TW201039064A

TW201039064A - Positive photoresist composition, method of forming photoresist pattern, and polymeric compound

Info

Publication number: TW201039064A
Application number: TW98146290A
Authority: TW
Inventors: Tomoyuki Hirano; Takahiro Dazai; Tasuku Matsumiya; Daiju Shiono
Original assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2009-02-10
Filing date: 2009-12-31
Publication date: 2010-11-01
Also published as: JP5325596B2; JP2010185987A; TWI471700B

Abstract

This invention provides a polymeric compound suitable for use as the substrate ingredient of positive photoresist composition, positive photoresist composition containing the polymeric compound and method of forming photoresist pattern using the positive photoresist composition. A positive photoresist composition comprises substrate ingredient (A) for increasing the solubility to basic developer with acid treatment and acid generator ingredient (B) for producing acid via exposure, wherein the substrate ingredient (A) is a polymeric compound (A1) having a structural unit (a0-1) represented by formula (a0-1) and a structural unit (a0-2) represented by formula (a0-2), wherein R and R1 each is hydrogen , C1-5 alkyl, C1-5 halogenated alkyl; R21 is branched alkyl; R22 is group capable of forming aliphatic monocyclic group with a carbon bonded therewith; R2 is bivalent bonding group; R3 is a cyclic group containing - SO2- in its cyclic skeleton.

Description

201039064 六、發明說明：【發明所屬之技術領域】本發明爲有關’可被利用作爲正型光阻組成物之基材成份之新穎之高分子化合物、含有該高分子化合物之正型光阻組成物’及使用該正型光阻組成物之光阻圖型之形成方法。 0 【先前技術】微影鈾刻技術中，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，介由形成特定圖型之遮罩 ’以光、電子線等放射線進行選擇性曝光，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〇之特性的光阻材料稱爲負型。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，對於較前述準分子雷射更短波長之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。 -5- 201039064 光阻材料，則尋求對於該些曝光光源具有感度，具有可重現微細尺寸圖型之解析性等微影蝕刻特性。可滿足前述要求之光阻材料，一般常用含有基於酸之作用使對鹼顯影液的溶解性產生變化之基材成份，與經由曝光產生酸之酸產生劑之化學增幅型光阻組成物。例如正型之化學增幅型光阻組成物，一般爲使用含有經由酸之作用而增大對鹼顯影液之溶解性的樹脂成份（基礎樹脂），與酸產生劑成份之光阻。使用該光阻組成物所形成之光阻膜，於光阻圖型之形成時進行選擇性曝光時，於曝光部中，經由酸產生劑所產生之酸，並經由該酸之作用而增大樹脂成份對鹼顯影液之溶解性，使曝光部對鹼顯影液爲可溶性。目前，ArF準分子雷射微影蝕刻等中所使用的光阻之基礎樹脂，就於193 nm附近具有優良透明性等觀點，一般爲使用主鏈具有（甲基）丙烯酸酯所衍生之結構單位的樹脂（丙烯酸系樹脂）等（例如專利文獻1〜2 )。於此，「 (甲基）丙烯酸」係指，α位鍵結氫原子之丙烯酸，與a位鍵結甲基之甲基丙烯酸之一者或二者之意。「（甲基）丙嫌酸醋（acrylic acid ester)」係指，α位鍵結氫原子之丙烯酸酯，與α位鍵結甲基之甲基丙烯酸酯之一者或二者之意。「（甲基）丙烯酸酯（acrylate )」係指，α位鍵結氫原子之丙烯酸酯，與α位鍵結甲基之甲基丙烯酸酯之一者或二者之意。又，目前，化學增幅型光阻用之基礎樹脂，爲提高微 -6- 201039064 影蝕刻特性等目的，而有使用含有多數結構單位之樹脂。例如正型之情形，通常，含有具有經由酸產生劑所產生之酸的作用而解離之酸解離性溶解抑制基之結構單位，此外，亦使用含有具有羥基等之極性基的結構單位、具有內酯結構之結構單位等之樹脂。該些樹脂中，具有內酯結構之結構單位，一般而言，可提高光阻膜對基板之密著性，提高與鹼顯影液之親和性等，而期待可提高微影蝕刻特性。 Ο [先前技術文獻] [特許文献1]特開2003-241385號公報 [特許文献2]特開2006-016379號公報【發明內容】今後，推測微影蝕刻技術將會更進步，應用領域會更爲擴大等，故對於微影飩刻用途所使用之新穎之材料具有〇種種要求。例如伴隨圖型之微細化，光阻材料亦要求解析性等各種微影蝕刻特性應更爲提升等。該些微影蝕刻特性之一例如遮罩缺陷因子-(MEF )。 MEF係指，於相同曝光量下，固定間距之狀態下，變化遮罩尺寸之際，不同尺寸之光阻圖型可何種程度忠實地重現 (遮罩重現性）之參數。以往之光阻組成物中，於光阻圖型形成之際，常因所使用之遮罩尺寸（通孔圖型中爲通孔直徑，或線路與空間圖型中爲線路寬）之變化而造成曝光部之受光量的増減結果，使所形成之光阻圖型之尺寸偏離 201039064 遮罩尺寸，或狭間距下形成微細圖型之際，造成形狀崩壞之疑慮。例如形成約1 〇〇nm以下之通孔口徑的通孔圖型之際，通孔之正圓性會有降低之疑慮。本發明，爲鑑於上述情事所提出者，以提供適合作爲正型光阻組成物之基材成份的有用新穎之高分子化合物、適合作爲該高分子化合物之單體的化合物、含有前述高分子化合物之正型光阻組成物，及使用該正型光阻組成物之光阻圖型之形成方法爲目的。爲達上述之目的，本發明爲採用以下之構成。即，本發明之第一之態樣爲，一種正型光阻組成物，其爲含有經由酸之作用而增大對鹼顯影液之溶解性的基材成份（A )，及經由曝光而發生酸之酸產生劑成份（B )，其特徵爲，前述基材成份（A)爲，含有具有下述通式（aO-1) 所表示之結構單位（aO-1 )，及下述通式（aO-2 )所表示之結構單位（aO-2)之高分子化合物（A1)，【化1】201039064 VI. Description of the Invention: [Technical Field] The present invention relates to a novel polymer compound which can be utilized as a substrate component of a positive photoresist composition, and a positive photoresist composition containing the polymer compound And a method of forming a photoresist pattern using the positive photoresist composition. 0 [Prior Art] In the lithography lithography technique, for example, a photoresist film obtained by a photoresist material is formed on a substrate, and a mask of a specific pattern is formed for the photoresist film by light, electron lines, or the like. The selective exposure of the radiation is carried out by applying a development treatment to form the photoresist film into a photoresist pattern having a specific shape. The portion of the exposure which is changed to have a property of dissolving in the developer is referred to as a positive type, and the portion of the photoresist which is exposed to have a property of not being dissolved in the developer 称为 is referred to as a negative type. In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, the pattern of the pattern has been rapidly refined with the progress of the lithography technique. The method of miniaturization is generally carried out in such a manner as to shorten the wavelength of the exposure light source. Specifically, conventionally, ultraviolet rays represented by g-line and i-line are used. However, KrF excimer lasers or ArF quasi-molecular 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 than the aforementioned excimer lasers have also been studied. -5- 201039064 Photoresist materials are sought to have sensitivity to these exposure light sources, and have lithographic etching characteristics such as resolution of reproducible fine-size patterns. A photoresist material which satisfies the above requirements is generally a chemically amplified photoresist composition containing a substrate component which changes the solubility of an alkali developer based on an acid action and an acid generator which generates an acid by exposure. For example, a positive-type chemically amplified resist composition generally uses a resin component (base resin) containing an acid generator to increase solubility in an alkali developer, and a photoresist having an acid generator component. When the photoresist film formed by the photoresist composition is selectively exposed during the formation of the photoresist pattern, the acid generated by the acid generator in the exposed portion is increased by the action of the acid. The solubility of the resin component in the alkali developer makes the exposed portion soluble in the alkali developer. At present, the base resin of the photoresist used in ArF excimer laser lithography etching and the like has excellent transparency at around 193 nm, and is generally a structural unit derived from a (meth) acrylate in a main chain. Resin (acrylic resin) or the like (for example, Patent Documents 1 to 2). Here, "(meth)acrylic acid" means one or both of acrylic acid having a hydrogen atom bonded to the α-position and one or both of the methyl methacrylate bonded to the a-position. "(acrylic acid ester)" means an acrylate of a hydrogen atom bonded to the α-position and one or both of a methacrylate of a methyl group bonded to the α-position. "(Meth)acrylate" means either an acrylate having a hydrogen atom bonded to the α-position, or a methacrylate having a methyl group bonded to the α-position or both. Further, at present, the base resin for chemically amplified photoresist is used for the purpose of improving the image etching characteristics of micro-6-201039064, and a resin containing a plurality of structural units is used. In the case of a positive type, for example, a structural unit containing an acid dissociable dissolution inhibiting group which is dissociated by an action of an acid generated by an acid generator is used, and a structural unit having a polar group having a hydroxyl group or the like is also used. A resin such as a structural unit of an ester structure. Among these resins, a structural unit having a lactone structure generally improves the adhesion of the photoresist film to the substrate and improves the affinity with the alkali developing solution, and is expected to improve the lithographic etching characteristics. 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 In order to expand, etc., there are various requirements for the novel materials used in lithographic engraving applications. For example, with the miniaturization of the pattern, the photoresist material also requires various lithographic etching characteristics such as resolution to be improved. One of the lithographic etching characteristics is, for example, a mask defect factor-(MEF). MEF refers to the degree to which the different size resist patterns can faithfully reproduce (mask reproducibility) when the mask size is changed at the same exposure level and at a fixed pitch. In the conventional photoresist composition, when the photoresist pattern is formed, it is often changed by the size of the mask used (the diameter of the through hole in the through hole pattern or the line width in the line and space pattern). As a result of the reduction in the amount of light received by the exposure portion, the size of the formed photoresist pattern deviates from the 201039064 mask size, or when a fine pattern is formed at a narrow pitch, the shape collapses. For example, when a via pattern of a via diameter of about 1 〇〇 nm or less is formed, the roundness of the via hole may be lowered. In view of the above, the present invention provides a useful novel polymer compound suitable as a substrate component of a positive photoresist composition, a compound suitable as a monomer of the polymer compound, and a polymer compound as described above. The positive resistive composition and the method of forming the photoresist pattern using the positive resist composition are for the purpose. 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 positive-type photoresist composition which comprises a substrate component (A) which increases the solubility to an alkali developer via an action of an acid, and which occurs via exposure. The acid generator component (B) characterized in that the substrate component (A) contains a structural unit (aO-1) represented by the following formula (aO-1), and the following formula Polymer compound (A1) of structural unit (aO-2) represented by (aO-2), [Chemical 1]

-8- 201039064 [式中，R1爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化烷基，R2爲2價之鍵結基，R3，爲其環骨架中含有-S〇2-之環式基，R爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化烷基，R21爲分支鏈狀之烷基；R22，爲可與該R22鍵結之碳原子共同形成脂肪族單環式基之基]。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正型 0 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，一種高分子化合物，其特徵爲，具有下述通式（aO-Ι)所表示之結構單位（aO-Ι) ’及下述通式（aO-2)所表示之結構單位（aO-2)，【化2】-8- 201039064 [In the formula, R1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R2 is a divalent bond group, and R3 is contained in the ring skeleton thereof. a cyclic group of S〇2-, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R21 is a branched chain alkyl group; R22 is a bond capable of bonding with R22 The carbon atoms of the junction together form the base of the aliphatic monocyclic group]. A second aspect of the present invention is a method for forming a photoresist pattern, which is characterized in that the step of forming a photoresist film using the positive-type photoresist composition of the first aspect is included on a support. a step of exposing the photoresist film and a step of causing the photoresist film to be alkali developed to form a photoresist pattern. According to a third aspect of the present invention, a polymer compound characterized by having a structural unit (aO-Ι) ' represented by the following formula (aO-Ι) and a formula (aO-2) The structural unit represented (aO-2), [Chemical 2]

[式中，Ri爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化院基，R2爲2價之鍵結基’ R3 ’爲其環骨架中含有- S〇2 -之環式基，R爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化烷基，爲分支鏈狀之烷基；R22,爲可與該R22鍵結之碳 -9 - 201039064 原子共同形成脂肪族單環式基之基]。本說明書與本申請專利範圍中，「脂肪族」爲，相對於芳香族之相對性槪念，係定義爲不具有芳香族性之基、化合物等之意。「烷基」，於無特別限定下，爲包含直鏈狀、分支鏈狀及環狀之1價之飽和烴基。「伸烷基」，於無特別限定下，爲包含直鏈狀、分支鏈狀及環狀之2價之飽和烴基。烷氧基中之烷基亦爲相同之內容。「鹵化烷基」爲，烷基之氫原子的一部份或全部被鹵素原子所取代之基、該鹵素原子，例如，氟原子、氯原子、溴原子、碘原子等。「氟化烷基」或「氟化伸烷基」爲，烷基或伸烷基之氫原子的一部份或全部被氟原子所取代之基之意。「結構單位」係指，構成高分子化合物（樹脂、聚合物、共聚物）之單體單位（monomer unit)之意。「丙烯酸酯所衍生之結構單位」係指，丙烯酸酯之乙烯性雙鍵開裂所構成之結構單位之意。「丙嫌酸酯」，除α位之碳原子上鍵結氫原子的丙稀酸酯以外，尙包含α位之碳原子鍵結有取代基（氫原子以外之原子或基）之槪念。該α位之碳原子鍵結之取代基，例如碳數1〜5之烷基、碳數1〜5之鹵化烷基、羥烷基等。又，丙烯酸酯之α位之碳原子，於無特別限定下，係指簾基所鍵結之碳原子之意。 -10 - 201039064 「曝光」，爲包含輻射線照射之全部槪念。本發明，爲提供一種可被利用作爲正型光阻組成物之基材成份之新穎之高分子化合物、含有該高分子化合物之正型光阻組成物，及使用該正型光阻組成物之光阻圖型之形成方法。 <正型光阻組成物> 0 本發明之正型光阻組成物（以下，亦有僅稱光阻組成物之情形）爲，含有經由酸之作用而增大對鹼顯影液之溶解性的基材成份（A )(以下，亦稱爲（A )成份），及經由輻射線之照射而發生酸之酸產生劑成份（B )(以下，亦稱爲（B )成份）。該正型光阻組成物中，經受到輻射線照射（曝光）時，會由（B)成份產生酸，經由該酸之作用而增大（A)成份對鹼顯影液之溶解性。因此，於光阻圖型之形成中，對〇使用該該正型光阻組成物所得之光阻膜進行選擇性曝光時 ’於使該光阻膜之曝光部增大對鹼顯影液之可溶性的同時，未曝光部對鹼顯影液之溶解性未有變化之情形下，進行鹼顯影之方式，而可形成光阻圖型。於此，「基材成份」係指，具有形成膜之能力的有機化合物。基材成份，較佳爲使用分子量500以上之有機化合物。該有機化合物之分子量爲500以上時，可提高膜形成能力，又，容易形成奈米程度之光阻圖型。作爲前述基材成份使用之「分子量爲5 00以上之有機 -11 - 201039064 化合物」，可大致區分爲非聚合物與聚合物。非聚合物，通常爲使用分子量500以上、未達4〇〇〇之物。以下，分子量爲5 00以上、未達4000之非聚合物稱爲低分子化合物。聚合物，通常爲使用分子量2 000以上之物。以下，分子量2000以上之聚合物稱爲高分子化合物。高分子化合物之情形，「分子量」爲使用GPC (凝膠滲透色層分析法）所得之聚苯乙烯換算之質量平均分子量。以下，高分子化合物亦有僅稱「樹脂」之情形。 < (A)成份 > [高分子化合物（A1 )] 高分子化合物（A1)(以下，亦稱爲（A1)成份）爲’含有前述通式（aO-Ι )所表示之結構單位（aO-Ι ) ’ 及前述通式（aO-2)所表示之結構單位（aO-2)。 (A1 )成份，除結構單位（a〇-l )，及（aO-2 )以外 ’以再具有與前述各結構單位相異之結構單位，且含有酸解離性溶解抑制基之丙烯酸酯所衍生之結構單位（a 1 )爲佳。 (A1 )成份，除結構單位（a0-l )，及（aO-2 )以外 ’或結構單位（a〇-l ) 、（ a0_2 )，及（al )以外，以再胃胃含有含內酯之環式基之丙烯酸酯所衍生之結構單位（ a 2 )爲佳。又’ （A1 )成份，除結構單位（aO-Ι )，及（aO-2 ) 以外’或結構單位（a〇—1 ) 、（ a〇-2 )，及（al )以外’ -12- 201039064 或結構單位（aO-l ) 、（ a〇-2 )，及（a2 )以外，或結構單位（aO-1) 、（aO-2) 、（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（aO-Ι)) 結構單位（aO-1 )，爲上述通式（a0_l )所表示之結 0 構單位。式（aO-Ι)中’ R1爲氫原子 '碳數1〜5之烷基或碳數 1〜5之鹵化烷基。 R1之烷基’以碳數1〜5之直鏈狀或分支鏈狀之烷基爲佳，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。 R1之碳數1〜5之鹵化烷基，例如前述碳數1〜5之烷基之氫原子的一部份或全部被鹵素原子所取代之基。該圈素 Q 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。 R1，以氫原子、碳數1〜5之烷基或碳數1〜5之氟化烷基爲佳，就工業上取得之容易度而言，以氫原子或甲基爲最佳。式（aO-Ι )中，R2爲2價之鍵結基。 R2 ’例如可具有取代基之2價之烴基、含有雜原子之2 價之鍵結基等爲較佳。該烴基之「具有取代基」係指，該烴基中氫原子之一 -13- 201039064 部份或全部被氫原子以外之基或原子所取代之意。該烴基可爲脂肪族烴基亦可、芳香族烴基亦可。脂肪族烴基爲不具有芳香族性之烴基之意。該脂肪族烴基，可爲飽和者亦可、不飽和者亦可，通常以飽和者爲佳。前述脂肪族烴基，更具體而言，例如直鏈狀或分支鏈狀之脂肪族烴基、構造中含有環之脂肪族烴基等。直鏈狀或分支鏈狀之脂肪族烴基，以碳數爲1〜10爲佳，以1〜8爲較佳，以1〜5爲更佳，以1〜2爲最佳。直鏈狀之脂肪族烴基，以直鏈狀之伸烷基爲佳，具體而言，例如，伸甲基[-CH2-]、伸乙基[-(CH2)2-]、伸三甲基[-(CH2)3-]、伸四甲基[-(CH2)4-]、伸五甲基[-(CH2)5-]等〇分支鏈狀之脂肪族烴基，以分支鏈狀之伸烷基爲佳，具體而言，例如，-ch(ch3)-、-CH(CH2CH3)-、-C(CH3)2-、-c(ch3)(ch2ch3)-、-c(ch3)(ch2ch2ch3)-、-C(CH2CH3)2-等之烷基伸甲基；-ch(ch3)ch2-、-CH(CH3)CH(CH3)-、 -C(CH3)2CH2-、-CH(CH2CH3)CH2- ' -C(CH2CH3)2-CH2-等之烷基伸乙基；-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2 -等之烷基伸三甲基；-ch(ch3)ch2ch2ch2-、-CH2CH(CH3)CH2CH2-等之烷基伸四甲基等之烷基伸烷基等。烷基伸烷基中之烷基，以碳數1〜5之直鏈狀之烷基爲佳。鏈狀之脂肪族烴基，可具有取代基亦可，不具有取代基亦可。該取代基’例如氟原子' 氟原子所取代之碳數1 *14- 201039064 〜5之氟化烷基、氧原子（ = 〇)等。構造中含有環之脂肪族烴基，例如環狀之脂肪族烴基 (脂肪族烴環去除2個氫原子所得之基）、該環狀之脂肪族烴基鍵結於前述鏈狀之脂肪族烴基的末端或介於鏈狀之脂肪族烴基之途中之基等。環狀之脂肪族烴基，以碳數爲3〜20爲佳，以3〜12爲更佳。 0 環狀之脂肪族烴基，可爲多環式基亦可，單環式基亦可。單環式基，例如碳數3〜6之單環鏈烷去除2個氫原子之基爲佳，該單環鏈烷例如環戊烷、環己烷等。多環式基 ’例如碳數7〜12之多環鏈烷去除2個氫原子之基爲佳，該多環鏈烷之具體例示，如金剛烷、原菠烷、異菠烷、三環癸烷、四環十二烷等。環狀之脂肪族烴基，可具有取代基亦可，不具有取代基亦可。取代基’例如碳數1〜5之烷基、氟原子、氟原子 Ο 所取代之碳數1〜5之氟化烷基、氧原子（ = 0)等。「含有雜原子之2價之鍵結基」中之雜原子係指，碳原子及氫原子以外原子’例如氧原子、氮原子、硫原子、鹵素原子等。含有雜原子之2價之鍵結基，具體而言，例如，-〇_ 、_C( = 〇)-' -C( = 〇)_〇_、碳酸酯鍵結（_〇_c( = 〇)_〇_)、_NH_ 、_NRQ4(Ri)4爲烷基）-、-NH-C( = 0)-、=N-等。又，該些「含有雜原子之2價之鍵結基」與2價之烴基之組合等。2價之煙基例如與上述可具有取代基之烴基爲相同之內容，又 -15- 201039064 以直鏈狀或分支鏈狀之脂肪族烴基爲佳。 R2，其結構中具有酸解離性部位亦可，不具有酸解離性部位亦可。「酸解離性部位」係指，該有機基内’經由曝光所發生之酸的作用而解離之部位之意。R2具有酸解離性部位之情形，較佳以具有具三級碳原子之酸解離性部位爲佳。本發明中，R2之2價之鍵結基，例如以伸烷基、2價之脂肪族環式基或含有雜原子之2價之鍵結基爲佳。其中又以伸烷基爲特佳。 R2爲伸烷基之情形，該伸烷基以碳數1〜1 〇爲佳，以碳數1〜6爲更佳，以碳數1〜4爲特佳，以碳數1〜3爲最佳。具體而言，例如與前述所列舉之直鏈狀之伸烷基、分支鏈狀之伸烷基爲相同之內容。 R2爲2價之脂肪族環式基之情形，該脂肪族環式基例如與前述「構造中含有環之脂肪族烴基」所列舉之環狀之脂肪族烴基爲相同之內容。該脂肪族環式基，以由環戊烷、環己烷、原菠烷、異菠烷、金剛烷、三環癸烷、四環十二烷去除2個以上氫原子所得之基爲特佳。 R2爲含有雜原子之2價之鍵結基之情形，該鍵結基中較佳者例如，-〇-、-c( = 〇)-o-、-c( = o)-、-0-C( = 0)-0-、 -C( = 0)-NH-、-NH- ( Η可被烷基、醯基等取代基所取代）、-S-、-S( = 0)2-、-8(==0)2-0-、式-Α_ Ο - Β_ 所表之基、式- [A-C( = 0)-0]m-B-所表示之基等。於此，A及B爲各自獨 -16- 201039064 立之可具有取代基之2價之烴基，m爲0〜3之整數。 R2爲-ΝΗ-之情形，其Η可被烷基、醯基等取代基所取代。該取代基（烷基、醯基等）以碳數爲1〜I 〇爲佳，以1 〜8爲較佳，以1〜5爲特佳。 -Α-0-Β-或-[A-C( = 0)-0]m-B-中，Α及 Β，各自獨立爲可具有取代基之2價之烴基。 A及B中之可有取代基之2價之烴基，例如與前述R2中 0 「可具有取代基之2價之烴基」所列舉者爲相同之內容。 A，以直鏈狀之脂肪族烴基爲佳，以直鏈狀之伸烷基爲較佳，以碳數1〜5之直鏈狀之伸烷基爲更佳，以伸甲基或伸乙基爲特佳。 B，以直鏈狀或分支鏈狀之脂肪族烴基爲佳，以伸甲基、伸乙基或烷基伸甲基爲更佳。該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之直鏈狀之烷基爲較佳，以甲基爲最佳。〇又，式-[A-C( = 〇)-〇]m-B-所表示之基中，m爲0〜3之整數，0〜2之整數爲佳’以〇或1爲更佳，以1爲最佳。式（aO-Ι)中，R3’爲其環骨架中含有- S02-之環式基〇 R3中之環式基係指’其環骨架中含有含- S02 -之環的環式基，以該環作爲一個環之方式計數，僅爲該環之情形爲單環式基，尙具有其他環構造之情形，則無關其構造皆稱爲多環式基。r3中之環式基’可爲單環式基亦可，多環式基亦可。 -17- 201039064 R3，特別是以其環骨架中含有S〇2-之環式基爲佳〇 R3中之環式基，以碳數爲3〜30爲佳，以4〜20爲較佳，以4〜15爲更佳，以4〜12爲特佳。其中，該碳數爲構成環骨架之碳原子之數，爲不含取代基中之碳數者。 R3中之環式基，可爲脂肪族環式基亦可，芳香族環式基亦可。較佳爲脂肪族環式基。 R3中之脂肪族環式基，例如前述中所列舉之構成環狀脂肪族烴基之環骨架的碳原子之一部份被-S02-或-o-so2-所取代之基等。更具體而言，例如，前述單環式基爲，構成該環骨架之-CH2-被-S02-所取代之單環鏈烷去除1個氫原子之基、構成該環之-ch2-ch2-被-o-so2-所取代之單環鏈烷去除1個氫原子之基等。又，前述多環式基爲，構成該環骨架之 -ch2-被-so2-所取代之多環鏈烷（二環鏈烷、三環鏈烷、四環鏈烷等）去除1個氫原子所得之基、構成該環之-CH2-ch2-被-0_S02-所取代之多環鏈烷去除1個氫原子所得之基等。 R3中之環式基，可具有取代基。該取代基，例如烷基、烷氧基、鹵素原子、鹵化烷基、羥基、氧原子（ = 0) ' -COOR，’、-oc( = o)r，’、羥烷基、氰基等。該取代基之烷基，例如以碳數1〜6之烷基爲佳。該烷基，以直鏈狀或分支鏈狀爲佳。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、 -18- 201039064 異戊基、新戊基、己基等。其中又以甲基或乙基爲佳，甲基爲特佳。該取代基之烷氧基，例如以碳數1〜6之烷氧基爲佳。該烷氧基以直鏈狀或分支鏈狀爲佳。具體而言，例如前述取代基之烷基所列舉之烷基中與氧原子（-〇-)鍵結之基等。該取代基之鹵素原子，例如，氟原子、氯原子、溴原 0 子、碘原子等，又以氟原子爲佳。該取代基之鹵化烷基，例如前述烷基之氫原子的一部份或全部被前述鹵素原子所取代之基等。該取代基之鹵化烷基，例如前述取代基之烷基所列舉之垸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。該鹵化烷基以氟化烷基爲佳，特別是以全氟烷基爲佳。前述-COOR”、-OC( = 0)R”中之R”，任一者皆爲氫原子 Q 或碳數1〜15之直鏈狀、分支鏈狀或環狀之烷基。 R”爲直鏈狀或分支鏈狀之烷基之情形時，以碳數丄〜 10爲佳，以碳數1〜5爲更佳，以甲基或乙基爲特佳。 R”爲環狀之烷基之情形時，以碳數3〜1 5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取代亦可，未取代亦可之單環鏈院、二環鏈烷、三環鏈烷、四環鏈烷等之多環鏈烷去除1個以上之氫原子所得之基等。更具體而言，例如環戊烷、環己烷等之單環鏈烷，或金剛烷、原菠烷、異菠烷、三環癸院 -19- 201039064 、四環十二烷等多環鏈烷去除1個以上之氫原子所得之基等。該取代基之羥烷基’例如以碳數爲1〜6者爲佳’具體而言，例如，前述取代基之烷基所列舉之烷基中之至少1 個氫原子被羥基所取代之基等。 R3，更具體而言’例如下述通式（3-1 )〜（3-4 )所 -,1... —» —L_ ·Α*Α* 表不之基寺。Wherein Ri is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated group having a carbon number of 1 to 5, and R 2 is a divalent bond group 'R3' having -S〇2 in its ring skeleton. a cyclic group, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, which is a branched chain alkyl group; R22 is a carbon-9 bondable to the R22 - 201039064 Atoms together form the base of an aliphatic monocyclic group]. In the present specification and the scope of the present patent application, "aliphatic" is a relative sympathy with respect to aromatics, and is defined as a group or a compound having no aromaticity. The "alkyl group" is a monovalent saturated hydrocarbon group containing a linear chain, a branched chain, and a cyclic group, unless otherwise specified. The "alkylene group" is a divalent saturated hydrocarbon group containing a linear chain, a branched chain, and a ring, unless otherwise specified. The alkyl group in the alkoxy group is also the same. The "halogenated alkyl group" is a group in which a part or all of a hydrogen atom of an alkyl group is substituted by a halogen atom, and the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The "fluorinated alkyl group" or "fluorinated alkyl group" means a group in which a part or all of a hydrogen atom of an alkyl group or an alkyl group is substituted by a fluorine atom. The "structural unit" means a monomer unit constituting a polymer compound (resin, polymer, copolymer). The "structural unit derived from acrylate" means the structural unit constituted by the cleavage of the ethylenic double bond of the acrylate. In the "acrylic acid ester", in addition to the acrylate having a hydrogen atom bonded to the carbon atom at the alpha position, the ruthenium contains a carbon atom bonded to the alpha atom with a substituent (an atom or a base other than a hydrogen atom). The substituent bonded to the carbon atom at the α-position is, for example, an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group. Further, the carbon atom at the α position of the acrylate means, unless otherwise specified, the meaning of the carbon atom to which the curtain group is bonded. -10 - 201039064 "Exposure" is the total mourning of radiation exposure. The present invention provides a novel polymer compound which can be utilized as a substrate component of a positive photoresist composition, a positive photoresist composition containing the polymer compound, and a positive photoresist composition using the same The formation method of the photoresist pattern. <Positive-type photoresist composition> 0 The positive-type photoresist composition of the present invention (hereinafter, also referred to as a photoresist composition only) contains a solution for increasing the dissolution of the alkali developing solution by the action of an acid. The substrate component (A) (hereinafter also referred to as (A) component) and the acid generator component (B) (hereinafter, also referred to as component (B)) which generate an acid by irradiation with radiation. In the positive resist composition, when irradiated with radiation (exposure), an acid is generated from the component (B), and the solubility of the (A) component to the alkali developer is increased by the action of the acid. Therefore, in the formation of the photoresist pattern, when the photoresist film obtained by using the positive photoresist composition is selectively exposed, the exposure portion of the photoresist film is increased to be soluble in the alkali developer. At the same time, in the case where the unexposed portion does not change in the solubility of the alkali developing solution, an alkali development method is employed to form a photoresist pattern. Here, the "substrate component" means an organic compound having the ability to form a film. The substrate component is 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 forming ability can be improved, and a photoresist pattern of a nanometer degree can be easily formed. The "organic -11 - 201039064 compound having a molecular weight of 500 or more" which is used as the substrate component can be roughly classified into a non-polymer and a polymer. The non-polymer is usually a substance having a molecular weight of 500 or more and less than 4 Å. Hereinafter, a non-polymer having a molecular weight of 500 or more and less than 4,000 is referred to as a low molecular compound. The polymer is usually a substance having a molecular weight of 2,000 or more. Hereinafter, a polymer having a molecular weight of 2,000 or more is referred to as a polymer compound. In the case of a polymer compound, "molecular weight" is a polystyrene-converted mass average molecular weight obtained by GPC (gel permeation chromatography). Hereinafter, the polymer compound may also be referred to as "resin". < (A) Component> [Polymer Compound (A1)] The polymer compound (A1) (hereinafter also referred to as (A1) component) is a structural unit represented by the above formula (aO-Ι) aO-Ι ) ' and the structural unit (aO-2) represented by the above formula (aO-2). The component (A1), other than the structural unit (a〇-l), and (aO-2), is derived from an acrylate having a structural unit different from each of the above structural units and containing an acid dissociable dissolution inhibiting group. The structural unit (a 1 ) is preferred. (A1) component, in addition to structural units (a0-l), and (aO-2) or structural units (a〇-l), (a0_2), and (al), containing lactones in the stomach The structural unit (a 2 ) derived from the cyclic acrylate is preferred. And '(A1) component, except for structural units (aO-Ι), and (aO-2)' or structural units (a〇-1), (a〇-2), and (al) other than '-12- 201039064 or structural units (aO-l), (a〇-2), and (a2), or structural units (aO-1), (aO-2), (al), and (a2) The structural unit (a3) derived from the acrylate having a polar group-containing aliphatic hydrocarbon group is preferred. (Structural unit (aO-Ι)) The structural unit (aO-1) is a unit of the structure represented by the above formula (a0-1). In the formula (aO-Ι), 'R1 is a hydrogen atom 'alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group of R1 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, 'for example, methyl group, ethyl group, propyl group, isopropyl group, η-butyl group or the like. Butyl, tert-butyl, pentyl, isopentyl 'neopentyl and the like. The halogenated alkyl group having 1 to 5 carbon atoms of R1, for example, a part or all of a hydrogen atom of the alkyl group having 1 to 5 carbon atoms is substituted by a halogen atom. The ring Q atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. R1 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, and is preferably a hydrogen atom or a methyl group in terms of ease of industrial availability. In the formula (aO-Ι), R2 is a divalent bond group. R2' is preferably a divalent hydrocarbon group having a substituent, a divalent bond group containing a hetero atom, or the like. The "having a substituent" of the hydrocarbon group means that one or all of the hydrogen atoms -13 - 201039064 in the hydrocarbon group are partially or completely replaced by a group or an atom other than a hydrogen atom. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group is intended to be a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be either saturated or unsaturated, and is usually saturated. More specifically, the aliphatic hydrocarbon group is, for example, a linear hydrocarbon group having a linear or branched chain structure, or an aliphatic hydrocarbon group having a ring in the structure. The linear or branched aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, preferably 1 to 8, more preferably 1 to 5, and most preferably 1 to 2. The linear aliphatic hydrocarbon group is preferably a linear alkyl group, specifically, for example, a methyl group [-CH2-], an ethylidene group [-(CH2)2-], or a trimethyl group [ -(CH2)3-], tetramethyl [-(CH2)4-], pentamethyl [-(CH2)5-], etc., branched-chain aliphatic hydrocarbon group, branched-chain alkylene The basis is preferably, for example, -ch(ch3)-, -CH(CH2CH3)-, -C(CH3)2-, -c(ch3)(ch2ch3)-, -c(ch3)(ch2ch2ch3) -, -C(CH2CH3)2-, etc. alkyl-methyl; -ch(ch3)ch2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2- A-alkyl group of -C(CH2CH3)2-CH2-, ethyl; -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, etc. alkyl-trimethyl; -ch(ch3)ch2ch2ch2-, -CH2CH (CH3) an alkyl group such as CH2CH2- or an alkyl group such as a tetramethyl group. The alkyl group in the alkylalkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms. The chain aliphatic hydrocarbon group may have a substituent or may have no substituent. The substituent ', for example, a fluorine atom substituted with a fluorine atom, has a carbon number of 1 * 14 - 201039064 to 5, a fluorinated alkyl group, an oxygen atom (= 〇), and the like. The structure contains a ring-shaped aliphatic hydrocarbon group, for example, a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group is bonded to the terminal of the aforementioned chain aliphatic hydrocarbon group. Or a group in the middle of a chain aliphatic hydrocarbon group. The cyclic aliphatic hydrocarbon group preferably has a carbon number of from 3 to 20, more preferably from 3 to 12. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic group, for example, a monocyclic alkane having 3 to 6 carbon atoms is preferable, and a base of 2 hydrogen atoms is preferably removed, and the monocyclic alkane is, for example, cyclopentane or cyclohexane. The polycyclic group 'e.g., a polycycloalkane having 7 to 12 carbon atoms is preferred to remove a base of 2 hydrogen atoms, and specific examples of the polycyclic alkane, such as adamantane, raw spinel, iso-aracone, and tricyclic anthracene Alkane, tetracyclododecane, and the like. The cyclic aliphatic hydrocarbon group may have a substituent or may have no substituent. The substituent ', for example, an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom 、, an oxygen atom (= 0), or the like. The hetero atom in the "bivalent bond group containing a hetero atom" means an atom other than a carbon atom and a hydrogen atom, such as an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom. A divalent bond group containing a hetero atom, specifically, for example, -〇_, _C( = 〇)-' -C( = 〇)_〇_, carbonate bond (_〇_c( = 〇) )_〇_), _NH_, _NRQ4(Ri)4 are alkyl groups -, -NH-C(=0)-, =N-, and the like. Further, these "bonding groups of a divalent group containing a hetero atom" and a combination of a divalent hydrocarbon group are used. The divalent ketone group is, for example, the same as the above-mentioned hydrocarbon group which may have a substituent, and -15-201039064 is preferably a linear or branched aliphatic hydrocarbon group. R2 may have an acid-dissociable site in its structure, and may have no acid-dissociable site. The "acid dissociable portion" means a portion in the organic group which is dissociated by the action of an acid generated by exposure. In the case where R2 has an acid dissociable portion, it is preferred to have an acid dissociable site having a tertiary carbon atom. In the present invention, the divalent bond group of R2 is preferably, for example, an alkylene group, a divalent aliphatic ring group or a divalent bond group containing a hetero atom. Among them, alkylene is particularly preferred. When R2 is an alkylene group, the alkylene group is preferably a carbon number of 1 to 1 Å, more preferably a carbon number of 1 to 6, a carbon number of 1 to 4, and a carbon number of 1 to 3. good. Specifically, for example, it is the same as the above-mentioned linear alkyl group or branched chain alkyl group. In the case where R2 is a divalent aliphatic cyclic group, the aliphatic cyclic group is the same as the cyclic aliphatic hydrocarbon group exemplified in the above-mentioned "aliphatic hydrocarbon group having a ring in the structure". The aliphatic cyclic group is particularly preferably obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, raw spinane, isopentane, adamantane, tricyclodecane or tetracyclododecane. . R2 is a case of a divalent bond group containing a hetero atom, and a preferred one of the bond groups is, for example, -〇-, -c(=〇)-o-, -c(=o)-, -0- C( = 0)-0-, -C( = 0)-NH-, -NH- (Η can be substituted by a substituent such as alkyl or fluorenyl), -S-, -S( = 0)2- , -8 (= = 0) 2-0 -, the formula - Α _ Ο - Β _ the basis of the formula, the formula - [AC ( = 0) - 0] mB - expressed base. Here, A and B are each a monovalent hydrocarbon group which may have a substituent, and m is an integer of 0 to 3. In the case where R2 is -ΝΗ-, the oxime may be substituted by a substituent such as an alkyl group or a fluorenyl group. The substituent (alkyl group, thiol group, etc.) is preferably a carbon number of 1 to I Torr, preferably 1 to 8, and particularly preferably 1 to 5. -Α-0-Β- or -[A-C( = 0)-0]m-B-, Α and Β, each independently a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group which may have a substituent in A and B is, for example, the same as those listed in the above-mentioned R2, "a divalent hydrocarbon group which may have a substituent". A, a linear aliphatic hydrocarbon group is preferred, a linear alkyl group is preferred, and a linear alkyl group having a carbon number of 1 to 5 is more preferred. The base is especially good. B, preferably a linear or branched aliphatic hydrocarbon group, more preferably a methyl group, an ethyl group or an alkyl group. The alkyl group of the alkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms, preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Further, in the base represented by the formula -[AC( = 〇)-〇]mB-, m is an integer of 0 to 3, and an integer of 0 to 2 is preferably 'preferably 〇 or 1 is better, and 1 is the most good. In the formula (aO-Ι), R3' is a cyclic group in the ring skeleton containing -S02- in the ring skeleton, and the ring group in the ring skeleton is a ring group having a ring containing -S02 - in the ring skeleton, The ring is counted as a ring, and only the case of the ring is a monocyclic group, and the case of the ring has other ring structures, and the structure is called a polycyclic group irrespective of its structure. The cyclic group in r3 may be a monocyclic group or a polycyclic group. -17- 201039064 R3, especially the ring group containing S〇2- in the ring skeleton is a ring group in the ring R3, preferably having a carbon number of 3 to 30, preferably 4 to 20, It is better to use 4 to 15 and 4 to 12 as the best. Here, the carbon number is the number of carbon atoms constituting the ring skeleton, and is the number of carbon atoms in the substituent. The cyclic group in R3 may be an aliphatic cyclic group or an aromatic cyclic group. It is preferably an aliphatic cyclic group. The aliphatic cyclic group in R3, for example, a part of the carbon atom of the ring skeleton constituting the cyclic aliphatic hydrocarbon group exemplified above is substituted by -S02- or -o-so2-. More specifically, for example, the monocyclic group is a group in which a monocyclic alkane which is substituted by -CH 2 - which constitutes the ring skeleton is removed by one hydrogen atom, and -ch2-ch 2 which constitutes the ring The monocyclic alkane substituted by -o-so2- removes one hydrogen atom or the like. Further, the polycyclic group is a polycyclic alkane (dicycloalkane, tricycloalkane or tetracycloalkane) substituted by -ch2- which is a ring skeleton of the ring skeleton, and one hydrogen atom is removed. The obtained group, a group obtained by removing one hydrogen atom from the polycyclic alkane in which -CH2-ch2- which is substituted by -0-S02- is removed. The cyclic group in R3 may have a substituent. The substituent, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= 0) '-COOR, ', -oc(=o)r, ', a hydroxyalkyl group, a cyano group, etc. . The alkyl group of the substituent is preferably, for example, an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably a linear or branched chain. Specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, η-butyl 'isobutyl group, tert-butyl group, pentyl group, -18-201039064 isopentyl group, neopentyl group, hexyl group and the like. Among them, methyl or ethyl is preferred, and methyl group is particularly preferred. The alkoxy group of the substituent is preferably, for example, an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably a linear or branched chain. Specifically, for example, the alkyl group exemplified in the alkyl group of the above-mentioned substituent is bonded to an oxygen atom (-〇-). The halogen atom of the substituent, 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 of the substituent is, for example, a part or all of a hydrogen atom of the above alkyl group, which is substituted by the above halogen atom. The halogenated alkyl group of the substituent, for example, a part or all of a hydrogen atom in the mercapto group exemplified for the alkyl group of the above substituent is substituted by the above halogen atom. The halogenated alkyl group is preferably a fluorinated alkyl group, particularly preferably a perfluoroalkyl group. Any of R-" in the above -COOR" and -OC(=0)R" is a hydrogen atom Q or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. In the case of a linear or branched chain alkyl group, a carbon number of 丄 10 is preferred, a carbon number of 1 to 5 is more preferred, and a methyl group or an ethyl group is particularly preferred. When R" is a cyclic alkyl group, it is preferably a carbon number of 3 to 15 and a carbon number of 4 to 12, more preferably a carbon number of 5 to 10. More specifically, for example, it may be fluorine. The atom or the fluorinated alkyl group may be substituted, and the polycyclic alkane such as a monocyclic chain, a bicycloalkane, a tricycloalkane or a tetracycloalkane which is unsubstituted may be a group obtained by removing one or more hydrogen atoms. More specifically, for example, a monocyclic alkane such as cyclopentane or cyclohexane, or adamantane, raw spinel, iso-araconne, tricyclic brothel-19-201039064, tetracyclododecane, etc. A group obtained by removing one or more hydrogen atoms from a cycloalkane, etc. The hydroxyalkyl group of the substituent is preferably, for example, a carbon number of 1 to 6', specifically, for example, an alkyl group of the above substituent a group in which at least one hydrogen atom in the alkyl group is substituted by a hydroxyl group, etc. R3, more specifically 'for example, the following formula (3-1) to (3-4)-, 1...-» L_ ·Α*Α* The base of the temple.

[式中，A ’爲可含有氧原子或硫原子之碳數1〜5之伸烷基、氧原子或硫原子，a爲0〜2之整數’ R6爲烷基、烷氧基、鹵化烷基、羥基、-COOR”、-〇C( = 0)R”、羥烷基或氰基，R”爲氫原子或烷基]。前述通式（3-1)〜（3-4)中’ A’爲可含有氧原子（ -〇-)或硫原子（-S-)之碳數1〜5之伸烷基、氧原子或硫原子。 A ’中之碳數1〜5之伸烷基’以直鏈狀或分支鏈狀之伸烷基爲佳，例如伸甲基、伸乙基、η-伸丙基、異伸丙基等該伸烷基含有氧原子或硫原子之情形，其具體例如， -20- 201039064 前述伸烷基之末端或碳原子間介有-〇-或-s-之基等，例如 -0-CH2-、-CH2-0-CH2-、-S-CH2-、-CH2-S-CH2-等。 A’，例如以碳數1〜5之伸烷基或-Ο-爲佳，以碳數1〜 5之伸烷基爲更佳，以伸甲基爲最佳。 a爲0〜2中任一者皆可，又以0爲最佳。 a爲2之情形，複數之R2可分別爲相同亦可，相異亦可〇 Q R6中之烷基、烷氧基、鹵化烷基、-COOR”、-OC(=0)R” 、羥烷基，以分別與前述R3中之環式基所可具有之取代基所列舉之烷基、烷氧基、鹵化烷基、-COOR”、-0C( = 0)R” 、羥烷基爲相同之內容。以下’將例TfC目ij述通式（3-1)〜（3-4)所表不之具體的環式基。又，式中之「Ac」爲乙醯基之意。 ❹ 21 - 201039064 【化4】[In the formula, A ' is an alkylene group, an oxygen atom or a sulfur atom which may have an oxygen atom or a sulfur atom of 1 to 5, and a is an integer of 0 to 2'. R6 is an alkyl group, an alkoxy group or an alkyl halide. a group, a hydroxy group, a -COOR", a -C(=0)R", a hydroxyalkyl group or a cyano group, and R" is a hydrogen atom or an alkyl group. In the above formula (3-1) to (3-4) 'A' is an alkylene group, an oxygen atom or a sulfur atom having a carbon number of 1 to 5 which may contain an oxygen atom (-〇-) or a sulfur atom (-S-). Aceene having a carbon number of 1 to 5 in A ' The base ' is preferably a linear or branched alkyl group, for example, a methyl group, an ethyl group, an η-propyl group, an iso-propyl group, etc., wherein the alkyl group contains an oxygen atom or a sulfur atom. Specifically, for example, -20-201039064, the terminal or alkyl group of the above alkyl group is interposed with -〇- or -s-, etc., such as -0-CH2-, -CH2-0-CH2-, -S-CH2 -, -CH2-S-CH2-, etc. A', for example, an alkylene group or a hydrazine having a carbon number of 1 to 5 is preferred, and an alkylene group having a carbon number of 1 to 5 is more preferably a methyl group. For the best, a is 0 to 2, and 0 is the best. When a is 2, the plural R2 can be the same or different. An alkyl group, an alkoxy group, an alkyl halide group, a -COOR", -OC(=0)R" or a hydroxyalkyl group in Q R6, as exemplified by the substituents which may be respectively present in the ring group in the above R3 The alkyl group, the alkoxy group, the alkyl halide group, the -COOR", the -0C(=0)R", and the hydroxyalkyl group are the same contents. The following 'will be an example of the formula TfC ij ij (III)~( 3-4) The specific ring group is not shown. In addition, the "Ac" in the formula is the meaning of the group. ❹ 21 - 201039064 【化4】

(3 — 1 一 5) (3 — 1—6) (3 — 1—7) (3 — 1—8)(3 - 1 - 5) (3 - 1 - 6) (3 - 1 - 7) (3 - 1 - 8)

co2ch3 (3 — 1—9) (3-1-10) (3 — 1 — 11) (3_ 1 — 12)Co2ch3 (3 — 1—9) (3-1-10) (3 — 1 — 11) (3_ 1 – 12)

o— O- cf3 // o // o (3 — 1—13) (3 —1—14) (3—1 — 15) (3 — 1—16) -22- 201039064O— O- cf3 // o // o (3 — 1–13) (3 —1—14) (3—1 — 15) (3 — 1–16) -22- 201039064

【化5【化5

Ο ο (3-1-18) (3-1-19)Ο ο (3-1-18) (3-1-19)

ο (3-1-20) (3-1-21)ο (3-1-20) (3-1-21)

-23- 201039064-23- 201039064

(3-1-30) (3-1 -31) (3-1-32) (3-1-33) 【化6】(3-1-30) (3-1 -31) (3-1-32) (3-1-33) [Chem. 6]

(3 — 2 — 1) (3 — 2 — 2) (3 — 3 — 1) (3 — 4 — 1) R3，於上述之中，又以下述通式（3-1)所表示之基爲佳，以使用前述化學式（3-1-1 ) 、（ 3-1-18 )、（ 3-3- 1 )及（3-4-1 )之任一所表示之基所成群所選擇之至少一種爲更佳，以化學式（3 -1 -1 )所表示之基爲最佳。本發明中，結構單位（aO-Ι )，以下述通式（aO-1-l 1 )所表示之結構單位爲特佳。 -24- 201039064 【化7】 R1(3 - 2 - 1) (3 - 2 - 2) (3 - 3 - 1) (3 - 4 - 1) R3, in the above, the base represented by the following formula (3-1) is Preferably, it is selected by using the group represented by any of the above chemical formulas (3-1-1), (3-1-18), (3-3-1), and (3-4-1) At least one is more preferable, and the group represented by the chemical formula (3 -1 -1 ) is most preferable. In the present invention, the structural unit (aO-Ι) is particularly preferably a structural unit represented by the following general formula (aO-1-l 1 ). -24- 201039064 【化7】 R1

❹ Ο—8¾¾. II 0 Ο ( a Ο — 1 — 1 1 ) [式中，R1與前述爲相同之內容’ R2’爲直鏈狀或分支鏈狀之伸烷基，A’與前述爲相同之內容]。 R2’中之直鏈狀或分支鏈狀之伸烷基，以碳數爲1〜10 爲佳，以1〜8爲較佳，以1〜5爲更佳，以1〜3爲特佳，以 ◎ 1〜2爲最佳。 A’以伸甲基、氧原子（-0-)或硫原子（-s_ )爲佳。結構單位（a 0 -1 )，可單獨使用1種亦可，或將2種以上組合使用亦可。 (A 1 )成份中之結構單位（a 〇 -1 )之比例，於使用含有該（A1)成份之正型光阻組成物形成光阻圖型之際，於提昇MEF、所形成之光阻圖型之形狀、CDU (面内均勻性 )、L WR (線路寬度不均）等，相對於構成（a ])成份之全結構單位’以1〜6 〇莫耳％爲佳，以5〜5 〇莫耳％爲較佳 -25- 201039064 ，以10〜45莫耳％爲更佳。 (結構單位（aO-2)) 結構單位（aO-2 )爲，上述通式（aO-2 )所表示之結構單位。又，爲不相當前述結構單位（a〇-l ) ’且含有酸解離性溶解抑制基之丙烯酸酯所衍生之結構單位。結構單位（aO-2 )中之酸解離性溶解抑制基，爲解離前具有使（A 1 )成份全體對鹼顯影液爲難溶之鹼溶解抑制性的同時，經由酸之解離而使該（A 1 )成份全體增大對鹼顯影液之溶解性之基。式（aO-2)中，R爲與前述式（aO-Ι)中之R1爲相同之內容。式（aO-2 )中，R22，爲可與該R22鍵結之碳原子共同形成脂肪族單環式基之基。於此，「脂肪族單環式基」係指，不具有芳香屬性之單環式基之意。 R22中之脂肪族單環式基’以碳數4〜8爲佳，以5〜8 爲更佳。其中，該碳數爲構成環骨架之碳原子之數，爲不含取代基中之碳數者。 R2 2中之脂肪族單環式基，可具有取代基亦可，不具有取代基亦可。取代基’例如碳數1〜5之院基、碳數1〜5 之院氧基、氟原子、氟原子所取代之碳數1〜5之氟化垸基、氧原子（=〇)等。 -26- 201039064 脂肪族單環式基去除取代基之基本的環構造，並不限定爲由碳及氫所形成之基（烴基），但以烴基爲佳。又，「烴基」可爲飽和或不飽和之任一者皆可，通常以飽和者爲佳。該脂肪族單環式基，例如，可被碳數1〜5之烷基、氟原子或氟化烷基取代亦可，未取代亦可之單環鏈烷去除1 個以上之氫原子所得之基等。更具體而言，例如環戊烷、 0 環己烷等之單環鏈烷去除1個以上之氫原子所得之基等。又，構成該些單環鏈烷去除1個以上之氫原子所得之基的環之碳原子的一部份被醚性氧原子（-0-)所取代者亦可〇式（aO-2)中，R21爲分支鏈狀之烷基。分支鏈狀之烷基，其碳數以3〜10爲佳，以3〜5爲更佳。具體而言，例如異丙基、異丁基、tert-丁基、異戊基、新戊基等，又以異丙基爲最佳。 Q 式（aO-2 )所表示之結構單位之具體例，例如下述式 (aO-2-l )〜（a〇-2-20 )所表示之結構單位等。 -27- 201039064 【化8】❹ Ο—83⁄43⁄4. II 0 Ο ( a Ο — 1 — 1 1 ) [wherein R1 is the same as the above-mentioned 'R2' is a linear or branched alkyl group, and A' is the same as the above Content]. The linear or branched chain alkyl group in R2' preferably has a carbon number of 1 to 10, preferably 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 3. ◎ 1 to 2 is the best. A' is preferably a methyl group, an oxygen atom (-0-) or a sulfur atom (-s_). The structural unit (a 0 -1 ) may be used singly or in combination of two or more. The ratio of the structural unit (a 〇-1 ) in the component (A 1 ) is such that when the photoresist pattern is formed using the positive photoresist composition containing the component (A1), the MEF and the formed photoresist are raised. The shape of the pattern, CDU (in-plane uniformity), L WR (uneven line width), etc., relative to the full structural unit constituting the component (a)) is preferably 1 to 6 〇 mol%, to 5~ 5 〇耳 % is preferably -253903, preferably 10 to 45 mole %. (Structural unit (aO-2)) The structural unit (aO-2) is a structural unit represented by the above formula (aO-2). Further, it is a structural unit derived from an acrylate which does not have the above structural unit (a?-1) and contains an acid dissociable dissolution inhibiting group. The acid dissociable dissolution inhibiting group in the structural unit (aO-2) has an alkali dissolution inhibitory property which is insoluble to the alkali developing solution before the dissociation, and is caused by dissociation of the acid (A) 1) The entire composition increases the solubility of the alkali developer. In the formula (aO-2), R is the same as R1 in the above formula (aO-Ι). In the formula (aO-2), R22 is a group which can form an aliphatic monocyclic group together with the carbon atom bonded to the R22. Here, the "aliphatic monocyclic group" means a monocyclic group having no aromatic character. The aliphatic monocyclic group in R22 is preferably a carbon number of 4 to 8, more preferably 5 to 8. Here, the carbon number is the number of carbon atoms constituting the ring skeleton, and is a number which does not contain the carbon number in the substituent. The aliphatic monocyclic group in R2 2 may have a substituent or may have a substituent. The substituent ', for example, a group having a carbon number of 1 to 5, a oxy group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated fluorenyl group having 1 to 5 carbon atoms substituted by a fluorine atom, and an oxygen atom (= fluorene). -26- 201039064 The basic ring structure of the aliphatic monocyclic group removing substituent is not limited to a group formed of carbon and hydrogen (hydrocarbon group), but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is usually preferred to saturate. The aliphatic monocyclic group may be, for example, substituted by an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, and the unsubstituted polycycloalkane may be obtained by removing one or more hydrogen atoms. Base. More specifically, for example, a monocyclic alkane such as cyclopentane or 0 cyclohexane is obtained by removing one or more hydrogen atoms. Further, a part of the carbon atom of the ring constituting the group obtained by removing one or more hydrogen atoms of the monocyclic alkane may be substituted by an etheric oxygen atom (-0-) (aO-2). In the above, R21 is a branched alkyl group. The branched chain alkyl group preferably has a carbon number of 3 to 10 and more preferably 3 to 5. Specifically, for example, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl or the like is preferred as isopropyl. Specific examples of the structural unit represented by the formula (aO-2) are, for example, structural units represented by the following formulas (aO-2-l) to (a〇-2-20). -27- 201039064 【化8】

(aO — 2-9) (a〇-2 — 10) (aO-2-11) (aO — 2—12)(aO — 2-9) (a〇-2 — 10) (aO-2-11) (aO — 2–12)

-28- 201039064-28- 201039064

RaRa

(a 0—2 — 1 7)(a 0—2 — 1 7)

(a〇-2-18) (aO-2-19) (a〇-2-20) [式中，Ra，表5 結構單位（ 0 上組合使用亦可 (A 1 )成份成（A1 )成份之 5 0莫耳％爲較佳 (結構單位（a 1 結構單位（及結構單位（a0 〇酯所衍生之結構結構單位（具有使（A1 )成的同時，經由酸影液之溶解性之幅型光阻用之基而言，係指與（之二級院酯之基離性溶解抑制基六氫原子、甲基或三氟甲基。] aO-2 ) ’可單獨使用1種亦可，或將2種以〇中之結構單位（a〇-2 )之比例，相對於構全結構單位’以1〜60莫耳％爲佳，以5〜，以10〜45莫耳％爲更佳。 )) al)爲，不相當於前述結構單位（ao-!) -2 )之含有酸解離性溶解抑制基之丙烯酸單位。 al )中之酸解離性溶解抑制基，爲解離前份全體對鹼顯影液爲難溶之鹼溶解抑制性之解離而使該（A1)成份全體增大對鹼顯基，其可使用目前爲止被提案作爲化學増礎樹脂的酸解離性溶解抑制基之物。一般甲基）丙烯酸等中之羧基形成環狀或鏈狀 :廣爲已知者例如院氧院基等縮醛型酸解等。又，「（甲基）丙烯酸酯」係指，〇； -29- 201039064 位鍵結氫原子之丙烯酸酯’與α位鍵結甲基之甲基丙烯酸酯之一者或二者之意。於此，「三級烷酯」係指’羧基之氫原子，被鏈狀或環狀之烷基所取代而形成酯，其羰氧基（-c (〇)-〇-)末端之氧原子’與前述鏈狀或環狀之烷基的三級碳原子鍵結所形成之構造。該三級烷酯中’經由酸作用時，可使氧原子與三級碳原子之間的鍵結被切斷。又，前述鏈狀或環狀之烷基可具有取代基。以下，與殘基構成三級院酯中，形成酸解離性之基，於方便上，將其稱爲「三級烷酯型酸解離性溶解抑制基」〇三級烷酯型酸解離性溶解抑制基，例如脂肪族分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。於此’ 「脂肪族分支鏈狀」係指具有不含芳香族性之分支鏈狀之構造之意。「脂肪族分支鏈狀酸解離性溶解抑制基」之構造’並不限定爲由碳及氫所形成之基（烴基），但以烴基爲佳。又，「烴基」可爲飽和或不飽和之任一者皆可，通常以飽和者爲佳。脂肪族分支鏈狀酸解離性溶解抑制基，例如， -0(1171)(尺72)(尺73)所表示之基等。式中，汉71〜1173，分別爲獨立之碳數1〜5之直鏈狀之烷基。-C(R71)(R72)(R73)所表示之基’以碳數4〜8爲佳’具體而言，例如tert-丁基、2-甲基-2 -丁基、2 -甲基-2-戊基、3 -甲基-3 -戊基等。特別是 -30- 201039064 以tert-丁基爲佳。「脂肪族環式基」爲不具有芳香族性之單環式基或多環式基。結構單位（a 1 )中之「脂肪族環式基」，可具有取代基亦可，不具有取代基亦可。取代基，例如碳數1〜5之烷基、碳數1〜5之烷氧基、氟原子、氟原子所取代之碳數1 〜5之氟化烷基、氧原子（ = 0)等。 0 「脂肪族環式基」之去除取代基之基本環之構造，並不限定爲由碳及氫所形成之基（烴基），但以烴基爲佳。又，「烴基」可爲飽和或不飽和之任一者皆可，通常以飽和者爲佳。「脂肪族環式基」以多環式基爲佳。脂肪族環式基，例如，可被碳數1〜5之烷基、氟原子或氟化烷基所取代亦可、未被取代亦可之單環鏈烷去除1 個以上之氫原子所得之基、二環鏈烷、三環鏈烷、四環鏈烷等之多環鏈烷去除1個以上之氫原子所得之基等。更具 Q 體而言，例如環戊烷、環己烷等之單環鏈烷去除1個以上之氫原子所得之基，或金剛烷、原菠烷、異菠烷、三環癸烷、四環十二烷等多環鏈烷去除1個以上之氫原子所得之基等。又，該些單環鏈烷去除1個以上之氫原子所得之基或多環鏈烷去除1個以上之氫原子所得之基之構成環的碳原子之一部份可被醚性氧原子（-〇-)所取代者亦可。含有脂肪族環式基之酸解離性溶解抑制基，例如，（ i) 1價之脂肪族環式基的環骨架上具有三級碳原子之基； (ii)具有1價之脂肪族環式基，與具有與其鍵結之三級碳 -31 - 201039064 原子的分支鏈狀伸烷基之基；等。 (i ) 1價之脂肪族環式基的環骨架上具有三級碳原子之基之具體例，例如，下述通式（1 -1 )〜（1 - 9 )所表示之基等。 (ii)具有1價之脂肪族環式基，與具有與其鍵結之三級碳原子的分支鏈狀伸烷基之基之具體例，例如，下述通式（2-1 )〜（2-6 )所表示之基等。(a〇-2-18) (aO-2-19) (a〇-2-20) [In the formula, Ra, Table 5 structural unit (0 combinations can also be used as (A 1 ) component into (A1) component 50% of the mole is preferred (structural unit (a 1 structural unit (and structural unit (a structural unit of a0 oxime ester) (having the solubility of the acid-forming solution while making (A1) The type of the photoresist is a hexahydro atom, a methyl group or a trifluoromethyl group which is a radically soluble inhibitor of the second-stage ester.] aO-2) ' , or the ratio of the two structural units (a〇-2) in the 〇, relative to the total structural unit '1 to 60% by mole, preferably 5 to 10 to 45% by mole. Good))))) is not equivalent to the above-mentioned structural unit (ao-!) -2) of the acrylic acid unit containing the acid dissociable dissolution inhibiting group. The acid dissociative dissolution inhibiting group in the al) is the former part of the dissociation It is possible to increase the (A1) component to the alkali base by dissolving the alkali-dissolving alkali dissolution inhibitor, and it is possible to use the acid dissociation dissolution which has been proposed as a chemical base resin. . The group are generally prepared meth) acrylic acid in the carboxyl group to form a cyclic or chain: acetal type widely known acid hydrolysis and the like by e.g. hospital hospital oxygen group. Further, "(meth) acrylate" means 〇; -29-201039064, the acrylate of a hydrogen atom bonded to a point, and one or both of a methyl methacrylate of an alpha bond. Here, the "trialkyl ester" means a hydrogen atom of a 'carboxy group, which is substituted with a chain or a cyclic alkyl group to form an ester, and the oxygen atom at the terminal of the carbonyloxy group (-c (〇)-〇-) 'Structure formed by the bonding of a tertiary carbon atom of the aforementioned chain or cyclic alkyl group. In the tertiary alkyl ester, when the acid acts, the bond between the oxygen atom and the tertiary carbon atom can be cut off. Further, the aforementioned chain or cyclic alkyl group may have a substituent. In the following, the base of the acid-dissociating group is formed in the third-stage ester with the residue, and it is referred to as "a tertiary alkyl ester type acid dissociable dissolution inhibiting group" for convenience. 〇Tribasic ester type acid dissociable dissolution The inhibitory group is, for example, an aliphatic branched chain acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, and the like. Here, "aliphatic branched chain" means a structure having a branched chain shape which does not contain aromaticity. The structure of the "aliphatic branched chain acid dissociable dissolution inhibiting agent" 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 usually preferred to saturate. The aliphatic branched chain acid dissociable dissolution inhibiting group is, for example, a group represented by -0 (1171) (foot 72) (foot 73). In the formula, Han 71 to 1173 are respectively independent linear alkyl groups having a carbon number of 1 to 5. The base ' represented by -C(R71)(R72)(R73) is preferably a carbon number of 4 to 8', specifically, for example, tert-butyl, 2-methyl-2-butyl, 2-methyl- 2-pentyl, 3-methyl-3-pentyl, and the like. In particular, -30- 201039064 is preferably tert-butyl. The "aliphatic cyclic group" is a monocyclic group or a polycyclic group having no aromaticity. The "aliphatic cyclic group" in the structural unit (a 1 ) may have a substituent or may have no substituent. The substituent is, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, and an oxygen atom (= 0). The structure of the basic ring of the substituent of the "aliphatic cyclic group" is not limited to the group formed by carbon and hydrogen (hydrocarbon group), but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is usually preferred to be saturated. The "aliphatic ring group" is preferably a polycyclic group. The aliphatic cyclic group may be, for example, substituted by an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, or a monocyclic alkane which is not substituted may be obtained by removing one or more hydrogen atoms. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane. Further, for the Q body, a monocyclic alkane such as cyclopentane or cyclohexane is used to remove one or more hydrogen atoms, or adamantane, raw spinane, iso-araconine, tricyclodecane, or tetra. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as cyclododecane. Further, a part of the carbon atoms of the constituent ring of the group obtained by removing one or more hydrogen atoms from the monocyclic alkane and removing one or more hydrogen atoms by the polycyclic alkane may be an etheric oxygen atom ( -〇-) can also be replaced. An acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, for example, (i) a group having a tertiary carbon atom on a ring skeleton of a monovalent aliphatic ring group; (ii) an aliphatic ring having a monovalent group a group having a branched chain alkyl group having a tertiary carbon-31 - 201039064 atom bonded thereto; (i) Specific examples of the group having a tertiary carbon atom in the ring skeleton of the monovalent aliphatic ring group, for example, a group represented by the following formula (1 -1 ) to (1 - 9 ). (ii) a specific example of a group having a monovalent aliphatic cyclic group and a branched chain alkyl group having a tertiary carbon atom bonded thereto, for example, the following general formula (2-1) to (2) -6) The base expressed.

[式中，R14爲烷基，g爲〇〜8之整數]。【化1 〇[wherein R14 is an alkyl group, and g is an integer of 〇~8]. 【化1〇

(2-1)(2-1)

(2-2) (2-3)(2-2) (2-3)

(2-6) [式中，R15及R16，爲分別獨立之烷基]。上述R14之烷基，以直鏈狀或分支鏈狀之烷基爲佳。該直鏈狀之烷基，以碳數1〜5爲佳，以1〜4爲較佳，以1或2爲更佳。具體而言，例如甲基、乙基、II-丙基、n- -32- 201039064 丁基、η-戊基等。其中又以甲基、乙基或n-丁基爲佳，以甲基或乙基爲更佳。該分支鏈狀之烷基，其碳數以3〜10爲佳，以3〜5爲更佳。具體而言，例如異丙基、異丁基、tert-丁基 '異戊基、新戊基等，又以異丙基爲最佳。其中，前述脂肪族環式基爲單環式基之情形，R14之烷基則不含分支鏈狀之烷基。 0 g以〇〜3之整數爲佳，以1〜3之整數爲更佳，以1或2 爲最佳。 R15〜R16之烷基，例如與R14之烷基爲相同之內容。上述式（1-1)〜（1-9) 、（2-1)〜（2-6)中，構成環之碳原子的一部份可被醚性氧原子（-〇-)所取代亦可 ° 又，式（1-1)〜（1-9) 、（2-1)〜（2-6)中，構成環之碳原子所鍵結之氫原子可被取代基所取代。該取代 ^ 基，例如碳數1〜5之院基、氣原子、氟化院基等。「縮醛型酸解離性溶解抑制基」，一般而言，爲取代羧基、羥基等鹼可溶性基末端之氫原子而與氧原子鍵結。隨後，經由曝光產生酸時，經由該酸之作用’而使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鍵結之氧原子之間的鍵結被切斷。縮醛型酸解離性溶解抑制基，例如，下述通式（p 1 ) 所表示之基等。 -33- 201039064 【化1 1】(2-6) [wherein, R15 and R16 are independently alkyl groups]. The alkyl group of the above R14 is preferably a linear or branched alkyl group. The linear alkyl group preferably has a carbon number of 1 to 5, preferably 1 to 4, more preferably 1 or 2. Specifically, for example, methyl, ethyl, II-propyl, n--32-201039064 butyl, η-pentyl, and the like. Among them, a methyl group, an ethyl group or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred. The branched chain alkyl group preferably has a carbon number of 3 to 10 and more preferably 3 to 5. Specifically, for example, isopropyl, isobutyl, tert-butyl 'isopentyl, neopentyl, etc., and isopropyl are most preferred. Wherein the above aliphatic cyclic group is a monocyclic group, and the alkyl group of R14 does not contain a branched alkyl group. 0 g is preferably an integer of 〇~3, more preferably an integer of 1 to 3, and most preferably 1 or 2. The alkyl group of R15 to R16 is, for example, the same as the alkyl group of R14. In the above formulae (1-1) to (1-9) and (2-1) to (2-6), a part of the carbon atoms constituting the ring may be substituted by an etheric oxygen atom (-〇-). Further, in the formulae (1-1) to (1-9) and (2-1) to (2-6), the hydrogen atom bonded to the carbon atom constituting the ring may be substituted with a substituent. The substituent ^ group is, for example, a hospital base having a carbon number of 1 to 5, a gas atom, a fluoride base, or the like. The "acetal type acid dissociable dissolution inhibiting group" is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or a hydroxyl group. Subsequently, when an acid is generated by exposure, the acetal type acid dissociable dissolution inhibiting group is blocked by the action of the acid, and the bond between the oxygen atom bonded to the acetal type acid dissociating dissolution inhibiting group is cut off. . The acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (p 1 ). -33- 201039064 【化1 1】

(pi) [式中，R1’，R2’表示各自獨立之氫原子或碳數1〜5之烷基，η表示0〜3之整數，Y表示碳數1〜5之烷基或脂肪族環式基]。前述式（Pi)中’ η以0〜2之整數爲佳’以0或1爲更佳，以〇爲最佳。 R1’，R2’之碳數1〜5之烷基，例如與上述R之碳數1〜5 之院基爲相同之內容，以甲基或乙基爲佳，以甲基爲最佳本發明中，R 1 ’，R2,之中以至少.1個爲氫原子爲佳。即，酸解離性溶解抑制基（p 1 ) ’以下述通式（P卜1)所表示之基爲佳。【化1 2】 f(pi) [wherein, R1', R2' represents a respective hydrogen atom or an alkyl group having 1 to 5 carbon atoms, η represents an integer of 0 to 3, and Y represents an alkyl group having 1 to 5 carbon atoms or an aliphatic ring. Formula base]. In the above formula (Pi), 'η is preferably an integer of 0 to 2', and 0 or 1 is more preferable, and 〇 is the most preferable. The alkyl group having 1 to 5 carbon atoms of R1' and R2' is, for example, the same as the group having the carbon number of 1 to 5 of R, preferably a methyl group or an ethyl group, and the methyl group is the most preferable invention. Among them, at least one of R 1 ' and R 2 is preferably a hydrogen atom. Namely, the acid dissociable dissolution inhibiting group (p 1 ) ' is preferably a group represented by the following formula (P 1 ). [化1 2] f

——C—o-(ch2)~~Y Η η …（ρ 1 - 1) [式中，R1’、η、Υ與上述爲相同之內容]。 Υ之碳數1〜5之烷基’例如與上述R之碳數1〜5之烷基爲相同之內容。 Υ之脂肪族環式基’可由以往ArF光阻等中被多數提案之單環或多環式之脂肪族環式基之中作適當之選擇使用’ 例如與上述「脂肪族環式基」爲相同之例不內容。 -34- 201039064 又，縮醛型酸解離性溶解抑制基，又例如下述通式（ p2 )所示之基。【化1 3】 R17 —0—Ο—R19 R18 …（Ρ2) [式中，R17、R18爲各自獨立之直鏈狀或分支鏈狀之烷基或爲氫原子；R19爲直鏈狀、分支鏈狀或環狀之烷基，或， R17及R19分別獨立爲直鏈狀或分支鏈狀之伸烷基，R17之末端與R19之末端可鍵結形成環]。 R17、R18中，烷基之碳數，較佳爲1〜15，可爲直鏈狀、分支鏈狀之任一者，又以乙基、甲基爲佳，以甲基爲最佳。特別是以R17、R18之一者爲氫原子，另一者爲甲基爲佳。 R19爲直鏈狀、分支鏈狀或環狀之烷基，碳數較佳爲1 〜1 5，可爲直鏈狀、分支鏈狀或環狀之任一者。 R 19爲直鏈狀、分支鏈狀之情形時，以碳數1〜5爲佳，以乙基、甲基爲更佳，特別是以乙基爲最佳。 R19爲環狀之情形時，以碳數4〜15爲佳，以碳數4〜 1 2爲更佳，以碳數5〜1 0爲最佳。具體而言，例如可被氟原子或氟化烷基取代亦可，未取代亦可之單環鏈烷、二環鏈烷、三環鏈烷、四環鏈烷等之多環鏈烷去除1個以上之氫原子所得之基等。具體而言，爲由環戊烷 '環己烷等之單環鏈烷，或金剛烷、原菠烷、異菠烷、三環癸烷、四環 -35- 201039064 十二烷等多環鏈烷去除1個以上之氫原子所得之基等。其中又以金剛烷去除1個以上之氫原子所得之基爲佳。又，上述式（P2 )中’ R17及R19爲分別獨立之直鏈狀或分支鏈狀之伸烷基（較佳爲碳數1〜5之伸院基）時， R19之末端與R17之末端可形成鍵結。此時，R17，與R19，與R19鍵結之氧原子中’該氧原子及R17鍵結之碳原子形成爲環式基。該環式基’以4〜7員環爲佳，以4〜6員環爲更佳。該環式基之具體例如，四氫吡喃基、四氫呋喃基等。縮醛型酸解離性溶解抑制基之具體例，例如，下述式 (p3-l)〜（p3-12)所表示之基等。【化1 4】- C - o - (ch2) ~ ~ Y Η η ... (ρ 1 - 1) [wherein, R1', η, Υ are the same as described above]. The alkyl group having 1 to 5 carbon atoms is the same as the alkyl group having 1 to 5 carbon atoms 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 in many conventional ArF photoresists, for example, and the above-mentioned "aliphatic cyclic group" is The same example does not contain content. Further, the acetal type acid dissociable dissolution inhibiting group is, for example, a group represented by the following formula (p2). [Chemical 1 3] R17 — 0—Ο—R19 R18 ((2) [wherein, R17 and R18 are independent linear or branched alkyl groups or hydrogen atoms; R19 is linear and branched. A chain or a cyclic alkyl group, or R17 and R19 are each independently a linear or branched alkyl group, and the terminal of R17 and the terminal of R19 may be bonded to form a ring]. In R17 and R18, the number of carbon atoms of the alkyl group is preferably from 1 to 15, and it may be either a linear chain or a branched chain, and an ethyl group or a methyl group is preferred, and a methyl group is most preferred. In particular, one of R17 and R18 is a hydrogen atom, and the other is preferably a methyl group. R19 is a linear, branched or cyclic alkyl group, and the carbon number is preferably from 1 to 15 and may be any of a linear chain, a branched chain or a ring. When R 19 is a linear or branched chain, it is preferably a carbon number of 1 to 5, more preferably an ethyl group or a methyl group, and particularly preferably an ethyl group. 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, for example, a fluorine atom or a fluorinated alkyl group may be substituted, and an unsubstituted polycyclic alkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane may be removed. The base obtained by more than one hydrogen atom, and the like. Specifically, it is a monocyclic alkane such as cyclopentane 'cyclohexane, or a polycyclic chain such as adamantane, raw spinane, isopentane, tricyclodecane or tetracyclo-35-201039064 dodecane. A group obtained by removing one or more hydrogen atoms from an alkane. Further, it is preferred that the adamantane is removed by removing one or more hydrogen atoms. Further, in the above formula (P2), when R17 and R19 are independently a linear or branched alkyl group (preferably a carbon number of 1 to 5), the end of R19 and the end of R17. A bond can be formed. At this time, R17, and R19, and the oxygen atom bonded to R19, the carbon atom and the carbon atom bonded to R17 form a ring group. The ring base is preferably a 4 to 7 member ring, and a 4 to 6 member ring is more preferred. Specific examples of the cyclic group include, for example, a tetrahydropyranyl group, a tetrahydrofuranyl group and the like. Specific examples of the acetal type acid dissociable dissolution inhibiting group are, for example, a group represented by the following formulas (p3-l) to (p3-12). [化1 4]

(p3-5)(p3-5)

J ch3 (p3-12) (p3 —11) -36- 201039064 [式中，R13爲氫原子或甲基，g與前述爲相同之內容]。結構單位（al)，更具體而言，例如下述通式（a1·0· 1)所表示之結構單位、下述通式（al-〇-2)所表示之結構J ch3 (p3-12) (p3 - 11) -36- 201039064 [wherein R13 is a hydrogen atom or a methyl group, and g is the same as described above]. The structural unit (al), more specifically, the structural unit represented by the following general formula (a1·0·1), and the structure represented by the following general formula (al-〇-2)

(al — 0 — 1) (al — 0 — 2) [式中，R爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化院基，X1爲酸解離性溶解抑制基’ Y2爲2價之鍵結基，X2爲酸解離性溶解抑制基]。通式（al-0-l)中，R與前述式（aO-Ι)中之R1爲相同之內容。 X1，只要爲酸解離性溶解抑制基時’並未有特別限定，例如可爲上述之三級烷酯型酸解離性溶解抑制基、縮醒型酸解離性溶解抑制基等，又以三級烷酯型酸解離性溶解抑制基爲佳。通式（al-0-2)中，R與上述爲相同之內容。 X2，與式（al-0-l)中之X1爲相同之內容。 Y2之2價之鍵結基，例如與前述式（aO-l)中之R2爲相同之內容。 -37- 201039064 Y2，以前述伸烷基、2價之脂肪族環式基或含有雑原子之2價之鍵結基爲佳。其中又以含有雜原子之2價之鍵結基爲佳，特別是以具有氧原子作爲雜原子之直鏈狀之基’ 例如含有酯鍵結之基爲特佳。其中又以則述_Α_〇·Β -或- A- C( = 0)-0-B-所表不之基爲佳，特別是以_(CH2)a-C( = 0)-0-(CH2)b-所表示之基爲佳。 a爲1〜5之整數，以1或2爲佳，以1爲最佳。 b爲1〜5之整數，以1或2爲佳，以1爲最佳。結構單位（a 1 )，更具體而言，例如下述通式（a 1 -1 )〜（al-4)所表示之結構單位等。(al — 0 — 1) (al — 0 — 2) [wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated group having a carbon number of 1 to 5, and X1 is an acid dissociable dissolution inhibiting group. 'Y2 is a divalent bond group, and X2 is an acid dissociable dissolution inhibitor group. In the formula (al-0-1), R is the same as R1 in the above formula (aO-Ι). X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and may be, for example, the above-described tertiary alkyl ester type acid dissociable dissolution inhibiting group or the awakening acid dissociating dissolution inhibiting group, and the like. The alkyl ester type acid dissociable dissolution inhibiting group is preferred. In the formula (al-0-2), R is the same as described above. X2 is the same as X1 in the formula (al-0-l). The two-valent bond group of Y2 is, for example, the same as R2 in the above formula (aO-1). -37- 201039064 Y2 is preferably an alkylene group, a divalent aliphatic ring group or a divalent bond group containing a ruthenium atom. Further, it is preferably a divalent bond group containing a hetero atom, and particularly a linear group having an oxygen atom as a hetero atom, for example, a group having an ester bond is particularly preferable. Among them, it is better to say that _Α_〇·Β -or- A- C( = 0)-0-B- is not the basis, especially _(CH2)aC( = 0)-0-( The base represented by CH2)b- is preferred. a is an integer of 1 to 5, preferably 1 or 2, and 1 is most preferred. b is an integer of 1 to 5, preferably 1 or 2, and 1 is most preferred. The structural unit (a 1 ), more specifically, for example, a structural unit represented by the following general formulae (a 1 -1 ) to (al-4).

n (al-1) (a 1-2) (a 1-3) (a1-4) [式中’ X’表示三級烷酯型酸解離性溶解抑制基，γ表示碳數1〜5之烷基，或脂肪族環式基；n表示〇〜3之整數；表示2價之鍵結基；R與前述爲相同之內容，Ri，、R2,表示各自獨立之氫原子或碳數1〜5之院基]。 -38- 201039064 前述式中，χ’爲與前述χ1中所例示之三級烷酯型酸解離性溶解抑制基爲相同之內容。 R1’、R2’、η、Y，分別與上述之「縮醛型酸解離性溶解抑制基」之説明中所列舉之通式（pi )中之R1’、R2’、η 、丫爲相同之內容。 Υ2，爲與上述通式（al-0-2)中之Υ2爲相同之內容。以下，將例示上述通式（a 1 - 1 )〜（a 1 _4 )所表示之 0 結構單位之具體例。以下之各式中，Ra，表示氫原子、甲基或三氟甲基。n (al-1) (a 1-2) (a 1-3) (a1-4) [wherein X' represents a tertiary alkyl ester type acid dissociable dissolution inhibiting group, and γ represents a carbon number of 1 to 5 An alkyl group, or an aliphatic cyclic group; n represents an integer of 〇~3; represents a divalent bond group; R is the same as defined above, and Ri, R2 represents an independent hydrogen atom or a carbon number of 1~ 5 yard base]. -38-201039064 In the above formula, χ' is the same as the tertiary alkyl ester type acid dissociable dissolution inhibiting group exemplified in the above χ1. R1', R2', η, and Y are the same as R1', R2', η, and 丫 in the general formula (pi) recited in the description of the "acetal type acid dissociable dissolution inhibiting group" described above. content. Υ2 is the same as Υ2 in the above formula (al-0-2). Hereinafter, specific examples of the 0 structural unit represented by the above general formula (a 1 - 1 ) to (a 1 _4 ) will be exemplified. In the following formulae, Ra represents a hydrogen atom, a methyl group or a trifluoromethyl group.

-39- 201039064 【化1 7】 Ra-f CH2_C"-39- 201039064 【化1 7】 Ra-f CH2_C"

RaRa

Ra *CH2—C-t0、 CH3Ra *CH2—C-t0, CH3

、ch3,ch3

ch2(ch2)2ch3Ch2(ch2)2ch3

RaRa

Ra CH2~~C— 〇、fel-1-9) Ra Ra C2H5Ra CH2~~C— 〇, fel-1-9) Ra Ra C2H5

-(-ch2-c-)- -^ch2-c-)- -(-ch2-c^- -|ch2-c-)- -^-ch2-c 〇=\ 0=4 0=4. 0=1 0=4 〇=\ A V 、· '一 v 〇-(-ch2-c-)- -^ch2-c-)- -(-ch2-c^- -|ch2-c-)- -^-ch2-c 〇=\ 0=4 0=4. 0 =1 0=4 〇=\ AV , · 'a v 〇

CH3 〇\/C2H5、0CH3 〇\/C2H5, 0

Ra Ra -CH2~c_Ra Ra -CH2~c_

RaRa

Ra Ra -ch2-c-)- -^-ch2-c-)- -^-c-c^-~(ch2-?-)- -(-ch2-c-}- -(-ch2-c^- 4 0=\ 0=A 0=A 、？，2H5、？。 Λ 。Ra Ra -ch2-c-)- -^-ch2-c-)- -^-cc^-~(ch2-?-)- -(-ch2-c-}- -(-ch2-c^- 4 0=\ 0=A 0=A , ?, 2H5, ?. Λ .

Ra oRa o

<5 C2H5 -40- 201039064 【化1 8<5 C2H5 -40- 201039064

RaI \ CH2—ό· 〇=ιRaI \ CH2—ό· 〇=ι

Ra Ra Ra -/-ch2—c-j- -/-ch2—c-^— -^-ch2—c-j—^ch2- CH 〇=l 〇=l I 〇 n C2H5 〇 O^JRa Ra Ra -/-ch2-c-j- -/-ch2-c-^- -^-ch2-c-j-^ch2- CH 〇=l 〇=l I 〇 n C2H5 〇 O^J

Ra—iRa-i

(al-1-22) Ra (al-1-23) (al-1-24) (al-1-25) (a1-1-26> ❹ ch3- 0=(al-1-22) Ra (al-1-23) (al-1-24) (al-1-25) (a1-1-26> ❹ ch3- 0=

(al-1-27)(al-1-27)

RaRa

(al-1-29) 【化1 9】 Ra R°(al-1-29) [Chem. 1 9] Ra R°

Ra -(CH2-C·)- -^CH2-C-)- _^CH2-C·)- -(cH2-C-)- -^CH2-C·}- _^ch2-C^--(ch2-c·)--(ch2-c 。气〇气 0=^ 〇气 οΑ 0=( 〇=\ 〇Jy ο ( ο 0=\ 0= ο ο οRa -(CH2-C·)- -^CH2-C-)- _^CH2-C·)- -(cH2-C-)- -^CH2-C·}- _^ch2-C^--( Ch2-c·)--(ch2-c. 〇气0=^ 〇气οΑ 0=( 〇=\ 〇Jy ο ( ο 0=\ 0= ο ο ο

〇 (al-2-1) (a 1-2-2) (βΙ-2-3) fel-2-4) Ra Ra Ra R* Ra〇 (al-2-1) (a 1-2-2) (βΙ-2-3) fel-2-4) Ra Ra Ra R* Ra

Ra Ra Ra Ra Ra Ra Ra Ra -(ch2-c-}- -(ch2-c)- -(ch2-c-)- -(ch2-c^- -(ch2-c-)- -^ch2-c·)- -(ch2-c-)- -(ch2-c-)- 〇4 〇4 〇4 — 〇4 〇=l V Λ ο Ο Λ r» λ Vv fel-2-9) fel-2-10)Ra Ra Ra Ra Ra Ra Ra Ra -(ch2-c-}- -(ch2-c)- -(ch2-c-)- -(ch2-c^- -(ch2-c-)- -^ch2- c·)- -(ch2-c-)- -(ch2-c-)- 〇4 〇4 〇4 — 〇4 〇=l V Λ ο Ο Λ r» λ Vv fel-2-9) fel-2 -10)

fel-2-12) (bl~2-13) (al-2-14) fel-2-15) fel-2-16) -41 - 201039064Fel-2-12) (bl~2-13) (al-2-14) fel-2-15) fel-2-16) -41 - 201039064

【化2 Ο】【化2 Ο】

-fcH2-C-)- -fCH2-C-j-和h才)· -f-CH^C-| ( CH3^C-^-。 n '〇 O h=0 ^=〇 ^=0-fcH2-C-)- -fCH2-C-j- and h ()) -f-CH^C-| ( CH3^C-^-. n '〇 O h=0 ^=〇 ^=0

O o h3c· fel-3-7)O o h3c· fel-3-7)

C2Hsiy HsC fel-3'8)C2Hsiy HsC fel-3'8)

C2H5·C2H5·

h3c-H3c-

fcl-3-10) fel-3-11)Fcl-3-10) fel-3-11)

RaRa

fel-3-13) fel-3-9)Fel-3-13) fel-3-9)

W-3-14) fel-3-15) fel-3-16)W-3-14) fel-3-15) fel-3-16)

Ra RaRa Ra

-42- 201039064 【化2 1-42- 201039064

Ra 卜 CH2—(p 十一(CH2-令 0=1 0=1 、〇 οRa Bu CH2—(p eleven (CH2-order 0=1 0=1, 〇 ο

Ra οRa ο

Ra [CH2-+寸〇人 .0 :0 ο: \ °Χ b 七 ο fel-3-19) fel-3-20) fel-3-21) fel-3-22) 【化2 2】 :0Ra [CH2-+ inch 〇人.0 :0 ο: \ °Χ b 七ο fel-3-19) fel-3-20) fel-3-21) fel-3-22) [chemical 2 2]: 0

FT Ra〇' 。人 P PFT Ra〇'. Person P P

Ra ~CH2 - —ΪΊΠ2 oRa ~CH2 - —ΪΊΠ2 o

Ra I XRa I X

Ra CH2^cH- -(ch2-c-U -fCH 0=Ra CH2^cH- -(ch2-c-U -fCH 0=

Ra2彳十 ·〇 o 0 0 0Ra2彳10 ·〇 o 0 0 0

PP

0= 0= 0= o o0= 0= 0= o o

=0 >=0 a 〇: 0= \ ， \。°Λ 0=<〇i0 ^ -b -b i0 "0 ，一 o_n«r、，-- --、 o fel-3-25) fel-3-26) Ra Ra 十 H2-0-A-々CH 〇4=0 >=0 a 〇: 0= \ , \. °Λ 0=<〇i0 ^ -b -b i0 "0 , an o_n«r, , --- --, o fel-3-25) fel-3-26) Ra Ra ten H2-0-A -々CH 〇4

Ra、〇 fel-3-27) fel-3-28) fel-3-29) fel-3-30) 0Ra, 〇 fel-3-27) fel-3-28) fel-3-29) fel-3-30) 0

=〇 y= 〇〇：Γ <X 0= o "3Θ fel-3-31) 0=〇 y= 〇〇:Γ <X 0= o "3Θ fel-3-31) 0

fel-3-32) -43- 201039064 【化2 3 -i1Fel-3-32) -43- 201039064 [Chemical 2 3 -i1

Ra icx(^CH〇^CH2〇\mwwRa icx(^CH〇^CH2〇\mww

QQ

〇 >=〇 0) Q O) o.〇 >=〇 0) Q O) o.

QQ

)Θ 治 Ό v fel~4~3) ^1-4-4) 4 5)备 1-4-6) fel-4_7)洫 1-4-8) fel-4-2) Ra Ra , Tx T T t Ra Ra (CH^ ^CH^-fcHj-ci)Θ治Ό v fel~4~3) ^1-4-4) 4 5) 1-4-6) fel-4_7)洫1-4-8) fel-4-2) Ra Ra , Tx TT t Ra Ra (CH^ ^CH^-fcHj-ci

0 00 0

oo

OO

o 0· 0 〇> ) o-o 0· 0 〇> ) o-

0° 穴0 Q 〇、 fel-4-9) ^l-4-Ιθί^ fel-4-*ll) fel-4-12) t) ^1-4-13) 61-4-14)0° hole 0 Q 〇, fel-4-9) ^l-4-Ιθί^ fel-4-*ll) fel-4-12) t) ^1-4-13) 61-4-14)

.0 ^1-4-15) 結構單位（al)，可單獨使用1種亦可，或將2種以上組合使用亦可。本發明中，特別是就解析性、光阻圖型之形狀等之微影蝕刻特性優良等觀點’結構單位（a 1厂’以具有由下述通式（a卜0-12)所表示之結構單位及下述通式（al-0-2) 所表示之結構單位所成群中所選擇之至少1種爲佳。【化2 4】.0 ^1-4-15) The structural unit (al) may be used singly or in combination of two or more. In the present invention, in particular, the lithographic etching characteristics such as the resolution and the shape of the resist pattern are excellent, and the structural unit (a factory has the following general formula (a, 0-12)). It is preferable that at least one selected from the group consisting of a structural unit and a structural unit represented by the following general formula (al-0-2). [Chemical 2 4]

201039064 [式中，R爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化烷基，R23爲烷基，R24 ’爲可與該R24鍵結之碳原子共同形成脂肪族多環式基之基，Y2爲2價之鍵結基，X2爲酸解離性溶解抑制基]。各式中，R、Y2、X2之説明爲與前述爲相同之內容。式（al-0-12)中，R23之烷基，爲與前述式（卜丨）〜 (1-9 )中之R14之烷基所列舉之烷基爲相同之內容，以異 0 丙基爲最佳。 R24爲可與該R24鍵結之碳原子共同形成脂肪族多環式基者，其例如與前述三級烷酯型酸解離性溶解抑制基中所列舉之脂肪族環式基中，爲多環式基之基爲相同之內容。式（al-0-l2 )所表示之結構單位之具體例如，前述式 (al-1-l)〜（al-1-15) 、（ al-1-26)〜（al-1-29)所表示之結構單位等。式（al-Ο-2 )所表示之結構單位，例如前述式（al 3 〇 )或（al-4)所表示之結構單位等，特別是以式（al_3) 所表示之結構單位爲佳。式（al-0-2 )所表示之結構單位，特別是以式中之γ2 爲前述- A-0-B-或-A-C( = 0)-0-B-所表示之基爲佳。該結構單位中，較佳之結構單位，例如下述通式（ al-3-Ol)所表示之結構單位；下述通式（al-3-〇2) 示之結構單位；下述通式（al-3-03)所表示之結構單位等 -45- 201039064 【化2 5】201039064 [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R23 is an alkyl group, and R24' is an aliphatic group which can bond with the carbon atom bonded to the R24. A group of a polycyclic group, Y2 is a divalent bond group, and X2 is an acid dissociable dissolution inhibiting group]. In the above formulas, the descriptions of R, Y2, and X2 are the same as described above. In the formula (al-0-12), the alkyl group of R23 is the same as the alkyl group exemplified for the alkyl group of R14 in the above formula (dipor) to (1-9), and is iso-propyl. For the best. R24 is an aliphatic polycyclic group which can form a carbon atom bonded to the R24, and is, for example, a polycyclic ring among the aliphatic cyclic groups exemplified in the above-mentioned tertiary alkyl ester type acid dissociable dissolution inhibiting group. The basis of the formula is the same content. Specific examples of the structural unit represented by the formula (al-0-l2) are, for example, the above formulas (al-1-l)~(al-1-15), (al-1-26)~(al-1-29) The structural unit represented, etc. The structural unit represented by the formula (al-Ο-2), for example, the structural unit represented by the above formula (al 3 〇 ) or (al-4), is particularly preferably a structural unit represented by the formula (al_3). The structural unit represented by the formula (al-0-2) is particularly preferably a group represented by the above-mentioned -A-0-B- or -A-C(=0)-0-B-. In the structural unit, a preferred structural unit is, for example, a structural unit represented by the following formula (al-3-Ol); a structural unit represented by the following formula (al-3-〇2); Al-3-03) The structural unit represented by -45- 201039064 [Chem. 2 5]

(a 1 - 3 - Ο 1 ) (式中，R、R14與前述爲相同之內容，R13爲氫原子或甲基，a爲1〜10之整數。）【化2 6】(a 1 - 3 - Ο 1 ) (wherein R and R14 are the same as defined above, R13 is a hydrogen atom or a methyl group, and a is an integer of 1 to 10.) [Chem. 2 6]

(a 1-3-02) (式中，R、R14與前述爲相同之內容，R13爲氫原子或甲基，a爲1〜10之整數，η’爲0〜3之整數。）【化2 7】(a 1-3-02) (wherein R and R14 are the same as those described above, R13 is a hydrogen atom or a methyl group, a is an integer of 1 to 10, and η' is an integer of 0 to 3.) 2 7]

Ο L 」n (a 1-3-03) [式中，R與前述爲相同之內容，Y2’及Y2”爲各自獨立之2 價之鍵結基，X’爲酸解離性溶解抑制基’ η爲0〜3之整數] -46- 201039064 式（al-3-Ol)〜（a卜3-02)中’ R13，以氫原子爲佳〇 a，以1〜8之整數爲佳’以1〜5之整數爲更佳，以i或 2爲最佳。 η’，以1或2爲佳，以2爲最佳。式（al -3 -0 1 )所表示之結構單位之具體例如，前述式 (al-3-25 )〜（al-3-26 )所表示之結構單位等。 0 式（al-3-02)所表示之結構單位之具體例如，前述式 (al-3-27)〜（al-3-28)所表示之結構單位等。式（al-3-03 )中’ Y2’、Y2”中之2價之鍵結基，爲與前述通式（al-3)中之Y2爲相同之內容。 Y2 ’，以具有取代基之2價之烴基爲佳，以直鏈狀之脂肪族烴基爲更佳，以直鏈狀之伸烷基爲最佳。其中又以碳數1〜5之直鏈狀之伸烷基爲佳，以伸甲基、伸乙基爲最佳〇〇 Y2”，以具有取代基之2價之烴基爲佳，以直鏈狀之脂肪族烴基爲更佳，以直鏈狀之伸烷基爲最佳。其中又以碳數1〜5之直鏈狀之伸烷基爲佳，以伸甲基、伸乙基爲最佳〇 X’中之酸解離性溶解抑制基，例如與前述爲相同之內容，以三級烷酯型酸解離性溶解抑制基爲佳，以上述（i )1價之脂肪族環式基的環骨架上具有三級碳原子之基爲更佳，其中又以前述通式（1-1)所表示之基爲佳。 η爲0〜3之整數，η以0〜2之整數爲佳，以0或1爲更佳 -47- 201039064 ，以1爲最佳。式（al-3-〇3)所表示之結構單位，以下述通式（al-3-03-1)或（a1·3 — 03 — 2)所表示之結構單位爲佳。其中又以式（al-3-〇3-l)所表不之結構單位爲佳’以前述式（ al-3-29)〜（a1·3-30)所表示之結構單位爲特佳。Ο L ′ n (a 1-3-03) [wherein R is the same as the above, Y2′ and Y2” are independent two-valent bond groups, and X′ is an acid dissociable dissolution inhibiting group. η is an integer of 0 to 3] -46- 201039064 In the formula (al-3-Ol)~(abu 3-02), 'R13, which is preferably a hydrogen atom, is preferably an integer of 1 to 8' An integer of 1 to 5 is more preferable, and i or 2 is the most preferable. η' is preferably 1 or 2, and 2 is optimal. The specific structural unit represented by the formula (al -3 -0 1 ) is, for example, , the structural unit represented by the above formula (al-3-25 ) to (al-3-26 ), etc. The specific structural unit represented by the formula (al-3-02) is, for example, the above formula (al-3- 27) The structural unit represented by ~(al-3-28), etc. The two-valent bond group in 'Y2' and Y2' in the formula (al-3-03) is the same as the above formula (al-3) Y2 is the same content. Y2' is preferably a divalent hydrocarbon group having a substituent, more preferably a linear aliphatic hydrocarbon group, and most preferably a linear alkyl group. Among them, a linear alkyl group having a carbon number of 1 to 5 is preferred, and a methyl group and an ethyl group are preferred as the 〇〇Y2", and a divalent hydrocarbon group having a substituent is preferred, and a linear chain is preferred. The aliphatic hydrocarbon group is more preferred, and the alkyl group is preferably a linear alkyl group. Among them, a linear alkyl group having a carbon number of 1 to 5 is preferred, and a methyl group and an ethyl group are most preferred. The acid dissociable dissolution inhibiting group in the oxime X', for example, the same as the above, preferably a tertiary alkyl ester type acid dissociable dissolution inhibiting group, and the above (i) monovalent aliphatic ring group More preferably, the group having a tertiary carbon atom in the ring skeleton is preferably a group represented by the above formula (1-1). η is an integer of 0 to 3, and η is preferably an integer of 0 to 2. Preferably, 0 or 1 is -47 to 201039064, and 1 is the best. The structural unit represented by the formula (al-3-〇3) is represented by the following formula (al-3-03-1) or (a1· 3 — 03 — 2) The structural unit represented is better. Among them, the structural unit represented by the formula (al-3-〇3-l) is better than the above formula (al-3-29)~(a1 · 3-30) The structural unit represented is particularly good.

【化2 8 I[2 2 I

〇=κ (h2c{〇=κ (h2c{

(a1—3 — 03-1) (al -3-03-2) [式中，r及R14分別與前述爲相同之內容’ R2()爲氫原子或甲基，a爲丨〜10之整數’ b爲1〜10之整數，1爲0〜3之整數]0 a以1〜5之整數爲佳，以1或2爲特佳。 b以1〜5之整數爲佳，以1或2爲特佳。 t以1〜3之整數爲佳，以1或2爲特佳。本發明中，特別是以至少具有2種結構單位（a 1 )爲佳。就提升良好之微影蝕刻特性之觀點，（A 1 )成份所具有之結構單位（a 1 )’以2〜4種爲佳，以2或3種爲更佳。 -48- 201039064 此時’該至少2種之中’至少1種爲，由前述通 al-0-12)所表示之結構單位及前述通式（al_〇_2)所之結構單位所成群中所選擇之至少1種爲佳。此時，該至少2種之結構單位（a i )，可僅由前式（al-0-12)所表示之結構單位及前述通式（al_〇_2 表示之結構單位所成群中所選擇者所構成亦可，或該構單位之至少1種，與不屬於該內容之結構單位（al ^ 組合亦可。可使用前述通式（al-〇-12)所表示之結構單位及通式（al-0-2 )所表示之結構單位所成群中所選出之3 種之組合，不屬於該等內容之結構單位（a 1 )，例如通式（al-Ι)之具體例所例示之包含式（al-1-l)〜 1-2) 、（al-1-7)〜（al-1-15)之下述通式（al_0_ 所表示之結構單位、前述通式（al -2 )所表示之結構、前述通式（al-4)所表示之結構單位等。〇前述通式（al-0-10)所表示之結構單位’特別是含前述式（al-1-l)〜式（ai_i-2)之下述通式（a1·1 )所表示之結構單位爲佳。式（表示述通 )所些結 )之前述 !少1 前述 (al-10 ) 單位以包 -101 -49- 201039064 【化2 9】(a1—3 — 03-1) (al -3-03-2) [wherein, r and R14 are respectively the same as described above. R 2 () is a hydrogen atom or a methyl group, and a is an integer of 丨 10 'b is an integer of 1 to 10, and 1 is an integer of 0 to 3] 0 a is preferably an integer of 1 to 5, and particularly preferably 1 or 2. b is preferably an integer of 1 to 5, and particularly preferably 1 or 2. t is preferably an integer of 1 to 3, and particularly preferably 1 or 2. In the present invention, it is particularly preferred to have at least two structural units (a 1 ). From the viewpoint of improving the fine lithographic etching characteristics, the structural unit (a 1 ) of the (A 1 ) component is preferably 2 to 4, more preferably 2 or 3. -48- 201039064 In this case, at least one of the at least two types is formed by the structural unit represented by the above-mentioned aal-0-12 and the structural unit of the above-mentioned general formula (al_〇_2). At least one selected from the group is preferred. In this case, the at least two structural units (ai) may be composed only of the structural unit represented by the former formula (al-0-12) and the structural unit represented by the above formula (al_〇_2). The selector may be configured or at least one of the structural units may be combined with a structural unit that does not belong to the content (al ^ may be used. The structural unit and formula represented by the above formula (al-〇-12) may be used. The combination of the three selected from the group of structural units represented by (al-0-2) does not belong to the structural unit of the content (a 1 ), for example, the specific example of the general formula (al-Ι) The structural formula represented by the formula (al-1-l) to 1-2), (al-1-7) to (al-1-15) (al_0_, the above-mentioned formula (al - 2) the structure shown, the structural unit represented by the above formula (al-4), etc. The structural unit represented by the above formula (al-0-10) particularly contains the above formula (al-1-l) The structural unit represented by the following formula (a1·1) of the formula (ai_i-2) is preferably the above formula: (Expression of the knot) of the above formula; less than 1 (al-10) unit is packaged -101 -49- 201039064 [Chem. 2 9]

RR

[式中，R與前述爲相同之內容，R25及R11爲分別獨立之碳數1〜5之直鏈狀之烷基，R2 4與前述爲相同之內容]。 (A 1 )成份中，結構單位（a 1 )之比例，相對於構成 (A1)成份之全結構單位，以1〇〜80莫耳％爲佳，以12〜 7 〇莫耳％爲更佳，以1 5〜5 0莫耳％爲最佳。於下限値以上時’作爲光阻組成物時可容易得到圖型，於上限値以下時可得到與其他結構單位之平衡。 (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。於此，含內酯之環式基係指，含有含-O-C(O)-構造之一個環（內酯環）的環式基。以內酯環作爲一個單位之環計數，僅爲內酯環之情形爲單環式基，尙具有其他環構造之情形，則無關其構造皆稱爲多環式基。結構單位（a2)之內酯環式基，於共聚物（A1)使用於光阻膜之形成之情形，可有效提高光阻膜對基盤之密著 -50- 201039064 性、提高與含有水之顯影液的親和性等。結構單位（a2 )，並未有特別限定，而可使用任意之單位。具體而言，含內醋之單環式基，例如4〜6員環內酯去除1個氫原子所得之基，例如β-丙內酯去除1個氫原子所得之基、r-丁內酯去除1個氫原子所得之基、δ-戊內酯去除1 個氫原子所得之基等。又，含內酯之多環式基，例如，具 0 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。結構單位（a2 )之例，更具體而言，例如’下述通式 (a2-l)〜（a2-5)所表示之結構單位等。 -51 - 201039064[In the formula, R is the same as described above, and R25 and R11 are each a linear alkyl group having a carbon number of 1 to 5, respectively, and R2 4 is the same as described above]. In the component (A 1 ), the ratio of the structural unit (a 1 ) is preferably from 1 to 80 mol%, more preferably from 12 to 7 mol%, based on the total structural unit constituting the component (A1). , with 1 5~5 0 mol% is the best. When the temperature is less than or equal to the lower limit ’, the pattern can be easily obtained as a photoresist composition, and the balance with other structural units can be obtained when the upper limit is less than or equal to 。. (Structural unit (a2)) The structural unit (a2) is a structural unit derived from an acrylate containing a lactone-containing cyclic group. Here, the lactone-containing cyclic group means a cyclic group containing a ring (lactone ring) having a -O-C(O)-structure. The ring count of the lactone ring as a unit is counted as a monocyclic group only for the lactone ring, and the other ring structure is the case of the ruthenium, and the structure is called a polycyclic group irrespective of its structure. The lactone ring group of the structural unit (a2), when the copolymer (A1) is used for the formation of the photoresist film, can effectively improve the adhesion of the photoresist film to the substrate - 50- 201039064, improve and contain water Affinity of the developer, etc. The structural unit (a2) is not particularly limited, and any unit can be used. Specifically, a monocyclic group containing a vinegar, for example, a group obtained by removing one hydrogen atom from 4 to 6 membered ring lactones, for example, a group obtained by removing one hydrogen atom from β-propiolactone, r-butyrolactone A group obtained by removing one hydrogen atom and a group obtained by removing one hydrogen atom from δ-valerolactone. Further, the polycyclic group having a lactone is, for example, a group obtained by removing a hydrogen atom from a dicycloalkane having a lactone ring, a tricycloalkane or a tetracycloalkane. The structural unit (a2) is more specifically, for example, a structural unit represented by the following general formulae (a2-l) to (a2-5). -51 - 201039064

[式中，R爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化烷基，R’分別獨立表示氫原子、碳數1〜5之院基、㈤數1〜5 之院氧基或_C〇〇R”，R”爲氫原子或烷基，R29爲單鍵或2 價之鍵結基，s”爲〇或1〜2之整數，A”可含有氧原子或硫原子之‘碳數1〜5之伸烷基、氧原子或硫原子，111爲〇或1之整數]。爲與前述結構單位乙基、丙基 ' η - 丁通式（a2-l )〜（a2-5 )中之R (al)中之R爲相同之內容。 R，之碳數1〜5之烷基’例如甲棊 -52- 201039064 基、tert-丁基等。 R’之碳數1〜5之烷氧基，例如甲氧基、乙氧基、η-丙氧基、iso-丙氧基、η-丁氧基、tert-丁氧基等。 R’，於考慮工業上容易取得等觀點，以氫原子爲佳。 R”爲直鏈狀或分支鏈狀之烷基之情形時，以碳數1〜 1〇爲佳，以碳數1〜5爲更佳。 R”爲環狀之烷基之情形時，以碳數3〜1 5爲佳，以碳 0 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取代亦可，未取代亦可之單環鏈烷、二環鏈烷、三環鏈烷、四環鏈烷等之多環鏈烷去除1個以上之氫原子所得之基等。具體而言，爲由環戊烷、環己烷等之單環鏈烷，或金剛烷、原菠烷、異菠烷、三環癸烷、四環十二烷等多環鏈烷去除1個以上之氫原子所得之基等〇 A”，例如以碳數1〜5之伸烷基或-〇-爲佳，以碳數1〜〇 5之伸烷基爲更佳，以伸甲基爲最佳。 R2 9爲單鍵或2價之鍵結基。2價之鍵結基’爲與前述通式（al-0-2)中之Y2所説明之2價之鍵結基爲相同之內容 ’其中又以，伸烷基、酯鍵結（-c( = 〇)-〇-) ’或該些之組合爲佳。R29中作爲2價之鍵結基的伸烷基，以直鏈狀或分支鏈狀之伸烷基爲更佳。具體而言’前述Y2中之A中脂肪族烴基所列舉之直鏈狀之伸烷基、分支鏈狀之伸烷基爲相同之內容。 s”以1〜2之整數爲佳。 -53- 201039064 以下爲前述通式（a2-1 )〜（a2-5 )所表示之結構單位之具體例示，。以下之各式中，Ra，表示氫原子、甲基或三氟甲基。【化3 1】[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and R' each independently represents a hydrogen atom, a hospital group having a carbon number of 1 to 5, and (5) a number of 1 to 5 Alkoxy or _C〇〇R", R" is a hydrogen atom or an alkyl group, R29 is a single bond or a divalent bond group, s" is an integer of 〇 or 1-2, and A" may contain an oxygen atom Or a sulfur atom having a carbon number of 1 to 5, an alkyl group, an oxygen atom or a sulfur atom, and 111 is an integer of 1 or 5. It is the same as R in the above structural unit ethyl, propyl ' η -butyl R (al) in the general formula (a2-l) to (a2-5). R, an alkyl group having 1 to 5 carbon atoms, such as formazan-52-201039064-based, tert-butyl, and the like. The alkoxy group having 1 to 5 carbon atoms of R', for example, a methoxy group, an ethoxy group, a η-propoxy group, an iso-propoxy group, an η-butoxy group, a tert-butoxy group or the like. R' is preferably a hydrogen atom from the viewpoint of easy industrial availability. When R" is a linear or branched chain alkyl group, it is preferably a carbon number of 1 to 1 Å, more preferably a carbon number of 1 to 5. When R" is a cyclic alkyl group, The carbon number is preferably from 3 to 15 and is preferably from 0 to 12 carbon atoms, preferably from 5 to 10 carbon atoms. Specifically, for example, a fluorine atom or a fluorinated alkyl group may be substituted, and an unsubstituted polycyclic alkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane may be removed. The base obtained by more than one hydrogen atom, and the like. Specifically, it is one monocyclic alkane such as cyclopentane or cyclohexane, or one polycyclic alkane such as adamantane, raw spinane, isopentane, tricyclodecane or tetracyclododecane. The radical 〇A" obtained by the above hydrogen atom is preferably, for example, an alkylene group or a hydrazine group having a carbon number of 1 to 5, more preferably an alkylene group having a carbon number of 1 to 5%, and a methyl group. Preferably, R2 9 is a single bond or a divalent bond group. The bond moiety of the 2 valence is the same as the bond of 2 valent as described in Y2 of the above formula (al-0-2). The content 'in this case, an alkyl group, an ester bond (-c(= 〇)-〇-)' or a combination thereof is preferred. The alkyl group as a divalent bond group in R29 is linear. The alkyl group having a branched or branched chain shape is more preferable. Specifically, the linear alkyl group and the branched chain alkyl group as exemplified in the aliphatic hydrocarbon group in the above Y2 are the same. "It is better to use an integer of 1 to 2. -53- 201039064 The following is a specific example of the structural unit represented by the above formula (a2-1) to (a2-5). In the following formulae, Ra represents a hydrogen atom, a methyl group or a trifluoromethyl group. [化3 1]

-54- 201039064 【化3 2-54- 201039064

Id:亇冬七A o=j o=| 〇=| o=| 〇=( 〇H 叫 A o 〇Id: 亇冬七 A o=j o=| 〇=| o=| 〇=( 〇H is called A o 〇

O O 0 〇 I 〇 ^ °VO O 0 〇 I 〇 ^ °V

q a r … 〇 o 〇妲 2-2-1) ^2-2-2) ^2-2-3) ^2-2-4) ^2-2-5) ^2-2-6) ^2-2-7) °-( oH °-Qar ... 〇o 〇妲2-2-1) ^2-2-2) ^2-2-3) ^2-2-4) ^2-2-5) ^2-2-6) ^2- 2-7) °-( oH °-

鉍2-2-8) 62-2-9) o ^2-2-10) &2-2-11)铋2-2-8) 62-2-9) o ^2-2-10) & 2-2-11)

(^2-2-12)洫 2-2-13) (^2-2-14) fe2-2-15) (a2-2-16) 62-2-17) 【化3 3】(^2-2-12)洫 2-2-13) (^2-2-14) fe2-2-15) (a2-2-16) 62-2-17) [Chemical 3 3]

-55- 201039064 【化3 4 1-55- 201039064 【化3 4 1

fe2-4-ll〉 ^2-4-12) 【化3 5】Fe2-4-ll〉 ^2-4-12) 【化3 5】

Ra Ra Ra R«七(^个j彳七j丨七〇i 〇ί H3C0°1 1Ra Ra Ra R«七(^个j彳七j丨七〇i 〇ί H3C0°1 1

u 0 '〇，0 s〇^° 、广〇 ^2-5-1) ^2-5-2) ^2-5-3) ^2-5-4)u 0 '〇,0 s〇^° ,广〇 ^2-5-1) ^2-5-2) ^2-5-3) ^2-5-4)

fe2—5—5) fe2_5-6) (A 1 )成份中，結構單位（a2 ) ’可單獨使用1種亦可，或將2種以上組合使用亦可° -56- 201039064 結構單位（a2)，以由前述通式（a2-l)〜（a2-5) 所表示之結構單位所成群所選擇之至少1種爲佳，以由通式（a2-l)〜（a2-3)所表示之結構單位所成群所選出之至少1種爲更佳。其中又以使用由化學式（a2-l-l )、（ a2-2-l) 、（a2-2-7) 、（a2-3-l)及（a2-3-5)所表示之結構單位所成群所選擇之至少1種爲佳。 (A 1 )成份中之結構單位（a2 )之比例，就使用含有 0 該（A 1 )成份之正型光阻組成物所形成之光阻膜對基板等之支撐體的密著性、與顯影液之親和性優良等觀點，相對於構成（A 1 )成份之全結構單位，以1〜5 0莫耳％以上爲佳’以5〜5 0莫耳％爲較佳，以1 〇〜4 5莫耳％爲更佳。又’ （A 1 )成份中，就各種微影蝕刻特性優良之觀點 ’前述結構單位（aO-Ι )、前述結構單位（aO-2 )，及結構單位（a2 )之合計比例（不具有結構單位（a2 )之情形時’爲結構單位（a〇-l )及（a0_2 )之合計比例），相對〇於構成（A1 )成份之全結構單位，以30〜85莫耳％爲佳， 3 5〜8 5莫耳％爲更佳，以3 5〜8 2莫耳％爲最佳。於上述範圍內時’可使MEF、CDU、圖型形狀達到更佳狀態。 (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)成份具有結構單位（a3)時，可提高（a)成份之親水性’提高與顯影液之親和性，提高曝光部之鹼溶 -57- 201039064 解性，而有助於提高解析性。極性基例如’羥基、氰基、羧基、烷基之氫原子的一部份被氟原子所取代之羥烷基等，特別是以羥基爲佳。脂肪族烴基，例如碳數1〜10之直鏈狀或分支鏈狀之烴基（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，被多數提案之物質中適當選擇使用。該多環式基之碳數以7〜30爲佳。其中又以含有含羥基、氰基 '羧基，或烷基之氫原子的一部份被氟原子所取代之羥烷基的脂肪族多環式基的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、四環鏈烷等去除2個以上之氫原子所得之基等。具體而言，由金剛烷、原菠烷、異菠烷、三環癸烷、四環十二烷等之多環鏈烷去除2個以上之氫原子所得之基等。該些多環式基之中，又以金剛烷去除2個以上之氫原子所得之基、原菠烷去除2個以上之氫原子所得之基、四環十二烷去除2個以上之氫原子所得之基於工業上爲佳。結構單位（a3 )中，含有極性基之脂肪族烴基中之烴基爲碳數1〜10之直鏈狀或分支鏈狀之烴基時，以丙烯酸之羥基乙基酯所衍生之結構單位爲佳，該烴基爲多環式基時，以下述式（a3-l )所表示之結構單位、（a3-2 )所表示之結構單位、（a3 -3 )所表示之結構單位爲較佳之例示 -58- 201039064 【化3 6】Fe2—5—5) fe2_5-6) In the (A 1 ) component, the structural unit (a2 ) ' may be used alone or in combination of two or more. -56- 201039064 Structural unit (a2) It is preferable that at least one selected from the group consisting of the structural units represented by the above formulas (a2-l) to (a2-5) is used, and the formula (a2-l) to (a2-3) It is more preferable that at least one selected from the group of structural units indicated is selected. Among them, the structural units represented by the chemical formulas (a2-ll), (a2-2-l), (a2-2-7), (a2-3-l), and (a2-3-5) are used. At least one selected by the group is preferred. The ratio of the structural unit (a2) in the component (A1) is the adhesion of the photoresist film formed of the positive-type photoresist composition containing the (A1) component to the support of the substrate or the like. The viewpoint of the affinity of the developer is excellent, and the total structural unit of the component (A 1 ) is preferably 1 to 50 mol% or more, preferably 5 to 50 mol%, and 1 〇. 4 5 moles is better. Further, in the '(A1) component, the total ratio of the above-mentioned structural unit (aO-Ι), the above-mentioned structural unit (aO-2), and the structural unit (a2) is excellent in various lithographic etching characteristics (there is no structure) In the case of the unit (a2), 'the total ratio of the structural units (a〇-l) and (a0_2)) is preferably 30 to 85 mol%, which is more than the total structural unit constituting the component (A1), 3 5 to 8 5 mol% is better, with 3 5 to 8 2 mol% is the best. When it is within the above range, the MEF, CDU, and pattern shape can be made better. (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) has a structural unit (a3), the hydrophilicity of the component (a) can be improved, the affinity with the developer is improved, and the alkali solubility of the exposed portion is improved, which contributes to the improvement of the resolution. . The polar group is, for example, a hydroxy group such as a hydroxyl group, a cyano group, a carboxyl group or a hydrogen atom of an alkyl group, and a hydroxyalkyl group substituted with a fluorine atom, and particularly preferably a hydroxyl group. The aliphatic hydrocarbon group is, for example, a linear or branched hydrocarbon group (preferably an alkylene group) having a carbon number of 1 to 10, or a polycyclic aliphatic hydrocarbon group (polycyclic group) or the like. The polycyclic group may be, for example, a resin for use in an ArF excimer laser photoresist composition, and is appropriately selected from most of the proposed materials. The number of carbon atoms of the polycyclic group is preferably from 7 to 30. Further, a structural unit derived from an aliphatic polycyclic acrylate having a hydroxyl group, a cyano 'carboxy group, or a hydroxyalkyl group in which a part of a hydrogen atom of an 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 dicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, a group obtained by removing two or more hydrogen atoms from a polycyclic alkane such as adamantane, prorotane, isopentane, tricyclodecane or tetracyclododecane. Among these polycyclic groups, a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from raw spinel, and a tetracyclododecane removing two or more hydrogen atoms. The results obtained are based on industry. 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, the structural unit derived from the hydroxyethyl acrylate is preferred. When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit represented by (a3-2), and the structural unit represented by (a3 - 3) are preferably exemplified -58 - 201039064 [Chem. 3 6]

(CN)k (a3-2) (a3-1) (CH2),(CN)k (a3-2) (a3-1) (CH2),

’CsF2S+i OH (a3-3) [式中，R與前述爲相同之內容’ j爲1〜3之整數’ k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。] 式（a3-l)中，j以1或2爲佳’以1爲更佳。j爲2之情形時，以經基鍵結於金剛院基之3位與5位者爲佳。j爲1之情形時’以羥基鍵結於金剛烷基之3位者爲佳。 j以1爲佳，特別是羥基鍵結於金剛烷基之3位者爲佳式（a3-2 )中，k以1爲佳。以氰基鍵結於原菠烷基之 5位或6位者爲佳。式（a3-3)中，t’以1爲佳。1以1爲佳。s以1爲佳。該些以丙稀酸之竣基末端鍵結2_原疲院基或3 -原疲院基者爲佳。氟化烷醇爲鍵結於原菠烷基之5或6位者爲佳。結構單位（a 3 )，可單獨使用1種亦可，或將2種以上組合使用亦可。 (A 1 )成份中之結構單位（a3 )之比例，相對於構成 -59- 201039064 (A1)成份之全結構單位’以5〜5〇莫耳％爲佳，以5〜40 莫耳。/〇爲更佳，以5〜2 5莫耳％爲最佳。 (其他結構單位）共聚物（A1)，於不損本發明之効果之範圍，可含有上述結構單位（al )〜（a3 )以外之其他結構單位（以下，亦稱爲結構單位（a4))。結構單位（a4) ’只要爲未分類爲上述之結構單位（ a 1 )〜（a3 )之其他結構單位時，則並未有特別之限定，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位。結構單位（a4 )，例如以含有非酸解離性之脂肪族多環式基之丙烯酸酯所衍生之結構單位等爲佳。該多環式基，例如，可例示與前述之結構單位（a 1 )之情形所例示者爲相同之內容，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）等之光阻組成物的樹月旨成份所使用之以往已知之多數之結構單位。特別是由三環癸基、金剛烷基、四烷十二烷基、異疲烷基、原菠烷基所選出之至少1種時，就工業上容易取得等觀點而言爲較佳。該些多環式基’可具有碳數1〜5之直鏈狀或分支鍵狀之院基作爲取代基。結構單位（a4 )，具體而言’例如’可例示如下述通式（a4-l)〜（a4-5)之構造者。 -60 - 201039064 【化3 7】'CsF2S+i OH (a3-3) [wherein R is the same as the above, 'j is an integer of 1 to 3' k is an integer of 1 to 3 't' is an integer of 1 to 3, and 1 is 1 An integer of ~5 's is an integer from 1 to 3. In the formula (a3-l), j is preferably 1 or 2, and more preferably 1 is used. When j is 2, it is better to use 3 and 5 digits of the base of the King Kong. When j is 1, it is preferred that the hydroxy group is bonded to the adamantyl group. Preferably, j is 1 or, in particular, the hydroxy group bonded to the adamantyl group is preferably (a3-2), and k is preferably 1. It is preferred that the cyano group is bonded to the 5- or 6-position of the original spinnyl group. In the formula (a3-3), t' is preferably 1. 1 is better than 1. s is better than 1. It is preferred that the thiol end bond of the acrylic acid is 2_the original tired base or the 3 - the original tired base. The fluorinated alkanol is preferably bonded to the 5 or 6 position of the original spinnyl group. The structural unit (a 3 ) may be used singly or in combination of two or more. The ratio of the structural unit (a3) in the component (A1) is preferably 5 to 5 mol%, and 5 to 40 mol%, relative to the total structural unit constituting the component of -59-201039064 (A1). /〇 is better, with 5~2 5 m% being the best. (Other structural unit) The copolymer (A1) may contain other structural units other than the above structural units (al) to (a3) insofar as the effects of the present invention are not impaired (hereinafter, also referred to as structural unit (a4)) . The structural unit (a4) 'is not particularly limited as long as it is other structural units not classified into the above structural units (a 1 ) to (a3), and can be used for ArF excimer laser, KrF excimer A plurality of conventionally known structural units used for resistive resins such as lasers (preferably for ArF excimer lasers). The structural unit (a4) is preferably, for example, a structural unit derived from an acrylate having a non-acid dissociable aliphatic polycyclic group. The polycyclic group may be, for example, the same as those exemplified in the case of the structural unit (a 1 ) described above, and may be used for ArF excimer laser or KrF excimer laser (preferably ArF). A conventionally known structural unit used for the composition of the photoresist composition of a photoresist composition such as an excimer laser. In particular, when at least one selected from the group consisting of a tricyclic fluorenyl group, an adamantyl group, a tetradecyldodecyl group, an iso-l-alkyl group, and a linalyl group is preferable, it is preferable from the viewpoint of industrial availability. These polycyclic bases may have a linear or branched bond group having a carbon number of 1 to 5 as a substituent. The structural unit (a4), specifically, 'for example', is exemplified by the following formula (a4-1) to (a4-5). -60 - 201039064 [Chem. 3 7]

(a4-1) [式中，R與前述爲相同之內容] 〇 ( A1 )成份中含有該結構單位（a4 )之情形，結構單位（a4 )之比例’相對於構成（A 1 )成份之全結構單位之合計，以1〜3 0莫耳°/。爲佳，以1 0〜2 〇莫耳％爲更佳。 (A1)成份’以具有結構單位（a〇-l)，及（aO-2) 之共聚物爲佳。該共聚物’例如，由上述結構單位（a-1 )、（aO-2 )，及（al )所形成之共聚物、結構單位（a0_ 1 ) 、（ aO-2 )，及（a3 )所形成之共聚物、結構單位（ a0_l ) 、（ aO-2 ) 、（ al )及（a3 )所形成之共聚物、結〇構單位（a〇-l) 、（aO-2) 、（ai) 、（a2)及（a3)所形成之共聚物等。本發明中，特別是該些共聚物中，結構單位（al)以具有由前述通式（al-0-12)所表示之結構單位及通式（ a 1 - 0 - 2 )所表示之結構單位所成群所選擇之至少1種爲佳。又’上述共聚物’如上所述般，以至少具有2種結構單位（a 1 )爲佳，該至少2種之中，至少1種爲，由前述通式（a卜0-12)所表示之結構單位及通式（al_〇_2)所表示之結構單位所成群中所選擇之結構單位爲佳。 -61 - 201039064 (A1)成份之質量平均分子量（Mw)(凝膠滲透色層分析法之聚苯乙烯換算基準），並未有特別限定，以 2000〜50000爲佳，以3000〜30000爲更佳，以5000〜 2 0 0 0 0爲最佳。小於該範圍之上限時，作爲光阻使用時對光阻溶劑具有充分之溶解性，大於該範圍之下限時，可得到良好之耐乾蝕刻性或光阻圖型截面形狀。又分散度（Mw/Mn)以1_0〜5.0爲佳，以1.0〜3.0爲更佳，以1.2〜2_5爲最佳。又，Μη表7Γ：數平均分子量。 (A )成份中，（A1 )成份，可單獨使用1種，或將2 種以上合倂使用亦可。 2種以上合倂使用之情形，可容易進行聚合物之合成，也可得到良好之微影蝕刻特性。此時，2種以上之（A 1 )成份，以具有相互不同之結構單位（a 1 )爲佳。又，該2種以上之（A1)成份之中，至少1種爲，由前述通式（al-0-12)所表示之結構單位及前述通式（al-0-2 )所表示之結構單位所成群中所選擇之至少1種爲佳。此時，該2種以上之（A 1 )成份所具有之相互不同之結構單位（al )，可僅由前述通式（al-0-12 )所表示之結構單位及前述通式（al-0-2 )所表示之結構單位所成群中所選擇者所構成亦可，或該些結構單位之至少1種，與不屬於該些內容之結構單位（al)之組合亦可。 (A )成份中之（A1 )成份之比例，相對於（A )成份之總質量，以2 5質量％以上爲佳，以5 0質量％爲較佳’ 以7 5質量％爲更佳，亦可爲1 〇〇質量％。該比例爲2 5質量％ -62- 201039064 以上時，可提高微影蝕刻特性等之効果。 (A 1 )成份，可將衍生各結構單位之單體，例如藉由使用偶氮二異丁腈（AIBN)等自由基聚合起始劑依公知之自由基聚合等進行聚合予以製得。又’ （A1 )成份中’於上述聚合之際，例如可倂用 HS-CH2-CH2-CH2-C(CF3)2-OH等鏈移轉劑，於末端導入 -C(CF3)2_〇H基。如此’院基之氫原子的一部份導入有氟 0 原子所取代之羥烷基所得之共聚物時，可有效降低顯影缺陷’或LER (線路邊緣凹凸：線路側壁具有不均勻的凹凸 )° 各結構單位所衍生之單體，可使用市售之物質，或利用公知之方法合成亦可。例如衍生結構單位（a0-1 )之單體，例如下述通式（ϊ )所表示之化合物（以下，亦稱爲化合物（I ))。【化3 8】 Ο 0(a4-1) [wherein R is the same as the above] The case where the structural unit (a4) is contained in the component (A1), and the ratio of the structural unit (a4) is relative to the component (A1) The total of the total structural units is 1 to 3 0 mol /. It is better to use 1 0~2 〇mol% as better. The (A1) component ' is preferably a copolymer having a structural unit (a〇-l) and (aO-2). The copolymer 'for example, a copolymer formed from the above structural units (a-1), (aO-2), and (al), structural units (a0-1), (aO-2), and (a3) Copolymer, structural unit (a0_l), (aO-2), (al) and (a3) formed copolymer, knot structure unit (a〇-l), (aO-2), (ai) , a copolymer formed by (a2) and (a3), and the like. In the present invention, particularly in the copolymers, the structural unit (al) has a structure represented by the structural formula represented by the above formula (al-0-12) and a structure represented by the formula (a 1 - 0 - 2 ) It is preferred that at least one of the units is selected in groups. Further, as described above, the above-mentioned copolymer is preferably at least two structural units (a 1 ), and at least one of the at least two is represented by the above formula (a). The structural unit selected from the structural unit and the structural unit represented by the general formula (al_〇_2) is preferably selected. -61 - 201039064 (A1) The mass average molecular weight (Mw) of the component (polystyrene conversion standard for gel permeation chromatography) is not particularly limited, preferably 2000 to 50000, and 3000 to 30000. Good, with 5000~2 0 0 0 is the best. When it is less than the upper limit of the range, it is sufficiently soluble in the resist solvent when used as a photoresist, and when it is larger than the lower limit of the range, a good dry etching resistance or a resist pattern cross-sectional shape can be obtained. Further, the degree of dispersion (Mw/Mn) is preferably 1_0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2_5. Further, Μη Table 7Γ: number average molecular weight. In the component (A), the component (A1) may be used singly or in combination of two or more. When two or more types are used together, the synthesis of the polymer can be easily performed, and good lithographic etching characteristics can be obtained. In this case, two or more kinds of (A 1 ) components are preferably different from each other (a 1 ). Further, at least one of the two or more (A1) components is a structural unit represented by the above formula (al-0-12) and a structure represented by the above formula (al-0-2). It is preferred that at least one selected from the group is a group. In this case, the structural units (al) which are different from each other in the two or more (A 1 ) components may be only the structural unit represented by the above formula (al-0-12) and the above formula (al- 0-2) The selected structural unit may be formed by a selected group, or at least one of the structural units may be combined with a structural unit (al) not belonging to the content. The ratio of the component (A1) in the component (A) is preferably 25 mass% or more, and preferably 50 mass%, more preferably 75 mass%, based on the total mass of the component (A). It can also be 1% by mass. When the ratio is 25 mass% -62 to 201039064 or more, the effect of the lithographic etching characteristics and the like can be improved. The component (A 1 ) can be obtained by polymerizing a monomer derived from each structural unit, for example, by radical polymerization or the like using a radical polymerization initiator such as azobisisobutyronitrile (AIBN). In the '(A1) component', at the time of the above polymerization, for example, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH can be used, and -C(CF3)2_〇 is introduced at the end. H base. When a copolymer of a hydroxyalkyl group substituted with a fluorine atom is introduced into a part of the hydrogen atom of the hospital base, the development defect 'or LER' (line edge unevenness: unevenness of the side wall of the line) can be effectively reduced. The monomer derived from each structural unit may be a commercially available one or may be synthesized by a known method. For example, a monomer derived from the structural unit (a0-1), for example, a compound represented by the following formula (ϊ) (hereinafter also referred to as a compound (I)). [化3 8] Ο 0

[式（I)中，R1〜R3分別與前述爲相同之內容]。該化合物（I )之製造方法並未有特別限定，其可利用公知之方法製造。例如，於鹼之存在下，於下述通式（ X-1)所表示之化合物（X-1 )溶解於反應溶劑所得之溶液中，添加下述通式（Χ-2 )所表示之化合物（Χ-2 )，使其進行反應結果，得上述化合物（I )。 -63- 201039064 鹼，例如氫化鈉、K2C〇3、Cs2C〇3等之無機鹼；三乙胺、4-二甲基胺基吡啶（DM AP )、吡啶等之有機鹼等。縮合劑，例如乙基二異丙基胺基碳二醯亞胺（EDCI )鹽酸鹽、二環己基羧醯亞胺（DCC )、二異丙基碳二醯亞胺、碳二咪唑等之碳二醯亞胺試劑或四乙基焦磷酸鹽、苯倂三唑-N-羥基三二甲基胺基鎸六氟磷化物鹽（Bop試劑）等。又，必要時也可以使用酸。酸，可使用脫水縮合等通常所使用之物質，具體而言，例如鹽酸、硫酸、磷酸等之無機酸類，或甲烷磺酸、三氟甲烷磺酸、苯磺酸、P-甲苯磺酸等之有機酸類等。該些可單獨使用亦可，或將2種類以上組合使用亦可。【化3 9】 Ο 0 R\/r2 \[In the formula (I), R1 to R3 are the same as those described above]. The method for producing the compound (I) is not particularly limited, and it can be produced by a known method. For example, a compound represented by the following formula (Χ-2) is added to a solution obtained by dissolving the compound (X-1) represented by the following formula (X-1) in a reaction solvent in the presence of a base. (Χ-2), the result of the reaction was carried out to obtain the above compound (I). -63- 201039064 A base such as an inorganic base such as sodium hydride, K2C〇3 or Cs2C〇3; an organic base such as triethylamine, 4-dimethylaminopyridine (DMAP) or pyridine. a condensing agent such as ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride, dicyclohexylcarboximine (DCC), diisopropylcarbodiimide, carbodiimidazole or the like A carbodiimide reagent or a tetraethyl pyrophosphate, a benzotriazole-N-hydroxytrimethylamine sulfonium hexafluorophosphide salt (Bop reagent) or the like. Also, acid can be used if necessary. As the acid, a substance which is usually used, such as dehydration condensation, can be used, and specifically, an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or P-toluenesulfonic acid or the like can be used. Organic acids, etc. These may be used singly or in combination of two or more types. [化3 9] Ο 0 R\/r2 \

、广 O’ '0H, wide O’ '0H

R3-〇H (X - 1 ) (X— 2 ) 本發明之光阻組成物中，（A )成份，可含有不屬於前述（A 1 )成份，經由酸之作用而增大對鹼顯影液之溶解性的基材成份（以下，亦稱爲（A2 )成份）。 (A2 )成份，並未有特別限定，其可任意地選擇使用作爲化學増幅型正型光阻組成物用之基材成份的以往已知之多數成份（例如ArF準分子雷射用、KrF準分子雷射用（較佳爲ArF準分子雷射用）等之基礎樹脂）。例如ArF準分子雷射用之基礎樹脂，爲具有前述結構單位（a 1 )爲必要 -64- 201039064 之結構單位，再具有任意之前述結構單位（a2 )〜（a4 ) 的樹脂。 (A2 )成份，可單獨使用1種亦可’或將2種以上組合使用亦可。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作調整即可。 ◎ < ( B )成份〉 (B)成份，並未有特別限定，其可使用目前爲止被提案作爲化學増幅型光阻用之酸產生劑的成份。該些酸產生劑，目前爲止，已知例如碘鑰鹽或锍鹽等之鎗鹽系酸產生劑、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）重氮甲烷類等之重氮甲烷系酸產生劑、硝基苄磺酸酯系酸產生劑、亞胺基磺酸酯系酸產生劑、二颯系酸產生劑等多種成份。 Q 鑰鹽系酸產生劑，例如可使用下述通式（b-1 )或（b- 2 )所表示之化合物。【化4 0】R3-〇H (X - 1 ) (X-2) In the photoresist composition of the present invention, the component (A) may contain a component which does not belong to the above (A 1 ) and is increased by an action of an acid to the alkali developer The soluble substrate component (hereinafter also referred to as (A2) component). The component (A2) is not particularly limited, and any of the conventionally known components (for example, ArF excimer laser, KrF excimer) which are used as a substrate component for a chemical smectic positive resist composition can be arbitrarily selected and used. A base resin for lasers (preferably for ArF excimer lasers). For example, the base resin for ArF quasi-mineral laser is a resin having a structural unit of the above-mentioned structural unit (a 1 ) of -64 to 201039064 and further having any of the above structural units (a2) to (a4). The component (A2) 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. ◎ < (B) Ingredient (B) The composition is not particularly limited, and a component which has been proposed as an acid generator for a chemical-type resist can be used. These acid generators have heretofore known, for example, a gun salt acid generator such as an iodine salt or a phosphonium salt, an oxime sulfonate acid generator, a dialkyl group or a bisarylsulfonyldiazomethane. , a diazomethane acid generator such as poly(disulfonyl)diazomethane, a nitrobenzylsulfonate acid generator, an imidosulfonate acid generator, a diterpene acid generator And many other ingredients. As the Q-key salt-based acid generator, for example, a compound represented by the following formula (b-1) or (b-2) can be used. [化4 0]

1} ^>l+ R4"S〇3 ... (b-2) [式中，R1”〜R3”，R5”〜R6，，，分別獨立表示芳基或烷基；式（b-Ι )中之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；R4”，表示可具有取代基之院基、_化院基、芳基，或燦基；R1’’〜R3，，中之至少1個 -65- 201039064 表示芳基，R5，，〜R6，，中之至少1個表示芳基]。式（b-l)中，R1，，〜R3，，分別獨立表示芳基或烷基。又，式（b-Ι)中之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，R1，，〜R3，，中，至少1個表示芳基。r1”〜r3”中’ 以2個以上爲芳基爲佳，R1，’〜R3，’之全部爲芳基爲最佳。 R 1，，〜R3，’之芳基，並未有特別限定，例如’爲碳數6 〜20之芳基，且該芳基之氫原子的一部份或全部可被烷基、烷氧基、鹵素原子、羥基等所取代亦可’未被取代亦可〇芳基，就可廉價合成等觀點’以碳數6〜10之芳基爲佳。具體而言，例如苯基、萘基等。可取代前述芳基之氫原子的烷基’例如以碳數1〜5之烷基爲佳，以甲基、乙基 '丙基、η-丁基、tert-丁基爲最佳。可取代前述芳基之氫原子的烷氧基，例如以碳數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-丁氧基爲佳，以甲氧基、乙氧基爲最佳。可取代前述芳基之氫原子的鹵素原子，例如，以氟原子爲佳。 R1 ”〜R3”之烷基，並未有特別限制，例如碳數1〜1 G 之直鏈狀、分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、 -66- 201039064 η-丙基、異丙基、n_ 丁基、異丁基、n_戊基、環戊基、己基、環己基 '壬基、癸基等，就具有優良解析性’且可廉價合成等觀點，例如甲基等。式（b-Ι)中之Ri”〜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〜 10員環者爲佳，以形成5〜7員環爲特佳。式（b-Ι)中之Ri”〜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，剩餘之1個，以芳基爲 Ο 佳。前述芳基爲與前述R1”〜R3”之芳基爲相同之內容。式（b-Ι)所表示之化合物之陽離子部中，較佳者例如，下述式（1-1-1)〜（I-卜10)所表示之陽離子部等。其中又以，式（1-1-1)〜（I-1-8)所表示之陽離子部等之具有三苯甲烷骨架者爲佳。下述式（1-1-9)〜（i-1-ιο)中’ R9、R1Q，分別爲獨立之可具有取代基之苯基、萘基或碳數1〜5之烷基、烷氧 Q 基、羥基。 u爲1〜3之整數，以1或2爲最佳。 -67- 201039064 【化4 1】1} ^>l+ R4"S〇3 ... (b-2) [wherein, R1" to R3", R5" to R6,, respectively, independently represent an aryl group or an alkyl group; In any of 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; R4" represents a substituent group which may have a substituent, a compound base, or an aryl group , or a decyl group; R1'' to R3, at least one of -65-201039064 represents an aryl group, R5,, R6, and at least one of which represents an aryl group. In the formula (b-1), R1, and R3 each independently represent an aryl group or an alkyl group. Further, in the formula (b-Ι), any one of R1, R3, and R2 may be bonded to each other and form a ring together with the sulfur atom in the formula. Further, R1, R3, At least one represents an aryl group. Among the r1"~r3"', it is preferable that two or more aryl groups are used, and all of R1, '~R3,' are aryl groups. R 1, R 3 , 'the aryl group is not particularly limited, for example, 'an aryl group having a carbon number of 6 to 20, and a part or all of the hydrogen atom of the aryl group may be an alkyl group or an alkoxy group. The group, the halogen atom, the hydroxyl group or the like may be substituted with an unsubstituted or arylene group, and it is preferable to use an aryl group having a carbon number of 6 to 10 from the viewpoint of inexpensive synthesis. Specifically, for example, a phenyl group, a naphthyl group or the like. The alkyl group which may be substituted for the hydrogen atom of the above aryl group is preferably, for example, an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl 'propyl group, an η-butyl group or a tert-butyl group. An alkoxy group which may be substituted for the hydrogen atom of the above aryl group, for example, an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy 'η-propoxy group, or an iso-propoxy group η- Butoxy and tert-butoxy are preferred, and methoxy and ethoxy are preferred. A halogen atom which may replace the hydrogen atom of the aforementioned aryl group is, for example, preferably a fluorine atom. The alkyl group of R1 " to R3" is not particularly limited, and examples thereof include a linear chain having a carbon number of 1 to 1 G, a branched chain or a cyclic alkyl group. From the viewpoints of excellent resolution and the like, it is preferred that the carbon number is 1 to 5. Specifically, for example, methyl, ethyl, -66-201039064 η-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, cyclopentyl, hexyl, cyclohexyl 'fluorenyl, hydrazine The base or the like has excellent analytical properties and can be inexpensively synthesized, such as a methyl group. In the case of Ri""r3" in the formula (b-Ι), any two of them may be bonded to each other and form a ring together with the sulfur atom in the formula, and it is preferred to form a ring of 3 to 10 members including a sulfur atom. It is particularly preferable to form a 5~7 member ring. In the formula (b-Ι), Ri"~R3,", any two of which can be bonded to each other and form a ring together with the sulfur atom in the formula, the remaining One is based on aryl. The aryl group is the same as the aryl group of the above R1" to R3". In the cation portion of the compound represented by the formula (b-Ι), a cation portion represented by the following formulas (1-1-1) to (I-b 10) is preferable. Further, it is preferred that the cation portion such as the formula (1-1-1) to (I-1-8) has a triphenylmethane skeleton. In the following formulas (1-1-9) to (i-1-ιο), 'R9 and R1Q are each independently a phenyl group having a substituent, a naphthyl group or an alkyl group having 1 to 5 carbon atoms, and an alkoxy group. Q group, hydroxyl group. u is an integer of 1 to 3, and 1 or 2 is optimal. -67- 201039064 【化4 1】

(1-1-2) O’(1-1-2) O’

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

R4” ’表示可具有取代基之烷基、鹵化烷基、芳基，或烯基。 -68- 201039064 R4”中之烷基，可爲直鏈狀、分支鏈狀、環狀中任一者皆可。前述直鏈狀或分支鏈狀之烷基，例如以碳數1〜10爲佳，以碳數1〜8爲較佳，以碳數1〜4爲最佳。前述環狀之烷基，例如以碳數4〜15爲佳，以碳數4〜 10爲更佳，以碳數6〜10爲最佳。 R4”中之鹵化烷基，例如前述直鏈狀、分支鏈狀或環 0 狀之烷基之氫原子的一部份或全部被鹵素原子所取代之基等。該鹵素原子，例如，氟原子、氯原子、溴原子、碘原子等，又以氟原子爲佳。鹵化烷基中，相對於該鹵化烷基所含之鹵素原子及氫原子之合計數，鹵素原子數之比例（鹵化率（％ ))，以 1 0〜1 0 0 %爲佳’以5 0〜1 0 0 %爲更佳，以1 0 〇 %爲最佳。該鹵化率越高時，以酸之強度越強而爲更佳。前述R4”中之芳基，以碳數6〜20之芳基爲佳。〇前述R4”中之烯基，以碳數2〜10之烯基爲佳。前述R4”中’ 「可具有取代基」係指，前述直鏈狀、分支鏈狀或環狀之烷基、鹵化烷基、芳基，或烯基中氫原子之一部份或全部取代基（氫原子以外之其他原子或基）可被取代之意。 R4”中取代基之數可爲1個，或2個以上亦可。前述取代基’例如，鹵素原子、雜原子、烷基、式： X-Q1-[式中’ Q1爲含有氧原子之2價之鍵結基，X爲可具有取代基之碳數3〜30之烴基]所表示之基等。 -69 - 201039064 前述鹵素原子、烷基，爲與R4”中，鹵化烷基中之鹵素原子、烷基所列舉者爲相同之內容。前述雜原子，例如氧原子、氮原子、硫原子等。 X-Q1-所表示之基中，Q1爲含有氧原子之2價之鍵結基〇 Q1，可含有氧原子以外之原子。氧原子以外之原子，例如碳原子、氫原子、氧原子、硫原子、氮原子等。含有氧原子之2價之鍵結基，例如，氧原子（醚鍵結 ;-〇 -)、酯鍵結（-C( = 0)-0-) ' 醯胺鍵結（-C( = 0)-NH- )、羰基（-c( = 0) -)、碳酸酯鍵結（-0-C( = 0)-0 -)等之非烴系之含氧原子的鍵結基；該非烴系之含氧原子的鍵結基與伸烷基之組合等。該組合，例如，-r91-〇-、-r92-o-c( = o)-、-c(=o)-o- R93-0-C( = 0)-(式中，R91〜R93爲分別獨立之伸烷基）等〇〜R93中之伸烷基，以直鏈狀或分支鏈狀之伸烷基爲佳，該伸烷基之碳數，以1〜1 2爲佳，以1〜5爲更佳，以1〜3爲特佳。該伸烷基，具體而言，例如，伸甲基[-CH2-]; -ch(ch3)-、-ch(ch2ch3)-、-c(ch3)2-、-c(ch3)(ch2ch3)-、-c(ch3)(ch2ch2ch3)-、-c(ch2ch3)2-等之烷基伸甲基 ;伸乙基[-ch2ch2-] ; -ch(ch3)ch2-、-ch(ch3)ch(ch3)-、-c(ch3)2ch2-、-ch(ch2ch3)ch2-等之烷基伸乙基；伸三甲基（η-伸丙基）[-CH2CH2CH2-] ; -CH(CH3)CH2CH2- -70- 201039064 、-CH2CH(CH3)CH2-等之烷基伸三甲基；伸四甲基[- ch2ch2ch2ch2-] ; -ch(ch3)ch2ch2ch2-、-ch2ch(ch3)ch2ch2-等之烷基伸四甲基；伸五甲基[-ch2ch2ch2ch2ch2-]等。 Q 1，以含有酯鍵結或醚鍵結的2價之鍵結基爲佳，其中又以，-R91-〇- 、 -R92-0-C( = 0)- -C( = 0)-0-R93-〇- c (=o)-爲佳。 X-Q1-所表示之基中，X之烴基，可爲芳香族烴基亦可 0 ，脂肪族烴基亦可。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〜 15爲特佳，以6〜12爲最佳。其中，該碳數爲不含取代基中之碳數者。芳香族烴基，具體而言，例如，苯基、聯苯基（ biphenyl )、荀基（fluorenyl )、萘基、蒽基（anthryl ) 、菲基等之由芳香族烴環去除1個氫原子所得之芳基、苄 Q 基、苯乙基、1-萘甲基、2_萘甲基、1-萘乙基、2-萘乙基等之芳烷基等。前述芳烷基中之烷基鏈之碳數，以1〜4爲佳，以1〜2爲更佳，以1爲特佳。該芳香族烴基，可具有取代基。例如該芳香族烴基所具有之構成芳香環之碳原子的一部份可被雜原子所取代亦可、該芳香族烴基所具有之鍵結芳香環之氫原子可被取代基所取代亦可。前者之例如，前述構成芳基之環的碳原子之一部份被氧原子、硫原子、氮原子等之雜原子所取代之雜芳基、前 -71 - 201039064 述芳烷基中構成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烷基等。後者之例示中之芳香族烴基的取代基，例如，烷基、烷氧基、鹵素原子、鹵化烷基 '羥基、氧原子（=〇)等。前述芳香族烴基之作爲取代基之烷基，例如以碳數1 〜5之烷基爲佳，以甲基、乙基、丙基、η-丁基、tert-丁基爲最佳。前述芳香族烴基之作爲取代基之烷氧基，例如以碳數 1〜5之烷氧基爲佳，以甲氧基、乙氧基、n-丙氧基、iSO-丙氧基、η-丁氧基、tert-丁氧基爲佳，以甲氧基、乙氧基爲最佳。前述芳香族烴基之作爲取代基之鹵素原子，例如，氟原子、氯原子、溴原子、碘原子等，又以氟原子爲佳。前述芳香族烴基之作爲取代基之鹵化烷基，例如前述院基之氫原子的一部份或全部被前述鹵素原子所取代之基等。 X中之脂肪族烴基’可爲飽和脂肪族烴基亦可、不飽和脂肪族烴基亦可。又’脂肪族烴基，可爲直鏈狀、分支鏈狀、環狀中任一者皆可。 X中’脂肪族烴基中’構成該脂肪族烴基之碳原子的一部份可被含有雜原子之取代基所取代亦可、構成該脂肪族烴基之氫原子的一部份或全部可被含有雜原子之取代基所取代亦可。 X中之「雜原子」’例如只要爲碳原子及氫原子以外 -72- 201039064 之原子時’則無特別限定’例如鹵素原子、氧原子、硫原子、氮原子等。齒素原子，例如’氟原子、氯原子、碘原子、溴原子等。含有雜原子之取代基，可僅由前述雜原子所構成者亦可’或含有前述雜原子以外之基或原子之基亦可。可取代一部份碳原子之取代基，具體而言，例如， -〇- ' -C( = 0)-0- ' -C( = 0)- ' -0-C( = 0)-0- ' -C( = 0)-NH- ' 0 -NH- ( Η可被烷基、醯基等取代基所取代）、-S_、-S( = 0)2-、-S( = 〇)2-〇-等《脂肪族烴基爲環狀之情形，該些取代基可包含於環構造中。取代一部份或全部氫原子之取代基，具體而言，例如，烷氧基、鹵素原子、鹵化烷基、羥基、氧原子（ = 〇)、氰基等。前述烷氧基，例如以碳數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 Q 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，例如碳數1〜5之烷基’例如甲基、乙基、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，以直鏈狀或分支鏈狀之飽和烴基、直鏈狀或分支鏈狀之1價不飽和烴基，或環狀之脂肪族烴基（脂肪族環式基）爲佳。 -73- 201039064 直鏈狀之飽和烴基（烷基），例如碳數以1〜2 0爲佳，以1〜1 5爲更佳，以1〜1 0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、十一烷基、十二烷基、十三烷基、異十三院基、十四院基、十五院基、十六院基、異十/、院基 '十七院基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基等。分支鏈狀之飽和烴基（烷基），以碳數爲3〜20爲佳，以3〜1 5爲更佳，以3〜1 0爲最佳。具體而言’例如’卜甲基乙基、1-甲基丙基、2-甲基丙基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1-乙基丁基、2-乙基丁基、1-甲基戊基、2·甲基戊基、3-甲基戊基、4-甲基戊基等。不飽和烴基，例如碳數以2〜1 0爲佳，以2〜5爲佳，以2〜4爲佳，以3爲特佳。直鏈狀之1價之不飽和烴基，例如，乙烯基、丙烯基（烯丙基）、丁烯基等。分支鏈狀之 1價之不飽和烴基，例如，1-甲基丙烯基、2-甲基丙烯基等〇不飽和烴基’於上述之中，又特別是以丙烯基爲佳。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爲佳，以5〜30爲較佳，以5〜20爲更佳，以6〜1 5爲特佳’以6〜1 2爲最佳。具體而言’例如，單環鏈烷去除1個以上之氫原子所得之基；一環鏈院、三環鏈院、四環鏈院等之多環鏈院去除1個以上之氫原子所得之基等。更具體而言，例如環戊 -74- 201039064 院、環己烷等之單環鏈烷去除丨個以上之氫原子所得之基 •’金剛烷、原菠烷、異菠烷、三環癸烷、四環十二烷等多環鏈烷去除1個以上之氫原子所得之基等。脂肪族環式基，其環構造中不含有含雜原子之取代基之倩形’脂肪族環式基，以多環式基爲佳，以多環鏈院去除1個以上之氫原子所得之基爲更佳，以金剛烷去除1個以上之氫原子所得之基爲最佳。脂肪族環式基，其環構造中含有含雜原子之取代基之基之情形，含有該雜原子之取代基，以-〇-、_c( = 0)-0-、 -S-、-S( = 0)2-、-S( = 0)2-〇-爲佳。該脂肪族環式基之具體例，例如下述式（L1 )〜（L5 ) 、（ S1 )〜（S4)等。R4"' represents an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent. -68- 201039064 The alkyl group in R4" may be any of a linear chain, a branched chain, and a cyclic group. Can be. The linear or branched alkyl group is preferably a carbon number of 1 to 10, preferably a carbon number of 1 to 8, and preferably a carbon number of 1 to 4. The cyclic alkyl group is preferably a carbon number of 4 to 15, more preferably a carbon number of 4 to 10, and most preferably a carbon number of 6 to 10. The halogenated alkyl group in R4", for example, a group in which a part or all of a hydrogen atom of the above-mentioned linear, branched or cyclic alkyl group is substituted by a halogen atom, etc. The halogen atom, for example, a fluorine atom a chlorine atom, a bromine atom, an iodine atom, etc., preferably a fluorine atom. In the halogenated alkyl group, the ratio of the number of halogen atoms to the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group (halogenation ratio ( % )), preferably from 1 0 to 1 0 0 %' is preferably from 50 to 100%, and most preferably from 10%. The higher the halogenation rate, the stronger the strength of the acid. More preferably, the aryl group in the above R4" is preferably an aryl group having 6 to 20 carbon atoms. The alkenyl group in the above R4" is preferably an alkenyl group having 2 to 10 carbon atoms. In the above R4", "may have a substituent" means the linear, branched or cyclic alkyl group, A part or all of a substituent (an atom other than a hydrogen atom) of a hydrogen atom in a halogenated alkyl group, an aryl group or an alkenyl group may be substituted. The number of the substituents in R4" may be one or two or more. The above substituent 'for example, a halogen atom, a hetero atom, an alkyl group, and a formula: X-Q1-[wherein Q1 is an oxygen atom-containing one. a divalent bond group, X is a group represented by a hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. -69 - 201039064 The above halogen atom or alkyl group is the same as the halogenated alkyl group in R4" The halogen atom and the alkyl group are the same. The aforementioned hetero atom is, for example, an oxygen atom, a nitrogen atom, a sulfur atom or the like. In the group represented by X-Q1, Q1 is a divalent bond group 〇 Q1 containing an oxygen atom, and may contain an atom other than an oxygen atom. An atom other than an oxygen atom, such as a carbon atom, a hydrogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or the like. A divalent bond group containing an oxygen atom, for example, an oxygen atom (ether bond; -〇-), an ester bond (-C(=0)-0-)' guanamine bond (-C(=0) a non-hydrocarbon oxygen atom-containing bond group such as -NH-), a carbonyl group (-c(=0)-), a carbonate bond (-0-C(=0)-0-), etc.; A combination of a bond group containing an oxygen atom and an alkyl group. The combination, for example, -r91-〇-, -r92-oc(=o)-, -c(=o)-o- R93-0-C( = 0)- (wherein, R91 to R93 are independent The alkyl group is equivalent to an alkylene group in the argon-R93 group, preferably a linear or branched chain alkyl group, and the carbon number of the alkyl group is preferably 1 to 12, and is 1 to 5 For better, 1 to 3 is especially good. The alkylene group, specifically, for example, a methyl group [-CH2-]; -ch(ch3)-, -ch(ch2ch3)-, -c(ch3)2-, -c(ch3)(ch2ch3) -, -c(ch3)(ch2ch2ch3)-, -c(ch2ch3)2-, etc. alkyl group methyl group; exoethyl [-ch2ch2-]; -ch(ch3)ch2-, -ch(ch3)ch( Ch3)-, -c(ch3)2ch2-, -ch(ch2ch3)ch2-, etc. alkyl-extended ethyl; trimethyl (η-propyl)[-CH2CH2CH2-]; -CH(CH3)CH2CH2- 70- 201039064, alkyl group of -CH2CH(CH3)CH2-, etc., trimethyl group; tetramethyl [-ch2ch2ch2ch2-]; -ch(ch3)ch2ch2ch2-, -ch2ch(ch3)ch2ch2-, etc. Base; stretch pentamethyl [-ch2ch2ch2ch2ch2-] and the like. Q 1, preferably a divalent bond group containing an ester bond or an ether bond, wherein -R91-〇-, -R92-0-C(=0)--C(=0)- 0-R93-〇- c (=o)- is preferred. In the group represented by X-Q1-, the hydrocarbon group of X may be an aromatic hydrocarbon group or may be an aliphatic hydrocarbon group. The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The carbon number of the aromatic hydrocarbon group is preferably from 3 to 30, more preferably from 5 to 30, more preferably from 5 to 20, most preferably from 6 to 15, and most preferably from 6 to 12. Here, the carbon number is those which do not contain the carbon number in the substituent. The aromatic hydrocarbon group, specifically, for example, a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthyl group, an phenanthryl group, or the like, which is obtained by removing one hydrogen atom from an aromatic hydrocarbon ring. An aralkyl group such as an aryl group, a benzyl Q group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group or a 2-naphthylethyl group. The carbon number of the alkyl chain in the above aralkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. The aromatic hydrocarbon group may have a substituent. For example, a part of the carbon atom constituting the aromatic ring which the aromatic hydrocarbon group has may be substituted by a hetero atom, or a hydrogen atom to which the aromatic hydrocarbon group has a bonded aromatic ring may be substituted by a substituent. In the former, for example, the heteroaryl group in which a part of the carbon atoms constituting the ring of the aryl group is substituted by a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and the aralkyl group described in the above-mentioned -71 - 201039064 constitute an aromatic group. A heteroarylalkyl group in which a part of a carbon atom of a hydrocarbon ring is substituted by the aforementioned hetero atom. The substituent of the aromatic hydrocarbon group in the latter exemplified is, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl 'hydroxy 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 most preferably a methyl group, an ethyl group, a propyl group, an 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 a methoxy group, an ethoxy group, an n-propoxy group, an iSO-propoxy group, and a η- group. Butoxy and tert-butoxy are preferred, and methoxy and ethoxy are preferred. The halogen atom as a substituent of the aromatic hydrocarbon group, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, is preferably a fluorine atom. The halogenated alkyl group as a substituent of the aromatic hydrocarbon group is, for example, a group in which a part or all of a hydrogen atom of the above-mentioned substituent group is substituted by the above halogen atom. The aliphatic hydrocarbon group 'in X may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic ring. In the 'aliphatic hydrocarbon group', a part of the carbon atom constituting the aliphatic hydrocarbon group may be substituted by a substituent containing a hetero atom, or a part or all of the hydrogen atom constituting the aliphatic hydrocarbon group may be contained. Substituents for heteroatoms can also be substituted. The "hetero atom" in X is not particularly limited as long as it is an atom of -72 to 201039064 other than a carbon atom or a hydrogen atom, for example, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or the like. A dentate atom, for example, a fluorine atom, a chlorine atom, an iodine atom, a bromine atom or the like. The substituent containing a hetero atom may be composed only of the above-mentioned hetero atom, or may contain a group other than the above-mentioned hetero atom or a group of atoms. Substituents which may replace a part of a carbon atom, specifically, for example, -〇- ' -C( = 0)-0- ' -C( = 0)- ' -0-C( = 0)-0- ' -C( = 0)-NH- ' 0 -NH- ( Η can be replaced by a substituent such as alkyl or fluorenyl), -S_, -S( = 0)2-, -S( = 〇)2 - 〇-etc. "In the case where the aliphatic hydrocarbon group is cyclic, the substituents may be included in the ring structure. The substituent which substitutes a part or all of a hydrogen atom, specifically, for example, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, an oxygen atom (= fluorene), a cyano group or the like. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an η-propoxy group, an iso-propoxy group, an η-butoxy group, and a tert-butyl group. The oxy group is preferred, and the methoxy group and the ethoxy group are most 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 halogenated alkyl group, for example, a part or all of a hydrogen atom in an alkyl group having a carbon number of 1 to 5, such as a methyl group, an ethyl group, a propyl group, an η-butyl group, a tert-butyl group or the like, is A group substituted by a 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). -73- 201039064 A linear saturated hydrocarbon group (alkyl group), for example, preferably having a carbon number of from 1 to 2 0, more preferably from 1 to 15 and most preferably from 1 to 10. Specifically, for example, 'methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, Different thirteen yard bases, fourteen yard bases, fifteen yard bases, sixteen yard bases, different tens, courtyard base 'seventeen bases, octadecyl, nineteen alkyl, eicosyl, twenty Monoalkyl, behenyl or the like. The branched saturated hydrocarbon group (alkyl group) preferably has a carbon number of 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, 'for example, 'methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl Base, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like. The unsaturated hydrocarbon group, for example, preferably has a carbon number of 2 to 10, preferably 2 to 5, preferably 2 to 4, and particularly preferably 3. A linear monovalent unsaturated hydrocarbon group, for example, a vinyl group, a propenyl group, a butenyl group or the like. The branched monovalent unsaturated hydrocarbon group, for example, an oxime unsaturated hydrocarbon group such as a 1-methylpropenyl group or a 2-methylpropenyl group, is particularly preferred as the propylene group. The aliphatic cyclic group 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, and most preferably from 6 to 15 is preferably from 6 to 12. Specifically, for example, a monocyclic alkane is obtained by removing one or more hydrogen atoms; and a polycyclic chain such as a ring chain, a tricyclic chain, or a tetracyclic chain is used to remove one or more hydrogen atoms. Wait. More specifically, for example, cyclopentane-74-201039064, monocycloalkane of cyclohexane or the like, which is obtained by removing more than one hydrogen atom, a 'adamantane, a raw spinane, an isoparaffin, a tricyclodecane A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as tetracyclododecane. An aliphatic cyclic group having a ring-shaped 'aliphatic ring group containing no substituent of a hetero atom in the ring structure, preferably a polycyclic group, and removing one or more hydrogen atoms by a polycyclic chain The base is more preferably, and the base obtained by removing one or more hydrogen atoms from adamantane is preferred. An aliphatic cyclic group having a ring structure containing a substituent of a hetero atom, and a substituent containing the hetero atom, -〇-, _c(=0)-0-, -S-, -S ( = 0)2-, -S( = 0)2-〇- is preferred. Specific examples of the aliphatic cyclic group include, for example, the following formulas (L1) to (L5), (S1) to (S4), and the like.

R95-, R94及R95分別獨立爲碳數1〜5之伸烷基，m爲〇或1之〇整數1。式中，Q，，、R94及R95中之伸烷基，分別與前述R R9 3中之伸烷基爲相同之內容。 -75- 201039064 該些脂肪族環式基，構成該環構造之碳原子所鍵結之氫原子的一部份可被取代基所取代。該取代基，例如烷基、烷氧基、鹵素原子、鹵化烷基、羥基、氧原子（ = 0)等。前述烷基，例如以碳數1〜5之烷基爲佳，甲基 '乙基、丙基、η-丁基、tert-丁基爲特佳。前述烷氧基、鹵素原子分別與前述取代一部份或全部氫原子之取代基所列舉之內容爲相同之內容。本發明中，X以可具有取代基之環式基爲佳。該環式基，爲可具有取代基之芳香族烴基亦可，可具有取代基之脂肪族環式基亦可，又以可具有取代基之脂肪族環式基爲佳。前述芳香族烴基，以可具有取代基之萘基，或可具有取代基之苯基爲佳。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，以前述多環鏈院去除1個以上之氫原子所得之基、前述（L2 )〜（L5) 、（S3)〜（S4)等爲佳。本發明中，R4”，以具有取代基爲X-Q1-者爲佳。此時，R4”以X-Q^Y1-[式中，Q1及X與前述爲相同之內容，γι 爲可具有取代基之碳數1〜4之伸烷基或可具有取代基之碳數1〜4之氟化伸院基]所表示之基爲佳。 X-Qi-Y1-所表不之基中’ Υ1之伸院基’爲與前述q1所列舉之伸烷基中，碳數1〜4之基爲相同之內容。氟化伸烷基例如，該伸烷基之氫原子的一部份或全部 -76- 201039064 被氟原子所取代之基等。 Y1，具體而言，例如，-〇？2-、-€?20?2-、-0?20?20?2_ 、-cf(cf3)cf2-、-cf(cf2cf3)-、-c(cf3)2-、-cf2cf2cf2cf2-、-cf(cf3)cf2cf2-、-cf2cf(cf3)cf2-、-cf(cf3)cf(cf3)-、 -C(CF3)2CF2-、-CF(CF2CF3)CF2-、-CF(CF2CF2CF3)·、 -C(CF3)(CF2CF3)- ； -CHF- ' -CH2CF2- ' -CH2CH2CF2- ' -CH2CF2CF2- ' -CH(CF3)CH2-、-CH(CF2CF3)-、-C(CH3)(CF3)-R95-, R94 and R95 are each independently an alkylene group having a carbon number of 1 to 5, and m is 〇 or 1 〇 an integer of 1. In the formula, the alkylene group in Q,, R94 and R95 is the same as the alkylene group in the above R R9 3 . -75- 201039064 The aliphatic cyclic group, a part of a hydrogen atom bonded to a carbon atom constituting the ring structure, may be substituted by a substituent. The substituent is, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= 0) or the like. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl 'ethyl group, a propyl group, an η-butyl group or a tert-butyl group is particularly preferred. The alkoxy group and the halogen atom are the same as those exemplified as the substituent of the above-mentioned partial or all hydrogen atom. In the present invention, X is preferably a cyclic group which may have a substituent. The cyclic group may be an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, and an aliphatic cyclic group which may have a substituent. The above aromatic hydrocarbon group is preferably a naphthyl group which may have a substituent or a phenyl group which may have a substituent. The aliphatic cyclic group which may have a substituent is preferably a polycyclic aliphatic ring group which may have a substituent. The polycyclic aliphatic cyclic group is preferably a group obtained by removing one or more hydrogen atoms from the polycyclic chain, and the above (L2) to (L5), (S3) to (S4), and the like. In the present invention, R4" is preferably one having a substituent of X-Q1-. In this case, R4" is XQ^Y1-[wherein, Q1 and X are the same as described above, and γι may have a substituent. The group represented by the alkylene group having 1 to 4 carbon atoms or the fluorinated stretching group having a carbon number of 1 to 4 having a substituent is preferred. In the base of X-Qi-Y1-, the "base of the Υ1" is the same as the group having the carbon number of 1 to 4 in the alkylene group exemplified in the above q1. The fluorinated alkyl group is, for example, a part or all of a hydrogen atom of the alkyl group - 76- 201039064, a group substituted by a fluorine atom or the like. Y1, specifically, for example, -〇? 2-, -€?20?2-, -0?20?20?2_, -cf(cf3)cf2-, -cf(cf2cf3)-, -c(cf3)2-, -cf2cf2cf2cf2-, -cf( Cf3)cf2cf2-, -cf2cf(cf3)cf2-, -cf(cf3)cf(cf3)-, -C(CF3)2CF2-, -CF(CF2CF3)CF2-, -CF(CF2CF2CF3)·, -C( CF3)(CF2CF3)- ; -CHF- ' -CH2CF2- ' -CH2CH2CF2- ' -CH2CF2CF2- ' -CH(CF3)CH2-, -CH(CF2CF3)-, -C(CH3)(CF3)-

、-ch2ch2ch2cf2-、-ch2ch2cf2cf2-、-ch(cf3)ch2ch2-、 -CH2CH(CF3)CH2-、-CH(CF3)CH(CF3)-、-C(CF3)2CH2- ; -ch2-' -CH2CH2- ' -CH2CH2CH2- ' -CH(CH3)CH2- ' -CH(CH2CH3)- ' -C(CH3)2- ' -CH2CH2CH2CH2- ' -CH(CH3)CH2CH2- ' -CH2CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、 -CH(CH2CH3)CH2-、-ch(ch2ch2ch3)-、-C(CH3)(CH2CH3)-等。 Y1，以氟化伸烷基爲佳，特別是鍵結於鄰接硫原子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- CF2-、-CF2CF2- ' -CF2CF2CF2- ' -CF(CF3)CF2- ' -CF2CF2CF2CF2- ' -CF(CF3)CF2CF2- ' -CF2CF(CF3)CF2- ' -CF(CF3)CF(CF3)-、-C(CF3)2CF2-、-CF(CF2CF3)CF2-; -CH2CF2- ' -CH2CH2CF2- ' -CH2CF2CF2- ; -CH2CH2CH2CF2-、-CH2CH2CF2CF2- ' -CH2CF2CF2CF2-等。其中又以-cf2-、 -CF2CF2-、-CF2CF2CF2-，或 CH2CF2CF2-爲佳，以-CF2-、-CF2CF2-或-CF2CF2CF2-爲更佳，-C F 2 -爲特佳。前述伸烷基或氟化伸烷基，可具有取代基。伸烷基或 -77- 201039064 氟化伸院基爲「具有取代基」係指，該伸院基或氟化伸院基中之氫原子或氟原子之一部份或全部可被氫原子及氟原子以外之原子或基所取代之意。伸烷基或氟化伸烷基所可具有之取代基，例如碳數1 〜4之烷基、碳數1〜4之烷氧基、羥基等。式（b-2 )中，R5”〜R6”分別獨立表示芳基或烷基。 R5”〜R6”中，至少1個表示芳基。R5”〜R6”之全部爲芳基爲佳。 R5”〜R6”之芳基，爲與R1”〜R3”之芳基爲相同之內容〇 R5”〜R6，’之烷基，爲與R1”〜R3”之烷基爲相同之內容〇該些之中，又以R5”〜R6”全部爲苯基爲最佳。式（b-2)中之R4，，爲與上述式（b-Ι)之R4”爲相同之內容。式（b-1) 、（b-2)所表示之鎗鹽系酸產生劑之具體例如，二苯基碑鑰之三氟甲院磺酸酯或九氟丁院磺酸酯、雙（4-tert-丁基苯基）碘鎗之三氟甲烷磺酸酯或九氟丁院磺酸酯、三苯基鏑之三氟甲烷磺酸醋、其七氟丙院礦酸醋或其九氟丁烷磺酸酯、三（4·甲基苯基）锍之三氟甲院礦酸酯、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、其七氟丙院擴酸醋或其九氟丁烷磺酸酯、單苯基二甲基蔬之三氟甲院擴酸醋、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯；二苯基單甲基硫 -78- 201039064 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_甲基苯基）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、（4-甲氧基苯基）二苯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、三（4-tert-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-(4-甲氧基）萘基）锍之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或 0 其九氟丁院擴酸酯、二（1-萘基）苯基鐘之三氟甲院擴酸酯、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、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯；1-(4-甲基苯基）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-(3,5-二甲基-4-羥苯基）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-(4_甲氧基萘-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 Q 丁烷磺酸酯；1-(4-乙氧基萘-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-( 4-n-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-苯基四氫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-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其九氟丁烷磺酸酯；1-(4-甲基苯基）四氫噻喃鏺之三氟 -79- 201039064 甲烷磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯等。又’亦可使用該些鐵鹽之陰離子部被甲烷磺酸酯、n-丙烷磺酸酯、η-丁烷磺酸酯、n_辛烷磺酸酯等之烷基磺酸酯所取代之鑰鹽。又，亦可使用該些鑰鹽之陰離子部被下述式（bl)〜 (b8 )之任一所表示之陰離子部所取代之鑰鹽。【化4 3】 (R7)r1\^\ γ\ ^ 〇 /、_O—(CH2)q「0—C一(CF2)p-S〇3 ο ο II II _ H2g+1Cgc—Ο—(CH2)q2-〇—c—(CF2)p-S〇3 ( b 2) (R7)丨 12-ch2ch2ch2cf2-, -ch2ch2cf2cf2-, -ch(cf3)ch2ch2-, -CH2CH(CF3)CH2-, -CH(CF3)CH(CF3)-, -C(CF3)2CH2-; -ch2-'-CH2CH2 - ' -CH2CH2CH2- ' -CH(CH3)CH2- ' -CH(CH2CH3)- ' -C(CH3)2- ' -CH2CH2CH2CH2- ' -CH(CH3)CH2CH2- ' -CH2CH(CH3)CH2-,- CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -ch(ch2ch2ch3)-, -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 adjacent to a sulfur atom. The fluorinated alkyl groups, for example, -CF2-, -CF2CF2-'-CF2CF2CF2-'-CF(CF3)CF2-'-CF2CF2CF2CF2-'-CF(CF3)CF2CF2-'-CF2CF(CF3)CF2-'- CF(CF3)CF(CF3)-, -C(CF3)2CF2-, -CF(CF2CF3)CF2-; -CH2CF2-'-CH2CH2CF2-'-CH2CF2CF2-; -CH2CH2CH2CF2-, -CH2CH2CF2CF2-'-CH2CF2CF2CF2-, etc. . Further, -cf2-, -CF2CF2-, -CF2CF2CF2-, or CH2CF2CF2- is preferable, and -CF2-, -CF2CF2- or -CF2CF2CF2- is more preferable, and -C F 2 - is particularly preferable. The aforementioned alkylene or fluorinated alkyl group may have a substituent. Alkyl or -77- 201039064 fluorinated and extended as a "substituent" means that a part or all of a hydrogen atom or a fluorine atom in the extended or fluorinated base may be hydrogen atoms and The meaning of replacing an atom or a group other than a fluorine atom. The substituent which the alkyl group or the fluorinated alkyl group may have, for example, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group or the like. In the formula (b-2), R5" to R6" each independently represent an aryl group or an alkyl group. At least one of R5" to R6" represents an aryl group. All of R5" to R6" are preferably an aryl group. The aryl group of R5" to R6" is the same as the aryl group of R1" to R3", and the alkyl group of R5" to R6, 'is the same as the alkyl group of R1" to R3". Among them, R5" to R6" are all preferably a phenyl group. R4 in the formula (b-2) is the same as R4" of the above formula (b-Ι). Specific examples of the gun salt-based acid generator represented by the formulas (b-1) and (b-2), for example, a diphenyl group of trifluoromethanesulfonate or a nonafluorobutyrate, a double (4) -tert-butylphenyl) iodine gun trifluoromethanesulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethanesulfonate vinegar, its heptafluoropropane ore vinegar or its nonafluoro Butane sulfonate, tris(4.methylphenyl)phosphonium triflate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, dimethyl (4-hydroxynaphthyl) Trifluoromethanesulfonate, its heptafluoropropane acid vinegar or its nonafluorobutane sulfonate, monophenyl dimethyl vegetable trifluoromethane vinegar, its heptafluoropropane sulfonate or Nonafluorobutane sulfonate; diphenylmonomethylsulfide-78-201039064 trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methylphenyl) Triphenylmethane trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, and heptafluoropropane Sulfonate or its nonafluorobutane sulfonate, (4-tert-butyl)phenylhydrazine trifluoromethanesulfonate, heptafluoropropanesulfonate or its nonafluorobutanesulfonate, diphenyl(1-(4-methoxy)naphthyl) Trifluoromethanesulfonate, its heptafluoropropane sulfonate or 0, its nonafluorobutanyl acid ester, bis(1-naphthyl)phenyl clock, trifluoromethyl ester, or heptafluoropropane sulfonate or Its nonafluorobutane sulfonate; 1-phenyltetrahydrothiophene key trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1-(4-methylphenyl) Tetrahydrothienyl trifluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate; 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene Fluoromethanesulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate; 1-(4-methoxynaphthalen-1-yl)tetrahydrothiophene-trifluoromethanesulfonate, heptafluoropropane sulfonate An acid ester thereof or a nonafluoro-butane sulfonate thereof; 1-(4-ethoxynaphthalen-1-yl)tetrahydrothiophene key trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane Sulfonate; 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene Methanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; trifluoromethanesulfonate of 1-phenyltetrahydrothiophene, its heptafluoropropane sulfonate or its nonafluorobutane sulfonic acid Ethyl ester; 1-(4-hydroxyphenyl)tetrahydrothienyl trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1-(3,5-dimethyl- 4-hydroxyphenyl)tetrahydrothienyl trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1-(4-methylphenyl)tetrahydrothiopyran Trifluoro-79-201039064 Methanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate. Further, the anion portion of the iron salt may be replaced by an alkylsulfonate such as methanesulfonate, n-propanesulfonate, η-butanesulfonate or n-octanesulfonate. Key salt. Further, a key salt in which the anion portion of the key salt is replaced by an anion portion represented by any one of the following formulas (b1) to (b8) may be used. [化4 3] (R7)r1\^\ γ\ ^ 〇/, _O—(CH2)q “0—C—(CF2)pS〇3 ο ο II II _ H2g+1Cgc—Ο—(CH2)q2 -〇—c—(CF2)pS〇3 ( b 2) (R7)丨12

οII c—o—(CH2)q3—(CF2)t3—S〇3 (b 3)IIII c—o—(CH2)q3—(CF2)t3—S〇3 (b 3)

(CH2)vi—0--C o (R7)w2(CH2)vi—0--C o (R7)w2

(CH2)v2-〇--C (CH2)v3-〇·(CH2)v2-〇--C (CH2)v3-〇·

OIIOII

oII 0II -c- -(CF2)FS〇3 n1 (b 4) -(cf2)「so; n2 (b 5) -(CF2)rSO; n3 (b 6) -80 0 201039064oII 0II -c- -(CF2)FS〇3 n1 (b 4) -(cf2)"so; n2 (b 5) -(CF2)rSO; n3 (b 6) -80 0 201039064

[式中，P爲1〜3之整數，ql〜q2爲分別獨立之1〜5之整數 ’ q3爲1〜12之整數，t3爲1〜3之整數，ri〜Γ2爲分別獨立之〇〜3之整數’ g爲1〜20之整數，R7爲取代基，η1〜“爲分別獨立之〇或1，vl〜v5爲分別獨立之〇〜3之整數，wl〜 w5爲分別獨立之0〜3之整數’ Q”與前述爲相同之內容]。 R7之取代基’爲與前述X中，脂肪族烴基所可具有之取代基、芳香族烴基所可具有之取代基所列舉者爲相同之內容。 R7所附之符號（rl、wl〜w5 )爲2以上之整數之情形，該化合物中之複數之r7可分別爲相同亦可，相異亦可。又，鐵鹽系酸產生劑亦可使用前述通式（b-l)或（b-2)中，陰離子部被下述通式（b-3)或（b-4)所表示之陰離子部所取代之鑰鹽系酸產生劑（陽離子部與（b-1 )或 (b-2)爲相同之內容）。【化4 4】 SOo-n[In the formula, P is an integer of 1 to 3, and ql to q2 are integers of 1 to 5, respectively, respectively.] q3 is an integer of 1 to 12, t3 is an integer of 1 to 3, and ri to Γ2 are independent 〇~ The integer of 3 'g is an integer of 1~20, R7 is a substituent, η1~" are independent 〇 or 1, vl~v5 are independent integers of 〇3, respectively, wl~w5 are independent 0~ The integer 'Q' of 3 is the same as the above]. The substituent "R7" is the same as those which may be contained in the above X, the substituent which the aliphatic hydrocarbon group may have, and the substituent which the aromatic hydrocarbon group may have. The symbol (rl, wl to w5) attached to R7 is an integer of 2 or more, and the plural r7 in the compound may be the same or different. Further, in the above-mentioned general formula (bl) or (b-2), the anion moiety may be replaced by an anion moiety represented by the following formula (b-3) or (b-4). The key salt acid generator (the cation moiety is the same as (b-1) or (b-2)). [化4 4] SOo-n

02S—Y" 02s—Z" [式中，X”表示至少1個氫原子被氟原子所取代之碳數2〜6 之伸院基；Y ”、Z ”，分別表示爲獨立之至少1個氫原子被 -81 - 201039064 氟原子所取代之碳數1〜10之烷基]。 X”爲至少1個之氫原子被氟原子所取代之直鏈狀或分支鏈狀之伸烷基，該伸烷基之碳數爲2〜6’較佳爲碳數3 〜5，最佳爲碳數3。 Y”、Z”，爲分別獨立之至少1個氫原子被氟原子所取代之直鏈狀或分支鏈狀之烷基，該烷基之碳數爲1〜10, 較佳爲碳數1〜7，更佳爲碳數1〜3。 X”之伸烷基之碳數或Y”、Z”之烷基之碳數於上述碳數之範圍内時，就對光阻溶劑具有良好之溶解性等理由，以越小越好。又，X”之伸烷基或Y”、Z”之烷基中，氟原子所取代之氫原子的數目越多時，該酸的強度越強，又可提高對2 00 nm以下之高能量光或電子線之透明性等而爲較佳。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%，最佳爲全部之氫原子被氟原子所取代之全氟伸烷基或全氟烷基。又，具有下述通式（b-5)或（b-6)所表示之陽離子部之锍鹽亦可作爲鑰鹽系酸產生劑使用。 -82 - 201039064 【化4 5】02S—Y"02s—Z" [wherein, X represents a radical of 2 to 6 carbon atoms substituted by at least one hydrogen atom; Y ′′, Z ′′, respectively denoted as at least one independent A hydrogen atom is an alkyl group having 1 to 10 carbon atoms which is substituted by a fluorine atom of -81 - 201039064. X" is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. The alkyl group has a carbon number of 2 to 6', preferably a carbon number of 3 to 5, most preferably a carbon number of 3. Y", Z" is a linear or branched alkyl group in which at least one hydrogen atom is independently substituted by a fluorine atom, and the carbon number of the alkyl group is from 1 to 10, preferably from 1 to 10. 7, more preferably a carbon number of 1 to 3. When the carbon number of the alkyl group of X" or the carbon number of the alkyl group of Y" or Z" is in the range of the above carbon number, the solubility in the resist solvent is good, and the smaller the better. In the alkyl group of X", the alkyl group of Y" or Z", the more the number of hydrogen atoms substituted by the fluorine atom, the stronger the strength of the acid, and the higher the energy of light below 200 nm. Or the transparency of the electron beam or the like is preferable. 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%, and most preferably the total fluorine atom is replaced by a fluorine atom. An alkyl or perfluoroalkyl group. Further, the onium salt having a cationic moiety represented by the following formula (b-5) or (b-6) can also be used as a key salt acid generator. -82 - 201039064 [Chem. 4 5]

基、羥基或羥烷基；iM-ns爲各自獨立之0〜3之整數爲0〜2之整數]。 R41〜:R46中，烷基以碳數1〜5之烷基爲佳，其中直鏈或分支鏈狀之烷基爲更佳，以甲基、乙基、丙基丙基、η-丁基，或tert-丁基爲特佳。烷氧基以碳數1〜5之烷氧基爲佳，其中又以直鏈支鏈狀之烷氧基爲更佳，以甲氧基、乙氧基爲特佳。羥烷基以上述烷基中之一個或複數個氫原子被羥取代之基爲佳，例如羥甲基、羥乙基、羥丙基等。 R41〜R46所附之符號ηι〜n6爲2以上之整數之情形數之R41〜R46可分別爲相同亦可，相異亦可。 ηι，較佳爲〇〜2，更佳爲0或1，最佳爲0。 ιΐ2及n3，較佳爲各自獨立之0或1，更佳爲0。 n4，較佳爲〇〜2，更佳爲0或1。 n5，較佳爲〇或1，更佳爲〇。 n6，較佳爲〇或1 ’更佳爲1。 Ό6 、羧，η6 又以、異或分基所，複 -83- 201039064 具有式（b-5 )或（b-6 )所表示之陽離子部之鏑鹽的陰離子部，並未有特別限定，其可使用與目前爲止被提案之鑰鹽系酸產生劑的陰離子部爲相同之內容。該陰離子部，例如上述通式（b-Ι )或（b-2 )所表示之鑰鹽系酸產生劑之陰離子部（R4’’S03_)等之氟化烷基磺酸離子；例如上述通式（b-3)或（b-4)所表示之陰離子部等。本說明書中，肟磺酸酯系酸產生劑係指，至少具有一個下述通式（B-1)所表示之基的化合物，且具有經由輻射線之照射而產生酸之特性者。該些肟磺酸酯系酸產生劑，常被使用於化學増幅型光阻組成物用，可由其中任意地選擇使用。【化4 6】 -C=N—Ο—S02—R31 R32 . . · ( b - 1 ) [式（B-1)中，R31、R32分別表示獨立之有機基] R31、R32之有機基，可具有含有碳原子之基，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）亦可。 R31之有機基，以直鏈狀、分支鏈狀或環狀之烷基或芳基爲佳。該些之烷基，芳基可具有取代基。該取代基’ 並未有特別限制，例如氟原子、碳數1〜6之直鏈狀、分支鏈狀或環狀之烷基等。於此，「具有取代基」係指’烷基或芳基之氫原子的一部份或全部被取代基所取代之意。烷基’例如以碳數1〜2 0爲佳，以碳數1〜1 0爲較佳’ 以碳數1〜8爲更佳，以碳數1〜6爲特佳、以碳數1〜4爲最 -84- 201039064 佳。烷基’特別是以部份或完全被鹵化之烷基（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之意，完全齒化之烷基係指’氫原子全部被鹵素原子所取代之烷基之意。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爲佳，以碳數4〜10爲更佳，以碳數 0 6〜10爲最佳。芳基特別是以部份或完全被鹵化之芳基爲佳。又’部份被鹵化之芳基係指，氫原子之一部份被鹵素原子所取代之芳基之意’完全被鹵化之芳基係指，氫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之烷基，或碳數1〜4之氟化院基爲佳。 R32之有機基，以直鏈狀、分支鏈狀或環狀之烷基、芳基或氰基爲佳。R32之烷基、芳基，爲與前述R31所列舉〇之烷基、芳基爲相同之內容。 R32，特別是以氰基、不具有取代基之碳數1〜8之烷基，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 )所表示之化合物等。【化4 7】 R34~C=N—Ο—S〇2—R35 R33 · (B-2) [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爲不具有取代基之烷基或鹵化烷基]。 -85- 201039064 【化4 8】 R37— 一c=N——Ο——S02——R38The base, the hydroxy group or the hydroxyalkyl group; iM-ns is an integer of 0 to 3 which is independently an integer of 0 to 2]. In R41 to R46, the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and a linear or branched alkyl group is more preferred, and a methyl group, an ethyl group, a propyl group, and a η-butyl group are preferred. Or tert-butyl is especially good. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a linear branched alkoxy group, particularly preferably a methoxy group or an ethoxy group. The hydroxyalkyl group is preferably a group in which one of the above alkyl groups or a plurality of hydrogen atoms is substituted with a hydroxyl group, such as a methylol group, a hydroxyethyl group, a hydroxypropyl group or the like. The symbols ηι to n6 attached to R41 to R46 are integers of 2 or more. The numbers R41 to R46 may be the same or different. Ηι, preferably 〇~2, more preferably 0 or 1, most preferably 0. Preferably, ιΐ2 and n3 are independently 0 or 1, more preferably 0. N4 is preferably 〇~2, more preferably 0 or 1. N5, preferably 〇 or 1, more preferably 〇. N6, preferably 〇 or 1 ' is more preferably 1. Ό6, carboxy, η6 Further, an iso- or a sub-group, and -83-201039064 An anion moiety having a sulfonium salt of a cation moiety represented by the formula (b-5) or (b-6) is not particularly limited. The same can be used for the anion portion of the key salt acid generator which has been proposed so far. The anion portion is, for example, a fluorinated alkylsulfonic acid ion such as an anion portion (R4''S03_) of a key salt acid generator represented by the above formula (b-Ι) or (b-2); An anion moiety or the like represented by the formula (b-3) or (b-4). In the present specification, the oxime sulfonate-based acid generator is a compound having at least one group represented by the following formula (B-1) and having a property of generating an acid by irradiation with radiation. These oxime sulfonate-based acid generators are often used in chemical ruthenium-type photoresist compositions, and can be arbitrarily selected and used. [Chemical 4 6] -C=N—Ο—S02—R31 R32 . . . ( b - 1 ) [In the formula (B-1), R31 and R32 respectively represent an independent organic group] and an organic group of R31 and R32, It may have a group containing a carbon atom, and 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.)). The organic group of R31 is preferably a linear, branched or cyclic alkyl or aryl group. The alkyl group, the aryl group may have a substituent. The substituent ' is not particularly limited, and examples thereof include a fluorine atom, a linear one having a carbon number of 1 to 6, a branched chain or a cyclic alkyl group. Here, the "having a substituent" means that a part or the whole of a hydrogen atom of the 'alkyl group or an aryl group is substituted with a substituent. The alkyl group ' is preferably a carbon number of 1 to 2 0, preferably a carbon number of 1 to 10 0. More preferably, a carbon number of 1 to 8 is preferred, and a carbon number of 1 to 6 is particularly preferred, and the carbon number is 1 to 6. 4 is the best -84- 201039064. The alkyl group is particularly preferably an alkyl group which is partially or completely halogenated (hereinafter, also referred to as a halogenated alkyl group). Further, a partially halogenated alkyl group means an alkyl group in which a part of a hydrogen atom is replaced by a halogen atom, and a completely entangled alkyl group means an alkyl group in which all hydrogen atoms are replaced by a halogen atom. . The halogen atom 'e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, particularly 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, more preferably a carbon number of 4 to 10, and most preferably a carbon number of 0 6 to 10. The aryl group is particularly preferably an aryl group which is partially or completely halogenated. Further, 'partially halogenated aryl means that the aryl group in which one part of the hydrogen atom is replaced by a halogen atom means the aryl group which is completely halogenated, and the aryl group in which the hydrogen atom is entirely replaced by a halogen atom. meaning. R31' is particularly preferably an alkyl group having 1 to 4 carbon atoms which does not have a substituent, or a fluorinated group having 1 to 4 carbon atoms. The organic group of R32 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 the same as those of the alkyl group and the aryl group exemplified in the above R31. R32 is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms which does not have a substituent, 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 4 7] R34~C=N—Ο—S〇2—R35 R33 · (B-2) [In the formula (B-2), R3 3 is a cyano group, an alkyl group having no substituent or an alkyl halide; base. R34 is an aryl group. R35 is an alkyl group or a halogenated alkyl group having no substituent. -85- 201039064 【化4 8】 R37—一c=N——Ο——S02——R38

I r36 .R j p" . · (B - 3 ) [式（B_3 )中，R36爲氰基、不具有取代基之烷基或鹵化烷基。R3 7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]。前述通式（B-2)中’ R3 3之不具有取代基之烷基或鹵化烷基，以碳數爲1〜1 〇爲佳，以碳數1〜8爲較佳，以碳數1〜6爲最佳。 R33，以鹵化烷基爲佳，以氟化烷基爲更佳。 R33中之氟化烷基，以烷基之氫原子被5 0%以上氟化者爲佳，被70%以上氟化者爲更佳，被90%以上氟化者爲特佳。 R34之芳基爲’由苯基、聯苯基（biphenyl)、芴基（ fluorenyl )、萘基、蒽基（anthryl )、菲基等之芳香族烴環去除1個氫原子所得之基，及構成該些之基的環之碳原子的一部份被氧原子、硫原子、氮原子等之雜原子所取代之雜芳基等。該些之中又以芴基爲佳。 R34之芳基，可具有碳數1〜1〇之烷基、鹵化烷基、烷氧基等之取代基。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佳。 R3 5之不具有取代基之烷基或鹵化烷基，以碳數爲！〜 10爲佳，以碳數1〜8爲較佳，以碳數1〜6爲最佳。 -86- 201039064 R35，以鹵化烷基爲佳，以氟化烷基爲更佳。 R3 5中之氟化烷基，以烷基之氫原子被50%以上氟化者爲佳，被70%以上氟化者爲更佳，被90%以上氟化者，以可提高所發生之酸的強度而爲特佳。最佳爲，氫原子被 100%氟所取代之完全氟化烷基。前述通式（B-3)中，R3 6之不具有取代基之烷基或鹵化烷基爲與上述R33之不具有取代基之烷基或鹵化烷基爲 0 相同之內容。 R37之2或3價之芳香族烴基，例如上述R34之芳基再去除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爲與上述R35之不具有取代基之烷基或鹵化烷基爲相同之內容。 p ”，較佳爲2。肟磺酸酯系酸產生劑之具體例如，α-(ρ·甲苯磺醯基氧亞胺基）_苄基氰化物（cyanide) 、α·(ρ-氯基苯磺醯 Q 基氧亞胺基）-苄基氰化物、α-( 4_硝基苯磺醯基氧亞胺基）-苄基氰化物、α - ( 4_硝基-2-三氟甲基苯磺醯基氧亞胺基）-苄基氰化物、α -(苯磺醯基氧亞胺基）-4-氯基苄基氰化物、α-(苯磺醯基氧亞胺基）-2,4-二氯基苄基氰化物、α -(苯磺醯基氧亞胺基）_2,6-二氯基苄基氰化物、α-(苯磺醯基氧亞胺基）-4-甲氧基苄基氰化物、α-( 2-氯基苯磺醯基氧亞胺基）-4-甲氧基苄基氰化物、α-( 苯磺醯基氧亞胺基）-噻嗯-2-基乙腈、α - ( 4-十二烷基苯磺醯基氧亞胺基）-苄基氰化物、α -[ ( ρ-甲苯磺醯基氧亞 -87- 201039064 胺基）-4 -甲氧基苯基]乙腈、《-[(十二院基苯擴醯基氧亞胺基）—4-甲氧基苯基]乙腈、α-(甲基擴醯氧亞胺基 )-4 -唾嗯基氰化物、〇：-(甲基擴酿基氧亞胺基）-1-環戊烯基乙腈、α-(甲基磺醯基氧亞胺基）-1-環己烯基乙腈、<2 -(甲基擴醯基氧亞胺基）-I -環庚稀基乙腈、甲基磺醯基氧亞胺基）-〗_環辛烯基乙腈、三氟甲基磺醯基氧亞胺基）-1-環戊烯基乙腈、α_(三氟甲基磺醯基氧亞胺基）-環己基乙腈' α-(乙基磺醯基氧亞胺基）-乙基乙腈、α-(丙基磺醯基氧亞胺基）-丙基乙腈、α-(環己基磺醯基氧亞胺基）-環戊基乙腈、α-(環己基磺醯基氧亞胺基）-環己基乙腈、α -(環己基擴醯基氧亞胺基）_ 1-環戊烯基乙腈、α-(乙基磺醯基氧亞胺基）-1-環戊烯基乙腈、α-(異丙基磺醯基氧亞胺基）-1-環戊烯基乙腈、α-(η -丁基磺醯基氧亞胺基）-卜環戊烯基乙腈、《-( 乙基磺醯基氧亞胺基）-1-環己烯基乙腈、α-(異丙基磺醯基氧亞胺基）-1-環己烯基乙腈、α-(η-丁基磺醯基氧亞胺基）-卜環己烯基乙腈、α-(甲基磺醯基氧亞胺基）_ 苯基乙腈、α-(甲基磺醯基氧亞胺基）-Ρ-甲氧基苯基乙腈、α-(三氟甲基磺醯基氧亞胺基）-苯基乙腈、α-(三氟甲基磺醯基氧亞胺基）-Ρ-甲氧基苯基乙腈、α-(乙基磺醯基氧亞胺基）-Ρ-甲氧基苯基乙腈、α-(丙基磺醯基氧亞胺基）-Ρ-甲基苯基乙腈、α-(甲基磺醯基氧亞胺基 )-ρ-溴基苯基乙腈等。又，也可使用特開平9-208554號公報（段落[0012]〜 -88 * 201039064 [0014]之[化18]〜[化19])所揭示之肟磺酸酯系酸產生劑、W02004 / 074242A2 ( 65~ 85M ^Examplel~ 40)所揭示之肟磺酸酯系酸產生劑。又，較佳之內容可例如以下之例示內容。【化4 9】I r36 .R j p" . (B - 3 ) [In the formula (B_3), R36 is a cyano group, an alkyl group having no substituent or a halogenated alkyl group. R3 7 is a 2 or 3 valent aromatic hydrocarbon group. R38 is an alkyl group or a halogenated alkyl group having no substituent. P" is 2 or 3]. In the above formula (B-2), the alkyl group or the halogenated alkyl group having no substituent of R3 3 is preferably a carbon number of 1 to 1 Torr, and a carbon number of 1 to 8 Preferably, the carbon number is preferably from 1 to 6. R33 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group. The fluorinated alkyl group in R33 is 50% by the hydrogen atom of the alkyl group. The above fluorination is preferred, more preferably 70% or more of fluorinated, and more preferably 90% or more of fluorinated. The aryl group of R34 is 'from phenyl, biphenyl, fluorenyl (fluorenyl) a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as a naphthyl group, an anthyl group or an phenanthryl group, and a part of a carbon atom of a ring constituting the group is an oxygen atom or a sulfur atom, a heteroaryl group substituted with a hetero atom such as a nitrogen atom, etc. Among these, a fluorenyl group is preferred. The aryl group of R34 may have an alkyl group having 1 to 1 Å, a halogenated alkyl group, an alkoxy group, or the like. 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 preferably a fluorinated alkyl group. An alkyl group or a halogenated alkyl group having no substituent The carbon number is preferably ~10, preferably 1 to 8 carbon atoms, and preferably 1 to 6 carbon atoms. -86- 201039064 R35, preferably a halogenated alkyl group and a fluorinated alkyl group. Preferably, the fluorinated alkyl group in R3 5 is preferably a fluorine atom of an alkyl group which is fluorinated by 50% or more, more preferably 70% or more of fluorinated, and more preferably 90% or more of fluorinated. It is particularly preferable that the strength of the acid to be generated is a completely fluorinated alkyl group in which a hydrogen atom is substituted by 100% fluorine. In the above formula (B-3), an alkyl group having no substituent of R3 6 or The halogenated alkyl group is the same as the alkyl group having no substituent or the halogenated alkyl group of R33 above. The aromatic hydrocarbon group of 2 or 3 of R37, for example, the aryl group of the above R34 is further removed by 1 or 2 hydrogen atoms. The obtained base or the like. The alkyl group or the halogenated alkyl group having no substituent of R3 8 is the same as the alkyl group or the halogenated alkyl group having no substituent of the above R35. p ", preferably 2. Specific examples of the sulfonate-based acid generator are, for example, α-(ρ·toluenesulfonyloxyimino)-benzyl cyanide (cyanide), α·(ρ-chlorophenylsulfonium Q-oxyimide) Base)-benzyl cyanide, α-(4-nitrobenzenesulfonyloxyimino)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxy) Amino)-benzyl cyanide, α-(phenylsulfonyloxyimino)-4-chlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-2,4-dichloro Benzyl cyanide, α-(phenylsulfonyloxyimino)_2,6-dichlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-4-methoxybenzyl Cyanide, α-(2-chlorophenylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(phenylsulfonyloxyimino)-thio-2-ylacetonitrile , α-(4-dodecylbenzenesulfonyloxyimino)-benzyl cyanide, α-[(ρ-toluenesulfonyloxy-87- 201039064 amino)-4-methoxy Phenyl]acetonitrile, "-[(12-yard phenyl)-methoxy phenylimido)- 4-methoxyphenyl]acetonitrile, α-(methylxanthoxyimino)-4 - Cyanide, 〇:-(methyl extended oxygen Imino)-1-cyclopentenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclohexenylacetonitrile, <2-(methyl-fluorenyloxyimino) -I-cycloheptyl acetonitrile, methylsulfonyl oxyimino)--cyclooctyl acetonitrile, trifluoromethylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α_ (trifluoromethylsulfonyloxyimino)-cyclohexylacetonitrile 'α-(ethylsulfonyloxyimino)-ethylacetonitrile, α-(propylsulfonyloxyimino)- Propyl acetonitrile, α-(cyclohexylsulfonyloxyimido)-cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylpropenyloxy) Imino) 1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)- 1-cyclopentenylacetonitrile, α-(η-butylsulfonyloxyimino)-bucyclopentenylacetonitrile, "-(ethylsulfonyloxyimino)-1-cyclohexene Acetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(η-butylsulfonyloxyimino)-cyclohexenylacetonitrile, α -(methylsulfonate Oxyimine) phenylacetonitrile, α-(methylsulfonyloxyimino)-fluorene-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-benzene Acetonitrile, α-(trifluoromethylsulfonyloxyimino)-fluorene-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-fluorene-methoxyphenylacetonitrile And α-(propylsulfonyloxyimino)-fluorene-methylphenylacetonitrile, α-(methylsulfonyloxyimino)-ρ-bromophenylacetonitrile, and the like. Further, the sulfonate-based acid generator disclosed in JP-A-9-208554 (paragraph [0012] to -88*201039064 [0014] [Chem. 18] to [Chem. 19]), W02004 / 074242A2 (65~85M ^Examplel~ 40) The sulfonate-based acid generator disclosed. Further, the preferred content can be exemplified below, for example. [化4 9]

N—Ο—S〇2—C4H9 H3c——C=N——OS〇2——(CH2}3CH3 H3C—C=N—0S02——(CH2)3CH3N—Ο—S〇2—C4H9 H3c——C=N——OS〇2——(CH2}3CH3 H3C—C=N—0S02——(CH2)3CH3

N一O—S〇2—C4F9 I (cf2)6-h C=N—O—S02—C4F9 <cf2)4-h 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（ p-甲苯磺醯基）重氮甲烷、雙（1,卜二甲基乙基磺醯基）重氮甲烷、雙（環己基磺醯基）重氮甲烷、雙（2,4-二甲基苯基磺醯基）重氮甲烷等。〇又’也可使用特開平11-035551號公報、特開平11- 035552號公報、特開平11-035573號公報所揭示之重氮甲烷系酸產生劑。又，聚（雙磺醯基）重氮甲烷類，例如，特開平11-322707號公報所揭示之1,3 -雙（苯基磺醯基重氮甲基磺醯基）丙烷、1，4-雙（苯基磺醯基重氮甲基磺醯基）丁烷、 1,6 -雙（苯基磺醯基重氮甲基磺醯基）己烷、1，10-雙（苯基磺醯基重氮甲基磺醯基）癸烷、1,2-雙（環己基磺醯基重氮甲基磺醯基）乙烷、1,3-雙（環己基磺醯基重氮甲基 -89 - 201039064 磺醯基）丙烷、1，6-雙（環己基磺醯基重氮甲基磺醯基）己烷、1,10-雙（環己基磺醯基重氮甲基磺醯基）癸烷等。 (B)成份，可單獨使用1種該些之酸產生劑，或將2 種以上組合使用亦可。本發明中，（B )成份以使用氟化烷基磺酸離子作爲陰離子之鑰鹽系酸產生劑爲佳。本發明之正型光阻組成物中之（B )成份之含量爲，相對於（A )成份1〇〇質量份，以〇.5〜50質量份爲佳，以1 〜40質量份爲更佳。於上述範圍內時，可充分進行圖型形成。又，可得到均勻之溶液、良好之保存安定性等，而爲較佳。 <任意成份> 本發明之正型光阻組成物中，任意之成份，可再含有含氮有機化合物（D )(以下，亦稱爲（D )成份）亦可〇 (D )成份’只要可作爲酸擴散控制劑，即可作爲抑制經由曝光而由前述（B )成份所發生之酸的抑制劑之作用的物質時’並未有特別限定，目前已有各式各樣成份之提案’只要由公知之內容中任意選擇使用即可，其中又以脂肪族胺、特別是二級脂肪族胺或三級脂肪族胺爲佳。於此’脂肪族胺係指具有1個以上之脂肪族基之胺，該脂肪族基以碳數1〜2 0爲佳。脂肪族胺’例如，氨NH3之氫原子的至少1個被碳數20 -90 - 201039064 以下之烷基或羥烷基所取代之胺（烷基胺或烷醇胺）或_ 式胺等。烷基胺及烷醇胺之具體例如，η-己胺、η-庚胺、胺、η-壬胺、n-癸胺等之單烷基胺；二乙基胺、二-n_丙基胺、一 -η-庚胺、二-η-辛胺、二環己基胺等之二院基胺；N-O-S〇2-C4F9 I (cf2)6-h C=N-O-S02-C4F9 <cf2)4-h Diazomethane acid generator, dialkyl or bisarylsulfonate Specific examples of the basic heavy nitrogen methanes are, for example, bis(isopropylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(1,b-dimethylethylsulfonyl) Nitrogen methane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and the like. Further, the diazo-based acid generator disclosed in Japanese Laid-Open Patent Publication No. Hei 11-035551, No. Hei. Further, poly(disulfonyl)diazomethane, for example, 1,3 -bis(phenylsulfonyldiazomethylsulfonyl)propane disclosed in JP-A-11-322707, 1,4 - bis(phenylsulfonyldiazomethylsulfonyl)butane, 1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(phenylsulfonate) Mercaptodiazepinemethanesulfonyl)decane, 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane, 1,3-bis(cyclohexylsulfonyldiazomethyl) -89 - 201039064 sulfonyl)propane, 1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, 1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl) ) decane, etc. (B) The component may be used alone or in combination of two or more. In the present invention, the component (B) is preferably a key salt acid generator using a fluorinated alkylsulfonic acid ion as an anion. The content of the component (B) in the positive resist composition of the present invention is preferably from 5 to 50 parts by mass, more preferably from 1 to 40 parts by mass, per part by mass of the component (A). good. When it is within the above range, the pattern formation can be sufficiently performed. Further, it is preferred to obtain a uniform solution, good storage stability, and the like. <Optional Component> In the positive resist composition of the present invention, any component may further contain a nitrogen-containing organic compound (D) (hereinafter, also referred to as (D) component) or may be a component (D). As long as it can be used as an acid diffusion controlling agent, it can be used as a substance for suppressing the action of an acid which is generated by the above-mentioned (B) component by exposure, and is not particularly limited, and various proposals have been made for various components. 'As long as it is arbitrarily selected from the well-known contents, an aliphatic amine, particularly a secondary aliphatic amine or a tertiary aliphatic amine is preferred. Here, the 'aliphatic amine' means an amine having one or more aliphatic groups, and the aliphatic group is preferably a carbon number of from 1 to 20%. The aliphatic amine 'equivalently, for example, an amine (alkylamine or alkanolamine) or an amine of at least one of the hydrogen atoms of the ammonia NH3 substituted with an alkyl group or a hydroxyalkyl group having a carbon number of 20 - 90 - 201039064 or less. Specific examples of the alkylamine and the alkanolamine are monoalkylamines such as η-hexylamine, η-heptylamine, amine, η-decylamine, n-decylamine, etc.; diethylamine, di-n-propyl a second amine group such as an amine, mono-n-heptylamine, di-η-octylamine, dicyclohexylamine or the like;

三甲基胺、三乙胺、三-η-丙基胺、三-η-丁基胺、三-；〇_己月女、二-η_戊基胺、三-η-庚胺、三-η-辛胺、三-η-壬胺、三-η-癸胺、三-η-十二烷胺等之三烷基胺；二乙醇胺、三乙醇胺、二異丙醇胺、三異丙醇胺、二-η-辛醇胺、三-η_ 辛醇胺、硬脂基二乙醇胺、月桂基二乙醇胺等之烷基醇胺等。其中又以三烷基胺及/或烷醇胺爲佳。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，可爲單環式者（脂肪族單環式胺）亦可 ’多環式者（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，例如以碳數爲6〜1 0爲佳，具體而言’例如’ 1，5 -二氮雜二環[4·3.0]-5 -壬烯、1，8-二氮雜二環[5·4.0]-7-·( 碳烯、六伸甲基四胺、1，4-二氮雜二環 [2.2.2]辛烷等。芳香族胺，例如苯胺、吡啶、4 -二甲基胺基吡啶、吡咯、吲哚、吡唑、咪唑或該些之衍生物、二苯基胺、三苯基胺、三苄基胺等。其他之脂肪族胺，例如三（2-甲氧基甲氧基乙基）胺 201039064 、三{2-(2 -甲氧基乙氧基）乙基}胺、三{2-(2 -甲氧基乙氧基甲氧基）乙基}胺、三{2-(1-甲氧基乙氧基）乙基}胺、三{2-(1-乙氧基乙氧基）乙基}胺、三丨2-(1-乙氧基丙氧基）乙基}胺、三[2-(2-(2-羥基乙氧基 )乙氧基}乙基胺等。該些可單獨使用，或將2種以上組合使用亦可。 (D )成份，相對於（A )成份1 00質量份，通常爲使用0.01〜5.0質量份之範圍。於上述範圍內時，可提高光阻圖型之形狀、存放之經時安定性等。本發明之正型光阻組成物中，就防止感度劣化，或提高光阻圖型之形狀、存放之經時安定性等目的，可含有任意成份之由有機羧酸、與磷之含氧酸及其衍生物所成群所選擇之至少1種之化合物（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。隣之含氧酸，例如隣酸、膦酸（Phosphonic acid)、次膦酸（phosPhinic aeid )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-η-丁酯、磷酸二苯酯等磷酸酯等。膦酸（P h 0 s P h 0 n i c a c i d )衍生物例如膦酸二甲酯、膦 -92- 201039064 酸-二-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’苯基次膦酸等次膦酸酯。 (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，相對於（A)成份100質量份，通常爲使 0 用0.01〜5.0質量份之範圍。本發明之正型光阻組成物，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，提昇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。本發明之正型光阻組成物，可將材料溶解於有機溶劑 (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〇之溶液即可，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，r -丁內酯等之內酯類；丙酮 '甲基乙基酮、環庚酮、環己酮、甲基-η-戊酮、甲基異戊酮、2-庚酮等之酮類；乙二醇、二乙二醇、丙二醇、二丙二醇等之多元醇類具有乙二醇單乙酸酯、二乙二醇單乙酸酯、丙二醇單乙酸酯’或二丙二醇單乙酸酯等酯鍵結之化合物、具有前 -93- 201039064 述多元醇類或前述酯鍵結之化合物之單甲基醚、單乙基醚、單丙基酸、單丁基酸等之單院基醚或具有單苯基醚等醚鍵結之化合物等多元醇類之衍生物[其中又以丙二醇單甲基醚乙酸酯（PGMEA)、丙二醇單甲基醚（PGME)爲佳] » 二噁烷等環式醚類’或乳酸甲酯、乳酸乙酯（EL)、乙酸甲酯、乙酸乙酯、酢酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等之酯類；苯甲醚、乙基苄基醚、甲酚甲基醚、二苯基醚、二苄基醚、苯***、丁基苯基醚、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。該些有機溶劑可單獨使用亦可’或以2種以上之混合溶劑形式使用亦可。其中又以丙二醇單甲基醚乙酸酯（pGM EA)、丙二醇單甲基醚（PGME ) 、EL爲佳。又，P G Μ E A與極性溶劑混合所得之混合溶劑亦爲佳。其添加比（質量比），可考慮PGMEA與極性溶劑之相溶性等再作適當決定即可，較佳爲1 : 9〜9 : 1，更佳爲2 : 8〜 8 : 2之範圍內爲佳。更具體而言，例如添加極性溶劑之EL時，PGMEA : EL之質量比’較佳爲1: 9〜9: 1’更佳爲2: 8〜8: 2。又，添加極性溶劑之p G Μ E時，P G Μ E A : P G Μ E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 -94- 201039064 又’ （s )成份，，其他例如以使用PGMEA及EL中所選擇之至少1種與7-丁內酯之混合溶劑亦佳。此時，混合比例’以前者與後者之質量比，較佳爲70 : 30〜95 : 5。 (S)成份之使用量並未有特別限定，其可配合可塗佈於基板等之濃度，適當地設定塗佈膜厚度，一般而言，光阻組成物之固形成份濃度可使用於1〜20質量％，較佳爲 0 2〜15質量％之範圍内。上述本發明之正型光阻組成物，及添加於該正型光阻組成物中之（A1 )成份，爲以往所未知之新穎物質。又’本發明之正型光阻組成物，可於基板等支撐體上形成良好密著性之光阻膜。又，本發明之正型光阻組成物 ’具有良好之感度、焦點景深寬度（DOF )、曝光量寬容度（EL )等之微影蝕刻特性。又，因具有優良之遮罩重現性（例如遮罩缺陷因子-(MEF ))，故可形成光阻圖型， Q 且具有良好之光阻圖型之形成形狀（例如形成通孔圖型之際之該通孔的正圓性等）。EL爲，變化曝光量下進行曝光之際，於標靶尺寸偏移爲於一定範圍内之尺寸時，仍可以形成光阻圖型之曝光量範圍，即可得到忠實反應遮罩圖型之光阻圖型的曝光量範圍之意，EL寬容度，其數値越大時，伴隨曝光量變動所造成之圖型尺寸變化量越小，而可提高製程之寬容度，而爲較佳。DOF爲，同一曝光量中，將焦點上下移動進行曝光之際，對標靶尺寸之偏移於一定範圍内之尺寸下，可形成光阻圖型之焦點景深之範圍，即可 -95- 201039064 得到忠實反應遮罩圖型之光阻圖型之範圍，其數値越大越佳。可得到上述効果之理由仍未明瞭，其主要原因，推測爲結構單位（a 0 -1 )中，於較長側鏈之末端，具有極性基之含有- S02 -之環式基，而可使（B)成份之分布達到均勻，因而可提高微影蝕刻特性。又，結構單位（aO-2 )中，因具有較低沸點之脂肪族單環式基，顯影處理及洗滌後，曝光所產生之分解産物不易殘留於光阻膜中，因而可提高微影蝕刻特性。 <光阻圖型之形成方法> 本發明之光阻圖型之形成方法，爲包含於支撐體上，使用前述本發明之正型光阻組成物形成光阻膜之步驟、使前述光阻膜曝光之步驟，及使前述光阻膜顯影以形成光阻圖型之步驟。本發明之光阻圖型之形成方法，例如可依以下之方式進行。即，首先使用旋轉塗佈器等將前述本發明之正型光阻組成物塗佈於支撑體上，於8 〇〜1 5 0 °C之温度條件下，進行40〜120秒鐘，較佳爲60〜90秒鐘之預燒焙（post Apply Bake ( PAB ))以形成光阻膜。隨後對其例如使用ArF曝光裝置、電子線描繪裝置、EUV曝光裝置等曝光裝置，介由遮罩圖型進行曝光’或不介由遮罩圖型以電子線直接照射進行描繪等選擇性曝光後，於8 〇〜1 5 0 t：之溫度條件下 -96 - 201039064 ，實施40〜120秒鐘，較佳爲60〜90秒鐘之PEB (曝光後加熱；Post Exposure Bake)。其次將其使用鹼顯影液，例如使用〇. 1〜1 0質量％氫氧化四甲基銨（TM AH )水溶液進行顯影處理，較佳爲使用純水進行水洗、乾燥。又，必要時，可於上述顯影處理後進行燒焙處理（後燒焙；Post B ake )亦可。如此，即可得到忠實反應遮罩圖型之光阻圖型。 0 支撐體並未有特別限定，其可使用以往公知之物品，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。電路圖型之材料，例如可使用銅、鋁、鎳、金等。Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-; 〇_hexa-female, di-η-pentylamine, tri-η-heptylamine, three a trialkylamine such as η-octylamine, tri-η-decylamine, tri-η-decylamine or tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropyl An alkyl alcohol amine such as an alkanolamine, a di-n-octanolamine, a tri-n-octanolamine, a stearyl diethanolamine or a lauryl diethanolamine. Among them, a trialkylamine and/or an alkanolamine is preferred. 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 one (aliphatic monocyclic amine) or a polycyclic one (aliphatic polycyclic amine). The aliphatic monocyclic amine is specifically, for example, piperidine, piperazine or the like. An aliphatic polycyclic amine, for example, preferably having a carbon number of 6 to 10, specifically, for example, '1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-di Azabicyclo[5·4.0]-7-·(carbene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, etc. Aromatic amines such as aniline, pyridine , 4-dimethylaminopyridine, pyrrole, hydrazine, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, etc. Other aliphatic amines, such as three (2-methoxymethoxyethyl)amine 201039064, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy) Ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, triterpenoid 2-(1 -Ethoxypropoxy)ethyl}amine, tris[2-(2-(2-hydroxyethoxy)ethoxy)ethylamine, etc. These may be used alone or in combination of two or more. (D) The composition is usually in the range of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A). When the above range is satisfied, the shape and storage of the resist pattern can be improved. The stability of the composition of the present invention, the positive resistive composition of the present invention may contain any component of the organic carboxylic acid for the purpose of preventing deterioration of sensitivity, or improving the shape of the resist pattern, the stability over time of storage, and the like. At least one compound (E) selected from the group consisting of phosphorus oxyacids and derivatives thereof (hereinafter referred to as (E) component). Organic carboxylic acids such as acetic acid, malonic acid, citric acid , malic acid, succinic acid, benzoic acid, salicylic acid, etc.. Oxyacids, such as ortho-acid, Phosphonic acid, phosphinic acid (phosPhinic aeid), etc., among which phosphonic acid is preferred The oxo acid derivative of phosphoric acid, for example, an ester obtained by substituting a hydrogen atom of the oxo acid with a hydrocarbon group, or the like, the above-mentioned hydrocarbon group, for example, an alkyl group having a carbon number of 1 to 5, an aryl group having a carbon number of 6 to 15, or the like. For example, a phosphate such as di-n-butyl phosphate or diphenyl phosphate, etc. Phosphonic acid (P h 0 s P h 0 nicacid ) derivatives such as dimethyl phosphonate, phosphine-92-201039064 acid-di-η Phosphonates such as butyl ester, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, etc. Phosphate Inic acid derivatives such as 'phosphinic acid esters such as 'phenyl phosphinic acid.' (E) may be used alone or in combination of two or more (E) components, relative to (A) components. 100 parts by mass, usually in the range of 0.01 to 5.0 parts by mass for the 0. The positive type resist composition of the present invention may 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 coating agent for improving coatability, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, a halo preventing agent, a dye, and the like. The positive resist composition of the present invention can be produced by dissolving a material in an organic solvent (hereinafter also referred to as (S) component). The (S) component is not particularly limited as long as it can dissolve the components to be used to form a uniform enthalpy. 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 r-butyrolactone; ketones such as acetone 'methyl ethyl ketone, cycloheptanone, cyclohexanone, methyl-η-pentanone, methyl isoamyl ketone, 2-heptanone, and the like Polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc. have ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetic acid a compound such as an ester-ester-bonded compound, a single-meridyl group having a monomethyl ether, a monoethyl ether, a monopropyl acid, a monobutyl acid or the like having a polyhydric alcohol or a compound bonded by the foregoing esters of the aforementioned -93-201039064 a derivative of a polyhydric alcohol such as an ether or a compound having an ether bond such as a monophenyl ether [wherein propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) is preferred] » dioxins Alkane and other cyclic ethers' or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl phthalate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, B Esters such as ethyl oxypropionate; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenylethyl ether, butylphenyl ether, B Benzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cumene, trimethylbenzene aromatic organic solvents and the like. These organic solvents may be used singly or in the form of a mixture of two or more kinds of solvents. Among them, propylene glycol monomethyl ether acetate (pGM EA), propylene glycol monomethyl ether (PGME), and EL are preferred. Further, a mixed solvent of P G Μ E A mixed with a polar solvent is also preferred. The addition ratio (mass ratio) may be appropriately determined by considering the compatibility of PGMEA with a polar solvent, and is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. good. More specifically, for example, when the EL of the polar solvent is added, the mass ratio 'PGMEA: EL is preferably 1: 9 to 9: 1' and more preferably 2: 8 to 8: 2. Further, when p G Μ E of a polar solvent is added, the mass ratio of PG EA EA : PG Μ E is preferably 1: 9 to 9: 1 'better 2: 8 to 8: 2' is preferably 3: 7 to 7: 3 -94 to 201039064 Further, it is also preferable to use a mixture solvent of at least one selected from the group consisting of PGMEA and EL and 7-butyrolactone. At this time, the mixing ratio 'the mass ratio of the former to the latter is preferably 70: 30 to 95: 5. The amount of the component (S) used is not particularly limited, and the thickness of the coating film can be appropriately set in accordance with the concentration which can be applied to a substrate or the like. In general, the solid concentration of the photoresist composition can be used for 1~ 20% by mass, preferably in the range of 0 2 to 15% by mass. The positive-type photoresist composition of the present invention and the (A1) component added to the positive-type photoresist composition are novel materials which have not been known in the past. Further, the positive resist composition of the present invention can form a photoresist film having good adhesion on a support such as a substrate. Further, the positive resist composition of the present invention has lithographic etching characteristics such as good sensitivity, focal depth of field (DOF), and exposure latitude (EL). Moreover, since it has excellent mask reproducibility (for example, mask defect factor-(MEF)), it can form a photoresist pattern, Q and has a good photoresist pattern forming shape (for example, forming a via pattern) The roundness of the through hole, etc.). When EL is used for exposure under varying exposure, when the target size shift is within a certain range, the exposure range of the resist pattern can still be formed, and the light of the faithful reaction mask pattern can be obtained. The range of the exposure amount of the resistive pattern, the EL latitude, and the larger the number, the smaller the amount of change in the pattern size caused by the variation in the amount of exposure, and the latitude of the process can be improved, which is preferable. DOF is the range of the depth of focus of the photoresist pattern that can be formed when the focus is shifted up and down for exposure in the same exposure. -95- 201039064 The range of the resist pattern of the faithful response mask pattern is obtained, and the larger the number, the better. The reason why the above effects can be obtained is still unclear. The main reason is that the structural unit (a 0 -1 ) has a polar group containing a ring group of -S02 - at the end of the longer side chain. (B) The distribution of the components is uniform, thereby improving the lithographic etching characteristics. Further, in the structural unit (aO-2), since the aliphatic monocyclic group having a lower boiling point is formed, the decomposition product generated by the exposure after the development treatment and washing is less likely to remain in the photoresist film, thereby improving the lithography etching. characteristic. <Formation method of photoresist pattern> The method for forming a photoresist pattern of the present invention is a step of forming a photoresist film by using the positive-type photoresist composition of the present invention on a support, and the light is formed a step of exposing the resist film and a step of developing the photoresist film to form a photoresist pattern. The method for forming the photoresist pattern of the present invention can be carried out, for example, in the following manner. That is, first, the positive-type photoresist composition of the present invention is applied onto a support by a spin coater or the like, and is subjected to a temperature of 8 Torr to 150 ° C for 40 to 120 seconds, preferably 40 minutes to 120 seconds. It is a post-bake (PAB) of 60 to 90 seconds to form a photoresist film. Then, for example, an exposure apparatus such as an ArF exposure apparatus, an electron beam drawing apparatus, or an EUV exposure apparatus is used, and exposure is performed by a mask pattern or a selective exposure is performed by direct irradiation with an electron beam through a mask pattern. , in the temperature range of -8 - 201039064 under 8 〇 ~ 1 50 0 t: 40 to 120 seconds, preferably 60 to 90 seconds of PEB (post exposure heating; Post Exposure Bake). Next, it is subjected to development treatment using an alkali developer, for example, an aqueous solution of 〜. 1 to 10% by mass of tetramethylammonium hydroxide (TM AH ), preferably washed with pure water and dried. Further, if necessary, baking treatment (post-baking; Post B ake) may be carried out after the above development treatment. In this way, a photoresist pattern of a faithful response mask pattern can be obtained. The support body is not particularly limited, and a conventionally known article such as a substrate for an electronic component or an article having a specific wiring pattern formed thereon may be used. More specifically, for example, a substrate made of a metal such as germanium wafer, copper, chromium, iron, or aluminum, or a glass substrate. For the material of the circuit pattern, for example, copper, aluminum, nickel, gold, or the like can be used.

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bArC 〇 )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。前述光阻組成物，以對Kr F準分子雷射、ArF準分子雷射、EB或EUV，特別是對ArF準分子雷射爲有效。光阻膜之曝光方法’可於空氣或氮氣等惰性氣體中進行之通常曝光（乾曝光）亦可，浸潤式曝光（Liquid -97- 201039064Further, for example, an inorganic or/or organic film may be provided on the substrate. An inorganic film such as an inorganic antireflection film (inorganic BARC). An organic film such as an organic antireflection film (organic bArC®). The wavelength used for exposure is not particularly limited, and an ArF excimer laser, a KrF excimer laser, an f2 excimer laser, an EUV (very ultraviolet ray), a VUV (vacuum ultraviolet ray), an EB (electron line) can be used. , X-ray, soft X-ray and other radiation. The aforementioned photoresist composition is effective for Kr F excimer laser, ArF excimer laser, EB or EUV, especially for ArF excimer laser. The exposure method of the photoresist film can be performed by usual exposure (dry exposure) in an inert gas such as air or nitrogen, and immersion exposure (Liquid -97- 201039064)

Immersion Lithography)亦可 ° 浸潤式曝光，爲預先於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（浸潤媒體），並於該狀態下進行曝光（浸潤曝光）之曝光方法。浸潤媒體，以使用具有較空氣之折射率爲大，且較被曝光之光阻膜所具有之折射率爲小之折射率的溶劑爲佳。該溶劑之折射率，只要爲前述範圍内時，並未有特別限制〇具有較空氣之折射率爲大，且較前述光阻膜之折射率爲小之折射率的溶劑，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，以含有C3HC12F5、 C4F9OCH3、C4F9OC2H5、C5H3F7等之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。氟系惰性液體爲具有上述範圍之沸點的液體時，於曝光結束後，可以簡便之方法去除浸潤用之媒體，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-四氫呋喃）（沸點1 0 2 °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。 -98- 201039064 浸潤式媒體，就費用、安全性、環境問題觀點，以使用水爲佳。 <高分子化合物> 本發明之高分子化合物爲，具有下述通式表示之結構單位（aO-l )，及下述通式（aO-2 結構單位（aO-2 )之高分子化合物。本發明之高分子化合物之説明，爲與前述型光阻組成物之（A 1 )成份中所説明者爲相同, 【化5 0】、廣泛性等Immersion Lithography) can also be immersed and exposed to a solvent (infiltration medium) having a refractive index higher than that of air between the lens at the lowermost position of the photoresist film and the exposure device, and in this state. Exposure method for exposure (wetting exposure). It is preferred to wet the medium to use a solvent having a refractive index larger than that of air and having a refractive index smaller than that of the exposed photoresist film. When the refractive index of the solvent is within the above range, there is no particular limitation, and a solvent having a refractive index larger than that of air and having a refractive index smaller than that of the above-mentioned photoresist film, for example, water or fluorine It is an inert liquid, an oxime solvent, a hydrocarbon solvent, etc. Specific examples of the fluorine-based inert liquid include a liquid containing a fluorine-based compound such as C3HC12F5, C4F9OCH3, C4F9OC2H5, or C5H3F7 as a main component, and a boiling point of 70 to 180 °c, preferably 80 to 160 °c. Better. When the fluorine-based inert liquid is a liquid having a boiling point within the above range, it is preferred to remove the medium for wetting in a simple manner after the completion of the exposure. 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 above perfluoroalkyl ether compound, for example, perfluoro(2-butyl-tetrahydrofuran) (boiling point of 120 ° C), the above perfluoroalkylamine compound such as perfluorotributylamine (boiling point 1 74 ° C) and so on. -98- 201039064 Infiltration media, in terms of cost, safety, and environmental issues, it is better to use water. <Polymer compound> The polymer compound of the present invention has a structural unit represented by the following formula (aO-1) and a polymer compound of the following formula (aO-2 structural unit (aO-2)) The description of the polymer compound of the present invention is the same as that described for the (A 1 ) component of the above-mentioned type of photoresist composition, and the broadness and the like.

(aO-l )所 )所表示之本發明之正之內容。The content of the present invention represented by (aO-l) is shown.

R1R1

[式中，R1爲氫原子、碳數1〜5之烷基或碳數烷基，R2爲2價之鍵結基，R3，爲其環骨架中環式基，R爲氫原子、碳數1〜5之烷基或碳數烷基，R21爲分支鏈狀之烷基；R22，爲可與該原子共同形成脂肪族單環式基之基]。 1〜5之鹵化言有-S〇2-之 1〜5之鹵化 L22鍵結之碳 -99 201039064 【實施方式】 [實施例] 以下’將以實施例對本發明作更詳細之說明，本發明並不受該些例示所限定。本實施例中’化學式（丨）所表示之單位記載爲「化合物（1 )」，其他式所表示之化合物亦爲相同之記載。 [單體合成例1 (化合物（1 )之合成）] 後述聚合物合成例所使用之化合物（1 )爲依以下之順序合成。在氮雰圍下、50 0ml之3 口燒瓶中，加入醇（1) 2〇g( 105,14mmol)、乙基二異丙基胺基碳二醯亞胺（EDCI)鹽酸鹽3 0.23 g ( 157,7 1mmol )及二甲基胺基吡啶（DMAP ) 0.6g(5mmol)之THF溶液300ml，於其中，氷冷下（<rc )加入前驅物（1) 16.67g(115_66mmol)後，於室溫下攪拌1 2小時。以薄層色層分析法（TLC )確認原料消失後，加入 5 0ml水使反應停止。將反應溶劑減壓濃縮，使用乙酸乙醋萃取3次所得之有機層，依序以水、飽和碳酸氫鈉、1N-HClaq順序洗淨。減壓下，使餾除溶劑所得之產物乾燥後，得化合物（1 )。所得化合物（η之機器分析結果，係如以下所示。 •H-NMR ( CDC13 ' 400MHz ) ·· δ ( ppm ) =6.22 ( s > 1H，Ha ) ，5.70 ( s，1H，Hb ) ，4 _ 7 1 - 4 · 8 5 ( m，2 Η，Hc，d -100 - 201039064 )，4.67 ( s，2H，Hk ) ，3.40-3.60 ( m，2H，He，f )， 2.5 8 -2.70 ( m，1H，Hg) ，2.11-2.21 ( m，2H，Hh)， 2.00 ( s > 3H，H1 ) ，1.76-2.09 ( m，2H，Hj ). 【化5 1】Wherein R1 is a hydrogen atom, an alkyl group having a carbon number of 1 to 5 or a C1 alkyl group, R2 is a divalent bond group, R3 is a cyclic group in the ring skeleton, and R is a hydrogen atom and a carbon number of 1 An alkyl group or a decyl group of 1-5, R21 is a branched alkyl group; and R22 is a group which can form an aliphatic monocyclic group together with the atom. 1 to 5 of the halogenated words -S〇2- 1 to 5 of halogenated L22 bonded carbon-99 201039064 [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples, the present invention It is not limited by these illustrations. In the present embodiment, the unit represented by the chemical formula (") is described as "compound (1)", and the compounds represented by the other formulae are also the same. [Monomer Synthesis Example 1 (Synthesis of Compound (1))] The compound (1) used in the polymer synthesis example described later was synthesized in the following order. Under a nitrogen atmosphere, a 50 ml 3-neck flask was charged with alcohol (1) 2 g (105, 14 mmol) and ethyl diisopropylaminocarbodiimide (EDCI) hydrochloride 3 0.23 g ( 300 ml of 157,7 1 mmol) and dimethylaminopyridine (DMAP) 0.6 g (5 mmol) in THF, and then added to the precursor (1) 16.67 g (115-66 mmol) under ice cooling (<rc), Stir at room temperature for 12 hours. After confirming the disappearance of the starting material by thin layer chromatography (TLC), 50 ml of water was added to stop the reaction. The reaction solvent was concentrated under reduced pressure, and the obtained organic layer was extracted three times with ethyl acetate and washed sequentially with water, saturated sodium hydrogen carbonate and 1N-HClaq. The product obtained by distilling off the solvent was dried under reduced pressure to give Compound (1). The results of the machine analysis of the obtained compound (η) are as follows. • H-NMR (CDC13 '400MHz) ··δ (ppm) =6.22 ( s > 1H, Ha ) , 5.70 ( s, 1H, Hb ) , 4 _ 7 1 - 4 · 8 5 ( m,2 Η,Hc,d -100 - 201039064 ),4.67 ( s,2H,Hk ) , 3.40-3.60 ( m,2H,He,f ), 2.5 8 -2.70 (m,1H,Hg) ,2.11-2.21 ( m,2H,Hh), 2.00 ( s > 3H,H1 ) , 1.76-2.09 ( m,2H,Hj ). [Chem. 5 1]

前驅物⑴Precursor (1)

醇⑴Alcohol (1)

化合物⑴Compound (1)

Ο [單體合成例2 (化合物（2 )之合成）] 後述聚合物合成例所使用之化合物（2 )爲依以下順序合成。於具備有溫度計、冷卻管及攪拌裝置之2 L之三口燒瓶中，加入二醇酸 37.6g(494mmol) 、DMF700mL、碳酸鉀 86.5g ( 626mmol )、碘化鉀 28.3g(170mmol)，於室溫下攪拌3 0分鐘。隨後，緩緩加入氯乙酸2 -甲基-2 -金剛烷酯 -101 - 201039064 100g(412mmol)之二甲基甲醯胺300mL溶液。升溫至40 °C，攪拌4小時。反應結束後，加入二乙基醚2000mL後過濾，所得溶液以蒸餾水500mL洗淨3次。以甲苯（300mL ) •庚烷（200mL )之混合溶液進行晶析，得目的物（2-( 2- ( 2-甲基-2-金剛烷基氧基）-2-側氧基乙氧基）-2-側氧基乙醇）之無色固體78g (產率67%、GC純度99%)。所得化合物之機器分析結果，係如以下所示。 ^H-NMR : 1 .59 ( d，2H，J=12.5Hz ) ，1.64 ( s，3H )单体 [Monomer Synthesis Example 2 (Synthesis of Compound (2))] The compound (2) used in the polymer synthesis example described later was synthesized in the following order. 37.6 g (494 mmol) of glycolic acid, 700 mL of DMF, 86.5 g of potassium carbonate (626 mmol), and 28.3 g of potassium iodide (170 mmol) were placed in a 2-L three-necked flask equipped with a thermometer, a cooling tube and a stirring device, and stirred at room temperature. 30 minutes. Subsequently, a solution of 2-methyl-2-adamantyl chloroacetate-101-201039064 100 g (412 mmol) of dimethylformamide in 300 mL was slowly added. The temperature was raised to 40 ° C and stirred for 4 hours. After completion of the reaction, 2000 mL of diethyl ether was added, followed by filtration, and the resulting solution was washed three times with 500 mL of distilled water. Crystallization was carried out in a mixed solution of toluene (300 mL) and heptane (200 mL) to give the desired compound (2-(2-methyl-2-adamantyloxy)-2-oxoxyethoxy) (2-oxoethanol) 78 g of a colorless solid (yield 67%, GC purity: 99%). The results of the machine analysis of the obtained compound are shown below. ^H-NMR: 1.59 (d, 2H, J = 12.5 Hz), 1.64 (s, 3H)

，1.71 〜1.99(m，10H) ，2.29(m，2H) ，2.63(t，1H ，J = 5,2Hz ) ，4.29 ( d，2H，J = 5.2Hz) ，4.67 ( s - 2H ) 0 13C-NMR ： 22.3 5，26.56，27.26，3 2.97，34.54 ’ 36.29 - 38.05 ， 60.54 ， 61.50 ， 89.87 > 165.97 > 172.81 ° GC-MS: 282 ( M+ ，0.02%) ，1 6 5 ( 0.09%) ，149 (4 0%) > 148 ( 1 00%) > 1 3 3 ( 22%) > 117(2.57%) ’ 8 9 ( 0.40%) ° 由上述結果得知，確認所得化合物爲2_ ( 2- ( 2-甲基-2-金剛烷基氧基）-2-側氧基乙氧基）-2-側氧基乙醇。隨後，於具備有溫度計、冷卻管及攪拌裝置之2L之二口燒瓶中，加入2 - ( 2 - ( 2 -甲基-2 -金剛院基氧基）·2 -側氧基乙氧基）-2-側氧基乙醇165g( 584mmol) 、THF2000mL 、三乙胺 105mL ( 754mmol ) 、p -甲氧基酚〇 _ 16 5 g ( 1 OOOppm )，使其溶解。溶解後，於氷浴下緩緩加入甲基丙烯醯氯62.7mL( 648mmol)後’升溫至室溫’攪伴3小 -102- 201039064 時。反應結束後，加入二乙基醚l〇〇〇mL ’以蒸餾水200mL 洗淨5次。濃縮萃取液，得目的物（化合物（2 ))之無色液體198g (產率97%、GC純度99%)。所得化合物（2 )之機器分析結果，係如以下所示。 W-NMR: 1.58( d，J=12.5Hz，2H) ，1-63 (s，3H), 1.71 ~ 1.99 (m, 10H), 2.29 (m, 2H), 2.63 (t, 1H, J = 5, 2Hz), 4.29 (d, 2H, J = 5.2Hz), 4.67 ( s - 2H ) 0 13C -NMR: 22.3 5,26.56, 27.26,3 2.97,34.54 ' 36.29 - 38.05 , 60.54 , 61.50 , 89.87 > 165.97 > 172.81 ° GC-MS: 282 ( M+ , 0.02%) , 1 6 5 ( 0.09%) , 149 (4 0%) > 148 ( 1 00%) > 1 3 3 ( 22%) > 117 (2.57%) ' 8 9 ( 0.40%) ° From the above results, it is confirmed that the obtained compound is 2_ (2-(2-Methyl-2-adamantyloxy)-2-oxoethoxyethoxy)-2-oxoethanol. Subsequently, in a 2 L two-necked flask equipped with a thermometer, a cooling tube and a stirring device, 2 -( 2 -( 2 -methyl-2 -adamantyloxy)·2 -sideoxyethoxy) was added. 1-2 g of oxyethanol 165 g (584 mmol), THF 2000 mL, triethylamine 105 mL (754 mmol), and p-methoxyphenol hydrazine _ 16 5 g (1 OOO ppm) were dissolved. After the dissolution, 62.7 mL (648 mmol) of methyl propylene chloride was slowly added to the ice bath, and then the temperature was raised to room temperature and stirred for 3 hours -102 to 201039064. After completion of the reaction, diethyl ether 1 mL mL was added and washed 5 times with 200 mL of distilled water. The extract was concentrated to give 198 g (yield: 97%, GC purity: 99%) as a colorless liquid of the object compound (2). The results of the machine analysis of the obtained compound (2) are shown below. W-NMR: 1.58 (d, J = 12.5 Hz, 2H), 1-63 (s, 3H)

，1.71〜1.89(m，8H) ，1.98(s，3H) ，2.〇〇(m，2H )，2.30 ( m，2H ) ，4.62 ( s，2H ) ，4.8〇 ( s，2H )， ◎ 5.66 (m，1H)，6.23(m，1H)。 13C-NMR ： 18.04，22.1 5，26.42，27.14，3 2.82， 34.3 8，36.11，3 7.92，60.44，6 1.28 , 89.42，1 26.79， 135.18 ， 165.61 ， 166.30 ， 167.20 ° GC-MS： 350 (M+ - 1.4%) ，2 0 6 ( 0.1 3%) ，149 ( 4 7%) ，1 4 8 ( 1 0 0 % ) > 1 33 ( 20%) ,69 ( 3 7%)。 [聚合物合成例1] Q 於設置有溫度計、迴流管、氮氣導入管之多口燒瓶中，使 15.80g ( 50.00mmol )之化合物（i ) 、5.83g ( 16.67mmol)之化合物（2) 、4.67g ( 20 83inmol)之化合物（4 ) 、3.93g ( 20.00mm〇l )之化合物（5 )溶解於 55_7lg之甲基乙基酮（MEK )中。於該溶液中，添加聚合起使劑之偶氮一異丁酸一甲酯（V-6〇i) 8.08mmol，使其溶解。將其將其於氮氣雰圍下’以3小時時間緩緩滴入溶解有 25_66g ( 97_92mol)之化合物（3)的 MEK3〇 33g、並加熱至8(TC所得之溶液中。滴入結束後，將反應液加熱攪 -103- 201039064 拌2小時，隨後，將反應液冷卻至室溫。將所得之反應聚合液滴入大量之n_庚院中進行析出聚合物之操作’將沈殺之白色粉體濾除’依序使用n_庚烷、異丙基醇、甲醇之順序洗淨、乾燥’得3 5 g之目的物之高分子化合物1 ° 該高分子化合物1，以GP C測定所求得之標準聚苯乙嫌換算之質量平均分子量（Mw)爲10,500，分子量分散度 (Mw / Μη )爲1.75。又，以碳13核磁共振圖譜（όΟΟΜΗζ 13C-NMR)所求得之共聚合組成比（構造式中之各結構單位之比例（莫耳比））爲，1/m/n/〇/p = 34‘3/9.4/ 33.0/11.0/12.3。【化5 2】, 1.71~1.89(m,8H), 1.98(s,3H), 2.〇〇(m,2H), 2.30 ( m,2H ) , 4.62 ( s,2H ) ,4.8〇( s,2H ), ◎ 5.66 (m, 1H), 6.23 (m, 1H). 13C-NMR : 18.04, 22.1 5,26.42, 27.14,3 2.82, 34.3 8,36.11,3 7.92,60.44,6 1.28 , 89.42,1 26.79, 135.18 , 165.61 , 166.30 , 167.20 ° GC-MS: 350 (M+ - 1.4%), 2 0 6 (0.1 3%), 149 (4 7%), 1 4 8 (100%) > 1 33 (20%), 69 (3 7%). [Polymer Synthesis Example 1] Q. In a multi-necked flask equipped with a thermometer, a reflux tube, and a nitrogen introduction tube, 15.80 g (50.00 mmol) of the compound (i) and 5.83 g (16.67 mmol) of the compound (2), 4.67 g (20 83 inmol) of the compound (4) and 3.93 g (20.00 mm 〇l) of the compound (5) were dissolved in 55-7 g of methyl ethyl ketone (MEK). To the solution, 8.08 mmol of a azo-isobutyric acid monomethyl ester (V-6〇i) of a polymerization initiator was added to dissolve it. This was slowly dropped into a solution of 25 g of the compound (3) dissolved in 25-66 g (97-92 mol) of MEK3(R) under a nitrogen atmosphere for 3 hours, and heated to 8 (TC obtained solution). After the completion of the dropwise addition, The reaction solution is heated and stirred-103-201039064 for 2 hours, and then the reaction solution is cooled to room temperature. The obtained reaction polymerization is dropped into a large amount of n_Gengyuan to carry out the operation of precipitating the polymer. The polymer is filtered and dried in the order of n-heptane, isopropyl alcohol, and methanol. The polymer compound 1 is obtained as a target compound of 3 5 g of the polymer compound 1 as determined by GP C. The standard polystyrene benzene has a mass average molecular weight (Mw) of 10,500 and a molecular weight dispersion (Mw / Μη) of 1.75. Further, the copolymerization composition obtained by carbon 13 nuclear magnetic resonance spectroscopy (όΟΟΜΗζ 13C-NMR) is obtained. The ratio (ratio of each structural unit in the structural formula (Mohr ratio)) is 1/m/n/〇/p = 34'3/9.4/33.0/11.0/12.3. [Chemical 5 2]

高分子化合物1 [聚合物合成例2〜7] 參考合成例〗之記載，變更單體種類、添加比例、聚合起始劑之使用量，以合成高分子化合物2〜7。 -104- 201039064 【化5 3】Polymer Compound 1 [Polymer Synthesis Examples 2 to 7] The polymer type 2 to 7 was synthesized by changing the monomer type, the addition ratio, and the amount of the polymerization initiator to be used in the description of the synthesis example. -104- 201039064 【化5 3】

/ 24.1/ 19.5/ 12.4 (莫耳比））【化5 4】/ 24.1/ 19.5/ 12.4 (Morbi)) [Chem. 5 4]

〇〇

OHOH

〇. 高分子化合物3 (Mw = 7,500 ' Mw/Mn=1.42、l/m/n/o/p = 36.4/21.9 / 15.9/ 14.0/ 11.8 (莫耳比））高分子. Polymer Compound 3 (Mw = 7,500 ' Mw/Mn=1.42, l/m/n/o/o = 36.4/21.9 / 15.9/ 14.0/ 11.8 (Morbi))

【化5 5 I[5 5 I

(Mw=8j 400 ' Mw//Mn=1.56' \ / m / η / ο / ^ = 1> S .2 / 22.3/16.1/13.8/12.6 (莫耳比）） -105- 201039064 【化5 6(Mw=8j 400 ' Mw//Mn=1.56' \ / m / η / ο / ^ = 1> S .2 / 22.3/16.1/13.8/12.6 (Morbi)) -105- 201039064 [Chem. 5 6

高分子化合物5 (Mw = 8，900、Mw/Mn=1.64、1/ m / η / 0 = 34.7 / 11.1/ 42.6 / 11.6 (莫耳比））。【化5 7】Polymer Compound 5 (Mw = 8,900, Mw/Mn = 1.64, 1 / m / η / 0 = 34.7 / 11.1/ 42.6 / 11.6 (mole ratio)). [化5 7]

高分子化合物ό (Mw = 7，5 0 0、M w / Μ η = 1 · 6 0、1 / m / η = 3 9 8 / 4 1 · 2 19.0 (莫耳比））。【化5 8】The polymer compound ό (Mw = 7,500, M w / Μ η = 1 · 60, 1 / m / η = 3 9 8 / 4 1 · 2 19.0 (mole ratio)). 【化5 8】

(M w = 6 > 700、Mw/ Μη=1.58、1 / m / η = 4 0 · 4 / 3 8 · 7 20.9 (莫耳比））。 [實施例1〜5、比較例1〜2] 依表1所示將各成份混合、溶解以製造正型光阻組成 -106- 201039064(M w = 6 > 700, Mw / Μη = 1.58, 1 / m / η = 4 0 · 4 / 3 8 · 7 20.9 (mr ratio)). [Examples 1 to 5, Comparative Examples 1 to 2] The components were mixed and dissolved as shown in Table 1 to produce a positive photoresist composition -106 - 201039064

[表i] (A)成份 (B戚份 (D诚份 (S诚份實施例1 (A)-l 『1〇〇1 (B)-l Π1.01 (D)-l [0.151 (S)-l 『27001 ⑶-2 [i〇l 實施例2 (A)-2 [1001 (B)-l 「11.01 (D)-l [0.151 (S)-l [27001 (S)-2 n〇i 實施例3 (A)-3 riooi (B)-l fll.oi (D)-l 『0.151 (S)-l [27001 (S)-2 『101 實施例4 (A)-4 『1001 (B)-l 『11.01 (D)-l [0.151 (S)_l [27001 (S)-2 [101 實施例5 (A)-5 「1001 (B)-l rn.oi (D)-l [0.151 (S)-l Γ2700] (S)-2 『101 比較例1 (A)-6 「1001 (B)-l 「11.01 (D)-l Γ0-51 (S)-l [27001 (S)-2 [101 比較例2 (A)-7 「1001 (B)-l Γ11.01 (D)-l [0.151 (S)-l [2700] (S)-2 「101 表1中，[]内之數値爲表示添加量（質量份）。又，表 1中之記號分別如以下所示內容。 (A) -1 :前述高分子化合物1。 (A) -2 :前述高分子化合物2。 (A) -3 :前述高分子化合物3。 (A) -4 :前述高分子化合物4。 (A) _5 :前述高分子化合物6。 (A) -6 :前述高分子化合物5。 (A) -7 :前述高分子化合物7。 (B) - 1 :下述化學式（B ) -1所表示之化合物。 (D ) -1 :三-η-戊基胺。 (S ) -1 : PGMEA/ PGME = 6/ 4 (質量比）之混合溶 -107- 201039064 劑。 (s ) -2 : r -丁內酯。【化5 9】[Table i] (A) Ingredients (B戚份(D Chengfen (S Chengcheng Example 1 (A)-l 『1〇〇1 (B)-l Π1.01 (D)-l [0.151 (S )-l 『27001 (3)-2 [i〇l Example 2 (A)-2 [1001 (B)-l "11.01 (D)-l [0.151 (S)-l [27001 (S)-2 n〇 i Example 3 (A)-3 riooi (B)-l fll.oi (D)-l 『0.151 (S)-l [27001 (S)-2 『101 Example 4 (A)-4 『1001 ( B)-l 『11.01 (D)-l [0.151 (S)_l [27001 (S)-2 [101 Example 5 (A)-5 "1001 (B)-l rn.oi (D)-l [ 0.151 (S)-l Γ2700] (S)-2 『101 Comparative Example 1 (A)-6 "1001 (B)-l "11.01 (D)-l Γ0-51 (S)-l [27001 (S) -2 [101 Comparative Example 2 (A)-7 "1001 (B)-l Γ11.01 (D)-l [0.151 (S)-l [2700] (S)-2 "101 Table 1, [] The number in the figure is the amount of addition (parts by mass). The symbols in Table 1 are as follows. (A) -1 : The polymer compound 1 described above. (A) -2 : The polymer compound 2 described above (A) -3 : The polymer compound 3 (A) -4 : The polymer compound 4 (A) _5 : The polymer compound 6 (A) -6 : The polymer compound 5 (A) -7 : The above polymer compound 7. (B) - 1 : The following chemical formula (B) ) Compound represented by -1 (D ) -1 : Tri-η-pentylamine (S ) -1 : PGMEA/ PGME = 6/ 4 (mass ratio) of mixed solution -107- 201039064. (s ) -2 : r - butyrolactone. [Chemical 5 9]

(合成方法於後敘述）使用所得之光阻組成物，依以下順序形成光阻圖型，並評估其微影蝕刻物性。 [光阻圖型之形成-1] 將有機系抗反射膜組成物「A R C 2 9 A」（商品名，普力瓦科技公司製）使用旋轉塗佈器塗佈於1 2英吋之矽晶圓上’熱壓板上進行205 °C、60秒鐘之燒焙、乾燥結果，形成膜厚8 9nm之有機系抗反射膜。將上述所製得之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，以90°C、60秒鐘進行預燒焙（PAB )處理，經乾燥，形成膜厚100nm之光阻膜。隨後，將保護膜形成用塗佈液「TILC-05 7」（商品名、東京應化工業股份有限公司製）使用旋轉塗佈器塗佈於前述光阻膜上，經90°C、60秒鐘加熱結果，形成膜厚35nm 之頂部塗覆。 -108- 201039064 隨後，使用ArF浸潤式曝光裝置NSR-S609B (理光公司製；NA (開口數）=1.〇7、2/ 3輪帶照明、縮小倍率1/ 4倍、浸潤媒體：水），將ArF準分子雷射（193nm)介由使用通孔直徑9〇nm /間距157.5nm之接觸孔圖型（以下，亦稱爲CH圖型）作爲標靶之遮罩圖型進行選擇性照射。隨後，進行80°C、60秒鐘之PEB處理，再於23°C下，以2.38質量％之TMAH水溶液NMD-3(東京應化工業股份有 0 限公司製）進行60秒鐘顯影，其後，再以30秒鐘，使用純水進行水洗，進行振動乾燥。其結果，無論任一例示中，皆形成有以通孔直徑90nm 、間距157.5 nm之CH圖型形成圖型。 [正圓性評估] 使用測長SEM (日立製作所公司製，製品名：S-9220 )’由上方觀察所形成之CH圖型，對各CH圖型中之25個〇通孔’以24方向測定由該通孔之中心至外緣之距離，由其結果算出標準偏差（σ )之3倍値（3 σ )。依此方式所求得之3 σ ，其數値越小表示比少該通孔之正圓性越高之意。其結果係如表2所示。 -109- 201039064 表2] 正圓性實施例1 6.6 實施例2 6.2 實施例3 6.7 實施例4 6.5 實施例5 7.0 比較節 7.1 比較例2 7.4 由上述結果明確得知，實施例1〜5之光阻組成物與比較例1〜2相比較時，所形成之通孔圖型具有較高之正圓性 [光阻圖型之形成-2] 使用實施例1〜2及比較例1之光阻組成物，依上述[光阻圖型之形成-1 ]相同方法，製得通孔直徑90nm (間距爲 157_:5nm)之CH圖型。形成該CH圖型之際的最佳EOP係如表3所示。 [焦點景深寬度（DOF)] 評估上述通孔直徑爲90nm之CH圖型中之焦點景深寬 & ( DOF)。於上述Ε Ο P中’將焦點適度地上下移動，則形成與上述相同之光阻圖型，求取製得通孔圖型之形狀的範圍之焦點景深之寬度（/i m )作爲「〇pen」。其結果係如表3所不。 -110- 201039064 [遮罩缺陷因子一（MEF)] 遮罩圖型’除使用通孔直徑之標靶尺寸分別爲94nm、 92nm、90nm、88nm、86nm之遮罩圖型（間距皆爲I57.5nm )’使用上述所求得之Εορ進行曝光以外，其他皆依上述[ 光阻圖型之形成1]相同方法形成接觸孔圖型。此時，使用標靶尺寸（ηχη )作爲横軸，使用各遮罩圖型所形成於光阻 0 膜之通孔之口径（nm )斜度作爲MEF算出。又，MEF ’其數値越接近1時，其遮罩重現性越爲良好之意。其結果係如表3所示。 [表3] 最佳EOP [mJ/cm2] DOF [ym] MEF 實施例1 45.7 0.300 4.261 實施例2 49.2 0.300 3.352 比較例1 55.6 0.270 4.666 〇如表3所示般，本發明之實施例1〜2之光阻組成物，與比較例1相比較時，顯示出良好之微影蝕刻特性。 < (B)成份之合成例> [(B) -1之合成] (i)於控制於20 °C以下之甲烷磺酸（60.74)中，少量添加氧化磷（8.538)與2,6-二甲基酚（8.81§)與二苯基亞颯（12.2g)。將溫度控制於I5〜20 t中進行30分鐘熟 -111 - 201039064 成後，升溫至4〇°C，進行2小時之熟成。隨後，將反應液滴入冷卻至l5°c以下之純水（l〇9.35g )中。滴入結束後，加入二氯甲烷（54.68g)，攪拌後，回收二氯甲烷層。於另外容器中，加入20〜25 °C之己烷（386.86g)，滴入二氯甲烷層。滴入結束後，於20〜2 5°C下熟成3〇分鐘後’ 經過濾得目的之中間體化合物（f_01 )(產率70·9% )。所得之中間體化合物（f-〇l )，以1H-NMR進行分析。 ^-NMR ( DMSO-d6 ' 600MHz ) ： δ ( ppm ) =7.61- 7.72 (m，l〇H，苯基），7.14(S，2H，HC) ，3.12(S’ 3H，Hb ) ，2.22 ( s，6H，Ha )。由上述分析結果，得知所得中間體化合物（f-〇 1 )具有下述所示構造。【化6 0】(Synthesis method will be described later) Using the obtained photoresist composition, a photoresist pattern was formed in the following order, and the photoetching property was evaluated. [Formation of Photoresist Pattern-1] The organic anti-reflective film composition "ARC 2 9 A" (trade name, manufactured by Puliwa Co., Ltd.) was applied to a crystal of 12 inches using a spin coater. The baking was performed on a hot plate at 205 ° C for 60 seconds, and drying was carried out to form an organic anti-reflection film having a film thickness of 89 nm. The photoresist composition prepared above was applied onto the anti-reflection film by a spin coater, and subjected to pre-baking (PAB) treatment at 90 ° C for 60 seconds on a hot plate. A photoresist film having a film thickness of 100 nm was formed. Then, the coating liquid for forming a protective film "TILC-05 7" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the resist film using a spin coater at 90 ° C for 60 seconds. As a result of the bell heating, a top coating having a film thickness of 35 nm was formed. -108- 201039064 Subsequently, the ArF immersion exposure apparatus NSR-S609B (made by Ricoh Co., Ltd.; NA (number of openings) = 1. 〇 7, 2 / 3 wheel illumination, reduction ratio 1 / 4 times, infiltration media: water) was used. The ArF excimer laser (193 nm) is selectively irradiated by using a contact hole pattern (hereinafter, also referred to as CH pattern) having a via diameter of 9 〇 nm / pitch of 157.5 nm as a target mask pattern. . Subsequently, the PEB treatment at 80 ° C for 60 seconds was carried out, and at 23 ° C, a 2.38 mass% TMAH aqueous solution NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used for development for 60 seconds. Thereafter, it was washed with pure water for 30 seconds, and subjected to vibration drying. As a result, in any of the examples, a pattern of a CH pattern having a via diameter of 90 nm and a pitch of 157.5 nm was formed. [Positive roundness evaluation] Using the length measuring SEM (manufactured by Hitachi, Ltd., product name: S-9220) 'The CH pattern formed by the above observation, the 25 〇 through holes in each CH pattern are in the 24 direction. The distance from the center of the through hole to the outer edge was measured, and the result was calculated to be 3 times 値(3 σ ) of the standard deviation (σ). The 3 σ obtained in this way, the smaller the number 値, means that the roundness of the through hole is higher than that of the through hole. The results are shown in Table 2. -109- 201039064 Table 2] Roundness Example 1 6.6 Example 2 6.2 Example 3 6.7 Example 4 6.5 Example 5 7.0 Comparison Section 7.1 Comparative Example 2 7.4 It is clear from the above results that Examples 1 to 5 When the photoresist composition was compared with Comparative Examples 1 to 2, the formed via pattern had a high roundness [Formation of Photoresist Pattern-2] Using the light of Examples 1 to 2 and Comparative Example 1 The resist composition was subjected to the same method as in the above [Formation of Photoresist Pattern-1] to obtain a CH pattern having a via diameter of 90 nm (pitch: 157 Å: 5 nm). The best EOP for forming this CH pattern is shown in Table 3. [Focus Depth of Field Width (DOF)] Evaluate the focal depth of field & (DOF) in the CH pattern with the above-mentioned through hole diameter of 90 nm. In the above-mentioned Ε Ο P, 'the focus is appropriately moved up and down, the same photoresist pattern is formed as described above, and the width (/im ) of the depth of focus of the range of the shape of the through-hole pattern is obtained as "〇pen "." The results are shown in Table 3. -110- 201039064 [Mask Defect Factor One (MEF)] Mask pattern 'The mask size of the target size of 94nm, 92nm, 90nm, 88nm, 86nm except the diameter of the through hole is I57. 5 nm) 'In addition to the exposure obtained by the above-mentioned Εορ, the contact hole pattern was formed in the same manner as in the above [Formation of the photoresist pattern 1]. At this time, the target size (??) was used as the horizontal axis, and the diameter (nm) of the through hole formed in the photoresist film of each mask pattern was used as the MEF. Moreover, the closer the MEF's number is to 1, the better the mask reproducibility is. The results are shown in Table 3. [Table 3] Best EOP [mJ/cm2] DOF [ym] MEF Example 1 45.7 0.300 4.261 Example 2 49.2 0.300 3.352 Comparative Example 1 55.6 0.270 4.666 As shown in Table 3, Example 1 of the present invention The photoresist composition of 2 showed good lithographic etching characteristics when compared with Comparative Example 1. <(B) Synthesis Example of Component> [Synthesis of (B)-1] (i) Phosphorus oxide (8.538) and 2,6 were added in a small amount in methanesulfonic acid (60.74) controlled below 20 °C. - Dimethylphenol (8.81 §) and diphenylarsin (12.2 g). The temperature was controlled in I5 to 20 t for 30 minutes, and the temperature was raised to 4 ° C, and the mixture was aged for 2 hours. Subsequently, the reaction liquid was dropped into pure water (10 〇 9.35 g) cooled to 15 ° C or less. After completion of the dropwise addition, dichloromethane (54.68 g) was added, and after stirring, a dichloromethane layer was collected. In a separate vessel, hexane (386.86 g) at 20 to 25 ° C was added, and a dichloromethane layer was added dropwise. After completion of the dropwise addition, the mixture was aged at 20 to 2 5 ° C for 3 minutes, and the desired intermediate compound (f_01) was obtained by filtration (yield 70.9%). The obtained intermediate compound (f-〇l) was analyzed by 1 H-NMR. ^-NMR (DMSO-d6 '600MHz) : δ (ppm) = 7.61 - 7.72 (m, l〇H, phenyl), 7.14 (S, 2H, HC), 3.12 (S' 3H, Hb ) , 2.22 ( s, 6H, Ha). From the above analysis results, it was found that the obtained intermediate compound (f-〇 1 ) had the structure shown below. [化60]

Ha Ha ^ HbHa Ha ^ Hb

(ii )使前述中間體化合物（f-O〗）（4g )溶解於二氯甲烷（79.8g)。確認溶解後，添加碳酸鉀（6.87g)，再添加溴乙酸2-甲基-2-金剛烷（3.42g )。迴流下，反應 24小時後，經過濾、水洗淨’以己烷晶析。所得粉體經減壓乾燥後得目的化合物3.98g (產率66%)。 -112- 201039064 該目的化合物，1H-NMR進行分析。其結果係如以下所示。 !H-NMR ( CDCI3 ' 600MHz) : δ ( ppm ) =7.83 -7.86 ( m，4H，苯基），7.69-7.78 (m，6H，苯基），7.51 (s’ 2H，Hd ) ，4.46 ( s，2H，Hc ) ，2.39 ( s，6H - Ha )， 2.33 ( s，2 H > Adamantane ) ，2.17 ( s，2H，Adamantane(ii) The above intermediate compound (f-O) (4 g) was dissolved in dichloromethane (79.8 g). After confirming dissolution, potassium carbonate (6.87 g) was added, and 2-methyl-2-adamantane (3.42 g) of bromoacetic acid was further added. After refluxing for 24 hours, it was filtered and washed with water to crystallize with hexane. The obtained powder was dried under reduced pressure to give the title compound 3.98 g (yield: 66%). -112- 201039064 The compound of interest was analyzed by 1H-NMR. The results are as follows. !H-NMR (CDCI3 '600MHz): 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, 2 H > Adamantane ) , 2.17 ( s, 2H, Adamantane

)，1 · 7 1 -1 · 976 ( m，1 1 H，Adamantane ) ，1.68 ( s，3 H ，Hb ) ，1 · 5 7-1 . 6 1 ( m，2H，Adamantane )。由上述分析結果得知，該目的化合物中，確認含有具有下述所示構造之化合物（f-1 )。【化6 1】), 1 · 7 1 -1 · 976 ( m, 1 1 H, Adamantane ) , 1.68 ( s, 3 H , Hb ) , 1 · 5 7-1 . 6 1 ( m, 2H, Adamantane ). From the results of the above analysis, it was confirmed that the compound (f-1) having the structure shown below was contained in the objective compound. 【化6 1】

He ：HeHe :He

此外，該目的化合物中，由離子色層分析法之測定結果確認，除化合物（f-Ι)以外，也含有陽離子部之NMR 數據與上述相同之化合物（f-2)及化合物（f-3)。該些化合物之比率爲，化合物（f-1 ) 21.4mol%、化合物（f-2 -113- 201039064 )1 1.4mol%、化合物（f-3 ) 67.2mol%。【化6 2】In addition, it was confirmed by the measurement result of the ion chromatography method that the NMR data of the cation part other than the compound (f-Ι) is the same as the above-mentioned compound (f-2) and the compound (f-3). ). The ratio of these compounds was 21.4 mol% of the compound (f-1), 1.4 mol% of the compound (f-2 - 113 - 201039064), and 67.2 mol% of the compound (f-3). 【化6 2】

(iii)使下述之化合物（IX) 5.00g溶解於純水50.0g 中，加入前述之化合物（f-3 ) 6.1 9g後，加入二氯甲烷 5 0.0 g，於室溫下攪拌1 〇小時。隨後，經分液取出有機層。該有機層以1 %HC1水溶液洗淨3次，再以1 %氨水溶液洗淨1次後，以純水洗淨4次，有機層經濃縮結果，得白色固體之目的化合物（化合物（B ) -1 ) 8.58g (產率：90.4% -114- 201039064(iii) 5.00 g of the following compound (IX) was dissolved in 50.0 g of pure water, and after adding 9.10 g of the above compound (f-3), 50.0 g of dichloromethane was added thereto, and the mixture was stirred at room temperature for 1 hour. . Subsequently, the organic layer was taken out by liquid separation. The organic layer was washed three times with a 1% aqueous HCl solution, and once with a 1% aqueous ammonia solution, and then washed with pure water for 4 times. The organic layer was concentrated to give the title compound ( Compound (B) -1 ) 8.58g (yield: 90.4% -114- 201039064

【化6 3】【化6 3】

所得化合物（B ) -1，以1H-NMR及19F-NMR進行分析 *H-NMR ( DMSO-d6 ' 400MHz) : δ ( ppm ) =1.47-The obtained compound (B)-1 was analyzed by 1H-NMR and 19F-NMR. *H-NMR (DMSO-d6 '400 MHz): δ (ppm) = 1.47-

1.95(m，15H，Ad，3H，陰離子），2.13-2.16 (m，2H ，Ad，1H，陰離子），2.30 ( s，6H，PhCH3 ) ，2.49 ( m ，：^，陰離子），3.48(111，111，陰離子），3.88(t，lH ，陰離子），4.58 (s，2H，CH2) 4.66 (t，1H，陰離子 )，4.78 (m，lH，陰離子），7.57(m，2H，Ph)， 7.72-7.84 ( m，10H，Ph ) · 19F-NMR ( DMSO-d6、400MHz ) ： 5 (ppm) -107.8 (m，2F，CF2)，（其中，六氟苯之波峰設定爲-16 Oppm 由上述結果得知，確認化合物（B ) -1具有上述式（g )所示構造。 -115-1.95 (m, 15H, Ad, 3H, anion), 2.13-2.16 (m, 2H, Ad, 1H, anion), 2.30 (s, 6H, PhCH3), 2.49 (m, :^, anion), 3.48 (111 , 111, anion), 3.88 (t, lH, anion), 4.58 (s, 2H, CH2) 4.66 (t, 1H, anion), 4.78 (m, lH, anion), 7.57 (m, 2H, Ph), 7.72-7.84 (m,10H,Ph) · 19F-NMR (DMSO-d6, 400MHz): 5 (ppm) -107.8 (m, 2F, CF2), (wherein the peak of hexafluorobenzene is set to -16 Oppm by From the above results, it was confirmed that the compound (B)-1 has the structure represented by the above formula (g).

Claims

201039064 七、申請專利範圍： 1. 一種正型光阻組成物，其爲含有經由酸之作用而增大對鹼顯影液之溶解性的基材成份（A)，及經由曝光而發生酸之酸產生劑成份（B)之正型光阻組成物，其特徵爲，前述基材成份（A)爲含有具有下述通式（aO-Ι)所表示之結構單位（aO-Ι )，及下述通式（aO-2 )所表示之結構單位（aO-2)之高分子化合物（A1)，【化1 I201039064 VII. Patent application scope: 1. A positive-type photoresist composition which is a substrate component (A) containing an increase in solubility to an alkali developer via an action of an acid, and an acid which generates acid by exposure. a positive-type photoresist composition of the component (B), characterized in that the substrate component (A) contains a structural unit (aO-Ι) represented by the following formula (aO-Ι), and a polymer compound (A1) of a structural unit (aO-2) represented by the formula (aO-2),

[式中，R1爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化烷基，R2爲2價之鍵結基，R3爲其環骨架中含有-S02-之環式基，R爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化烷基，R21爲分支鏈狀之烷基；R22爲可與該R22鍵結之碳原子共同形成脂肪族單環式基之基]。 2 ·如申請專利範圍第1項之正型光阻組成物，其中，前述R3爲其環骨架中含有- 0-S02-之環式基。 3 ·如申請專利範圍第2項之正型光阻組成物，其中， 201039064 前述R3爲下述通式（3-1 )所表示者’ 【化2】Wherein R1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R2 is a divalent bond group; and R3 is a ring group containing -S02- in the ring skeleton thereof. a group, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R21 is a branched chain alkyl group; and R22 is an aliphatic group which can bond with the carbon atom bonded to the R22. Monocyclic base]. 2. The positive-type photoresist composition according to claim 1, wherein the above R3 is a cyclic group containing -0-S02- in the ring skeleton. 3. The positive-type photoresist composition according to item 2 of the patent application scope, wherein, the above-mentioned R3 is represented by the following general formula (3-1).

Ο [式中，A，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，a爲0〜2之整數，R1爲烷基 '院氧基、鹵化烷基、羥基、-COOR，，、-0C( = 0)R，’、羥烷基或氰基，R”爲氫原子或烷基]。 4 ·如申請專利範圍第1項之正型光阻組成物，其中，前述高分子化合物（A1 )爲具有與前述結構單位（aO-Ι ) 及（aO-2 )相異之結構單位，且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 )。 5 .如申請專利範圍第1項之正型光阻組成物，其中，前述高分子化合物（A1)至少具有2種前述結構單位（al -117- 1 .如申請專利範圍第1項之正型光阻組成物，其中，前述高分子化合物（A1)中，前述結構單位（al)爲具有由下述通式（al-0-12 )所表示之結構單位及下述通式（ a 1-0-2 )所表示之結構單位所成群中所選擇之至少1種， 201039064Ο [In the formula, A is a stretching group, an oxygen atom or a sulfur atom having a carbon number of 1 to 5 which may contain an oxygen atom or a sulfur atom, a is an integer of 0 to 2, and R1 is an alkyl group; Alkyl group, hydroxy group, -COOR,, -0C(= 0)R, ', hydroxyalkyl or cyano group, R" is a hydrogen atom or an alkyl group. 4 · Positive light as in claim 1 The polymer compound (A1) is derived from an acrylate having a structural unit different from the structural unit (aO-Ι) and (aO-2) and containing an acid dissociable dissolution inhibiting group. The structural unit (al). The positive-type resist composition according to claim 1, wherein the polymer compound (A1) has at least two of the aforementioned structural units (al-117-1). In the above-mentioned polymer compound (A1), the structural unit (al) has a structural unit represented by the following general formula (al-0-12) and the following At least one selected from the group consisting of structural units represented by the general formula (a 1-0-2 ), 201039064

[式中，R爲氫原子、碳數1〜5之烷基或碳數1〜5之鹵化烷基，R23爲烷基，R24爲可與該R24鍵結之碳原子共同形成脂肪族多環式基之基，Y2爲2價之鍵結基，X2爲酸解離性溶解抑制基]。 7 .如申請專利範圍第1項之正型光阻組成物，其中，前述高分子化合物（A 1 )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（a 3 )。 8 .如申請專利範圍第1項之正型光阻組成物，其爲含有含氮有機化合物（D)。 9. 一種光阻圖型之形成方法，其特徵爲包含，使用申請專利範圍第1項之正型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，及使前述光阻膜鹼顯影以形成光阻圖型之步驟。 10. —種高分子化合物，其特徵爲，具有下述通式（ aO-Ι)所表示之結構單位（a〇-i)，及下述通式（a〇_2) 所表示之結構單位（a 0 - 2 )， -118- 201039064 【化4】Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R23 is an alkyl group; and R24 is a carbon atom bonded to the R24 to form an aliphatic polycyclic ring. The base of the formula, Y2 is a divalent bond group, and X2 is an acid dissociable dissolution inhibiting group]. 7. The positive-type resist composition according to claim 1, wherein the polymer compound (A 1 ) has a structural unit (a 3 ) derived from an acrylate containing a polar group-containing aliphatic hydrocarbon group. 8. A positive-type photoresist composition according to claim 1 which contains a nitrogen-containing organic compound (D). A method for forming a photoresist pattern, comprising: a step of forming a photoresist film on a support using a positive-type photoresist composition of the first application of the patent scope, and a step of exposing the photoresist film, And a step of causing the aforementioned photoresist film to be alkali developed to form a photoresist pattern. 10. A polymer compound characterized by having a structural unit (a〇-i) represented by the following formula (aO-Ι) and a structural unit represented by the following formula (a〇_2) (a 0 - 2 ), -118- 201039064

(a Ο - 1 ) (a Ο - 2 ) R1 [式中，R1爲氫原子、碳數1〜5之烷基或碳烷基，R2爲2價之鍵結基，R3爲其環骨架中1 式基，R爲氫原子、碳數1〜5之烷基或碳數基，R21爲分支鏈狀之烷基；R22爲可與該R22 共同形成脂肪族單環式基之基]。 1 1 .如申請專利範圍第1 〇項之高分子化 q 前述R3爲其環骨架中含有-〇-S02-之環式基者 1 2 .如申請專利範圍第1 1項之高分子化前述R3爲下述通式（3-1)所表示者，【化5】(a Ο - 1 ) (a Ο - 2 ) R1 [wherein R1 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a carbon alkyl group, R2 is a divalent bond group, and R3 is a ring skeleton thereof. A radical of the formula: wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a carbon number group, R21 is a branched chain alkyl group; and R22 is a group which can form an aliphatic monocyclic group together with the R22. 1 1. The macromolecularization of the first aspect of the patent application, wherein R3 is a ring-form base containing -〇-S02- in the ring skeleton, and is as described above in the macromolecule of claim 1 R3 is represented by the following formula (3-1), [Chemical 5]

〇 ( 3 - 1 ) [式中，A ’爲可含有氧原子或硫原子之碳數、氧原子或硫原子，a爲0〜2之整數，R6爲數1〜5之鹵化含有-S02-之環 1〜5之鹵化烷 4建結之碳原子合物，其中，〇合物，其中， 1〜5之伸烷基院基、院氧基 -119-〇( 3 - 1 ) [wherein A ' is a carbon number, an oxygen atom or a sulfur atom which may contain an oxygen atom or a sulfur atom, a is an integer of 0 to 2, and R6 is a halogenated number of 1 to 5 containing -S02- a carbon alkoxide formed by a halogenated alkane 4 of the ring 1 to 5, wherein, a chelating compound, wherein, 1 to 5 of an alkyl group, an alkoxy group -119-

201039064 、鹵化烷基、羥基、-COOR”、-〇C( = 0)R”、經院基，R”爲氫原子或院基]。 1 3 .如申請專利範圍第1 0項之高分子化合物’ 前述高分子化合物（A1)爲具有與前述結構單位（及（aO-2 )相異之結構單位’且含有酸解離性溶解之丙烯酸酯所衍生之結構單位（al)。 1 4 .如申請專利範圍第1 〇項之高分子化合物，具有2種前述結構單位（a 1 )。 1 5 .如申請專利範圍第1 〇項之高分子化合物’ 前述結構單位（al)具有由下述通式（al-〇-12)所結構單位及下述通式（al-0-2)所表示之結構單位中所選擇之至少1種，【化6】 [式中，R爲氫原子、碳數1〜5之烷基或碳數1〜5之基，R23爲烷基，R24爲可與該R24鍵結之碳原子共同肪族多環式基之基’ Y2爲2價之鍵結基，X2爲酸解解抑制基]。 1 6 .如申請專利範圍第1 〇項之高分子化合物， -120- 或氰基其中， a0 -1 ) 抑制基其至少其中，表不之所成群鹵化烷形成脂離性溶其尙具 201039064 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 )。201039064 , Halogenated alkyl, hydroxy, -COOR", -〇C( = 0)R", trans-group, R" is a hydrogen atom or a hospital base]. 1 3. A polymer compound as claimed in item 10 of the patent scope The polymer compound (A1) is a structural unit (al) derived from an acrylate having a structural unit different from the above structural unit (and (aO-2) and containing an acid dissociablely dissolved acrylate. 1 4 . The polymer compound of the first aspect of the invention has two kinds of the above structural units (a 1 ). The polymer compound of the above-mentioned structural item (a) has the following general formula: (al-〇-12) at least one selected from the structural unit and the structural unit represented by the following general formula (al-0-2), wherein R is a hydrogen atom or a carbon number. An alkyl group of 1 to 5 or a group having 1 to 5 carbon atoms, R 23 is an alkyl group, and R 24 is a bond group of Y 2 which is a divalent group of a heteropolycyclic group which may be bonded to a carbon atom bonded to the R 24 , X2 is an acid-decomposing inhibitor group]. 16. A polymer compound according to the first aspect of the patent application, -120- or a cyano group, wherein a0-1) an inhibitor group Wherein at least, of the table does not form an alicyclic halogenated alkyl groups of from 201,039,064 solution having yet have a structure in which units (a3) acrylate containing a polar group-containing aliphatic hydrocarbon group is derived from the sum.

-121 - 201039064 四、指定代表圖： (一）本案指定代表圖為：無 (二）本代表圖之元件符號簡單說明：無-121 - 201039064 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No

〇 201039064 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：無〇 201039064 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none