coater or the like, and then subjected to a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60-90 seconds post-application bake (PAB), which is selected by the expected mask pattern by ArF excimer laser light by, for example, an ArF exposure apparatus. After exposure, then at 8 0~1 5 0. (Under temperature conditions, 40 to 120 seconds, preferably 60 to 90 seconds of post exposure bake 'PEB.) Next, use an alkali developer, for example, 0 · 1 to 1 The 0% by mass aqueous solution of tetramethylammonium hydroxide (TM A Η ) is subjected to alkali development treatment, preferably after washing with pure water, and then dried, and if necessary, can be subjected to baking treatment after the above alkali development treatment (after Baked). Thus, a photoresist pattern of a faithful reaction mask pattern can be obtained. The support is not particularly limited, and a conventionally known article can be used, for example, a substrate for an electronic component. An article or the like having a specific wiring pattern is formed thereon. More specifically, for example, a substrate made of a metal such as a germanium wafer, copper, chromium, iron, or aluminum, or a glass substrate, etc., for example, copper, In addition, a support, for example, an inorganic or organic film may be provided on the substrate. An inorganic film such as an inorganic antireflection film (inorganic BARC) may be used. Membrane, such as an organic anti-reflective film (organic ❹ BARC), etc. The wavelength used for exposure is not particularly limited, and ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), Radiation is performed by EB (electron line), X-ray, soft X-ray, etc. The above-mentioned photoresist composition is effective for KrF excimer laser, ArF excimer laser, EB or EUV, especially for ArF excimer laser. Effective. Exposure of the photoresist film can be carried out in an inert gas such as air or nitrogen. Normal exposure (dry exposure) or immersion exposure. Immersion exposure, as described above, is applied during exposure. In the past, a portion between a lens filled with an inert gas such as air or nitrogen and a photoresist film on a wafer is exposed to a state in which a solvent having a refractive index higher than that of air (infiltrated medium) is exposed. In the immersion exposure, a solvent having a refractive index higher than that of air (infiltrated medium) is filled between the photoresist film obtained as described above and the lens at the lowest position of the exposure device, and in this state, , by expectation The photoresist pattern is implemented by exposure (immersion exposure). -129- 200947126 The immersion medium has a photoresist film having a refractive index higher than that of air and exposed to the immersion exposure. A solvent having a refractive index of a small refractive index is preferred. The refractive index of the solvent is not particularly limited as long as it is within the above range. The refractive index is larger than that of air, and the refractive index of the resist film is larger than that of the resist film. The solvent having a small refractive index is, for example, water, a fluorine-based inert liquid, an oxime-based solvent, a hydrocarbon-based solvent, etc. Specific examples of the fluorine-based inert liquid are, for example, a liquid such as C3HC12F5 or a fluorine-based compound such as 4F9OCH3, C4F9OC2H5 or C5H3F7. Etc., preferably with a boiling point of 70~180 °c, preferably 80~160 °c. In the fluorine-based inert liquid, when the boiling point is in the above range, the medium used for the wetting type can be removed by a simple method after the completion of the exposure, and is preferable. The fluorine-based inert liquid is particularly preferably a perfluoroalkyl compound obtained by substituting all hydrogen atoms in the alkyl group with fluorine atoms. A perfluoroalkyl compound, specifically, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound. Further, more specifically, the perfluoroalkyl ether compound, for example, perfluoro(2-butyltetrahydrofuran) (boiling point: 102 ° C), the perfluoroalkylamine compound, for example, perfluorotributylamine (boiling point) 1 74 ° C) and so on. [Embodiment] [Embodiment] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the examples. In each of the following examples, the compound represented by the chemical formula (II) is described as - "compound (II)", and the compounds represented by other chemical formulas are also described in the same manner. [Synthesis Example 1] 4.34 g (purity·_ 94.1%) of compound (Π), 3.14 g of 2-benzyloxyethanol, and 43.4 g of toluene were mixed with 'p-toluenesulfonic acid monohydrate 〇.47 g, 1051: Under reflux for 20 hours. 20 g of hexane was added to the reaction solution through the 泸'0 filter, and the mixture was stirred. After filtration again, the filtrate was dried to give Compound (III) 1 · 4 1 g (yield: 43 · 1%).化r°^°: HOx^t VNf (II) (10) The obtained compound (III) was analyzed by NMR. - NMR (DMSO - d6, 400MHz) : &lt;5 (ppm) =4.74 〇-4_83(t,lH,OH), 4.18-4.22(t,2H,Ha) '3.59 -3.64 ( q,2H,Hb ) . 19F-NMR (DMSO-d6, 3 76MHz): δ (ppm) = -106.6. From the above results, it was confirmed that the compound (III) has the structure shown below. -131 - 200947126 【化7 6】

S03 Na 〔實施例1〕 對化合物（III) l.OOg及乙腈3.00g，於冰冷下滴入1 一金剛烷羰基氯化物〇.82g及三乙基胺〇.397g。滴入結束 後，於室溫下攪拌20小時，將其過濾。將濾液濃縮乾燥 ，使其溶解於二氯甲烷30g中，進行3次水洗。有機層經 濃縮乾燥後得化合物（IV) 0.82g (產率：41%)。 【化7 7】 f2S03 Na [Example 1] To a solution of 1.0 g of the compound (III) and 3.00 g of acetonitrile, 1-adamantylcarbonyl chloride 〇.82 g and triethylamine 〇.397 g were added dropwise under ice cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 20 hours, and filtered. The filtrate was concentrated to dryness, dissolved in 30 g of dichloromethane, and washed with water three times. The organic layer was concentrated to dryness to give compound (IV) (yield: 41%). [化7 7] f2

η〇^〇Λ( 對所得化合物（IV )，以NMR進行分析。 !H - NMR ( DMSO - d6 ' 400MHz) : δ ( ppm ) =8.8 1 (s，1H，Hc) ' 4.37 - 4.44 ( t · 2H &gt; Hd ) 、4.17-4.26 ( t，2H，He) 、3.03-3.15 (q，6H，Hb) 、1.61-1.98 (m ，15H，Adamantane) 、1.10 — 1.24(t，9H，Ha)。 19F-NMR (DMSO— d6、376MHz) : δ ( ppm )= —1 0 6 · 6 〇 由上述結果得知，化合物（IV)具有下述所示構造。 -132- 200947126 【化7 8】〇〇^〇Λ (Analysis of the obtained compound (IV) by NMR. !H-NMR (DMSO - d6 '400 MHz) : δ (ppm) = 8.8 1 (s, 1H, Hc) ' 4.37 - 4.44 ( t · 2H &gt; Hd ) , 4.17-4.26 ( t, 2H, He) , 3.03-3.15 (q, 6H, Hb) , 1.61-1.98 (m , 15H, Adamantane) , 1.10 — 1.24 (t, 9H, Ha) 19F-NMR (DMSO-d6, 376 MHz): δ (ppm) = -1 0 6 · 6 〇 From the above results, the compound (IV) has the structure shown below. -132- 200947126 [Chem. 7 8]

〔實施例2〕[Example 2]

將化合物（II ) 4.3 4 g (純度：94 · 1 % ) 、2 _苯甲基 氧代乙醇3.14g、甲苯43.4g混合，添加p -甲苯磺酸一 水合物0.4 7g，於105 °C下迴流20小時，冷卻後，添加三 乙基胺鹽酸鹽3.18g，於室溫下攪拌3小時。反應液中添 加二氯甲烷3 1 .4g，將其過濾。使濾液濃縮乾燥後，得化 合物（V11 ) 1 . 3 1 g (產率：1 9 · 8 % )。 【化7 9】4.3 μg of compound (II ) (purity: 94 · 1 % ), 3.14 g of 2-benzyloxyethanol, 43.4 g of toluene, and 0.47 g of p-toluenesulfonic acid monohydrate were added at 105 ° C. After refluxing for 20 hours, after cooling, 3.18 g of triethylamine hydrochloride was added, and the mixture was stirred at room temperature for 3 hours. Methylene chloride 3 1. 4 g was added to the reaction mixture, which was filtered. After the filtrate was concentrated to dryness, the compound (V11) (1,1 1 g) (yield: 19.9 %) was obtained. [化7 9]

X.S〇e3Nfg -ο (II) Ο θ Η-Ν- (VII) 對所得化合物（VII )，以NMR進行分析。 *Η — NMR ( DMSO — d6 ' 400MHz) : δ ( ppm) =9.20X.S〇e3Nfg -ο (II) θ θ Η-Ν- (VII) The obtained compound (VII) was analyzed by NMR. *Η — NMR ( DMSO — d6 ' 400MHz) : δ ( ppm) =9.20

(s，lH，Hc) 、4.80(s，lH，Hf) 、4.19-4.21 (t，2H(s, lH, Hc), 4.80 (s, lH, Hf), 4.19-4.21 (t, 2H

，Hd) 、3.58— 3.59 (m，2H，He) 、3_04— 3.10(q，6H ，Hb ) 、1 · 1 3 — 1 _2 1 ( t，9H，Ha )。 19F — NMR ( DMSO — d6 ' 376MHz) : δ ( ppm)= 一 106.7 。 -133- 200947126 由上述結果得知，確認化合物（VII )具有下述所示 構造。 【化8 0】, Hd), 3.58 - 3.59 (m, 2H, He), 3_04 - 3.10 (q, 6H, Hb), 1 · 1 3 - 1 _2 1 ( t, 9H, Ha ). 19F - NMR (DMSO - d6 ' 376MHz) : δ (ppm) = a 106.7. -133-200947126 From the above results, it was confirmed that the compound (VII) had the structure shown below. [化8 0]

〔實施例3〕 對化合物（VII) 1.33g及乙腈3.00g，於水冷下滴入 1-金剛烷羰氯化物0.82g及三乙基胺0.397g。滴入結束 後，於室溫下攪拌20小時將其過濾。將濾液濃縮乾燥， 使其溶解於二氯甲烷30g中，進行3次水洗。有機溶劑層 經濃縮乾燥後得化合物（IV ’）0 · 8 6 g (產率：4 3 · 1 % )。 【化8 1】[Example 3] 1.33 g of the compound (VII) and 3.00 g of acetonitrile were added dropwise with 0.82 g of 1-adamantanecarbonyl chloride and 0.397 g of triethylamine under water cooling. After the completion of the dropwise addition, the mixture was stirred at room temperature for 20 hours and filtered. The filtrate was concentrated to dryness, dissolved in 30 g of dichloromethane, and washed with water three times. The organic solvent layer was concentrated to dryness to give Compound (IV s) 0 · 8 6 g (yield: 4 3 · 1 %). [化8 1]

對所得化合物（IV')，以NMR進行分析結果’確認 得到與〔實施例1〕所得之化合物（IV )爲相同之圖譜。 〔實施例4〕 使化合物（V) 〇.3 84g溶解於二氯甲烷3.84g與水 3.84g中，添加化合物（IV ) 0.40g。攪拌1小時後’以分 -134- 200947126 液處理回收有機層，以水3.8 4g進行3次水洗淨。所得有 機層經濃縮乾固後得化合物（VI ) 0.44g (產率81.5%)The analysis result of NMR of the obtained compound (IV') was confirmed to be the same as that of the compound (IV) obtained in [Example 1]. [Example 4] The compound (V) 〇.3 84 g was dissolved in 3.84 g of dichloromethane and 3.84 g of water, and 0.40 g of the compound (IV) was added. After stirring for 1 hour, the organic layer was recovered by treatment with a liquid of -134-200947126, and washed with water three times with 3.8 4 g of water. The obtained organic layer was concentrated and dried to give Compound (VI) 0.44 g (yield 81.5%).

【化8 2】[化8 2]

對所得化合物（VI )，以NMR進行分析。 !Η — NMR ( DMSO — d6 ' 400MHz) : δ ( ppm) =7.57 -7.87 ( m，14H，Phenyl ) 、4.4 0 — 4 · 4 2 ( t，2 Η，Hb )、 4.15-4.22 (t，2H，Ha) 、2.43 (s’ 3H，Hc) 、1.60 -1.93 ( m，15H，Adamantane )。 19F — NMR ( DMSO - d6、3 76MHz ) ： δ (ppm)= 一 106.7 。The obtained compound (VI) was analyzed by NMR. Η — NMR ( DMSO — d6 ' 400MHz) : δ ( ppm ) =7.57 -7.87 ( m,14H,Phenyl ), 4.4 0 — 4 · 4 2 ( t,2 Η,Hb ), 4.15-4.22 (t, 2H, Ha), 2.43 (s' 3H, Hc), 1.60 - 1.93 (m, 15H, Adamantane). 19F - NMR (DMSO - d6, 3 76MHz) : δ (ppm) = a 106.7.

由上述結果得知，確認化合物（V I )具有下述所示構 造。 【化8 3】From the above results, it was confirmed that the compound (V I ) had the structure shown below. [化8 3]

-135- 200947126 〔實施例5〕 (i) 對控制於20°C以下之甲烷磺酸60.75g’少量添加氧 化磷8.53g與2,5—二甲基酚8.81g與二苯基亞楓12.2g。 將溫度控制於1 5〜20 °C下進行3 0分鐘熟成後，升溫至 4 0 °C後進行2小時熟成。其後，將反應液滴入冷卻至1 5 °C 以下之純水l〇9.35g。滴入結束後’加入二氯甲烷54.68g ，於攪拌後，回收二氯甲烷層。 於另外容器中加入20〜25°C之己烷3 86.86g，將二氯 甲烷層滴入其中。滴入結束後，於20〜25 °C進行30分鐘 熟成後，經過濾後得目的化合物（i) 17.14g (產率70.9% )° 對所得化合物（i )，以NMR進行分析。 *Η— NMR ( DMSO— d6 ' 600MHz) : δ ( ppm) =7.61 — 7.72 ( m &gt; 10H，phenyl) 、7.14 ( s ’ 2H ’ Hc ) 、3.12 ( s，3H，Hb )、2.22 ( s，6H，Ha )。 由上述結果得知，確認化合物（i )具有下述所示構 造。 -136- 200947126 【化8 4】-135- 200947126 [Example 5] (i) Add 8.53 g of phosphorus oxide and 2.81 g of 2,5-dimethylphenol and diphenyl sulfoxide 12.2 to a small amount of 60.75 g of methanesulfonic acid controlled below 20 °C. g. The temperature was controlled at 35 to 20 ° C for 30 minutes, and the temperature was raised to 40 ° C, followed by aging for 2 hours. Thereafter, the reaction was dropped into a pure water of 9.35 g cooled to 15 ° C or lower. After the completion of the dropwise addition, 54.68 g of dichloromethane was added, and after stirring, a dichloromethane layer was recovered. To the other vessel, 8 86.86 g of hexane at 20 to 25 ° C was added, and the methylene chloride layer was dropped thereinto. After the completion of the dropwise addition, the mixture was aged at 20 to 25 ° C for 30 minutes, and the obtained compound (i) was obtained by filtration (yield: 70.9%). The obtained compound (i) was analyzed by NMR. *Η—NMR ( DMSO— d6 ' 600MHz) : δ ( ppm ) =7.61 — 7.72 ( m &gt; 10H, phenyl) , 7.14 ( s ' 2H ' Hc ) , 3.12 ( s, 3H, Hb ), 2.22 ( s , 6H, Ha). From the above results, it was confirmed that the compound (i) has the structure shown below. -136- 200947126 【化8 4】

使化合物（i ) 4g溶解於二氯甲烷79.8g中。確認溶 解後，添加碳酸鉀 6.87g，再添加溴乙酸甲基金剛烷 3.4 2 g。於迴流下’反應2 4小時後，進行過濾、水洗淨， 以己烷晶析。所得粉體經減壓乾燥後得目的化合物（Π ) 3.98g (產率 66%)。 對所得化合物（Π )，以NMR進行分析。 JH- NMR ( CDC13 ' 400MHz ) ： δ ( ppm ) =7.83 - 7.86 ( m，4H，Phenyl ) 、7.69 — 7.78 ( m，6H，Phenyl )4 g of the compound (i) was dissolved in 79.8 g of dichloromethane. After confirming the dissolution, 6.87 g of potassium carbonate was added, and then 3.4 2 g of methyl adamantane bromoacetate was added. After reacting for 24 hours under reflux, it was filtered, washed with water, and crystallized from hexane. The obtained powder was dried under reduced pressure to give the title compound (d) (yield: 66%). The obtained compound (Π) was analyzed by NMR. JH- NMR ( CDC13 ' 400MHz ) : δ ( ppm ) =7.83 - 7.86 ( m,4H,Phenyl ), 7.69 — 7.78 ( m,6H,Phenyl )

、7_51 ( s，2H，Hd ) 、4.46 ( s，2H，Hc ) 、2.39 ( s，6H ，Ha ) 、2.33 ( s，2H » Adamantane ) 、2.17 ( s，2H，, 7_51 ( s, 2H, Hd ), 4.46 ( s, 2H, Hc ) , 2.39 ( s, 6H , Ha ) , 2.33 ( s, 2H » Adamantane ) , 2.17 ( s, 2H,

Adamantane ) 、1.71— 1.98 ( m，1 1H ’ Adamantane )、 1.68 ( s，3H，Hb ) 、1.57— 1.61 ( m &gt; 2H &gt; Adamantane) 由上述結果得知，確認化合物（ii )具有下述所示構 造。 -137- 200947126 【化8 5】Adamantane ) , 1.71 - 1.98 ( m, 1 1H ' Adamantane ), 1.68 ( s, 3H, Hb ) , 1.57 - 1.61 ( m &gt; 2H &gt; Adamantane) From the above results, it was confirmed that the compound (ii) has the following The configuration shown. -137- 200947126 【化8 5】

(ΐϋ ) 使化合物（Π) 4.77g溶解於二氯甲烷2 3.83 g與水 23.83 g中，添加化合物（IV ) 3.22g。攪拌1小時後，以 分液處理回收有機層，以水3.84g進行3次水洗淨。所得 有機層經濃縮乾固後得化合物（X ) 4.98g (產率87% )。 【化8 6】(ΐϋ) 4.77 g of the compound (Π) was dissolved in dichloromethane 3.3 g and 23.83 g of water, and compound (IV) 3.22 g was added. After stirring for 1 hour, the organic layer was recovered by liquid separation, and washed with water three times with 3.84 g of water. The obtained organic layer was concentrated to dryness to give compound (X) 4.98 g (yield: 87%). [化8 6]

對所得化合物（X )，以NMR進行分析。 lH- NMR ( DMSO - d6 ' 400MHz) ： δ ( ppm ) =7.76 -138- 200947126 -7.88 ( m，10H，Phenyl ) 、7.62 ( s，2H，Phenyl )、 4.64 ( s &gt; 2H，Hb ) 、4.43 - 4.44 ( t &gt; 2H，Ha ) 、4.22 — 4-.23 ( t 5 2H，Hd ) 、1.5 1 — 2.3 6 ( m，3 8 H，Adam ant an e +The obtained compound (X) was analyzed by NMR. lH-NMR ( DMSO - d6 ' 400MHz) : δ ( ppm ) =7.76 -138- 200947126 -7.88 ( m,10H,Phenyl ), 7.62 ( s,2H,Phenyl ), 4.64 ( s &gt; 2H,Hb ) , 4.43 - 4.44 ( t &gt; 2H,Ha ) , 4.22 — 4-.23 ( t 5 2H,Hd ) , 1.5 1 — 2.3 6 ( m,3 8 H,Adam ant an e +

Ha + Hc)。 19F - NMR ( DMSO - d6、376MHz ) ： δ ( ppm )= 一 106.7 。 由上述結果得知，確認化合物（X )具有下述所示構Ha + Hc). 19F-NMR (DMSO-d6, 376MHz): δ (ppm) = a 106.7. From the above results, it was confirmed that the compound (X) has the following structure

造。 【化8 7】Made. [化8 7]

〔實施例6〕 於反應容器中加入三乙基胺鹽酸鹽1.99g與乙腈 25.00g’於其中添加化合物（VIII) 5.00g。於室溫下攪拌 1 5小時，將反應液過濾，濾液於減壓下將溶劑餾除。所 得物質以二氯甲烷（2 9 g )再溶解，以純水（5 · 8 g )進行2 次水洗。將有機相分液，滴入己烷（4 3 5 g )中後得目的化 合物（IX) 1.2g (產率 20%)。 -139- 200947126 【化8 8】 ϋ Ο F2 (VIII) ©[Example 6] 1.99 g of triethylamine hydrochloride and 25.00 g of acetonitrile were added to the reaction vessel, and 5.00 g of the compound (VIII) was added thereto. After stirring at room temperature for 15 hours, the reaction liquid was filtered, and the filtrate was evaporated under reduced pressure. The resulting material was redissolved in dichloromethane (29 g) and washed twice with purified water (5·8 g). The organic phase was separated and added dropwise to hexane (4 3 5 g) to give the desired compound (IX) 1.2 g (yield 20%). -139- 200947126 【化8 8】 ϋ Ο F2 (VIII) ©

cP CH3CN, r.t. (IX) 對所得化合物（IX )，以NMR進行分析。 4 - NMR ( DMSO - d6、400MHz ) ： δ (ppm) =8.8 1cP CH3CN, r.t. (IX) The obtained compound (IX) was analyzed by NMR. 4 - NMR ( DMSO - d6, 400MHz ) : δ (ppm) =8.8 1

(brs，1H，NH ) 、5.46 ( t &gt; 1H，oxo — norbornene )、 4.97 ( s，1H，oxo — norbornene ) 、4.71 ( d，1H，oxo — norbornene ) 、4.57 ( d，1H，oxo— norbornene) 、3.09 ( q，6H，NCH2 ) 、2.69 — 2.73 ( m，1H，oxo — norbornene )、2.06 — 2.16 ( m 5 2H » oxo — norbornene) ' 1.15 ( t 5 9H，CH3 )。 19F- NMR ( DMSO - d6、3 76MHz ) ： δ ( ppm )= —107.1。(brs,1H,NH ) , 5.46 ( t &gt; 1H, oxo — norbornene ), 4.97 ( s, 1H, oxo — norbornene ) , 4.71 ( d,1H, oxo — norbornene ) , 4.57 ( d,1H,oxo— Norbornene), 3.09 (q, 6H, NCH2), 2.69 - 2.73 (m, 1H, oxo - norbornene ), 2.06 - 2.16 ( m 5 2H » oxo - norbornene) ' 1.15 ( t 5 9H, CH3 ). 19F-NMR (DMSO - d6, 3 76MHz) : δ (ppm) = -107.1.

由上述結果得知，確認化合物（IX )具有上述所示構 造。 〔實施例7〕 對化合物（III) 2.42g及乙腈7.26g，於冰冷下滴入 十一烷基羰基氯化物2.19g及三乙基胺l.Olg。滴入結束 後’於室溫下攪拌20小時，將其過濾。將濾液濃縮乾燥 ’溶解於二氯甲烷20g中進行3次水洗。有機層經濃縮乾 燥後得化合物（XI ) 3.41 g (產率：80.4% )。 -140- 200947126 【化8 9】From the above results, it was confirmed that the compound (IX) had the above-described constitution. [Example 7] 2.42 g of the compound (III) and 7.26 g of acetonitrile were added dropwise 1.19 g of undecylcarbonyl chloride and 1.0 g of triethylamine under ice cooling. After the completion of the dropwise addition, the mixture was stirred at room temperature for 20 hours, and filtered. The filtrate was concentrated to dryness and dissolved in 20 g of dichloromethane to wash water three times. The organic layer was concentrated to dryness to give compound (XI) 3.41 g (yield: 80.4%). -140- 200947126 【化8 9】

(XI) 對所得化合物（XI )，以NMR進行分析。(XI) The obtained compound (XI) was analyzed by NMR.

*Η— NMR ( DMSO— d6 ' 400MHz) ·· δ ( ppm) =8.81 (s，lH，Hf) 、4·39— 4.41(t，2H，Hd) 、4.23-4.39( t，2H，He) 、3.06-3.10 (q,6H，Hh) &gt; 2.24 - 2.29 ( t ，2H，Hc) 、1.09 — 1.51 (m，25H，Hb+Hg) ' 0.83-0.89 ( t，3H，Ha )。 19F _ NMR ( DMSO - d6、3 76MHz ) ： &lt;5 ( ppm )= -106.8 。 由上述結果得知，化合物（XI )具有下述所示構造。 【化9 0】*Η— NMR ( DMSO— d6 ' 400MHz) ·· δ ( ppm) =8.81 (s,lH,Hf) , 4.39— 4.41(t,2H,Hd), 4.23-4.39( t,2H,He) , 3.06-3.10 (q,6H,Hh) &gt; 2.24 - 2.29 ( t ,2H,Hc) , 1.09 — 1.51 (m,25H,Hb+Hg) ' 0.83-0.89 ( t,3H,Ha ). 19F _ NMR (DMSO - d6, 3 76MHz): &lt;5 (ppm) = -106.8. From the above results, the compound (XI) has the structure shown below. [化9 0]

〔實施例8〕 使化合物（ΧΙΓ) 1.68g溶解於二氯甲烷8.41g與水 8.41g中，添加化合物（XI) 2.00g。攪拌1小時後，以分 -141 - 200947126 液處理回收有機層，以水3.84g進行3次水洗淨。所得有 機層經濃縮乾固後得化合物（XII) 2.20g (產率81.5%) 【化9 1】[Example 8] 1.68 g of the compound (ΧΙΓ) was dissolved in 8.41 g of dichloromethane and 8.41 g of water, and 2.00 g of the compound (XI) was added. After stirring for 1 hour, the organic layer was recovered by treatment with a solution of -141 - 200947126, and washed with water three times with 3.84 g of water. The obtained organic layer was concentrated and dried to obtain Compound (XII) 2.20 g (yield 81.5%).

_) 對所得化合物（ΧΠ )，以NMR進行分析。 !H - NMR ( DMSO - d6 ' 400MHz) : &lt;5 ( ppm ) =7.74 —7.90 ( m，15H，Phenyl ) 、4.39 — 4.42 ( t，2H，He )、 ❹ 4.21— 4.24 (t，2H，Hd) 、2.25— 2.89 (t，3H，Hc)、 1.17— 1.50 (m，15H，Hb) 、0.79-0.88 (t，3H，Ha)。 19F — NMR ( DMSO - d6、3 76MHz ) : δ (ppm)= —106.8 。 由上述結果得知，化合物（xn )具有下述所示構造 -142 - 200947126 【化9 2】_) The obtained compound (ΧΠ) was analyzed by NMR. !H-NMR ( DMSO - d6 ' 400MHz) : &lt;5 ( ppm ) =7.74 —7.90 ( m,15H,Phenyl ) , 4.39 — 4.42 ( t,2H,He ), ❹ 4.21— 4.24 (t,2H, Hd), 2.25 - 2.89 (t, 3H, Hc), 1.17 - 1.50 (m, 15H, Hb), 0.79 - 0.88 (t, 3H, Ha). 19F - NMR (DMSO - d6, 3 76MHz) : δ (ppm) = -106.8. From the above results, the compound (xn) has the structure shown below -142 - 200947126 [Chemical 9 2]

〔實施例9〕 將三乙基胺鹽酸鹽2.50g、化合物（XIII) 3.19g、乙 腈15.00g於室溫下攪拌15小時。將反應液過濾，濾液於 減壓下餾除溶劑後，得化合物（XIV ) 4.0 1 g (產率9 5.6 % )0 【化9 3】[Example 9] 2.50 g of triethylamine hydrochloride, 3.19 g of compound (XIII), and 15.00 g of acetonitrile were stirred at room temperature for 15 hours. The reaction solution was filtered, and the filtrate was evaporated under reduced pressure to give compound (XIV) 4.0 1 g (yield 9 5.6 %) 0 [chemical 9 3]

(XIV) ❹ H〇Ac.S03Na F2 (xm) 對所得化合物（XIV )，以NMR進行分析。 1 Η — N M R ( D M S Ο — d 6、4 0 0 Μ H z ) : &lt;5 (ppm) =9.20 (s，lH，Hc) ' 3.02-3.13 ( q &gt; 6H - Hb ) 、1.11-1.24 (t，9H，Ha)。 I9F — NMR ( DMSO — d6 ' 376MHz) : δ ( ppm)= -106.7 。 -143- 200947126 由上述結果得知，化合物（XIV )具有下述所示構造 【化9 4】(XIV) ❹ H〇Ac.S03Na F2 (xm) The obtained compound (XIV) was analyzed by NMR. 1 Η — NMR ( DMS Ο — d 6 , 4 0 0 Μ H z ) : &lt;5 (ppm) =9.20 (s,lH,Hc) ' 3.02-3.13 ( q &gt; 6H - Hb ) , 1.11-1.24 (t, 9H, Ha). I9F - NMR (DMSO - d6 ' 376MHz) : δ (ppm) = -106.7. -143- 200947126 It is known from the above results that the compound (XIV) has the structure shown below.

〔實施例1 〇、比較例1〕 將表1所示各成份混合、溶解以製作正型之光阻組成 物。 〔表1〕 (A)成份 (Β)成份 (D)成份 (Ε)成份 (S) 成份 實施例10 (A)-1 [100] (Β)-1 Γ9. 14] (D)-1 「1.2] (Ε)-1 [1.32] (S)-1 [10] (S)-2 [2200] 比較例1 (A)-1 Γ100] (ΒΊ-1 Γ8· 0] (D)_1 Γ1. 2] (Ε)-1 Γ1. 32] (S)-1 [10] (S)-2 [2200] 表1中各簡稱具有以1&quot; 之數値爲添加量（質量份） 又，表1中，（B ) 一 之8.0質量份爲等莫耳量° (A ) - 1 :下述化學式 45/35/20 (莫耳比））所 :意義。又，表1中之〔〕内 之9.14質量份與（B’）一 1 (A) — 1(式中，l/m/n = g 示之 Mw= 7000、Mw/Mn 200947126 前述化合物（VI ))。 (B1) — 1:下述化學式（Β·) — 1所表示之化合物。 (D) — 1:三一 η-戊基胺。 (Ε ) — 1 :水楊酸。 (S) — 1: r —丁 內酯。 (S)-2:PGMEA/PGME=6/4(質量比）。 【化9 5】[Example 1 〇, Comparative Example 1] Each component shown in Table 1 was mixed and dissolved to prepare a positive-type photoresist composition. [Table 1] (A) Component (Β) Component (D) Component (Ε) Component (S) Component Example 10 (A)-1 [100] (Β)-1 Γ9. 14] (D)-1 " 1.2] (Ε)-1 [1.32] (S)-1 [10] (S)-2 [2200] Comparative Example 1 (A)-1 Γ100] (ΒΊ-1 Γ8· 0] (D)_1 Γ1. 2] (Ε)-1 Γ1. 32] (S)-1 [10] (S)-2 [2200] Each of the abbreviations in Table 1 has the number of 1&quot; as the added amount (parts by mass). Medium, (B) 8.0 parts by mass is equal molar amount ° (A ) - 1 : the following chemical formula 45/35/20 (Morbi)): meaning. Also, in [] in Table 1 9.14 parts by mass and (B') -1 (A) - 1 (wherein, l/m/n = g shows Mw = 7000, Mw/Mn 200947126, the aforementioned compound (VI)). (B1) - 1: The compound represented by the formula (Β·)-1 (D) — 1: Tri-n-pentylamine. (Ε) — 1 : Salicylic acid. (S) — 1: r — Butyrolactone. S)-2: PGMEA/PGME=6/4 (mass ratio). [Chem. 9 5]

使用所得光阻組成物進行以下之評估。 〇The following evaluation was carried out using the obtained photoresist composition. 〇

〔光阻圖型之形成〕 將有機系抗反射膜組成物「ARC29A」（商品名，普 利瓦科技公司製）使用旋轉塗佈器塗佈於8英吋之矽晶圓 上，再於熱壓板上進行205 °C、60秒鐘燒焙、乾燥，而形 成膜厚82nm之有機系抗反射膜。隨後，將上述光阻組成 物分別使用旋轉塗佈器塗佈於該抗反射膜上，於熱壓板上 -145- 200947126 依1 ltrc、60秒鐘之條件下進行預燒焙（PAB )處理，經 乾燥後，形成膜厚150nm之光阻膜。 其次，對於前述光阻膜，使用 ArF曝光裝置NSR — S302(理光公司製；NA(開口數）= 0.60，2/3輪帶照 明），將ArF準分子雷射（193nm )介由遮罩圖型進行選 擇性照射。隨後，於1 1 〇 °C、60秒鐘之條件下進行曝光後 加熱（PEB )處理，再於23°C之2·38質量％氫氧化四甲基 銨（ΤΜΑΗ)水溶液30秒鐘之條件下顯影，其後再以30 秒鐘，使用純水進行水洗後，進行振動乾燥。 其結果，無論任一例示中，於前述光阻膜上皆形成有 線寬120nm、間距240nm之線路與空間之光阻圖型（以 下，亦稱爲L/ S圖型）。 求取形成上述線寬120nm、間距240nm之L/S圖型 之最佳曝光量Eop(mJ/cm2)。又，求取解析性之上述 Eop中之臨界解析度。該些結果係如表2所示。 又，使用掃描型電子顯微鏡（商品名：S — 9220，曰 立製作所公司製）對依上述方式所形成之線寬1 20nm、間 距240nm之L/S圖型的截面形狀進行觀察。其結果得知 ，實施例1 〇之光阻圖型形狀與比較例1相比較時，其線 路側壁具有高度垂直性，且可抑制與基板界面之邊緣捲曲 等，而顯示出高度之矩形性。 〔LWR評估〕[Formation of the photoresist pattern] The organic anti-reflective film composition "ARC29A" (trade name, manufactured by Privah Technology Co., Ltd.) was applied onto a 8 inch wafer using a spin coater, followed by heat. The plate was baked and dried at 205 ° C for 60 seconds to form an organic anti-reflection film having a film thickness of 82 nm. Subsequently, the photoresist composition is applied to the anti-reflection film by using a spin coater, and pre-baked (PAB) is performed on a hot plate at -145-200947126 at 1 ltrc for 60 seconds. After drying, a photoresist film having a film thickness of 150 nm was formed. Next, for the above-mentioned photoresist film, an ArF exposure device NSR-S302 (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 0.60, 2/3 wheel illumination) was used, and an ArF excimer laser (193 nm) was masked. The type is selectively irradiated. Subsequently, the post-exposure heating (PEB) treatment was carried out under conditions of 1 1 〇 ° C for 60 seconds, and then an aqueous solution of 3.8 mass% tetramethylammonium hydroxide (hydrazine) at 23 ° C for 30 seconds was used. The lower development was carried out, and after that, it was washed with pure water for 30 seconds, and then subjected to vibration drying. As a result, in any of the examples, a photoresist pattern (hereinafter, also referred to as an L/S pattern) having a line width of 120 nm and a pitch of 240 nm is formed on the photoresist film. The optimum exposure amount Eop (mJ/cm2) of the L/S pattern having the above line width of 120 nm and a pitch of 240 nm was obtained. Further, the critical resolution in the above-described Eop of analyticity is obtained. The results are shown in Table 2. Further, a cross-sectional shape of an L/S pattern having a line width of 1 20 nm and a pitch of 240 nm formed in the above manner was observed using a scanning electron microscope (trade name: S-9220, manufactured by Sigma). As a result, it was found that the shape of the photoresist pattern of Example 1 was compared with that of Comparative Example 1, and the side wall of the line was highly perpendicular, and the edge curl of the interface with the substrate was suppressed, and the squareness of the height was exhibited. [LWR assessment]

使用測長SEM (掃描型電子顯微鏡，加速電壓800V 200947126 ，商品名：S — 9220，日立製作所公司製）對前述 形成之線寬120nm、間距240nm之L/ S圖型，依 長度方向測定5處線寬，計算該結果所得之標準D )之3倍値（3s)作爲顯示LWR之尺度。其結果 所示。該3 s之値越小時，表示線寬之粗糙度越小 得到更具有均勻寬度之L/S圖型之意。 Q 〔 EL寬容度評估〕 除將曝光量分別變更以外，其他皆依上述相同 成線寬120nm、間距240nm之作爲標靶尺寸之L/ 〇 此時，求取L/S圖型之線路形成標靶寸法 12〇nm )之 ±5% ( 1 14nm、126nm )之際的曝光量， 求取E L寬容度（單位：％ )。其結果如表2所示。 EL 寬容度（％) = ( |Ε1-Ε2|/Εορ) χΙΟΟ Ο ’ El表示形成線寬1 14nm之L/S圖型之際的曝 mJ/cm2) ，E2表示形成線寬126nm之L/S圖型 曝光量（mJ/cm2)〕。 〔表2〕 Εορ所 線路之 i差（s 如表2 ，而可 順序形 S圖型 (線寬 依下式 〔式中 光量（ 之際的 實施例10 比較例1 Eop (mJ/cm2 ) 36. 0 31. 5 解析性（nm) 110 110 LWR(nm) 8. 1 10. 4 EL寬容度（％) 7. 37 5. 70 -147- 200947126 〔遮罩缺陷因子（MEF)評估〕 於上述Εορ中，分別使用線寬130nm、間距260nm 之以L/S圖型爲標靶之遮罩圖型，與線寬120nm、間距 260nm之L/S圖型爲標靶之遮罩圖型形成L/S圖型， 依以下計算式求取MEF之値。 MEF= | CD130 — CDi2〇l / 丨 MDi3〇_MDi2〇| 上述式中，CD13Q、CD12〇爲分別使用線寬 130nm、 1 2 Onm作爲標靶之遮罩圖型所形成之L/S圖型之實際線 寬（nm) 。MD13〇、MD12〇爲分別使用該遮罩圖型作爲標 靶之線寬（nm) ，MD13Q=130、MDi2〇=120。該 MEF 之 値越接近1時，表示可形成忠實反應遮罩圖型之光阻圖型 〇 其結果得知，實施例10爲2.0，比較例1爲2.0，爲 相同之內容。 〔遮罩線性評估〕 於上述Εορ中，將遮罩圖型之L/ S比（線寬與空間 寬之比）固定爲1:1，將遮罩尺寸（線寬）於110〜 15 0nm之範圍內，以每l〇nm變化分別形成L/S圖型， 測定所形成之L/ S圖型之尺寸（線寬）。其結果如表3 所示。 如表3所示般，實施例1〇中，120nm之Εορ，即使 尺寸由120nm偏離下，相較於比較例1也能更忠實的反 應遮罩尺寸而忠實地形成L/ S圖型，實施例1 0之光阻組 -148 - 200947126 成物，確認相較於比較例1之光阻組成物具有更優良之遮 罩重現性。 〔表3〕 賨施例10 比較例1 110nm 93.5 89.5 120nm 121.9 119.9 130nm 118.8 139.1 140nm 147.4 153.1 150nm 163.2 ' 167.0 〇 如上述結果所示般，實施例10之光阻組成物顯示出 優良之微影蝕刻特性。 〔實施例11〜1 3、比較例2〕 將表4所示各成份混合、溶解’以製作正型之光阻組 成物。 ^ 〔表 4〕 實施例11 (A)成份 (A)-1 Γ100] (B) (B)—2 Γ2 531 成份 (B’）-2 Γ9. 2] fD)成份 -(D)^ n.〇] (S) (S)-1 [10] ⑻一2 [2200] 實施例12 (A)-1 Γ100] (B)-2 [6. 33] (B，）-2 Γ5. 75± (D) 1 Γ1. 〇] [10] [2200] -TdT^ Γ1. 0]_ (S)-1 ㈣ (S)-1 -L1Q3 ⑻一2 [2200] (S)-2 [2200] 實施例13 (A)-1 J2〇2L· (A)-1 Γ100] (B)-2 [13. 0] (B，）一7 Γ11. 5] 比較例2 表 4 中，（A ) — 1、 2係與表1中之（A) -1 P ) - 1 ' (S) - 1、( S )- (D)—丄、（S) -1、（S) _ 149 - 200947126 一 2具有相同之意義，其他之簡稱分別具有以下之意義。 又，〔〕内之數値爲添加量（質量份）。 又，實施例11〜13及比較例2之（B)成份的添加量 (合計量）分別爲等莫耳量。 (B) - 2:下述化學式（B) — 2所表示之化合物（ 前述化合物（X ))。 (B') - 2:下述化學式（B’ ）— 2所表示之化合物 【化9 6】Using the length measuring SEM (scanning electron microscope, accelerating voltage 800V 200947126, trade name: S-9220, manufactured by Hitachi, Ltd.), the L/S pattern having a line width of 120 nm and a pitch of 240 nm was measured, and five lengths were measured in the longitudinal direction. The line width is calculated by calculating the result of the standard D) by 3 times 3 (3s) as a measure of the LWR. The result is shown. The smaller the 3 s is, the smaller the roughness of the line width is, and the L/S pattern with a uniform width is obtained. Q [Evaluation of EL Tolerance] In addition to changing the exposure amount, the other is the same as the above-mentioned line width of 120 nm and the pitch of 240 nm as the target size L/ 〇 At this time, the line formation of the L/S pattern is obtained. The exposure amount at ±5% (1 14 nm, 126 nm) of the target method of 12 〇 nm was determined by EL latitude (unit: %). The results are shown in Table 2. EL latitude (%) = ( |Ε1-Ε2|/Εορ) χΙΟΟ Ο ' El indicates the exposure of the L/S pattern with a line width of 1 14 nm (mJ/cm2), and E2 indicates the formation of a line width of 126 nm. S pattern exposure (mJ/cm2)]. [Table 2] The difference between the lines of Εορ (s as shown in Table 2, and the S pattern can be sequentially formed (the line width is as follows) (the amount of light in the equation (Example 10 in the case of Comparative Example Eop (mJ/cm2) 36 0 31. 5 Analytical (nm) 110 110 LWR(nm) 8. 1 10. 4 EL latitude (%) 7. 37 5. 70 -147- 200947126 [Mask defect factor (MEF) evaluation] In Εορ, the mask pattern with the L/S pattern as the target with a line width of 130 nm and a pitch of 260 nm is used, and the L/S pattern with a line width of 120 nm and a pitch of 260 nm is used as the target mask pattern to form L. /S pattern, the MEF is obtained according to the following formula: MEF= | CD130 — CDi2〇l / 丨MDi3〇_MDi2〇| In the above formula, CD13Q and CD12〇 are respectively used with line widths of 130 nm and 1 2 Onm. The actual line width (nm) of the L/S pattern formed by the mask pattern of the target. MD13〇, MD12〇 are the line width (nm) using the mask pattern as the target, MD13Q=130, MDi2 〇 = 120. The closer the ME of the MEF is to 1, the photo resistive pattern of the faithful reaction mask pattern can be formed. As a result, the example 10 is 2.0, and the comparative example 1 is 2.0, which is the same content. Cover Linear evaluation] In the above Εορ, the L/S ratio (ratio of line width to space width) of the mask pattern is fixed to 1:1, and the mask size (line width) is in the range of 110 to 150 nm. The L/S pattern was formed by changing every 10 nm, and the size (line width) of the formed L/S pattern was measured. The results are shown in Table 3. As shown in Table 3, Example 1 Between 120 nm and Ερ, even if the size is deviated from 120 nm, the L/S pattern can be faithfully formed in comparison with Comparative Example 1 to form a faithful mask size, and the photoresist layer of Example 10 is -148 - 200947126. It was confirmed that the mask reproducibility was better than that of the photoresist composition of Comparative Example 1. [Table 3] Example 10 Comparative Example 1 110 nm 93.5 89.5 120 nm 121.9 119.9 130 nm 118.8 139.1 140 nm 147.4 153.1 150 nm 163.2 ' 167.0 As shown in the above results, the photoresist composition of Example 10 exhibited excellent lithographic etching characteristics. [Examples 11 to 13 and Comparative Example 2] The components shown in Table 4 were mixed and dissolved. A positive photoresist composition was produced. ^ [Table 4] Example 11 (A) Ingredient (A)-1 Γ100] (B) (B) 2 Γ2 531 Composition (B')-2 Γ9. 2] fD) Composition-(D)^n.〇] (S) (S)-1 [10] (8)1-2 [2200] Example 12 (A)- 1 Γ100] (B)-2 [6. 33] (B,)-2 Γ5. 75± (D) 1 Γ1. 〇] [10] [2200] -TdT^ Γ1. 0]_ (S)-1 (4) (S)-1 - L1Q3 (8) - 2 [2200] (S)-2 [2200] Example 13 (A)-1 J2〇2L· (A)-1 Γ100] (B)-2 [13. 0 [B,) a 7 Γ 11. 5] Comparative Example 2 In Table 4, (A) - 1, 2, and (A) -1 P ) - 1 ' (S) - 1 , ( S ) - (D) - 丄, (S) - 1, (S) _ 149 - 200947126 A 2 has the same meaning, and the other abbreviations have the following meanings. Further, the number in [] is the amount of addition (parts by mass). Further, the amounts (total amounts) of the components (B) of Examples 11 to 13 and Comparative Example 2 were respectively equal molar amounts. (B) - 2: a compound represented by the following chemical formula (B)-2 (the aforementioned compound (X)). (B') - 2: a compound represented by the following chemical formula (B') - 2 [Chemical 9 6]

C· S03C· S03

© 使用所得之光阻組成物進行以下之評估。 〔光阻圖型之形成〕 將有機系抗反射膜組成物「ARC29A」（商品名、普 利瓦科技公司製）使用旋轉塗佈器塗佈於8英吋之矽晶圓 上，於熱壓板上進行205 °C、60秒鐘燒焙、乾燥而形成膜 厚89nm之有機系抗反射膜。隨後，將上述光阻組成物分 別使用旋轉塗佈器塗佈於該抗反射膜上，再於熱壓板上以 1 10t、60秒鐘之條件進行預燒焙（PAB )處理，經乾燥 後形成膜厚150nm之光阻膜。 -150- 200947126 其次，將保護膜形成用塗佈液「TILC— 03 5」（商品 名，東京應化工業公司製）使用旋轉塗佈器塗佈於前述光 阻膜上，於90°C下經60秒鐘加熱後，形成膜厚90nm之 頂部塗覆層。 其次’使用ArF浸潤式曝光裝置NSR— S609B (理光 公司製；NA(開口數）=ι.〇7，σ0.97)，介由通孔圖型 之遮罩’對形成有頂部塗覆層之前述光阻膜，以ArF準分 ◎ 子雷射（1 9 3 n m )進行選擇性之照射。 其後’於1 0 5 °C、6 0秒鐘之條件下進行曝光後加熱（ PEB )處理’再於23t下使用2.38質量％氫氧化四甲基銨 (TMAH )水溶液顯影30秒鐘，其後再以30秒鐘，使用 純水進行水洗，振動乾燥。 其結果’無論任一例示，於前述光阻膜上，皆形成有 通孔直徑90nm之通孔以等間隔（間距丨8〇nm )配置所得 之接觸孔圖型（以下，亦稱爲DenceCH圖型）。 〇 其次，對於形成前述Dence CH圖型之最佳曝光量© Use the resulting photoresist composition for the following evaluation. [Formation of the photoresist pattern] The organic anti-reflective film composition "ARC29A" (trade name, manufactured by Privah Technology Co., Ltd.) was applied onto a 8 inch silicon wafer by a spin coater, and hot pressed. The plate was baked at 205 ° C for 60 seconds, and dried to form an organic anti-reflection film having a film thickness of 89 nm. Subsequently, the photoresist composition is applied to the anti-reflection film by using a spin coater, and then pre-baked (PAB) is performed on a hot plate at 1 10 t for 60 seconds. A photoresist film having a film thickness of 150 nm was formed. -150-200947126 Next, a coating liquid for forming a protective film "TILC-03" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the resist film using a spin coater at 90 ° C. After heating for 60 seconds, a top coat layer having a film thickness of 90 nm was formed. Secondly, 'ArF immersion exposure apparatus NSR-S609B (manufactured by Ricoh Co., Ltd.; NA (number of openings) = ι.〇7, σ0.97) was used, and the mask of the through-hole pattern was formed to form a top coating layer. The photoresist film was selectively irradiated with ArF quasi-sorted laser (1 3 3 nm). Thereafter, the post-exposure heating (PEB) treatment was carried out at 1 0 5 ° C for 60 seconds, and then developed under an aqueous solution of 2.38 mass % tetramethylammonium hydroxide (TMAH) at 23 t for 30 seconds. After 30 seconds, it was washed with pure water and shaken dry. As a result, in any of the examples, a contact hole pattern (hereinafter, also referred to as a DenceCH pattern) in which via holes having a via diameter of 90 nm are formed at equal intervals (pitch 丨8 〇 nm) is formed on the photoresist film. type). 〇 Secondly, the optimal exposure for forming the aforementioned Dence CH pattern

Eop ( mJ/ cm2),形成通孔直徑90nm之通孔以等間隔（ 間距57〇nm)配置所得之接觸孔圖型（以下，亦稱爲is〇 CH圖型）。 對上述直徑90nm之is〇 Ch圖型之微影蝕刻特性進行 評估。其結果如表5所示。 〔焦點景深寬度（DOF)評估〕 於上述Eop中’將焦點適度的上下移動，並依上述〔 -151 - 200947126 光阻圖型之形成〕相同方法形成光阻圖型，求取上述之 Iso CH圖型於標靶尺寸±5% (即85.5〜94.5nm)之尺寸變 化率之範圍内所形成之焦點景深寬度（D OF，單位：nm ) 。其結果如表5所示。 〔MEF評估〕 於上述Εορ中，分別使用通孔之直徑的標靶尺寸爲 61nm、63nm、65nm、67nm、69nm 之遮罩圖型，形成間 距5 70nm之Iso CH圖型。此時，使標靶尺寸（nm)作爲 橫軸，求取形成於使用各遮罩圖型之光阻膜的通孔圖型之 口徑（nm)作爲縱軸進行繪圖時之直線的傾斜度作爲 MEF。MEF (直線之傾斜度）之値越接近於1時，顯示出 遮罩重現性良好之意。所得之結果係如表5所示。 〔EL寬容度評估〕 求取直徑90nm之Iso CH圖型以標靶尺寸（通孔直徑 90nm)之±5% ( 85.5nm、94.5nm)形成之際的曝光量，其 次依計算式求取EL寬容度（單位：％ )。其結果如表5 所示。 EL 寬容度（％) = ( | El-E2| /Eop) xl〇〇〔式中 ，El爲形成通孔直徑85.5nm之CH圖型之際的曝光量（ mJ/cm2) ，E2爲形成通孔直徑94.5nm之CH圖型之際 的曝光量（mJ/cm2)〕。 -152- 200947126 〔表5〕 實施例11 實施例12 實施例13 比較例2 Eop(mJ/cmz) 37.1 39.4 42.1 41.7 DOF(nm) 0.15 0.14 0.15 0.14 MEF 3.03 3.32 2.98 3.52 EL寬容度（％) 9.5 9.46 9.27 8.58 如表5所示般，實施例1 1〜1 3之光阻組成物，與比 較例2之光阻組成物相比較時，顯示出更佳之MEF、EL 0 寬容度，且DOF亦爲同等以上。 由上述結果得知，本發明之第六之態樣之化合物（b0 -1 )，極適合作爲酸產生劑之有用化合物的中間體，本 發明之第三之態樣之化合物（b 1 — 1 )，爲適合作爲酸產 生劑之有用化合物。 〔實施例1 4〜2 0〕 將表6所示各成份混合、溶解，以製作正型之光阻組 〇 成物。 〔表6〕 (A)成份 ⑻成份 (D)成份 ⑻成份 實施例14 (A)-2 [50] (A)-3 [50] (B)-1 [5_ 0] (D)-1 [〇. 25] (S)-2 [1800] 實施例1 5 (A)-2 [50] (A)-3 [50] (B)-1 [7. 5] (D) — 1 [0. 25] (S)-2 [1800] 實施例16 (A)-2 [50] (A)-3 [50] (B)-1 [7. 5] (D)-1 [0. 40] (S)-2 [1800] 實施例17 (A)-2 [50] (A)-3 [50] (B)-1 [7. 5] (D)-1 [0. 55] (S)-2 [1800] 實施例18 (A)-2 [50] (A)-3 [50] (B)-1 [10. 〇] (D)-1 [0. 40] (S)-2 [1800] 實施例1 9 (A)-2 [50] (A)-3 [50] (B)-1 [10. 0] (D)-1 [0. 55] (S)-2 [1800] 實施例20 (A)-2 [50] (A)-3 [50] (B)-1 [10. 〇] (D)-1 [1. 2] (S)-2 [1800] -153- 200947126 表 6 中，（B) — 1、（D) — 1、（S) — 2 爲與表 1 中之（B) — 1、（D) — 1、 （S) - 2具有相同之意義’ 其他簡稱分別爲具有以下之意義。 〕内之數値爲添加量（質量份）° X，例14〜20之（B)成份的添加量（合計量） 分別爲等莫耳量。 (A) 一 2:下述化學式（A) —2(式中’ l/m/n = 30/50/20 (莫耳比））所表示之 Mw = 10000、Mw/Mn =2.0之共聚物。 (A) 一 3:下述化學式（A) — 3(式中，l/m/n = 40/40/20 (莫耳比））所表示之 Mw = 10000、Mw/Mn =2.0之共聚物。 【化9 7】Eop (mJ/cm2), a contact hole pattern (hereinafter, also referred to as an is CH pattern) in which via holes having a via hole diameter of 90 nm are formed at equal intervals (pitch 57 〇 nm). The lithographic etching characteristics of the above-described 90 nm is〇 Ch pattern were evaluated. The results are shown in Table 5. [Focus Depth of Field Width (DOF) Evaluation] In the above Eop, 'the focus is moderately moved up and down, and the photoresist pattern is formed in the same way as the above [-151 - 200947126 photoresist pattern formation], and the above Iso CH is obtained. The depth of field of focus (D OF, in units of nm) formed by the pattern within the range of the dimensional change rate of the target size ± 5% (ie, 85.5 to 94.5 nm). The results are shown in Table 5. [MEF evaluation] In the above Εορ, a mask pattern having a diameter of a through hole of 61 nm, 63 nm, 65 nm, 67 nm, and 69 nm was used to form an Iso CH pattern having a pitch of 5 70 nm. In this case, the target size (nm) is taken as the horizontal axis, and the inclination of the straight line when the aperture (nm) of the via pattern formed using the mask pattern of each mask pattern is plotted as the vertical axis is obtained as MEF. The closer the MEF (inclination of the line) is to 1, the better the reproducibility of the mask. The results obtained are shown in Table 5. [EL latitude evaluation] The exposure amount of the Iso CH pattern of 90 nm in diameter is formed by ±5% (85.5 nm, 94.5 nm) of the target size (via hole diameter: 90 nm), and the EL is calculated by the calculation formula. Tolerance (unit: %). The results are shown in Table 5. EL latitude (%) = ( | El-E2| /Eop) xl〇〇 [wherein, El is the exposure amount (mJ/cm2) at the time of forming the CH pattern of the via hole diameter of 85.5 nm, and E2 is formed Exposure amount (mJ/cm2) at the CH pattern of a hole diameter of 94.5 nm]. -152-200947126 [Table 5] Example 11 Example 12 Example 13 Comparative Example 2 Eop (mJ/cmz) 37.1 39.4 42.1 41.7 DOF (nm) 0.15 0.14 0.15 0.14 MEF 3.03 3.32 2.98 3.52 EL latitude (%) 9.5 9.46 9.27 8.58 As shown in Table 5, the photoresist compositions of Examples 1 1 to 13 exhibited better MEF, EL 0 latitude, and DOF when compared with the photoresist composition of Comparative Example 2. It is equal to or above. From the above results, it is understood that the sixth aspect of the present invention (b0-1) is extremely suitable as an intermediate of a useful compound of an acid generator, and the third aspect of the present invention (b 1 - 1) ) is a useful compound suitable as an acid generator. [Example 1 4 to 2 0] Each component shown in Table 6 was mixed and dissolved to prepare a positive-type photoresist composition. [Table 6] (A) Component (8) Component (D) Component (8) Component Example 14 (A)-2 [50] (A)-3 [50] (B)-1 [5_ 0] (D)-1 [ 〇. 25] (S)-2 [1800] Example 1 5 (A)-2 [50] (A)-3 [50] (B)-1 [7. 5] (D) — 1 [0. 25] (S)-2 [1800] Example 16 (A)-2 [50] (A)-3 [50] (B)-1 [7. 5] (D)-1 [0. 40] ( S)-2 [1800] Example 17 (A)-2 [50] (A)-3 [50] (B)-1 [7. 5] (D)-1 [0. 55] (S)- 2 [1800] Example 18 (A)-2 [50] (A)-3 [50] (B)-1 [10. 〇] (D)-1 [0. 40] (S)-2 [1800 Example 1 9 (A)-2 [50] (A)-3 [50] (B)-1 [10. 0] (D)-1 [0. 55] (S)-2 [1800] Implementation Example 20 (A)-2 [50] (A)-3 [50] (B)-1 [10. 〇] (D)-1 [1. 2] (S)-2 [1800] -153- 200947126 In Table 6, (B) - 1, (D) - 1, (S) - 2 have the same meaning as (B) - 1, (D) - 1, (S) - 2 in Table 1 'Others The abbreviations have the following meanings. The number in the 〕 is the amount of addition (parts by mass) ° X, and the amount of the components (B) of the components (B) of Examples 14 to 20 is equal to the molar amount. (A) A 2: a copolymer of the formula (A) - 2 (wherein l / m / n = 30 / 50 / 20 (mr ratio)) represented by Mw = 10000, Mw / Mn = 2.0 . (A) A3: a copolymer of the formula (A) - 3 (wherein, l/m/n = 40/40/20 (mole ratio)) represented by Mw = 10000, Mw/Mn = 2.0 . [化9 7]

使用所得之光阻組成物進行以下之評估。 -154-The following evaluation was carried out using the obtained photoresist composition. -154-

200947126 〔光阻圖型之形成〕 將有機系抗反射膜組成物「ARC29A」（商品 利瓦科技公司製）使用旋轉塗佈器塗佈於1 2英防 圓上，再於熱壓板上進行205 °C、60秒鐘燒焙、章 形成膜厚70ηηι之有機系抗反射膜。隨後，將上劲 成物分別使用旋轉塗佈器塗佈於該抗反射膜上，东 上依1 10°C、60秒鐘之條件下進行預燒焙（PAB ) 經乾燥後，形成膜厚1 70nm之光阻膜。 其次，對於前述光阻膜，使用ArF曝光裝置 S308FC理光公司製；NA(開口數）= 0.85，σ = ’將ArF準分子雷射（193 nm)介由遮罩圖型進f 照射。隨後，於90 °C、60秒鐘之條件下進行曝为 (PEB)處理，再於23°C之2.38質量％氫氧化四甲 ΤΜ AH )水溶液3 0秒鐘之條件下顯影，其後再以 ，使用純水進行水洗後，進行振動乾燥。 其結果’無論任一例示中，於前述光阻膜上碧 通孔直徑1 1 〇nm之通孔以等間隔（間距2 1 Onm ) Dense CH 圖型。 其次，於前述形成Dence CH圖型之最佳曝为 (mJ / cm2 )中，形成通孔直徑1 ΐ〇ηιη之通孔以等 間距780nm)配置之Iso CH圖型。 評估上述直徑llOnm之Dense/Iso之各CH 之微影餓刻特性。其結果係如表7所示。 j名，普 f&quot;之砂晶 ί燥，而 【光阻組 t熱壓板 處理， NSR — :0.95) :選擇性 :後加熱 1基銨（ 3 0秒鐘 1形成有 配置之 :量 Εορ i間隔（ 圖型中 -155- 200947126 〔焦點景深寬度（DOF)評估〕 於上述Εορ中，將焦點適度的上下移動，並依上述〔 光阻圖型之形成〕相同方法形成光阻圖型，求取上述之各 CH圖型於標靶尺寸±5% (即 1〇4·5〜115.5nm)之尺寸變 化率之範圍内所形成之焦點景深寬度（DOF，單位：nm) 〔MEF評估〕 分別使用通孔直徑之標靶尺寸於ll〇nm±5nm之範圍 內以每1 nm變化所得之遮罩圖型，於上述Εορ中，形成 各個 CH 圖型（間距爲，Dense: 210nm、Iso: 780nm)。 此時，使遮罩尺寸（nm)作爲橫軸，求取形成於使用各 遮罩圖型之光阻膜的通孔圖型之口徑（nrn)作爲縱軸進 行繪圖時之直線的傾斜度作爲MEF。MEF (直線之傾斜度 )之値越接近於1時，顯示出遮罩重現性良好之意。 〔CDU (通孔直徑之均勻性）評估〕 對所得之各個CH圖型，分別測定其通孔之直徑（ Dense: 54個、Iso: 26個），求出由其結果算出之標準 偏差（σ)之3倍値（3σ)。依此方式求得之3σ，其 數値越小時，形成於該光阻膜之各通孔的CDU越高，即 ，存在於一定範圍内之通孔的直徑之偏差越小之意。 〔正圓性評估〕 -156- 200947126 對於各CH圖型中之通孔形狀，使用測長SEM (日立 製作所公司製，製品名：S — 9220 )進行觀測，並依以下 之基準進行評估。 A:正圓性極高（由上方觀察時，未發現通孔圖型之 圓周部之凹凸，具有非常良好之形狀）。 B:高正圓性（由上方觀察時，於通孔圖型之圓周部 發現少許凹凸，全體而言爲具有高正圓性之形狀）。 〇 〔表7〕200947126 [Formation of the photoresist pattern] The organic anti-reflective film composition "ARC29A" (manufactured by Liwa Technology Co., Ltd.) was applied onto a 12-inch anti-circle using a spin coater, and then on a hot plate. The organic anti-reflection film was baked at 205 ° C for 60 seconds and formed into a film thickness of 70 ηηι. Subsequently, the upper strength product is coated on the anti-reflection film by using a spin coater, and pre-baked (PAB) is dried at a temperature of 10 ° C for 60 seconds to form a film thickness of 1 70nm photoresist film. Next, for the above-mentioned photoresist film, an ArF exposure apparatus S308FC Ricoh Co., Ltd. was used; NA (number of openings) = 0.85, σ = ', and an ArF excimer laser (193 nm) was irradiated through a mask pattern into f. Subsequently, exposure to (PEB) treatment was carried out at 90 ° C for 60 seconds, and development was carried out under an aqueous solution of 2.38 mass % tetramethylhydrazine hydroxide (AH) at 23 ° C for 30 seconds, and then After washing with pure water, it was subjected to vibration drying. As a result, in any of the examples, the through holes having a diameter of 1 〇 nm on the resist film were equally spaced (pitch 2 1 Onm ) Dense CH pattern. Next, in the optimum exposure (mJ / cm2) for forming the Dence CH pattern, an Iso CH pattern in which via holes having a via diameter of 1 ΐ〇ηη is formed at equal intervals of 780 nm) is formed. The lithography characteristics of each CH of Dense/Iso having the above diameter llOnm were evaluated. The results are shown in Table 7. j name, general f&quot; sand crystal ί dry, and [photoresist group t hot plate treatment, NSR -: 0.95): selectivity: after heating 1 base ammonium (30 seconds 1 formed with a configuration: amount Εορ i interval (in the pattern -155- 200947126 [focus depth of field (DOF) evaluation] In the above Εορ, the focus is moderately moved up and down, and the photoresist pattern is formed in the same way as the above [form of the photoresist pattern]. Find the focal depth of field (DOF, unit: nm) formed by the above-mentioned CH pattern in the range of the dimensional change rate of the target size ± 5% (ie, 1〇4·5 to 115.5 nm) [MEF evaluation] The mask patterns obtained by changing the target size of the via diameter in the range of ll 〇 nm ± 5 nm at intervals of 1 nm are respectively formed, and in the above Εορ, the respective CH patterns are formed (the spacing is Dense: 210 nm, Iso: 780 nm) At this time, the mask size (nm) is taken as the horizontal axis, and the line diameter (nrn) of the via pattern formed using the photoresist pattern of each mask pattern is determined as a straight line when drawing as the vertical axis. The inclination is MEF. The closer the MEF (the inclination of the line) is to 1, the better the reproducibility of the mask is. [CDU (uniformity of through-hole diameter)] For each CH pattern obtained, the diameter of the through-hole (Dense: 54, Iso: 26) was measured, and the standard deviation calculated from the result was obtained. 3 times ((3σ) of (σ). 3σ obtained in this way, the smaller the number 値, the higher the CDU formed in each through hole of the photoresist film, that is, the through hole existing in a certain range The smaller the deviation of the diameter is, the smaller the meaning of the diameter is. </ </ STRONG> 156- 200947126 For the shape of the through hole in each CH pattern, the length measurement SEM (manufactured by Hitachi, Ltd., product name: S-9220) is used for observation. It is evaluated according to the following criteria: A: The roundness is extremely high (when viewed from above, the unevenness of the circumferential portion of the through-hole pattern is not found, and it has a very good shape.) B: High roundness (when viewed from above, A little unevenness was observed in the circumferential portion of the through-hole pattern, and the shape was high roundness as a whole.) 〇[Table 7]

實施例 14 實施例 15 實施例 16 實施例 17 實施例 18 實施例 19 實施例 20 EOP(n nJ/cm^) 53 31.5 36.3 42.2 26.4 29.8 46.5 DOFCnm) Dense 0.21 0.14 0.16 0.13 0.13 0.12 0.11 Iso 0.13 0.12 0.12 0.12 0.14 0.11 0.12 MEF Dense 2.46 2.65 2.68 2.5 2.8 2.82 2.98 Iso 1.79 2.16 1.91 1.96 2.31 2.65 3.06 CDU Dense 6.23 4.73 4.32 4.61 5.33 4.06 5.35 Iso 8.03 4.84 5.78 4.96 5,11 4.87 5.9 正圓性 Dense B A A A A A B Iso B A A A A A A 如表7所示般，實施例14〜2 0之光阻組成物，於 Dense/Iso CH圖型之二者，皆具有優良之微影蝕刻特性 (DOF、MEF、CDU、正圓性）。有關CDU及正圓性之通 孔形狀’特別是實施例1 5〜1 9之光阻組成物則顯示出良 好之效果。 由上述結果得知’確認本發明之第六之態樣之化合物 (b0 - 1 ) ’適合作爲酸產生劑之有用化合物的中間體， 本發明之第三之態樣之化合物（bl- 1)，適合作爲酸產 生劑之有用化合物。 -157- 200947126 〔實施例2 1〕 對化合物（III ) 8.00g及二氯甲烷1 50.00g，於水冷 下滴入1 一金剛烷乙醯氯化物7.〇2g及三乙基胺3.18g。 滴入結束後，於室溫下攪拌20小時，將其過濾。濾液以 純水5 4.6 g洗淨3次，有機層經濃縮乾燥後得化合物（ XV ) 14.90g (產率：88.0% )。 【化9 8】Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 EOP(n nJ/cm^) 53 31.5 36.3 42.2 26.4 29.8 46.5 DOFCnm) Dense 0.21 0.14 0.16 0.13 0.13 0.12 0.11 Iso 0.13 0.12 0.12 0.12 0.14 0.11 0.12 MEF Dense 2.46 2.65 2.68 2.5 2.8 2.82 2.98 Iso 1.79 2.16 1.91 1.96 2.31 2.65 3.06 CDU Dense 6.23 4.73 4.32 4.61 5.33 4.06 5.35 Iso 8.03 4.84 5.78 4.96 5,11 4.87 5.9 Round Dense BAAAAAB Iso BAAAAAA As shown, the photoresist compositions of Examples 14 to 20 have excellent lithographic etching characteristics (DOF, MEF, CDU, roundness) in both Dense/Iso CH patterns. The shape of the through hole of the CDU and the roundness, particularly the photoresist composition of Examples 15 to 19, showed a good effect. From the above results, it was found that 'the compound of the sixth aspect of the present invention (b0-1)' is suitable as an intermediate of a useful compound of an acid generator, and the third aspect of the present invention (bl-1) It is a useful compound suitable as an acid generator. -157-200947126 [Example 2 1] To a solution of 8.00 g of the compound (III) and 15.00 g of methylene chloride, 1 - adamantane acetonitrile chloride 7. 〇 2 g and triethylamine 3.18 g were added dropwise under water cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 20 hours, and filtered. The filtrate was washed 3 times with 5 4.6 g of pure water, and the organic layer was concentrated to dryness to give compound (XV) 14.90 g (yield: 88.0%). [化9 8]

(1 i 1 ) (XV) 對所得化合物（XV )，以NMR進行分析。 NMR ( DMSO ' 400MHz) ： &lt;5 (ppm) =8.81 (br s，lH，Hc)、4.40(t，2H，Hd)、4.20(t，2H，He) ' 3.08(q，6H，Hb)、2.05(s，2H，Hf)、1.53-1.95 (m ，15H，Adamantane ) 、1.17 ( t * 9H，Ha )。 19F — NMR ( DMSO、376MHz) : δ (ppm)= -106.90 。 由上述結果得知，化合物（xv)具有下述所示彳冓^ 【化9 9】(1 i 1 ) (XV) The obtained compound (XV) was analyzed by NMR. NMR ( DMSO ' 400 MHz) : &lt;5 (ppm) = 8.81 (br s, lH, Hc), 4.40 (t, 2H, Hd), 4.20 (t, 2H, He) ' 3.08 (q, 6H, Hb) , 2.05 (s, 2H, Hf), 1.53-1.95 (m, 15H, Adamantane), 1.17 (t * 9H, Ha). 19F - NMR (DMSO, 376MHz): δ (ppm) = -106.90. From the above results, it is known that the compound (xv) has the following structure.

-158 - 200947126 〔實施例22〕 使化合物（V) 7.04g溶解於二氯甲烷7〇.4g與水 7〇.4g中，添加化合物（XV ) 9.27g。攪拌1小時後，以 分液處理回收有機層，以l%HClaq 70.4g洗淨1次、純水 70.4g進行水洗淨4次。所得有機層經濃縮乾固結果，得 化合物（XVI) 11.59g (產率 90.6%)。 【化1 0 0】-158 - 200947126 [Example 22] 7.04 g of the compound (V) was dissolved in 7 g of dichloromethane and 7 g of water, and 9.27 g of a compound (XV) was added. After stirring for 1 hour, the organic layer was recovered by liquid separation, washed once with 1% HClaq 70.4 g and 70.4 g of pure water, and washed with water four times. The obtained organic layer was concentrated to dryness to give the compound (XVI) 11.59 g (yield: 90.6%). [化1 0 0]

(V) (XV) (XVI) 對所得化合物（XVI )，以NMR進行分析。 *H - NMR ( DMSO ' 400MHz ) ： &lt;5 (ppm) =7.50 - 7.87 ( m - 14H，Phenyl ) 、4.42 ( s，2H &gt; Hc ) 、4.23 ( s， 2H，Hb ) 、2.43 ( s，3H，Ha ) 、2.01 ( s，2H，Hf )、 1.94 ( s » 2H，Adamantane ) 、1.52— 1.61 ( m，13 H，(V) (XV) (XVI) The obtained compound (XVI) was analyzed by NMR. *H - NMR ( DMSO ' 400MHz ) : &lt;5 (ppm) = 7.50 - 7.87 ( m - 14H, Phenyl ) , 4.42 ( s, 2H &gt; Hc ) , 4.23 ( s, 2H, Hb ) , 2.43 ( s , 3H, Ha ) , 2.01 ( s, 2H, Hf ), 1.94 ( s » 2H, Adamantane ), 1.52 — 1.61 ( m, 13 H,

Adamantane ) ° 19F — NMR ( DMSO、3 76MHz ) ： δ ( ppm )= 一 106.49 。 由上述結果得知，確認化合物（XVI )具有下述所示 構造。 -159- 200947126Adamantane ) ° 19F — NMR ( DMSO, 3 76MHz ) : δ ( ppm ) = a 106.49 . From the above results, it was confirmed that the compound (XVI) had the structure shown below. -159- 200947126

〔實施例23〕 將化合物（XX) 21.6g與水53.0g與二氯甲烷69.7g 於室溫下攪拌，於其中添加化合物（IV) 12.9g。攪拌1 小時後，以分液處理回收有機層，以l%HCIaq 34.9g洗淨 1次、純水69.7g進行水洗淨2次。所得之有機層以濃縮 乾固後，得化合物（XXI ) 9.94g (產率61.4% )。 【化1 0 2】[Example 23] 21.6 g of the compound (XX) and 53.0 g of water and 69.7 g of dichloromethane were stirred at room temperature, and 12.9 g of the compound (IV) was added thereto. After stirring for 1 hour, the organic layer was recovered by liquid separation, washed once with 1% HCIaq 34.9 g and 69.7 g of pure water, and washed twice with water. The obtained organic layer was concentrated to dryness to give the compound (XXI) 9.94 g (yield 61.4%). [化1 0 2]

(XX)(XX)

對所得化合物（XXI )，以NMR進行分析。 — NMR ( DMSO、400MHz ) ： δ ( ppm ) =8.00 ( d ，2H，Hf) 、7.75 ( t，1H，Hj ) 、7 · 5 8 ( t，2 Η，Hg )、 5.30 ( s，2H，He ) 、4.37 - 4.44 ( t，2H，Ha ) ' 4.17- 4.26(t，2H，Hb) 、3.54(m，4H，Hd) 、2.49-2.18 (m ，4H’ Hc ) 、1.93 — 1.60 (m1 15H，一 Adamantane)。 19F— NMR (DMSO、376MHz) : δ (ppm) =-106.2 -160- 200947126 由上述結果得知，確認化合物（χχι)具有下述所示 構造。 【化1 0 3】The obtained compound (XXI) was analyzed by NMR. — NMR ( DMSO, 400 MHz ) : δ ( ppm ) = 8.00 ( d , 2H, Hf ) , 7.75 ( t, 1H, Hj ) , 7 · 5 8 ( t, 2 Η, Hg ), 5.30 ( s, 2H, He ) , 4.37 - 4.44 ( t,2H,Ha ) ' 4.17- 4.26(t,2H,Hb) , 3.54(m,4H,Hd) , 2.49-2.18 (m ,4H' Hc ) , 1.93 — 1.60 (m1 15H, an Adamantane). 19F-NMR (DMSO, 376 MHz): δ (ppm) = -106.2 - 160 - 200947126 From the above results, it was confirmed that the compound (χχι) had the structure shown below. [化1 0 3]

〇 〔實施例24〜26〕 將表8所示各成份混合、溶解以製作正型之光阻組成 物。 〔表8〕 組成L質量份] PEB rc/秒） (A)成份 (B)成份 (D)成份 (S)成份 實施例24 (A)-4 [100] (B)-3 Γ11 _ 2] — (D)-2 [〇. 5] (S)-1 [2200] 80/60 實施例25 (A) — 5 [100] (B) — 3 [11.2] 一 (D)-2 [〇. 5] (S)-1 [2200] 90/60 實施例26 (A)-6 [100] (B)-1 [6. 0] (B)-4 [5. 83] (D)-2 [〇. 3] (S)-1 [2200] 90/60 表8中，（B)— 1、 （S) — 2係與表1中之（B) — 1、（S) - 2具有相同之意義’其他之簡稱分別具有以下 之意義。又，〔〕内之數値爲添加量（質量份）° 又，實施例24〜26之（B)成份之添加量（合計量） 分別爲等莫耳量。 (A) —4:下述化學式（A) _4(式中，l/m/n== 200947126 30/50/20 (莫耳比））所表示之 Mw = 10,000、Mw/ Mn= 2.0之共聚物。 (A) - 5:下述化學式（A) _5(式中，= 30/50/20 (莫耳比））所表示之 Mw = 10,000、Mw/ Μη = 2.0之共聚物。 (Α) - 6:高分子化合物（A) - 6(依後述參考例3 所合成）。 (B) — 3:下述化學式（B) - 3所表示之化合物（ 前述化合物（XVI ))。 (B) — 4:下述化學式（B) - 4所表示之化合物（ 前述化合物（XXI))。 (D) — 2:硬脂基二乙醇胺。 【化1 0 4】实施 [Examples 24 to 26] The components shown in Table 8 were mixed and dissolved to prepare a positive photoresist composition. [Table 8] Composition L parts by mass] PEB rc/sec) (A) Component (B) Component (D) Component (S) Component Example 24 (A)-4 [100] (B)-3 Γ11 _ 2] — — — — — — — — — — — — — — — — — — — — — 5] (S)-1 [2200] 90/60 Example 26 (A)-6 [100] (B)-1 [6. 0] (B)-4 [5. 83] (D)-2 [ ]. 3] (S)-1 [2200] 90/60 In Table 8, (B)-1, (S)-2 are identical to (B)-1 and (S)-2 in Table 1. The meaning of 'other abbreviations' has the following meanings. Further, the number of 値 in [] is the amount of addition (parts by mass). Further, the amounts (total amounts) of the components (B) of Examples 24 to 26 are each a molar amount. (A) -4: copolymerization of Mw = 10,000 and Mw / Mn = 2.0 represented by the following chemical formula (A) _4 (wherein, l/m/n == 200947126 30/50/20 (mole ratio)) Things. (A) - 5: a copolymer of Mw = 10,000 and Mw / Μ η = 2.0 represented by the following chemical formula (A) _5 (wherein, 30/50/20 (mole ratio)). (Α) - 6: Polymer compound (A)-6 (synthesized according to Reference Example 3 described later). (B) - 3: a compound represented by the following chemical formula (B) - 3 (the aforementioned compound (XVI)). (B) - 4: a compound represented by the following chemical formula (B) - 4 (the aforementioned compound (XXI)). (D) — 2: Stearyl diethanolamine. [化1 0 4]

-162 - 200947126-162 - 200947126

【化1 Ο 5】[化1 Ο 5]

(Β) -4 〔高分子化合物（A) — 6之合成例〕 〔參考例1〕(Β) -4 [Synthesis Example of Polymer Compound (A)-6] [Reference Example 1]

於1L之3 口燒瓶中放入氫化鈉（NaH ) 4.8g，於冰 浴中保持〇°C下，加入300g之四氫呋喃（THF )，再於攪 拌中加入124g之化合物（1 )，進行1〇分鐘之攪拌。其 後於攪拌中加入30g之化合物（2)，進行12小時之反應 。反應結束後，將反應液吸引過濾，由回收之濾液中’以 減壓濃縮方式去除THF。其後’於濃縮液中加入水及乙酸 乙酯後進行萃取’將所得乙酸乙醋溶液減壓濃縮’以管柱 色層分析（Si〇2，庚烷：乙酸乙酯=8: 2)精製，以蒸發 器減壓濃縮，再經減壓乾燥後得化合物（3 ) 1 2 g ° 【化1 0 6】In a 1-L 3-neck flask, 4.8 g of sodium hydride (NaH) was placed, and the mixture was kept at 〇 ° C in an ice bath, 300 g of tetrahydrofuran (THF) was added, and 124 g of the compound (1) was added thereto with stirring to carry out 1 Torr. Stir in minutes. Thereafter, 30 g of the compound (2) was added thereto with stirring, and the reaction was carried out for 12 hours. After completion of the reaction, the reaction solution was suction-filtered, and THF was removed from the recovered filtrate by concentration under reduced pressure. Thereafter, water and ethyl acetate were added to the concentrate, followed by extraction, and the obtained ethyl acetate solution was concentrated under reduced pressure to be purified by column chromatography (Si 2 , heptane: ethyl acetate = 8: 2). Concentrated under reduced pressure in an evaporator and dried under reduced pressure to give compound (3) 1 2 g ° [1 10 6]

-163- 200947126 對所得化合物（3 )，以1 Η — NMR測定。 其結果如以下所示。 !Η - NMR (溶劑：CDC13、400MHz ) : (5 ( ppm ) = 4.09(s，2H(Ha) ) 、3.75(t，2H(Hb) ) 、3.68(t， 2H ( Hc ) ) 、3_03(brs，2H(Hd)) ' 1.51-2.35 (m&gt; 17H ( He))。 由上述結果得知，化合物（3)具有下述所示構造。 【4匕1 0 7】-163- 200947126 The obtained compound (3) was determined by 1 Η-NMR. The results are shown below. !Η - NMR (solvent: CDC13, 400MHz) : (5 (ppm) = 4.09(s,2H(Ha) ) , 3.75(t,2H(Hb) ) , 3.68(t, 2H ( Hc ) ) , 3_03( Brs, 2H(Hd)) ' 1.51-2.35 (m&gt; 17H (He)) From the above results, the compound (3) has the structure shown below. [4匕1 0 7]

〔參考例2〕 於30 0mL之3 口燒瓶中加入5g之化合物（3)、 3.04g之三乙基胺（Et3N)及10g之THF，攪拌10分鐘。 其後加入2_09g之化合物（4)及l〇g之THF，於室溫下 反應12小時。反應結束後，將反應液吸引過濾，由回收 之濾液中，減壓濃縮將THF去除。其後，於濃縮液中加 入水及乙酸乙酯進行萃取。對所得之乙酸乙酯溶液，使用 管柱色層分析（Si〇2，庚烷：乙酸乙酯=8: 2)進行精製 ’以蒸發器減壓濃縮，再經減壓乾燥後得化合物（5 ) 4.9 g。 -164- 200947126 【化1 Ο 8】[Reference Example 2] 5 g of the compound (3), 3.04 g of triethylamine (Et3N) and 10 g of THF were placed in a 30 mL three-necked flask, and the mixture was stirred for 10 minutes. Thereafter, 2 to 09 g of the compound (4) and 1 g of THF were added, and the mixture was reacted at room temperature for 12 hours. After completion of the reaction, the reaction solution was suction-filtered, and the recovered filtrate was concentrated under reduced pressure to remove THF. Thereafter, water and ethyl acetate were added to the concentrate for extraction. The obtained ethyl acetate solution was purified by column chromatography (Si 〇 2, heptane: ethyl acetate = 8: 2), which was concentrated under reduced pressure in an evaporator, and then dried under reduced pressure to give compound (5) ) 4.9 g. -164- 200947126 【化1 Ο 8】

對所得化合物（5 ) ’以1Η — NMR測定。其結果係如 以下所示。 Q 4 一 NMR (溶劑：CDC13、400MHz ) : 5 ( ppm ) =6.15 ( s &gt; 1H ( Ha ) ) 、5.58(s，lH(Hb)) ' 4.35 ( t ，2H ( Hc) ) 、4.08 ( s，2H ( Hd ) ) 、3.8 0 ( t，2 H ( He ))、1.51-2.35 (m，20H ( Hf))。 由上述結果得知，化合物（5 )具有下述所示構造。 【化1 0 9】The obtained compound (5)' was measured by 1 NMR. The results are shown below. Q 4 - NMR (solvent: CDC13, 400MHz): 5 (ppm) = 6.15 ( s &gt; 1H ( Ha ) ) , 5.58 (s, lH(Hb)) ' 4.35 ( t , 2H ( Hc) ) , 4.08 ( s, 2H ( Hd ) ) , 3.8 0 ( t, 2 H ( He )), 1.51-2.35 (m, 20H (Hf)). From the above results, the compound (5) has the structure shown below. [化1 0 9]

Ha HbHa Hb

〔參考例3(高分子化合物（A) - 6之合成）〕 使 6.30g( 30.30mmol)之化合物（6) 、7.00g( 20_83mmol)之化合物（5) 、2.83g ( 11.99mmol)之化合 物（7 )溶解於64.5 2g之甲基乙基酮中。於該溶液中，加 入和光純藥製V—601(聚合引發劑）n.68mm〇i，使其溶 解。將其於氮氣氛圍下，以6小時時間，滴入加熱至75 -165- 200947126 °C之甲基乙基酮26.88g中。滴入結束後，將反應液進行1 小時加熱攪拌，其後，將反應液冷卻至室溫。 使該聚合液濃縮至固形分爲30質量％，於室溫下滴 入3 20mL之η —庚烷中，使共聚物析出。隨後，製作此共 聚物之THF溶液54g，滴入η -庚烷320mL中使共聚物析 出。 將此共聚物分散於甲醇/水= 60/40 (體積比）之混 合溶液中進行洗淨共聚物之操作，隨後，使其分散於甲醇 /水=70/ 30 (體積比）之混合溶液中，進行洗淨共聚物 之操作後，以過濾方式回收。 將依此方式所得之共聚物於40 t下乾燥3日，得 12.0g之白色粉體（產率74%)。 使所得共聚物作爲高分子化合物（A) _6，其結構 式係如以下所示。對該高分子化合物（A ) - 6 ,以13C -NMR ( 600MHz )測定結果’得知其聚合物組成（下述結 構式中之各結構單位之比例（莫耳比））爲，l/m/n== 5 2.6/ 27.5 / 1 9.9。又’以GPC測定所求得之標準聚苯乙 烯換算的質量平均分子量（Mw)爲5,300，分散度（Mw /Μη)爲1 .97。由該結果得知’確認所得之高分子化合 物（A ) — 6 ’爲化合物（6 )與化合物（5 )與化合物（7 )之共聚物。 -166- 200947126 【化1 1 0】[Reference Example 3 (Synthesis of Polymer Compound (A)-6)] 6.30 g (30.30 mmol) of the compound (6), 7.00 g (20-83 mmol) of the compound (5), 2.83 g ( 11.99 mmol) of the compound ( 7) Dissolved in 64.5 2 g of methyl ethyl ketone. To the solution, V-601 (polymerization initiator) n.68 mm〇i, manufactured by Wako Pure Chemical Industries, was added to dissolve it. This was added dropwise to 26.88 g of methyl ethyl ketone heated to 75 - 165 - 200947126 ° C under a nitrogen atmosphere over a period of 6 hours. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, and then the reaction liquid was cooled to room temperature. The polymerization solution was concentrated to a solid content of 30% by mass, and dropped into 3 20 mL of η-heptane at room temperature to precipitate a copolymer. Subsequently, 54 g of this THF solution of the copolymer was prepared, and the mixture was dropped into 320 mL of η-heptane to precipitate a copolymer. The copolymer is dispersed in a mixed solution of methanol/water = 60/40 (volume ratio) to carry out the operation of washing the copolymer, followed by dispersing it in a mixed solution of methanol/water = 70/30 (volume ratio). After the operation of washing the copolymer, it is recovered by filtration. The copolymer obtained in this manner was dried at 40 t for 3 days to obtain 12.0 g of a white powder (yield 74%). The obtained copolymer was designated as the polymer compound (A)_6, and its structural formula is as follows. The polymer compound (A)-6 was measured by 13C-NMR (600 MHz), and the polymer composition (the ratio of each structural unit in the following structural formula (mole ratio)) was found to be 1/m. /n== 5 2.6/ 27.5 / 1 9.9. Further, the standard polystyrene-equivalent mass average molecular weight (Mw) obtained by GPC measurement was 5,300, and the degree of dispersion (Mw / Μη) was 1.97. From the results, it was confirmed that the polymer compound (A)-6' obtained was a copolymer of the compound (6) and the compound (5) and the compound (7). -166- 200947126 【化1 1 0】

【化1 11】【化11 11】

使用所得之光阻組成物，依以下順序形成光阻圖型， 並評估其微影蝕刻特性。 〔光阻圖型之形成〕 將有機系抗反射膜組成物「ARC29」（商品名，普利 瓦科技公司製）使用旋轉塗佈器塗佈於12英吋之矽晶圓 上，再於熱壓板上進行2 05 °C、60秒鐘燒焙、乾燥，而形 成膜厚89nm之有機系抗反射膜。隨後，將上述所得之實 施例24〜26之正型光阻組成物分別使用旋轉塗佈器塗佈 -167- 200947126 於該抗反射膜上，於熱壓板上依9(TC、60秒鐘之條件下 進行預燒焙（PAB)處理，經乾燥後，形成膜厚12 0nm之 光阻膜。 其次，將保護膜形成用塗佈液「TSRC - 002」（商品 名，東京應化工業公司製）使用旋轉塗佈器塗佈於前述光 阻膜上，經由90°C、60秒鐘加熱結果，形成膜厚28nm 之頂部塗覆層。 其次，對形成頂部塗覆層之前述光阻膜，使用浸潤式 用ArF曝光裝置NSR— S609B(理光公司製；NA(開口數 )=1 .07、2/ 3輪帶照明、縮小倍率1 / 4倍、浸潤式媒 體：水），使ArF準分子雷射（193 nm)介由遮罩圖型（ 6%半色調（halftone))進行選擇性照射。 其次，使用保護膜去除液「TS — Rememover—S」（ 商品名，東京應化工業公司製）去除頂部塗覆層，其後依 表8所記載之條件進行PEB處理，再於23°C之2.38質量 %之TMAH水溶液NMD — W(商品名，東京應化工業公司 製）以30秒鐘之條件下進行鹼顯影，其後再以25秒鐘’ 使用純水進行水洗，振動乾燥。 其結果得知，無論任一例示，皆形成有直徑70nm、 間距13 1 nm之CH圖型。此時之最佳曝光量Eop ( mJ/ cm2)，即I，感度如表9所示。 〔正圓性評估〕 對各CH圖型中之通孔形狀，使用測長SEM (日立製 -168- 200947126 作所公司製’製品名：S - 9 2 2 0 )進行觀測，並依實施例 14〜20相同基準進行評估。其結果如表9所示。 〔表9〕Using the resulting photoresist composition, a photoresist pattern was formed in the following order, and its lithographic etching characteristics were evaluated. [Formation of the photoresist pattern] The organic anti-reflective film composition "ARC29" (trade name, manufactured by Privah Technology Co., Ltd.) was applied onto a 12-inch silicon wafer using a spin coater, followed by heat. The platen was baked at 2 05 ° C for 60 seconds, and dried to form an organic anti-reflection film having a film thickness of 89 nm. Subsequently, the positive-type photoresist compositions of Examples 24 to 26 obtained above were coated on the anti-reflection film using a spin coater, respectively, on a hot plate for 9 (TC, 60 seconds). The pre-baking (PAB) treatment was carried out, and after drying, a photoresist film having a film thickness of 120 nm was formed. Next, the coating liquid for forming a protective film "TSRC-002" (trade name, Tokyo Yinghua Industrial Co., Ltd.) The coating was applied to the photoresist film using a spin coater, and the top coating layer having a film thickness of 28 nm was formed by heating at 90 ° C for 60 seconds. Next, the photoresist film forming the top coating layer was formed. , using the immersion ArF exposure apparatus NSR-S609B (manufactured by Ricoh Co., Ltd.; NA (number of openings) = 1.07, 2/3 wheel illumination, reduction ratio 1/4 times, infiltration medium: water), making ArF The molecular laser (193 nm) is selectively irradiated by a mask pattern (6% halftone). Next, a protective film removal liquid "TS — Rememover-S" is used (trade name, Tokyo Yinghua Industrial Co., Ltd.) The top coating layer was removed, followed by PEB treatment according to the conditions described in Table 8, and then 23 The 2.38 mass% TMAH aqueous solution NMD-W (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was subjected to alkali development under a condition of 30 seconds, and then washed with pure water for 25 seconds', and dried by vibration. As a result, it was found that, regardless of any of the examples, a CH pattern having a diameter of 70 nm and a pitch of 13 1 nm was formed. The optimum exposure amount Eop (mJ/cm2) at this time, i, is as shown in Table 9. Roundness evaluation] The shape of the through hole in each CH pattern was observed using a length measuring SEM (product name: S - 9 2 2 0 manufactured by Hitachi Ltd. - 168-200947126), and according to Example 14 The evaluation was carried out on the same basis as -20. The results are shown in Table 9. [Table 9]

實施例24 實施例261 Eoo(mJ/cm2、 31 20 正圓性 A 1 B 1 B I 由表9之結果得知，本發明之第六之態樣之化合物（ bO — 1 )，極適合作爲酸產生劑之有用化合物的中間體， 本發明之第三之態樣之化合物（bl - 1) ’極適合作爲酸 產生劑之有用化合物。Example 24 Example 261 Eoo (mJ/cm2, 31 20 roundness A 1 B 1 BI From the results of Table 9, the sixth aspect of the present invention (bO-1) is highly suitable as an acid. The intermediate of the useful compound of the generating agent, the compound of the third aspect of the invention (bl - 1) 'is very suitable as a useful compound for the acid generator.

-169--169-

Claims (1)

200947126 十、申請專利範圍 1. 一種光阻組成物’其爲含有經由酸之作用而對鹼顯 影液之溶解性產生變化之基材成份（A)，及經由曝光而 發生酸之酸產生劑成份（B)之光阻組成物，其特徵爲， 前述酸產生劑成份（B)爲含有下述通式（bl- 1)所 表示之化合物所形成之酸產生劑（B 1 )， 【化1】200947126 X. Patent application scope 1. A photoresist composition which is a substrate component (A) containing a change in solubility of an alkali developer via an action of an acid, and an acid generator component which generates an acid via exposure The photoresist composition of (B), wherein the acid generator component (B) is an acid generator (B 1 ) formed by a compound represented by the following formula (bl-1); 】 RX—Q3—〇一q2__Y1___s〇~ …(b，_ τ》 〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；γΐ爲碳 數1〜4之伸烷基或氟化伸烷基；Ζ +爲有機陽離子（但下 述通式（w— 1)所表示之離子除外）〕 【化2】 R3 R6—r!l—R4 15 R5 …(w— 1〉RX—Q3—〇一q2__Y1___s〇~ ...(b, _ τ) [wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 are independent single bonds or two-valent bonds, respectively) ΐ ΐ is an alkylene group or a fluorinated alkyl group having a carbon number of 1 to 4; Ζ + is an organic cation (except for the ion represented by the following formula (w-1)) [Chemical 2] R3 R6— r!l—R4 15 R5 ...(w-1) 〔式中’ R3〜R6分別爲獨立表不氫原子’或可具有 取代基之烴基，R3〜R6中之至少1個爲前述烴基，R3〜 R6中之至少2個可分別鍵結形成環亦可〕。 2. 如申請專利範圍第1項之光阻組成物，其中，前述 酸產生劑（B1)爲下述通式（bl — 1— 1)所表示之化合物 所成， -170- / 200947126 【化3】 Ο 〇 χ ιι f R, ~~c—ο—r*—ο一c一yiso; …化卜卜” 〔式中，Rx、Y1及Z +分別與前述通式（bl— 1)中 之Rx、Y1及z+爲相同之內容；R1爲伸烷基〕。 3. 如申請專利範圍第1項之光阻組成物，其中，前述 S材·成份（A)爲基於酸之作用而增大對鹼顯影液之溶解 〇 性的基材成份。 4. 如申請專利範圍第3項之光阻組成物，其中，前述 基材成份（A)爲含有基於酸之作用而增大對鹼顯影液之 溶解性的樹脂成份（A1 )，該樹脂成份（A1 )爲具有含 酸解離性溶解抑制基之丙烯酸酯所衍生之結構單位（al ) 〇 5 ·如申請專利範圍第4項之光阻組成物，其中，前述 樹脂成份（A1)尙具有含有含內酯之環式基的丙烯酸酯 © 所衍生之結構單位（a2 )。 6. 如申請專利範圍第4項之光阻組成物，其中，前述 樹脂成份（A1)尙具有含有含極性基之脂肪族烴基的丙 烯酸酯所衍生之結構單位（a3)。 7. 如申請專利範圍第1項之光阻組成物，其尙含有含 氮有機化合物（D )。 8. —種光阻圖型之形成方法，其特徵爲，包含於支撐 體上，使用申請專利範圍第1〜7項中任一項之光阻組成 物形成光阻膜之步驟，使前述光阻膜曝光之步驟，及使前 -171 - 200947126 述光阻膜鹼顯影以形成光阻圖型之步驟。 9. 一種下述通式（bl—l)所表示之化合物， 【化4】 rX—q3—〇一Q2__y1一5〇~ 2* …(bl ~ 1) 〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；Y1爲碳 數1〜4之伸烷基或氟化伸烷基；Z +爲有機陽離子（但下 述通式（w-l)所表示之離子除外）〕 【化5】 R3 R6—^—R4 R® —(w—1) 〔式中，R3〜R6分別爲獨立表示氫原子，或可具有 取代基之烴基，R3〜R6中之至少1個爲前述烴基，R3〜 R6中之至少2個可分別鍵結形成環亦可〕。 10. 如申請專利範圍第9項之化合物，其爲下述通式 (bl — 1— 1)所表示之化合物， 【化6】 Ο Ο RX—C—〇—R1—〇—-c—~Y1—so; …(n.··_Ί) 〔式中’ Rx ' Y1及Z +分別與前述通式（bl— 1)中之 Rx、Y1及Z+爲相同之內容；R1爲伸烷基〕。 11. 一種化合物之製造方法，其特徵爲包含，使下述 通式（b0— 1)所表示之化合物（bO-1)，與下述通式（ -172- 200947126 bo— 02 )所表示之化合物（bO— 02 )反應，以製得下述通 式（bl— 1)所表不之化合物（bl—l)之步驟， 【化7】 *{bO—1} •Cb1 —1) RX~~Q3.—。一Q2—γ%—S〇3 VV4 2 A *(b0-02) Rx—Q3—O一〇2—y1—SO3 zH[wherein R3 to R6 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, at least one of R3 to R6 is a hydrocarbon group, and at least two of R3 to R6 may be bonded to form a ring, respectively. can〕. 2. The photoresist composition according to claim 1, wherein the acid generator (B1) is a compound represented by the following formula (bl-1 to 1), -170- / 200947126 3] Ο 〇χ ιι f R, ~~c-ο-r*-ο一c一 yiso; ...化卜卜" [wherein, Rx, Y1 and Z + are respectively in the above formula (bl-1) Rx, Y1 and z+ are the same contents; R1 is an alkylene group. 3. The photoresist composition according to claim 1, wherein the S material and the component (A) are increased based on the action of the acid. The base material component of the large-sized alkali developer solution. 4. The photoresist composition according to claim 3, wherein the substrate component (A) contains an acid-based effect and increases alkali development. a solvent-soluble resin component (A1) which is a structural unit derived from an acrylate having an acid-dissociable dissolution inhibiting group (al) 〇 5 · a photoresist as disclosed in claim 4 a composition in which the aforementioned resin component (A1) has a structural unit derived from an acrylate containing a cyclic group containing a lactone. 6. The photoresist composition according to claim 4, wherein the resin component (A1) has a structural unit (a3) derived from an acrylate containing a polar group-containing aliphatic hydrocarbon group. For example, the photoresist composition of claim 1 has a nitrogen-containing organic compound (D). 8. A method for forming a photoresist pattern, which is characterized in that it is included in a support, and the patent application scope is used. The step of forming a photoresist film by the photoresist composition according to any one of items 1 to 7, the step of exposing the photoresist film, and the alkali development of the photoresist film of the first-171 to 200947126 to form a photoresist pattern Step 9. A compound represented by the following formula (bl-1), [Chemical 4] rX—q3—〇Q2__y1-5〇~ 2* (bl ~ 1) [wherein Rx may have a hydrocarbon group of a substituent (except for a nitrogen atom); Q2 and Q3 are each a single bond or a divalent bond group; Y1 is a C 1 to 4 alkyl or a fluorinated alkyl group; Z + is an organic Cation (except for the ion represented by the following formula (wl)) [Chemical 5] R3 R6—^—R4 R® —(w—1) In the formula, R3 to R6 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent, and at least one of R3 to R6 is the hydrocarbon group, and at least two of R3 to R6 may be bonded to form a ring, respectively. 10. A compound of the ninth aspect of the patent application, which is a compound represented by the following formula (bl-1 to 1), which is a compound represented by the following formula (bl-1 to 1), which is a compound represented by the following formula (bl-1 to 1), RX-C-〇-R1—〇—c— ~Y1—so; ...(n.··_Ί) [wherein Rx 'Y1 and Z + are the same as Rx, Y1 and Z+ in the above general formula (bl-1); R1 is an alkylene group ]. A method for producing a compound, which comprises expressing a compound (bO-1) represented by the following formula (b0-1) and a formula represented by the following formula (-172-200947126 bo-02) The compound (bO-02) is reacted to obtain a compound (bl-1) represented by the following formula (bl-1), [Chem. 7] *{bO-1} • Cb1 -1) RX~ ~Q3.—. A Q2—γ%—S〇3 VV4 2 A *(b0-02) Rx—Q3—O—〇2—y1—SO3 zH 〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；Y1爲碳 數1〜4之伸烷基或氟化伸烷基；W +爲鹼金屬離子或下述 通式（w—l)所表示之離子；Z+爲有機陽離子（但下述 通式（w-l)所表示之離子除外）：A·爲非親核性陰離子 ) 【化8】 R3 Re—rl—R4 15 〔式中，R3〜R6分別爲獨表不氫原子，或可具有 取代基之烴基，R3〜R6中之至少1個爲前述烴基，R3〜 R0中之至少2個可分別鍵結形成環亦可〕。 1 2 .如申請專利範圍第1〗項之製造方法，其中，前述 化合物（bO — 1)爲下述通式（b0— 01)所表示之化合物 (b0— 〇1)，前述化合物（bl—1)爲下述通式（bl—卜 1 )所表示之化合物（b 1 - 1 — 1 )， -173- 200947126 【化9】 Ο 〇 χ II , II „ + Rx—C—〇—R}—.〇—C一Υ’一S〇3 w …(b0_01》 ο ο rX一C一〇—〇—〇—γΐ—so; z+ (bi一卜” 〔式中，Rx、Y1及W +與前述通式（bO — 1 )中之Rx 、Y1及W +爲相同之內容；Z +與前述通式（bl— 1)中之 Z +爲相同之內容；R1爲伸烷基〕。 13.—種酸產生劑，其特徵爲，由申請專利範圍第9 項之化合物所形成者。 1 4 ·如申請專利範圍第1 3項之酸產生劑，其係由下述 通式（bl-1— 1)所表示之化合物所形成者， 【化1 0】 ο 〇 Rx__c__〇__Ri__〇_c一Yi—S〇~ 2+ 〔式中’RX'Y1及Z +與前述通式（bl— 1)中之Rx 、Y1及z +爲相同之內容；R1爲伸烷基〕。 15.—種下述通式（bO—l)所表示之化合物， 【化1 1】 Rx—Q3—〇—Q2—yi一s〇;Wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 are each a single bond or a divalent bond group; Y1 is an alkyl group having 1 to 4 carbon atoms or fluorinated An alkyl group; W + is an alkali metal ion or an ion represented by the following formula (w-1); Z+ is an organic cation (except for the ion represented by the following formula (wl)): A· is a non-parent (Nuclear anion) R3 Re-rl-R4 15 wherein R3 to R6 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and at least one of R3 to R6 is the aforementioned hydrocarbon group. At least two of R3 to R0 may be bonded to form a ring, respectively. The manufacturing method of the first aspect of the invention, wherein the compound (bO-1) is a compound represented by the following formula (b0-01) (b0 - 〇1), and the compound (b) 1) is a compound represented by the following formula (bl-b 1) (b 1 - 1 - 1 ), -173- 200947126 [Chemical 9] Ο 〇χ II , II „ + Rx—C—〇—R} —〇—C一Υ'一S〇3 w...(b0_01) ο ο rX一C一〇—〇—〇—γΐ—so; z+ (bi一卜” [where Rx, Y1 and W + Rx, Y1 and W+ in the above formula (bO-1) are the same; Z+ is the same as Z+ in the above formula (bl-1); and R1 is an alkylene group. An acid generator characterized by being formed by a compound of claim 9 of the patent application. 1 4 · An acid generator according to claim 13 of the patent application, which is represented by the following formula (bl-1) — 1) The compound formed by the compound, [Chemical 1 0] ο 〇Rx__c__〇__Ri__〇_c_Yi-S〇~ 2+ [wherein 'RX'Y1 and Z + and the above formula ( Rx, Y1 and z + in bl-1) are the same; R1 is alkylene . 15.- compounds by the following formula (bO-l) are represented, the [11] of the Rx-Q3-square-Q2-yi a s〇; CbO —1) 〔式中’ Rx爲可具有取代基（但氮原子除外）之烴 -174- 200947126 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基； 數1〜4之伸烷基或氟化伸烷基；R3〜R6分別爲獨 氯原子’或可具有取代基之烴基，R3〜R6中之至^ 爲則述徑基，R3〜R6中之至少2個可分別鍵結形 可〕。 1 6 ·如申請專利範圍第〗5項之化合物，其爲下 (b〇 — 1 . N ^ 1 ~ 1 )所表示之化合物， 〇 【化1 2】 f1爲碳 立表示 &gt; 1個 成環亦 述通式 rX〜Q3〜〇- 〇II C- R3-Y1—SO; R62 上—R4 b〇 或 〔式中，Rx、Q3、Y1、R3〜R6分別爲與前述 1 )中之Rx、Q3、Y1、R3〜r6爲相同之內容， 1 7.如申請專利範圍第16項之化合物，其I (b〇 - 1 . , N i—U)或（b〇-l— 12)所表示之化合較 【化1 3】 通式（ η爲0 述通式 Rb- 〇II 〇 R3_S〇3 R®~N—R4 RC〜Q4— OII -c- _ (bO — 1 -11) -Y1—S〇I R6-±^|—R4 -175- 200947126 〔式中，η、Y1、R3〜R6分別爲與前述通式（b0— 1 一1)中之η、Y1、R3〜R6爲相同之內容，R1爲伸烷基’ …及Re爲分別獨立之可具有取代基（但氮原子除外）之 烴基’Q4爲單鍵或伸烷基〕。 18· —種化合物之製造方法，其特徵爲包含，使下述 通式（1—11)所表示之化合物（1 一 11)，與下述通式（ 12)所表示之化合物（1—12)，與胺或銨鹽反應以製 得下述通式（bo— 1)所表示之化合物（bO— 1)之步驟， 【化1 4] H0—Q2_Y1—s〇-3 M+。一”） RX-Q3_X21 ...(1_12) RX—q3—〇一Q2 一丫1 一 S〇; —R4 R5 .“(b〇-1) 〔式中’ Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；Y1爲碳 數1〜4之伸烷基或氟化伸烷基；R3〜R6分別爲獨立表示 氫原子’或可具有取代基之烴基，R3〜R6中之至少丨個 爲前述烴基’ R3〜R6中之至少2個可分別鍵結形成環亦 可；X21爲鹵素原子；M +爲鹼金屬離子〕。 H一種化合物之製造方法，其特徵爲包含，使下述 通式（1一21)所表示之化合物（1— 21)，與下述通式（ 12)所表示之化合物（1— 12)，與胺或銨鹽反應以製 得下述通式（bO—l)所表示之化合物（bo—o之步驟， -176- 200947126 【化1 5】 R3, Η〇—〇2_γΐ—SO3 R6，-iCbO —1) [wherein Rx is a hydrocarbon which may have a substituent (except for a nitrogen atom)-174-200947126; Q2 and Q3 are each a single bond or a divalent bond; respectively; An alkyl group or a fluorinated alkyl group; R3 to R6 are each a chlorine atom or a hydrocarbon group which may have a substituent, and R3 to R6 are each a ring group, and at least two of R3 to R6 may be respectively bonded. The shape can be]. 1 6 · For the compound of the ninth paragraph of the patent application, it is a compound represented by the lower (b〇-1. N ^ 1 ~ 1), 〇 [Chemical 1 2] f1 is a carbon stand &gt; 1 The ring is also a formula of RX~Q3~〇-〇II C-R3-Y1-SO; R62 is -R4 b〇 or (wherein, Rx, Q3, Y1, R3 to R6 are respectively the same as in the above 1) , Q3, Y1, R3~r6 are the same content, 1 7. As the compound of claim 16 of the patent, I (b〇-1, N i-U) or (b〇-l-12) The compound represented by the formula is (Chemical Formula 1). The formula (η is 0) Rb- 〇II 〇R3_S〇3 R®~N—R4 RC~Q4—OII -c- _ (bO — 1 -11) -Y1 —S〇I R6-±^|—R4 -175- 200947126 [wherein, η, Y1, R3 to R6 are the same as η, Y1, R3 to R6 in the above formula (b0-1 to 1), respectively. In the above, R1 is an alkylene group ... and Re is a hydrocarbon group which has a substituent (except for a nitrogen atom), and the hydrocarbon group 'Q4 is a single bond or an alkyl group. In order to contain, the compound represented by the following formula (1-11) (1-11), a step of reacting a compound (1-12) represented by the formula (12) with an amine or an ammonium salt to obtain a compound (bO-1) represented by the following formula (bo-1); ] H0—Q2_Y1—s〇-3 M+. A”) RX-Q3_X21 (1_12) RX—q3—〇一Q2 一丫1 一S〇; —R4 R5 .”(b〇-1) [ Wherein 'Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 are independently a single bond or a divalent bond group; Y1 is an alkylene group or a fluorinated alkylene group having a carbon number of 1 to 4. R3 to R6 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and at least two of R3 to R6 are at least two of the above hydrocarbon groups 'R3 to R6 may be bonded to each other to form a ring; X21 It is a halogen atom; M + is an alkali metal ion]. H. A method for producing a compound, which comprises a compound (1-21) represented by the following formula (1-21) and a compound (1-12) represented by the following formula (12), Reaction with an amine or an ammonium salt to obtain a compound represented by the following formula (bO-1) (step of bo-o, -176-200947126) R3, Η〇-〇2_γΐ-SO3 R6,- i —R4， R® --(1 —21) RX—Q3—X21 -(1-12) R3 RX—Q3_〇一q2_y1_S〇- Re.tfJj 一R4 l5 Ο ❹ R5 …(b〇-1) 〔式中，Rx爲可具有取代基（但氮原子除外）之烴 基；Q2及Q3分別爲獨立之單鍵或2價之鍵結基；Y1爲碳 數1〜4之伸烷基或氟化伸烷基；R3〜R6分別爲獨立表示 氫原子，或可具有取代基之烴基，R3〜R6中之至少1個 爲前述烴基，R3〜R6中之至少2個可分別鍵結形成環亦 可；R3_〜R6’分別爲獨立表示氫原子，或可具有取代基之 烴基，R3’〜R6'中之至少丨個爲前述烴基，R3’〜r6_中之至 少2個可分別鍵結形成環亦可；χ2ι爲鹵素原子〕。 2 0.—種下述通式（1—21)所表示之化合物， 【化1 6】 R3, HO—Q2—Y1—S〇3 ^~—R4, R® --(1 —21) RX—Q3—X21 —(1-12) R3 RX—Q3_〇一q2_y1_S〇- Re.tfJj A R4 l5 Ο ❹ R5 ...(b〇-1) 〔 Wherein Rx is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q2 and Q3 are each a single bond or a divalent bond group; Y1 is an alkyl group having a carbon number of 1 to 4 or a fluorinated extension. The alkyl group; R3 to R6 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent; at least one of R3 to R6 is the hydrocarbon group, and at least two of R3 to R6 may be bonded to each other to form a ring; R3_~R6' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, and at least one of R3' to R6' is a hydrocarbon group, and at least two of R3'~r6_ may be bonded to each other to form a ring.可; χ2ι is a halogen atom]. 2 0. A compound represented by the following formula (1-21), [Chem. 1 6] R3, HO—Q2—Y1—S〇3 ^~ —p4' R5 …(1-21) 〔式中，Q2爲單鍵或2價之鍵結基；γΐ爲碳數1〜4 之伸烷基或氟化伸烷基；R3'〜R6’分別爲獨立表示氫原子 ，或可具有取代基之烴基，R3_〜R6'中之至少1個爲前述 -177- 200947126 烴基，R3_〜R6'中之至少2個可分別鍵結形成環亦可〕^ 21. —種化合物之製造方法，其特徵爲包含，使下述 通式（1一11)所表示之化合物（1 一 n)，與銨鹽反應以 製得下述通式（1— 21)所表示之化合物（1一 21)之步驟 【化1 7】 M+ …（1-1 1) HO—Q2—丫1一SO;—p4′ R5 (1-21) wherein Q 2 is a single bond or a divalent bond group; γ ΐ is an alkyl or fluorinated alkyl group having a carbon number of 1 to 4; and R 3 ' to R 6 ' respectively In order to independently represent a hydrogen atom, or a hydrocarbon group which may have a substituent, at least one of R3_~R6' is the aforementioned -177-200947126 hydrocarbon group, and at least two of R3_~R6' may be bonded to form a ring, respectively. A method for producing a compound, which comprises reacting a compound (1 - n) represented by the following formula (1-11) with an ammonium salt to obtain the following formula (1-21) The step of the represented compound (1-21) [Chemical 1 7] M+ (1-1 1) HO-Q2 - 丫 1 - SO; HO—Q2—Y1—s〇3 〔式中’ Q2爲單鍵或2價之鍵結基；Y1爲碳數1〜4 之伸烷基或氟化伸烷基；R3_〜R6'分別爲獨立表示氫原子 ’或可具有取代基之烴基，R3’〜R6'中之至少1個爲前述 煙基’ R3’〜R6·中之至少2個可分別鍵結形成環亦可；M + 爲驗金屬離子〕。 22. —種化合物之製造方法，其特徵爲包含，使下述 通式（1—13)所表示之化合物（1 一 13)，與銨鹽反應以 製得下述通式（1— 14)所表示之化合物（1— 14)之步驟 -178- 200947126 【化1 8】 Rc—Q4—O- Rc—Q4—〇- OII-c- 〇·II-c- -Y1—SO3 mh _Y1—SO; R4. 〔式中，Re爲可具有取代基（但氮原子除外）之烴 基；Q4爲單鍵或2價之鍵結基；η爲0或1IY1爲碳數1 〜4之伸烷基或氟化伸烷基；R3’〜R6’分別爲獨立表示氫 原子，或可具有取代基之烴基，R3'〜R6’中之至少1個爲 前述烴基，R3'〜R6’中之至少2個可分別鍵結形成環亦可 ;Μ +爲驗金屬離子〕。HO—Q2—Y1—s〇3 [wherein Q2 is a single bond or a divalent bond group; Y1 is an alkyl or fluorinated alkyl group having a carbon number of 1 to 4; and R3_~R6' are independently a hydrogen atom or a hydrocarbon group which may have a substituent, and at least one of R3' to R6' may be at least two of the above-mentioned nicotyl groups 'R3' to R6· may be bonded to form a ring, respectively; Metal ion〕. A method for producing a compound, which comprises reacting a compound (1-13) represented by the following formula (1-13) with an ammonium salt to obtain the following formula (1-4) The step of the represented compound (1-14) -178- 200947126 [Chemical 1 8] Rc-Q4-O- Rc-Q4-〇- OII-c- 〇·II-c- -Y1-SO3 mh _Y1-SO R4. [wherein, Re is a hydrocarbon group which may have a substituent (except for a nitrogen atom); Q4 is a single bond or a divalent bond group; η is 0 or 1IY1 is an alkylene group having a carbon number of 1 to 4 or Fluorinated alkyl; R3' to R6' are each independently a hydrogen atom or a hydrocarbon group which may have a substituent; at least one of R3' to R6' is the aforementioned hydrocarbon group, and at least two of R3' to R6' It can also be bonded to form a ring separately; Μ + is a metal ion]. -179- 200947126 無 明 說 單 無簡 JfkG :號 為符 圖件 表元 代之 定圖 :指表 圖案代 表本本 代 定一二 指 Γ' Γ. ' 七 οο 200947126 4 八 本案若有化學式時，請揭示最能顯示發明特徵的化學-179- 200947126 无明说单无简JfkG: No. is a map of the map element on behalf of the map: refers to the table design represents the book one or two fingers Γ. ' 七οο 200947126 4 Eight cases if there is a chemical formula, please Reveal the chemistry that best shows the characteristics of the invention
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