TW588218B - Stimulation-sensitive composition and compound - Google Patents
Stimulation-sensitive composition and compound Download PDFInfo
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- TW588218B TW588218B TW091118279A TW91118279A TW588218B TW 588218 B TW588218 B TW 588218B TW 091118279 A TW091118279 A TW 091118279A TW 91118279 A TW91118279 A TW 91118279A TW 588218 B TW588218 B TW 588218B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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Abstract
Description
588218 五、發明說明（1 ) 技術領域 本發明係有關一種1C等之半導體製造工程、液晶、熱 針頭等電路基板之製造、平版印刷板、酸硬化組成物、自 由基硬化組成物、以及其他光學應用工程所使用的感刺激 性組成物、及使用於該感刺激性組成物之化合物。更詳言 之，使用250nm以下之遠紫外線等作爲曝光光源時適合使 用的感光性組成物及該感光性組成物所使用的化合物。 先前技術 化學增幅型感光性組成物係爲藉由遠紫外線等放射線照 射、在曝光部產生酸、以該酸作爲觸媒之反應、使活性放 射線之照射部與非照射部對顯像液之溶解性變化，在基板 上形成圖樣之圖樣形成材料。 以KrF準分子雷射作爲曝光光源時，主要使用在248nm 範圍之吸收小、以聚（羥基苯乙烯）爲基本骨架之樹脂作爲 主成分時，形成高感度、高解像度、形成良好圖樣、且與 習知萘醌二疊氮/酚醛淸漆樹脂系相比爲良好系。 然而，使用更短波長之光源、例如ArF準分子雷射 (193nm)作爲曝光光源時，由於具有芳香族基之化合物本 質上在193nm範圍具有大的吸收，故上述化學增幅型不足 夠。 而且，在193nm波長範圍中吸收小的聚合物利用聚（甲 基）丙嫌酸醋，如】· Vac· Sci. Technol.，B9， 3357 ( 1 991 )記載，該聚合物一般而言對半導體製造工程中 588218 五、發明說明（2) 進行乾式蝕刻而言之耐性，會有較具芳香族基之習知苯酚 樹脂爲低的問題。 此外，於日本專利第2965990號公報及日本專利第 29650 1 6號公報中記載作爲酸發生劑之具有2-羰基烷基的 毓鹽。然而，此等記載的毓鹽對220nm以下之光而言透明 性高、特別是對193nm之光而言幾乎完全不具吸收，即使 大量添加仍無法產生充分量之酸、導致感度降低。另外， 於特開2000- 29291 7號公報中記載使用混合有作爲酸發生 劑之三芳基毓鹽與苯醯甲基毓鹽之混合物的光阻劑組成物 ，惟由於三芳基銃鹽與苯醯甲基銃鹽具有芳香環構造，特 別是對193nm之光而言吸收過大、多量添加此等之光阻劑 時由於光無法到達光阻膜之底部，故形成稱爲錐形之外型 〇 發_明所欲解決的問顆 因此，本發明之目的係提供一種藉由使用對2 50nm以下 之光、特別是248nm、193nm、157nm之光、電子線而言具 有適當吸收性、且酸發生效率高的通式（I )或（11 )所示化 合物作爲酸發生劑，具有高感度、高解像力之感光性組成 物。 本發明係爲下述構成之感光性組成物，藉此可達成本發 明之上述目的。 (1 ) 一種感刺激性組成物，其特徵爲具有（A )因來自外部 之刺激產生酸或自由基之下述通式（I)或（II)所示化合物，588218 V. Description of the Invention (1) Technical Field The present invention relates to a semiconductor manufacturing process such as 1C, the manufacture of circuit substrates such as liquid crystals, hot needles, lithographic printing plates, acid hardening compositions, radical hardening compositions, and other optical The irritant composition used in the application process and the compound used in the irritant composition. More specifically, a photosensitive composition and a compound used for the photosensitive composition which are suitable for use when the far-ultraviolet rays of 250 nm or less are used as the exposure light source. In the prior art, the chemically amplified photosensitive composition is irradiated with radiation such as far ultraviolet rays, generates an acid in the exposed portion, and reacts with the acid as a catalyst to dissolve the imaging solution in the irradiated and non-irradiated portions of the active radiation. As the material changes, a pattern forming material is used to form a pattern on the substrate. When KrF excimer laser is used as an exposure light source, a resin with a small absorption in the range of 248 nm and a poly (hydroxystyrene) as the basic skeleton is used as the main component to form a high sensitivity, high resolution, good pattern, and It is known that naphthoquinonediazide / phenolic lacquer resin system is a good system. However, when a light source with a shorter wavelength, such as an ArF excimer laser (193 nm) is used as the exposure light source, the compound having an aromatic group has a large absorption in the 193 nm range in nature, so the above-mentioned chemical amplification type is insufficient. In addition, a polymer having a small absorption in the 193 nm wavelength range uses poly (meth) propionic acid vinegar, as described in Vac · Sci. Technol., B9, 3357 (1 991). This polymer is generally used for semiconductors. Manufacturing process 588218 V. Description of the invention (2) The resistance to dry etching is lower than that of conventional phenol resins with aromatic groups. In addition, Japanese Patent No. 2965990 and Japanese Patent No. 29650 16 describe a salt of a 2-carbonylalkyl group as an acid generator. However, the alum salts described in these are highly transparent to light below 220 nm, and in particular have almost no absorption to light at 193 nm, and even if added in large amounts, a sufficient amount of acid cannot be generated, resulting in a decrease in sensitivity. In addition, Japanese Patent Application Laid-Open No. 2000-29291 7 describes a photoresist composition using a mixture of a triaryl sulfonium salt and a benzamidine methyl sulfonium salt as an acid generator. Methyl sulfonium salt has an aromatic ring structure. Especially for 193nm light, it absorbs too much. When a large amount of these photoresist is added, the light cannot reach the bottom of the photoresist film. _The problem that Ming wants to solve Therefore, the object of the present invention is to provide an acid absorption efficiency and an acid generation efficiency by using light and electron rays of light below 2 50 nm, especially 248 nm, 193 nm, and 157 nm. A compound having a high general formula (I) or (11) as an acid generator has a high-sensitivity and high-resolution photosensitive composition. The present invention is a photosensitive composition having the following constitution, thereby achieving the above-mentioned object of the present invention. (1) An irritating composition characterized by having (A) a compound represented by the following general formula (I) or (II) that generates an acid or a free radical due to an external stimulus,
588218 五、發明說明（1〇) Ri或R2、與R3鍵結形成的環構造、Ri或R2、與R4或R5鍵 結形成的環構造、R3、與R4或R5鍵結形成的環構造、h、 與R2、與R4或R5鍵結形成的環構造、I、與R2、與R3、 與R4或R5鍵結形成的環構造、Yi與Y2鍵結與通式（I)或 (II)中S +形成環構造。 Rl或R2、與R3鍵結形成的環構造時，Rl或r2、與r3鍵 結形成的基以碳數1〜1 0之伸烷基較佳，例如伸甲基、伸 乙基、伸丙基、伸丁基、伸戊基、伸己基等。 Rl或r2、與r4或r5鍵結形成的環構造時，Ri或R2、與 R4或R5鍵結形成的基例如伸烷基、羧基等。伸烷基以碳數 1〜1 0之伸烷基，例如伸甲基、伸乙基、伸丙基、伸丁基 、伸戊基、伸己基等。 R3、與R4或R5鍵結形成的環構造時，R3、與R4或R5鍵 結形成的基以碳數1〜1 0之伸烷基，例如伸甲基、伸乙基 、伸丙基、伸丁基、伸戊基、伸己基等。 I、與r2、與r4或r5鍵結形成的環構造時，Ri、與r2 、與R4或R5鍵結形成的基例如碳數5〜1 5之二環式縮合 環構造，亦可在環內具有雜原子。 丫1與Y2鍵結與通式（ί)或（II)中S +形成環構造時，亦可 以環構造。 此時，Yi與γ2鍵結形成的基例如碳數4〜10之伸烷基 ’以伸丁基、伸戊基、伸己基較佳，更佳者爲伸丁基、伸 戊基。 -12- 588218 五、發明說明（11 ) 而且，Yi與Y2鍵結與通式（I)或（II)中S +形成環構造時 ，亦可以含有雜原子。 上述烷基、烯基、芳基、芳烷基、芳香族基、環狀構造 ，各例如可以硝基、鹵素原子、羧基、羥基、鑛基、胺基 、氰基、院氧基（較佳者爲碳數1〜5)等取代。另外，芳基 、芳烷基亦可以烷基（較佳者碳數1〜5 )取代。 另外，烷基之取代基以鹵素原子、羥基、烷氧基較佳。 X·之非親核性陰離子例如磺酸陰離子、羧酸陰離子、雙 (烷基磺醯基）醯亞胺基陰離子、參（烷基磺醯基）甲基陰離 子等。 非親核性陰離子係爲引起親核反應之能力顯著降低的陰 離子，係爲可抑制分子內藉由親核反應經時分解之陰離子 。藉此可提高光阻劑之經時安定性。 磺酸陰離子例如烷基磺酸陰離子、芳基磺酸陰離子、茨 磺酸陰離子等。 羧酸陰離子例如有烷基羧酸陰離子、芳基羧酸陰離子、 芳烷基羧酸陰離子等。 烷基磺酸陰離子之烷基以碳數1〜30之烷基較佳，例如 甲基、乙基、丙基、異丙基、正丁基、異丁基、第2-丁基 、戊基、新戊基、己基、庚基、辛基、壬基、癸基、十一 烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六 烷基、十七烷基、十八烷基、十九烷基、二十烷基、環丙 基、環戊基、環己基、金剛烷基、原菠烷基、冰片烷基等 -13- 588218 五、發明說明（12 ) 〇 芳基磺酸陰離子之芳基以碳數6〜14之芳基較佳，例如 苯基、甲苯基、萘基等。 上述烷基磺酸陰離子及芳基磺酸陰離子之烷基及芳基亦 可具有取代基。 取代基例如有鹵素原子、烷基、烷氧基、烷硫基等。 鹵素原子例如氯原子、溴原子、氟原子、碘原子等。 烷基以碳數1〜1 5之烷基較佳，例如甲基、乙基、丙基 、異丙基、正丁基、異丁基、第2 -丁基、戊基、新戊基、 己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、 十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、 十八烷基、十九烷基、二十烷基。 烷氧基以碳數1〜5之烷氧基較佳，例如甲氧基、乙氧 基、丙氧基、丁氧基等。 烷硫基以碳數1〜1 5之烷硫基較佳，例如甲硫基、乙硫 基、丙硫基、異丙硫基、正丁硫基、異丁硫基、第2-丁硫 基、戊硫基、新戊硫基、己硫基、庚硫基、辛硫基、壬硫 基、癸硫基、十一烷硫基、十二烷硫基、十三烷硫基、十 四烷硫基、十五烷硫基、十六烷硫基、十七烷硫基、十八 烷硫基、十九烷硫基、二十烷硫基等。而且，烷基、烷氧 基、烷硫基亦可另以鹵素原子（較佳者爲氟原子）取代。 烷基羧酸陰離子之烷基例如爲與烷基磺酸陰離子之烷基 相同者。588218 V. Description of the invention (10) Ri or R2, ring structure formed by bonding with R3, Ri or R2, ring structure formed by bonding with R4 or R5, R3, ring structure formed by bonding with R4 or R5, h, ring structure formed by bonding with R2, R4 or R5, I, ring structure formed by bonding with R2, R3, and R4 or R5, bond between Yi and Y2 and general formula (I) or (II) The middle S + forms a ring structure. In the ring structure formed by R1 or R2 and R3 bonding, the group formed by R1 or r2 and r3 bonding is preferably an alkylene group having 1 to 10 carbon atoms. Base, butyl, pentyl, and hexyl. When R1 or r2, or a ring structure formed by bonding to r4 or r5, Ri or R2, or a group formed by bonding to R4 or R5, for example, an alkylene group, a carboxyl group, or the like. The alkylene group is an alkylene group having a carbon number of 1 to 10, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexamethylene group, and the like. In the ring structure formed by R3 and R4 or R5 bonding, R3 and R4 or R5 bonding are formed by an alkylene group having 1 to 10 carbon atoms, such as methylene, ethylene, propyl, Butyl, pentyl, and hexyl. I. In the ring structure formed by bonding with r2 and r4 or r5, the group formed by bonding with Ri, r2, and R4 or R5 is, for example, a bicyclic condensed ring structure with 5 to 15 carbon atoms. Has heteroatoms inside. When Y 1 and Y 2 are bonded to form a ring structure with S + in the general formula (ί) or (II), a ring structure may also be used. At this time, the group formed by the bond between Yi and γ2 is, for example, an alkylene group having 4 to 10 carbon atoms, but is preferably butylene, pentenyl, and hexyl, and more preferably, butyl and pentenyl. -12- 588218 5. Description of the invention (11) Furthermore, when Yi and Y2 are bonded to form a ring structure with S + in the general formula (I) or (II), they may also contain heteroatoms. Each of the above-mentioned alkyl, alkenyl, aryl, aralkyl, aromatic group, and cyclic structure may be, for example, a nitro group, a halogen atom, a carboxyl group, a hydroxyl group, a mineral group, an amine group, a cyano group, or a oxy group (preferably The number of carbon atoms is 1 to 5). In addition, the aryl group and the aralkyl group may be substituted with an alkyl group (preferably having 1 to 5 carbon atoms). The substituent of the alkyl group is preferably a halogen atom, a hydroxyl group, or an alkoxy group. Examples of the non-nucleophilic anion of X · include a sulfonic acid anion, a carboxylic acid anion, a bis (alkylsulfonyl) fluorenimide anion, and a (alkylsulfonyl) methyl anion. Non-nucleophilic anions are anions that significantly reduce the ability to cause nucleophilic reactions, and are anions that inhibit the intramolecular decomposition by nucleophilic reactions over time. This can improve the stability of the photoresist over time. Examples of the sulfonic acid anion include an alkylsulfonic acid anion, an arylsulfonic acid anion, a sulfonic acid anion, and the like. Examples of the carboxylic acid anion include an alkylcarboxylic acid anion, an arylcarboxylic acid anion, and an aralkylcarboxylic acid anion. The alkyl group of the alkylsulfonic acid anion is preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, and pentyl. , Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, cetyl, ten Heptadecyl, octadecyl, undecyl, eicosyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, orthospinyl, norbornyl, etc.-13- 588218 V. Invention Note (12) The aryl group of the arylsulfonic acid anion is preferably an aryl group having 6 to 14 carbon atoms, such as phenyl, tolyl, naphthyl, and the like. The alkyl and aryl groups of the alkylsulfonic acid anion and arylsulfonic acid anion may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an alkylthio group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. The alkyl group is preferably an alkyl group having 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, pentyl, neopentyl, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptyl, deca Octyl, undecyl, eicosyl. The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy and the like. The alkylthio group is preferably an alkylthio group having 1 to 15 carbon atoms, such as methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, and 2-butylthio group. Base, pentylthio, neopentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, undecylthio, dodecylthio, tridecylthio, ten Tetraalkylthio, pentadecylthio, hexadecylthio, heptadecylthio, octadecylthio, nonadecanylthio, eicosylthio, and the like. The alkyl group, alkoxy group, and alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom). The alkyl group of the alkyl carboxylic acid anion is, for example, the same as the alkyl group of the alkyl sulfonic acid anion.
-14- 588218 五、發明說明（13 ) 芳基磺酸陰離子之芳基例如爲與芳基磺酸陰離子之烷基 相同者。 芳烷基羧酸陰離子之芳烷基以碳數6〜12之芳烷基較佳 ，例如苯甲基、苯乙基、萘甲基、萘乙基等。 上述烷基羧酸陰離子、芳基羧酸陰離子及芳烷基羧酸陰 離子之烷基、芳基及芳烷基亦可具有取代基，取代基例如 與芳基磺酸陰離子之鹵素原子、烷基、烷氧基、烷硫基相 同者。 雙（烷基磺醯基）醯亞胺基陰離子、參（烷基磺醯基）甲基 陰離子之烷基以碳數1〜5之烷基較佳，例如甲基、乙基 、丙基、異丙基、正丁基、第2 -丁基、戊基、新戊基等。 此等之烷基亦可具有取代基，取代基例如有鹵素原子、烷 氧基、烷硫基等。 其他非親核性陰離子例如氟化磷、氟化硼、氟化銻等。 X·之非親核性陰離子以磺酸之α-位以氟原子取代的鏈烷 基磺酸陰離子、以氟原子或具有氟原子之基取代的芳基磺 酸陰離子、烷基以以氟原子取代的雙（烷基磺醯基）醯亞胺 陰離子、烷基以氟原子取代的參（烷基磺醯基）甲基化物陰 離子較佳，更佳者爲碳數1〜8個全氟鏈烷基磺酸陰離子 ，最佳者爲九氟丁烷磺酸陰離子、全氟辛烷磺酸陰離子。 於通式（I )或（I I )中，Ri〜R3、R4、R5、Yi、及Υ2中任一 位置經由鍵結基鍵結、亦可具有2個以上通式（I )或（11 ) 之構造。-14-588218 V. Description of the invention (13) The aryl group of the arylsulfonic acid anion is, for example, the same as the alkyl group of the arylsulfonic acid anion. The aralkyl group of the aralkylcarboxylic acid anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl, and the like. The alkyl, aryl, and aralkyl groups of the above-mentioned alkyl carboxylic acid anion, aryl carboxylic acid anion, and aralkyl carboxylic acid anion may also have a substituent, and the substituent is, for example, a halogen atom or an alkyl group with an aryl sulfonic acid anion , Alkoxy, and alkylthio are the same. The alkyl group of the bis (alkylsulfonyl) sulfonium imide anion and the (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, Isopropyl, n-butyl, 2-butyl, pentyl, neopentyl, and the like. These alkyl groups may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, and an alkylthio group. Other non-nucleophilic anions such as phosphorus fluoride, boron fluoride, antimony fluoride, and the like. The non-nucleophilic anion of X · is an alkylsulfonic acid anion substituted with a fluorine atom at the α-position of the sulfonic acid, an arylsulfonic anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group with a fluorine atom Substituted bis (alkylsulfonyl) fluorenimide anions, and para (alkylsulfonyl) methylide anions in which alkyl groups are substituted with fluorine atoms are preferred, and more preferred are 1 to 8 carbon perfluoro chains The alkyl sulfonic acid anion is preferably nonafluorobutane sulfonic acid anion and perfluorooctane sulfonic acid anion. In the general formula (I) or (II), any of Ri to R3, R4, R5, Yi, and Υ2 is bonded via a bonding group, and may have two or more general formulas (I) or (11) Of the structure.
-15- 588218 五、發明說明（彳4) 本發明之酸發生劑（A)，其特徵爲具有與羰基共軛的雙 鍵，藉此可使激勵狀態安定化、提高酸發生能。 而且，爲h、與R2、與R4或R5鍵結形成的環構造時， Rl、與r2、與r4或r5鍵結形成的環構造時，立體構造被 平行固定於羰基之π*啓動與C-S + σ起動、提高酸發生能係 更佳。 於酸發生劑（A)中，η以1或2較佳、更佳者η= 1。 R5中任二個以經由伸烷基鍵結、形成5〜7碳環或 含有5〜7碳環之多環環狀構造較佳。 R4、：^以氫原子或烷基較佳。 Yi、Y2以經由伸烷基鍵結、形成5〜7碳環較佳。 於下述中，係爲本發明之上述通式（I )或（11 )所示化合 物中較佳的具體例，惟本發明不受此等所限制。 •16- 588218 五、發明說明（15【化11】 'CF3S〇3- (1-1) L ? .sO CF3CFrOCF2CF2S〇3-， (1-4) AJ 〇' 人v •".Ο _ :CF3(CF2).3S(V* '^CF3(CF2)7S〇3- (1-2) (1-3) ' L ? sO ； -m(so2cf 山 .-N(S02CdF9〉2 (I - 5) (1^6) n r、 J S4-.7-15- 588218 5. Description of the invention (彳 4) The acid generator (A) of the present invention is characterized by having a double bond conjugated to a carbonyl group, thereby stabilizing the excitation state and increasing the acid generating energy. In the case of a ring structure formed by h, R2, R4, or R5, and a ring structure formed by R1, r2, and r4 or r5, the three-dimensional structure is fixed in parallel to the π of the carbonyl group. + σ is better for starting and increasing acid generation. In the acid generator (A), η is preferably 1 or 2, and more preferably η = 1. Any two of R5 are preferably bonded through an alkylene group to form a 5 to 7 carbocyclic ring or a polycyclic cyclic structure containing 5 to 7 carbocyclic rings. R4,: ^ is preferably a hydrogen atom or an alkyl group. Yi and Y2 are preferably bonded through an alkylene group to form a 5 to 7 carbon ring. In the following, preferred examples of the compound represented by the general formula (I) or (11) of the present invention are given, but the present invention is not limited thereto. • 16- 588218 V. Description of the invention (15 [化 11] 'CF3S〇3- (1-1) L? .SO CF3CFrOCF2CF2S〇3-, (1-4) AJ 〇' person v • " .〇 _: CF3 (CF2) .3S (V * '^ CF3 (CF2) 7S〇3- (1-2) (1-3)' L? SO; -m (so2cf mountain.-N (S02CdF9> 2 (I-5 ) (1 ^ 6) nr, J S4-.7
,.LX -C(S02CF3)3 (1-7). Me CF 3OCF3CF2 OCF3CF2OCH2 S〇3~ (1-8), .LX -C (S02CF3) 3 (1-7). Me CF 3OCF3CF2 OCF3CF2OCH2 S〇3 ~ (1-8)
Bu CFa (CF2) 3SO3- S^D / Bu CF3 (CF2) 3S〇3^ (1-10) Oil.) T 0 JD.· . .CF3SO3- CF3· (CF2) 3S03 - .· (I-L3)； (1-14) • ?. i^y ^ CF3S03- .、·义·. s〇 · CF3 (CF2) 3S〇3~ (1-16) (1-17) t· sO CFaSOa- (1-19) IK)十卿0:「 .(1-9) Bu CH2CH2OH · Λ、户^CH2CH20H CF3 (CR2) 3SO3-'(1-12) 0 sO . CF3 (CF2) 7SO3"， .<•1-15) · CF3 -O3S-• (1-18) cf3 ΛBu CFa (CF2) 3SO3- S ^ D / Bu CF3 (CF2) 3S〇3 ^ (1-10) Oil.) T 0 JD. ·.. CF3SO3- CF3 · (CF2) 3S03-. · (I-L3 ); (1-14) •?. I ^ y ^ CF3S03 -..., ···. CF3 (CF2) 3S〇3 ~ (1-16) (1-17) t · sO CFaSOa- (1 -19) IK) Shiqing 0: ". (1-9) Bu CH2CH2OH · Λ, household ^ CH2CH20H CF3 (CR2) 3SO3-'(1-12) 0 sO. CF3 (CF2) 7SO3 ",. ≪ • 1-15) CF3 -O3S- • (1-18) cf3 Λ
sO 0 I sO CF3SO3—(1-22) C4H9’、〆，、 CF3(CF2)3S〇3- (1-20) f .sO、广V〆々丨 CF3(CF2)3S〇3- :·. (1-23) sO- OSs CF3(CF2)7S〇3~ (1-21) ..? 's〇 、丫〜 I cf3(cf2)7so3, (1-24) -17- 588218 五、發明說明（16 【化1 2】 .CF3S〇3-(1-25)sO 0 I sO CF3SO3— (1-22) C4H9 ′, 〆 ,, CF3 (CF2) 3S〇3- (1-20) f. sO, Guang V〆々 丨 CF3 (CF2) 3S〇3-: ... (1-23) sO- OSs CF3 (CF2) 7S〇3 ~ (1-21) ..? 'S〇, Ya ~ I cf3 (cf2) 7so3, (1-24) -17- 588218 V. Description of the invention (16), CF3S〇3- (1-25)
0· Jl .s〇 .〇 .ΓΛ CF3SO3·" (1-28) CF3(CF2) 3S〇3~ (1-26)As0 . H CF3(CF2)3S〇r (1-29)0 · Jl .s〇 .〇 .ΓΛ CF3SO3 · " (1-28) CF3 (CF2) 3S〇3 ~ (1-26) As0. H CF3 (CF2) 3S〇r (1-29)
cf3(cf2)3so3- (I-2.T) 0cf3 (cf2) 3so3- (I-2.T) 0
s〇 · CF3OCF3CF2OCF3CF2OCF2SO3- (1-30) ^S〇 CF3S03- (1-31) ' · CF3(CF2)3S〇3- (1-32)s〇 CF3OCF3CF2OCF3CF2OCF2SO3- (1-30) ^ S〇 CF3S03- (1-31) 'CF3 (CF2) 3S〇3- (1-32)
(CH2)3〇H 人 Λ(〇η2)3〇η CF3 (CF2〉3S0：f (1-33) s0 (1-34) :s〇 CF3SO3- ,s〇 ^0 >0 CF3(CF2)3S〇3- . · CF3CF2-O-CF2CF2SO3- (I-3S)· . (1-36)(CH2) 3〇H human Λ (〇η2) 3〇η CF3 (CF2> 3S0: f (1-33) s0 (1-34): s〇CF3SO3-, s0 ^ 0 > 0 CF3 (CF2) 3S〇3-. · CF3CF2-O-CF2CF2SO3- (I-3S). (1-36)
00
CF3(CF2)3S〇r (1-38)CF3 (CF2) 3S〇r (1-38)
M©(T、〆.CF3 (CF2) 3SO3- . (1-41)M © (T, 〆.CF3 (CF2) 3SO3-. (1-41)
CF3(CF2〉3S〇3 -.(1-39)CF3 (CF2> 3S〇3-. (1-39)
n-BuO • 0 ryJ(y CF3(CF2)3S03- (1-42) -18- 588218 五、發明說明（17 【化13】n-BuO • 0 ryJ (y CF3 (CF2) 3S03- (1-42) -18- 588218 V. Description of the invention (17 [化 13]
〇 r\ ,CF3 (CF2) 3SO3· (1-44)〇 r \, CF3 (CF2) 3SO3 · (1-44)
S+、 0 cf3(cf2)3so3 - (1-45) ·S +, 0 cf3 (cf2) 3so3-(1-45)
〇 CF3SO3-(1-46) · 0〇 CF3SO3- (1-46) · 0
MeO CF3SO3- (1-49) :s〇: CF3SO3- (1-52) 0 CF3 (CF2) 3S〇3~ .,(1-47) &S〇 .. MeO . #3 (CF2) 3SO3一 (1-50) /.CF^iCF^)sSOsr p^严3 .1 . CH2CH3 · 〇 CF3(CF2)sS〇3 - (1-48)Λ5〇MeO CF3SO3- (1-49): s〇: CF3SO3- (1-52) 0 CF3 (CF2) 3S〇3 ~., (1-47) & S〇 .. MeO. # 3 (CF2) 3SO3 一(1-50) /.CF^iCF^)sSOsr p ^ strict 3.1.1. CH2CH3. 〇CF3 (CF2) sS〇3-(1-48) Λ5〇
MeO -N(S02M2 (1-51) -St ·MeO -N (S02M2 (1-51) -St ·
F 0F 0
LsO CF3SO.3-(1-55).LsO CF3SO.3- (1-55).
(1-53) 0 s〇 CF3 (CF2) 3SO3-(1-56)·. ...jl. .pi (1-54)X,s〇. -N(S02CF2CF3)2 (1-57)(1-53) 0 s〇 CF3 (CF2) 3SO3- (1-56) ... jl..pi (1-54) X, s〇.-N (S02CF2CF3) 2 (1-57)
MeO U nBu -c(so2cf3)： (1-58). . -19- 588218 五、發明說明（w•【化14】 0 0 ··〇， CF3S0；r (ί-59)【0 0 5 7】【化1.5】 .。/、女0 . CF3(CF2)3S〇3- (1-60).MeO U nBu -c (so2cf3): (1-58).. -19- 588218 V. Description of the invention (w • [化 14] 0 0 ·· 〇, CF3S0; r (ί-59) [0 0 5 7 ] [Chem 1.5]. /, Female 0. CF3 (CF2) 3S〇3- (1-60).
- O3S α-62)-O3S α-62)
ο 〇i 0H33SO3" (1-65)ο 〇i 0H33SO3 " (1-65)
XsO cp3 U -〇3sh0 (1-68) Cp3 【0 0 5.8】 【化1 6】·XsO cp3 U -〇3sh0 (1-68) Cp3 [0 0 5.8] [Chemical 1 6] ·
0e〇· (1-63)0e〇 · (1-63)
N c4f0so3—N c4f0so3—
OO
CF3<CF2)10COO- (1—64)0 -r\ G F3( C「2)3 s 〇3-(1-67) 1-70 -20- 588218CF3 < CF2) 10COO- (1-64) 0 -r \ G F3 (C 「2) 3 s 〇3- (1-67) 1-70 -20- 588218
588218 五、發明說明（2〇 【化18】 —· CF3SO3·· (IA-25) 0588218 V. Description of the invention (20) [CF3SO3 ... (IA-25) 0
IsO • O〇s〇 . CF3(CF2)3S〇3_ (1A-26)^5ls〇. cf3$〇3-IsO • O〇s〇. CF3 (CF2) 3S〇3_ (1A-26) ^ 5ls〇. Cf3 $ 〇3-
GF3(CF2)3S〇3- (IA-27)AsO (ΙΑ-28) CF3(CF2)3S〇3- (ΪΑ-29) CF3OCF3CF2OCF3CF2OCF2SO3- (IA-30) 0GF3 (CF2) 3S〇3- (IA-27) AsO (ΙΑ-28) CF3 (CF2) 3S〇3- (ΪΑ-29) CF3OCF3CF2OCF3CF2OCF2SO3- (IA-30) 0
Cls〇 0 GF3SO3- CF3(CF2)3S〇3 -(ΓΑ-32) 0Cls〇 0 GF3SO3- CF3 (CF2) 3S〇3-(ΓΑ-32) 0
nBu I ,.S 十、 nBu、 CF3(CF2)3s〇r (IA-33)nBu I, .S X, nBu, CF3 (CF2) 3s〇r (IA-33)
0 «Α-31)0 «Α-31)
.CF3SO3-(IA-34).CF3SO3- (IA-34)
0 o0 o
CF3(CF?)3S〇3~ (IA-35) CF3CF2-0-CF2CF2SO3- 0 0CF3 (CF?) 3S〇3 ~ (IA-35) CF3CF2-0-CF2CF2SO3- 0 0
(IA-40). 0 ^ CF3(GF2)3S〇3- '0 〇〇A-36) CF3(CF2)3S〇3- 〇·. (IA-38) (1A-39)(IA-40). 0 ^ CF3 (GF2) 3S〇3- '0 〇〇A-36) CF3 (CF2) 3S〇3- 〇. (IA-38) (1A-39)
O ,0O, 0
Me〇 Xcf3ccf2)3so3- n"Bu0^ o CIA-41) CF3(CF2)3S〇3-^ <IA-42).Me〇 Xcf3ccf2) 3so3- n " Bu0 ^ o CIA-41) CF3 (CF2) 3S〇3-^ < IA-42).
-22- 588218 五、發明說明（21 )【化19.】 / • . CF3S03- (IA-43). Ο-22- 588218 V. Description of the invention (21) [Chem. 19.] / •. CF3S03- (IA-43). Ο
0 (ΙΑ - 44) Ο Ο0 (ΙΑ-44) Ο Ο
ΟΟ
Me^S+、M CF3(CF2)3S〇3- β Μβ cf3〈gf2)3so3- (ΙΑ，45)Me ^ S +, M CF3 (CF2) 3S〇3- β Μβ cf3 <gf2) 3so3- (ΙΑ, 45)
〇 CF3SO3-(ΙΑ-46) 0〇 CF3SO3- (ΙΑ-46) 0
Et • CF3CCF2)3S〇3- WeO …Ό .. ΜβΟ .0 CF3(CF2)3S〇3* (IA-47) 0 o (IA-50) -M(S〇2G4Fs)2 (IA-49) Ο 〔〇· (IA-52)Et • CF3CCF2) 3S〇3- WeO… Ό .. ΜβΟ .0 CF3 (CF2) 3S〇3 * (IA-47) 0 o (IA-50) -M (S〇2G4Fs) 2 (IA-49) 〇 [〇 · (IA-52)
:F F' -〇3S-^Qv-f F F O59/ CF3(CF2)3S〇3~..ao CIA-53) •Q+J^X 又 sO 2 CF3(CF2)3S03-.(IA-55) aO OMe CF3(CF2)3S〇3-: FF '-〇3S- ^ Qv-f FF O59 / CF3 (CF2) 3S〇3 ~ ..ao CIA-53) • Q + J ^ X and sO 2 CF3 (CF2) 3S03-. (IA-55) aO OMe CF3 (CF2) 3S〇3-
OMe (ΪΑ-58) CF3(CF2)3S〇3~ (IA-5S) 0 | 0 0 .. cf3(cf2)3so3 - OA-48) 0 CF3(CF 之)3SO(T-o CIA-5” -N(S02CF2CF3)2 t>〇.... (ΙΛ-54) CFa(CF2)3S〇3- (IA-57) 0OMe (ΪΑ-58) CF3 (CF2) 3S〇3 ~ (IA-5S) 0 | 0 0 .. cf3 (cf2) 3so3-OA-48) 0 CF3 (CF 之) 3SO (To CIA-5 ”-N (S02CF2CF3) 2 t> 〇 .... (ΙΛ-54) CFa (CF2) 3S〇3- (IA-57) 0
cf3(cf2)10coo- (IA-60) 0 •人cf3 (cf2) 10coo- (IA-60) 0 • people
0 CF3(CF2)3S03-(ΪΑ-59) 00 CF3 (CF2) 3S03- (ΪΑ-59) 0
C16H33SO3-· (1A-62) -23- 588218 五、發明說明（22 ) 【化20】C16H33SO3- · (1A-62) -23- 588218 V. Description of the invention (22) [化 20]
上述通式（I )或（11 )之化合物可以單獨一種使用或2種 以上組合使用。 通式（I )或（11 )所示化合物可藉由對應的不飽和縮酮化 合物在鹼性條件下、以三甲基甲矽烷基氯化物予以甲矽烷 醇醚化後，與亞楓反應成毓鹽、藉由鹽交換合成。 而且，通式（I)或（II)所示化合物可藉由對應不飽和縮 酮化合物之縮酮的（X位或烯丙基爲以溴或溴化銅鹵化、形 成α-鹵素取代不飽和縮酮或烯丙基位爲鹵化的不飽和縮酮 後，於其中使硫醚化合物在無觸媒或銀觸媒存在下反應成 銳鹽、藉由鹽交換合成。 (A )成分之化合物在本發明感光性組成物中的含量，以 組成物之固成分爲基準以0 · 1〜20重量％較佳、更佳者爲 0.5〜10重量％、最佳者爲1〜7重量％。 倂用（A )成分外之酸發生化合物 於本發明中，另可倂用除（A )成分外藉由活性光線或放 射線照射分解、產生酸之化合物。 本發明（A)成分倂用的酸發生劑之使用量以莫耳比（成分 (A)/其他酸發生劑），通常爲100/0〜20/80、較佳者爲The compounds of the general formula (I) or (11) may be used alone or in combination of two or more. The compound represented by the general formula (I) or (11) can be reacted with a maple by etherifying the corresponding unsaturated ketal compound with silyl alcohol by trimethylsilyl chloride under basic conditions. Yu salt, synthesized by salt exchange. In addition, the compound represented by the general formula (I) or (II) can be substituted with an unsaturated ketal compound by ketal (X position or allyl is halogenated with bromine or copper bromide to form α-halogen substituted unsaturated After the ketal or unsaturated ketal having an allyl position is halogenated, the thioether compound is reacted into an acute salt in the absence of a catalyst or a silver catalyst, and is synthesized by salt exchange. (A) The compound of the component is The content of the photosensitive composition of the present invention is based on the solid content of the composition, and is preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and most preferably 1 to 7% by weight. In the present invention, an acid-generating compound other than the component (A) may be used in addition to the component (A) to decompose and generate an acid by irradiation with active light or radiation. The acid used in the component (A) of the present invention The amount of the agent used is the molar ratio (ingredient (A) / other acid generator), usually 100/0 ~ 20/80, preferably the
-24- 588218 五、發明說明（23 ) 100/0 〜40/60、更佳者爲 100/0 〜50/50。 特別是具有芳香環構造之酸發生劑時，其使用量以重量 比爲全部酸發生劑之60%以下較佳、更佳者爲50%以下。 該可倂用的酸發生劑可適當選自於光陽離子聚合之光起 始劑、光自由基聚合的光起始劑、色素類之光消色劑、光 變色劑、或微光阻劑等所使用的藉由活性光線或放射線照 射分解、產生酸之習知化合物及此等之混合物。 例如二偶氮鐵鹽、鱗鹽、鋪鹽、碘鐵鹽、醯亞胺基磺酸 鹽、肟磺酸鹽、二偶氮二楓、二珮、鄰-硝基苯甲基磺酸 鹽。 更佳者爲毓鹽，以三芳基毓鹽、苯醯甲基毓鹽、具有2 -羰基烷基之毓鹽最佳。 另外，此等藉由活性光線或放射線照射產生酸之基、或 使化合物導入聚合物主鏈或側鏈之化合物，例如美國專例 第3,849，137號、德國專利第39 1 4407號、特開昭63-2665 3號、特開昭5 5 - 1 64824號、特開昭62 - 6926 3號、特 開昭6 3 - 1 46038號、特開昭62 - 1 5 385 3號、特開昭63-1 46029號等記載的化合物。 此外，亦可使用美國專利第3，779, 778號、歐洲專利第 1 26，7 1 2號等記載的藉由光產生酸之化合物。 可倂用的藉由活性光線或放射線照射分解、產生酸之化 合物中，更佳的化合物例如下述通式（ZI)、（ZII)、（ZIII) 所示化合物。-24- 588218 V. Description of the invention (23) 100/0 to 40/60, more preferably 100/0 to 50/50. In particular, in the case of an acid generator having an aromatic ring structure, the amount used is preferably 60% or less of the total acid generator in a weight ratio, and more preferably 50% or less. The usable acid generator may be appropriately selected from the group consisting of a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, a photochromic agent, or a microphotoresist. Conventional compounds and mixtures thereof which are decomposed by irradiation with active light or radiation to generate acids are used. For example, diazo iron salt, scaly salt, salt, ferric iodide, sulfonium iminosulfonate, oxime sulfonate, diazodimaple, difluorene, o-nitrobenzylsulfonate. The more preferred is a salt of tris, a triaryl salt, a benzylmethyl salt, and a salt of 2-carbonyl alkyl. In addition, these compounds generate an acidic group by introducing active light or radiation, or introduce a compound into a polymer main or side chain, for example, U.S. Patent No. 3,849,137, German Patent No. 39 1 4407, Japanese Patent Application Laid-Open Sho 63-2665 3, JP Sho 5 5-1 64824, JP Sho 62-6926 3, JP Sho 6 3-1 46038, JP Sho 62-1 5 385 3, JP Sho 63-1 46029 and other compounds. In addition, a compound which generates an acid by light as described in U.S. Patent No. 3,779,778, European Patent No. 126, 7 1 2 and the like can also be used. Among the compounds that can be used to decompose and generate acid by irradiation with active light or radiation, more preferable compounds are, for example, compounds represented by the following general formulae (ZI), (ZII), (ZIII).
-25- 588218 五、發明說明（24 ) 【化21】 fj^2D1 ^2〇2-f ^203 rzqa一lpR2〇5 x- Zll.-25- 588218 V. Description of the invention (24) [Chem. 21] fj ^ 2D1 ^ 2〇2-f ^ 203 rzqa-lpR205 05-Zll.
0 n2 o ί! II II ^20β 一^一U—S一R2Q7 Z II . II 於上述通式（zi)中’ R2Q1、R2Q2及R2Q3係各表示獨立的有 機基。. X-係表示非親核陰離子，與通式（I)、（ 11)中X·之非親 核陰離子相同者。 尺2〇1、^202及^203之有機基的碳數一般爲1〜30、較佳者 爲1〜2 0 〇 而且 ’ R2〇l、R 2 0 2 及 hen 中任二個可鍵結形成環構造，環 內亦可含有氧原子、硫原子、酯鍵、醯胺鍵、羰基。 R201、R2〇2及R2Q3中二個鍵結形成之基例如有伸烷基（例 如伸丁基、伸戊基）。 R2(H、R2〇2及R2Q3之有機基的具體例如對應下述化合物 (ZI-1)、（ZI-2)、（ZI-3)之基。 此外，亦可以爲具有數個通式（ZI)所示構造之化合物。 例如可以爲通式（ZI)所示化合物之R2()1〜R2()3中至少一個 與通式（ZI)所示另一化合物之r2()1〜R2Q3中至少一個鍵結 構造的化合物。 更佳的（ZI )成分例如下述說明的化合物（zi - 1 )、（ZI-2) 、及（ZI-3)。 -26- 588218 五、發明說明（25 ) 化合物（ZI -1)係爲上述通式（ZI)之各R2Q1〜 R2()3爲芳基 之三芳基毓化合物·、即以三芳基毓爲陽離子之化合物。 三芳基毓陽離子之芳基以苯基、萘基較佳，更佳者爲苯 基。具有3個三芳基銃陽離子之芳基可以相同或不同。 各芳基亦可具有烷基（例如碳數丨〜丨5 )、烷氧基（例如碳 數1〜1 5 )、鹵素原子、羥基、苯硫基作爲取代基。較佳的 取代基有碳數1〜12之直鏈、支鏈或環狀烷基、碳數1〜 12之直鏈、支鏈或環狀烷氧基，最佳者爲碳數1〜4之烷 基、碳數1〜4之烷氧基。可以取代取代基之3個芳基中 任一個，亦可以3個全部取代。而且，取代基以芳基之對 位取代較佳。 其次，說明有關化合物（ZI-2)。 化合物（ZI-2)係式（ZI)中R2Q1〜r2Q3各爲獨立的不含芳 香環之有機基的化合物。此處，芳香環亦包含含雜原子之 芳香族環。 ί?2(Π〜R203之不含芳香環的有機基，一般碳數爲1〜30、 較佳者碳數爲1〜20。 R2〇1〜R2〇3係以各表示獨立的烷基、2-羰基烷基、烷氧基 羰基甲基、烯丙基、乙烯基較佳，更佳者爲直鏈、支鏈、 環狀2-羰基烷基、烷氧基羰基甲基，最佳者爲直鏈、支鏈 之2-羰基烷基。 1^201〜^203之院基可以爲直鏈、支鏈、或環狀，較佳者爲 碳數1〜10之直鏈或支鏈烷基（例如甲基、乙基、丙基、0 n2 o ί! II II ^ 20β a ^ U-S-R2Q7 Z II. II In the above general formula (zi), ′ R2Q1, R2Q2, and R2Q3 each represent an independent organic base. X- represents a non-nucleophilic anion and is the same as the non-nucleophilic anion of X · in the general formulae (I) and (11). The number of carbons of the organic groups of CHI 201, ^ 202 and ^ 203 is generally 1 to 30, preferably 1 to 2 0, and any two of 'R 2 0l, R 2 0 2 and hen can be bonded. Forms a ring structure, and the ring may also contain an oxygen atom, a sulfur atom, an ester bond, an amidine bond, and a carbonyl group. Examples of the group formed by the two bonds in R201, R202, and R2Q3 include an alkylene group (e.g., butylene, and butyl). Specific examples of the organic group of R2 (H, R2O2, and R2Q3 correspond to the groups of the following compounds (ZI-1), (ZI-2), and (ZI-3). In addition, they may have several general formulas ( A compound having a structure represented by ZI). For example, at least one of R2 () 1 to R2 () 3 of a compound represented by general formula (ZI) and r2 () 1 to R2Q3 of another compound represented by general formula (ZI) Compounds made of at least one of the bond structures. More preferred (ZI) components are, for example, compounds (zi-1), (ZI-2), and (ZI-3) described below. -26- 588218 5. Description of the invention ( 25) The compound (ZI -1) is a triaryl compound in which each of R2Q1 to R2 () 3 of the general formula (ZI) is an aryl group, that is, a compound having triaryl group as a cation. The phenyl group is preferably a phenyl group or a naphthyl group, and the phenyl group is more preferred. The aryl groups having three triarylsulfonium cations may be the same or different. Each aryl group may also have an alkyl group (for example, carbon number 5 to 5), Alkoxy (for example, 1 to 15 carbons), halogen atom, hydroxyl group, and phenylthio group are used as substituents. Preferred substituents are linear, branched or cyclic alkyl groups with 1 to 12 carbon numbers, and carbon number. 1 ~ 12 Straight-chain, branched-chain or cyclic alkoxy, the most preferred is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Any one of the three aryl groups which may be substituted may be substituted. All three are substituted. Moreover, it is preferable that the substituent is substituted in the para position of the aryl group. Next, the related compound (ZI-2) will be explained. The compound (ZI-2) is a group of R2Q1 to r2Q3 in the formula (ZI). A compound containing an organic group containing an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom. The organic group containing no aromatic ring 2 (Π ~ R203, generally has a carbon number of 1 to 30, preferably The number of carbon atoms is 1 to 20. R 2 0 1 to R 2 03 are each an independent alkyl group, a 2-carbonyl alkyl group, an alkoxycarbonyl methyl group, an allyl group, or a vinyl group. Straight-chain, branched, cyclic 2-carbonylalkyl, alkoxycarbonylmethyl, the best is straight-chain, branched 2-carbonylalkyl. 1 ^ 201 ~ ^ 203 can be straight chain , Branched chain, or cyclic, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl,
-27- 588218 五、發明說明（26) 丁基、戊基）、碳數3〜1〇之環狀烷基（環戊基、環己基、 原菠烷基）。 R2〇1〜R2〇3之2-羰基烷基可以爲直鏈、支鏈、或環狀， 較佳者爲上述烷基之2位上具有> C = 0之基。 R201〜R203之丨兀氧基幾基甲基的院氧基以碳數1〜5之院 基（甲基、乙基、丙基、丁基、戊基）較佳。 R201〜R2〇3可以另以鹵素原子、烷氧基（例如碳數1〜5) 、羥基、氰基、硝基取代。 R2CM〜R2Q3中可以2個鍵結形成環，在環內亦可含有氧原 子、硫原子、酯鍵、醯胺鍵、羰基。R2Q1〜r2Q3中2個鍵結 形成之基例如伸烷基（例如伸丁基、伸戊基）。 化合物（ZI-3)係爲下述通式（ZI_3)所示化合物、係爲具 有苯醯甲基銃鹽構造之化合物。 【化22】-27- 588218 V. Description of the invention (26) Butyl, pentyl), cyclic alkyl (cyclopentyl, cyclohexyl, orthospinyl) having 3 to 10 carbon atoms. The 2-carbonylalkyl group of R2O1 to R2O3 may be a straight chain, a branched chain, or a cyclic group, and is preferably a group having > C = 0 at the 2-position of the alkyl group. Among the Roxy groups of R201 to R203, the oxomethyl group is preferably an oxo group having 1 to 5 carbon atoms (methyl, ethyl, propyl, butyl, and pentyl). R201 to R203 may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and a nitro group. In R2CM to R2Q3, two bonds may be formed to form a ring, and the ring may also contain an oxygen atom, a sulfur atom, an ester bond, an amidine bond, and a carbonyl group. Examples of the groups formed by the two bonds in R2Q1 to r2Q3 are alkylene (such as butyl and pentayl). The compound (ZI-3) is a compound represented by the following general formula (ZI_3), and is a compound having a benzamidinemethylsulfonium salt structure. [Chemical 22]
Ru〜R5。係各表示獨立的氫原子、烷基、烷氧基、或鹵 素原子。 R6c及R7e係各表不獨立的氫原子、院基、或芳基。 Rx及Ry係各表示獨立的烷基、2-羰基烷基、烷氧基、 -28 - 588218 五、發明說明（27 ) 羰基甲基、烯丙基、或乙烯基。 Rlc〜R7e〜中有2個、及Rx與Ry可以各鍵結形成環構造 ，該環構造可以含有氧原子、硫原子、酯鍵、醯胺鍵。 Zc·係表示非親核陰離子，可例如與通式（I)、（II)之Γ 之非親核陰離子相同者。 Rlc〜R5。之烷基可以爲直鏈、支鏈、或環狀，例如碳數 1〜10之烷基，較佳者爲碳數1〜5之直鏈及支鏈烷基（例 如甲基、乙基、直鏈或支鏈丙基、直鏈或支鏈丁基、直鏈 或支鏈戊基）、碳數3〜8之環狀烷基（例如環戊基、環己 基” Rlc〜R5。之烷氧基可以爲直鏈、支鏈、或環狀，例如碳 數1〜10之烷氧基，較佳者爲碳數.1〜5之直鏈及支鏈烷 氧基（例如甲氧基、乙氧基、直鏈或支鏈丙氧基、直鏈或 支鏈丁氧基、直鏈或支鏈戊氧基）、碳數3〜8之環狀烷氧 基（例如環戊氧基、環己氧基）。 較佳的h。〜R5。中任一個爲直鏈、支鏈、環狀烷基、或 直鏈、支鏈、環狀烷氧基，更佳者爲h。〜R5e之碳數和爲 2〜1 5。藉此可提高溶劑溶解性、且於保存時抑制粒子產 生。 R6c及R7。之烷基例如與Rle〜R5。之烷基相同者。芳基例 如碳數6〜1 4之芳基（例如苯基）。 Rx及Ry之烷基例如與Ru〜R5。之烷基相同者。 2-羰基烷基例如Rle〜R5。之烷基2位上具有>c=0之基Ru ~ R5. Each represents an independent hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. R6c and R7e are each independent hydrogen atom, academic group, or aryl group. Rx and Ry each independently represent an alkyl group, a 2-carbonylalkyl group, an alkoxy group, -28 to 588218. 5. Description of the Invention (27) A carbonylmethyl group, an allyl group, or a vinyl group. Two of Rlc ~ R7e ~, and Rx and Ry may be bonded to each other to form a ring structure, and the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, and an amidine bond. Zc · represents a non-nucleophilic anion, and may be, for example, the same as the non-nucleophilic anion of Γ of the general formulae (I) and (II). Rlc ~ R5. The alkyl group may be linear, branched, or cyclic, for example, an alkyl group having 1 to 10 carbon atoms, preferably a linear and branched alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, Straight or branched propyl, straight or branched butyl, straight or branched pentyl), cyclic alkyl with 3 to 8 carbons (eg cyclopentyl, cyclohexyl "Rlc ~ R5. The oxy group may be linear, branched, or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms (for example, methoxy, Ethoxy, straight or branched propoxy, straight or branched butoxy, straight or branched pentoxy), cyclic alkoxy having 3 to 8 carbon atoms (such as cyclopentyloxy, Cyclohexyloxy). Preferred h. ~ R5. Any one is straight chain, branched chain, cyclic alkyl group, or straight chain, branched chain, cyclic alkoxy group, more preferably h. ~ R5e The sum of carbon numbers is 2 to 15. This improves solvent solubility and suppresses particle generation during storage. R6c and R7. The alkyl group is, for example, the same as the alkyl group of Rle to R5. The aryl group is, for example, the carbon number 6 ~ 1 4 aryl groups (such as phenyl). Rx and Ry alkyl groups such as ... Ru~R5 the same alkyl group are alkyl groups such as 2-oxo Rle~R5 of the alkyl group having 2 > c = 0 the group
-29- 588218 五、發明說明（28 ) 烷氧基羰基甲基之烷氧基例如h。〜R5。與之烷氧基相同 者。 Rx及Ry鍵結形成的基例如伸丁基、伸戊基等。 通式（ZII)、（ZIII)中R2()4〜R2()7係各表示獨立的可具取 代基之芳基或可具取代基之烷基。 R2〇4〜R2〇7之芳基以苯基、萘基較佳，更佳者爲苯基。 R 2 0 4〜R2Q7之烷基可以爲直鏈、支鏈、環狀，例如碳數1 〜10之直鏈或支鏈烷基（例如甲基、乙基、丙基、丁基、 戊基）、碳數3〜10之環狀烷基（環戊基、環己基、原菠烷 基）。 R 2 0 4〜R2〇7亦可具有取代基例如烷基（例如碳數1〜15)、 芳基（例如碳數6〜1 5 )、烷氧基（例如碳數1〜1 5 )、鹵素 原子、羥基、苯硫基等。 XI系表示非親核性陰離子，與通式（I)、（II)中X·之非 親核性陰離子相同者。 可倂用的藉由活性光線或放射線照射分解、產生酸之化 合物中，更佳者例如下述者。-29- 588218 5. Description of the invention (28) Alkoxycarbonylmethyl alkoxy such as h. ~ R5. Same as alkoxy. Examples of the group formed by bonding of Rx and Ry include butyl and pentyl. In the general formulae (ZII) and (ZIII), R2 () 4 to R2 () 7 each represent an independently substituted aryl group or a substituted alkyl group. The aryl groups of R204 to R207 are preferably phenyl and naphthyl, and more preferably phenyl. The alkyl group of R 2 0 4 ~ R2Q7 can be straight chain, branched chain, or cyclic. ), A cyclic alkyl group (cyclopentyl, cyclohexyl, orthospinyl) having 3 to 10 carbon atoms. R 2 0 4 to R 2 07 may also have a substituent such as an alkyl group (for example, a carbon number of 1 to 15), an aryl group (for example, a carbon number of 6 to 15), an alkoxy group (for example, a carbon number of 1 to 15), A halogen atom, a hydroxyl group, a phenylthio group, and the like. XI represents a non-nucleophilic anion and is the same as the non-nucleophilic anion of X · in the general formulae (I) and (II). Among the compounds which can be used and decomposed by irradiation with active light or radiation to generate an acid, the following are more preferred.
-30- 588218 五、發明說明（29 ) 【化23】-30- 588218 V. Description of the Invention (29) [化 23]
-31 - 588218 五、發明說明（3〇 【化24】-31-588218 V. Description of the invention (3〇 [化 24]
99
(之 13) C4F9SO3(Of 13) C4F9SO3
〇3S〇3S
.0 (215) <0^丨+ (216).0 (215) < 0 ^ 丨 + (216)
FF
^ -OaSHj： )>-F CH3C0° V (Z18) (Z17)^ -OaSHj:) > -F CH3C0 ° V (Z18) (Z17)
CF3SO3CF3SO3
CF3SO3' 0 (z20) -32- 588218 五、發明說明（31 ) 【化25】CF3SO3 '0 (z20) -32- 588218 V. Description of the invention (31) [化 25]
-33- 588218 五、發明說明（32 【化26】-33- 588218 V. Description of the invention (32 [化 26]
cf3so3- (z 35) U38) CF3(CF2)3S〇3' . CF3(CF2)7S03- U 36) ·. ;37)cf3so3- (z 35) U38) CF3 (CF2) 3S〇3 '. CF3 (CF2) 7S03- U 36) ·.; 37)
[2 ] ( B )藉由酸作用分解、增大對鹼顯像液之溶解度樹脂 (稱爲「酸分解性樹脂」） 本發明正型感光性組成物所使用的藉由酸分解、增大對 鹼顯像液之溶解度的樹脂係爲在樹脂之主鏈或側鏈、或主 鏈及側鏈兩方具有以酸分解所得之基（以下稱爲「酸分解[2] (B) Resin that decomposes and increases solubility in alkali developing solution by acid action (referred to as "acid-decomposable resin") The positive-type photosensitive composition used in the present invention decomposes and increases The resin having solubility in an alkali developing solution is a group having a base obtained by acid decomposition in the main chain or side chain of the resin, or both the main chain and the side chain (hereinafter referred to as "acid decomposition"
-34- 588218 五、發明說明（33 ) 性基」）的樹脂。其中，以在側鏈上具有以酸分解所得基 的樹脂更佳。 以酸分解所得之基以-COOH基、-0H基之氫原子以酸分 解性基取代的基較佳。 酸分解性基以甲矽烷醚基、枯酯基、縮醛基、四氫呋喃 醚基、乙醇醚基、乙醇酯基、3級烷醚基、3級烷酯基、3 級烷基羧酸酯基等較佳。更佳者爲3級烷酯基、3級烷基 羧酸酯、枯酯基、縮醛基、四氫呋喃醚基。 以此等酸分解所得之基作爲側鏈鍵結時之母體樹脂係爲 在側鏈具有-0H或-COOH基之鹼可溶性樹脂。例如下述之 鹼可溶性樹脂。 此等鹼可溶性樹脂之鹼可溶性速度以0.261N四甲銨氫 氧化物（TMAH)測定（23°C )、以170A/秒以上較佳。特別是 爲3 30A/秒以上更佳（A爲埃）。 就該觀點而言，更佳的鹼可溶性樹脂係爲鄰-、間-、對 -聚（羥基苯乙烯）及此等之共聚物、氫化聚（羥基苯乙烯） 、鹵素或烷基取代聚（羥基苯乙烯）、聚（羥基苯乙烯）之部 分、鄰烷基化或鄰醯化物、苯乙烯-羥基苯乙烯共聚物、 ex-甲基苯乙烯-羥基苯乙烯共聚物、氫化酚醛淸漆樹脂等 具有羥基苯乙烯構造單位之鹼可溶性樹脂。 本發明所使用的成分（B)係如歐洲專利254853號、特開 平2 - 25850號、同- 223860號、同4 - 2 5 1 29號等揭示，在 鹼可溶性樹脂中使以酸分解所得基之前驅體反應、或使各-34- 588218 V. Description of the invention (33) Resin "). Among them, a resin having a group obtained by acid decomposition on a side chain is more preferable. The group obtained by acid decomposition is preferably a group substituted by a -COOH group and a -HH group with an acid-decomposable group. The acid-decomposable group includes a silyl ether group, a cumyl group, an acetal group, a tetrahydrofuran ether group, an ethanol ether group, an ethanol ester group, a tertiary alkyl ether group, a tertiary alkyl ester group, and a tertiary alkyl carboxylate group. And so on. More preferred are tertiary alkyl ester groups, tertiary alkyl carboxylic acid esters, cumyl groups, acetal groups, and tetrahydrofuran ether groups. The base resin when a base obtained by such acid decomposition is used as a side chain bond is an alkali-soluble resin having a -H or -COOH group in a side chain. For example, the alkali-soluble resin described below. The alkali-soluble rate of these alkali-soluble resins is measured at 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C), and preferably 170A / s or more. In particular, it is more preferably 3 30 A / sec or more (A is Angstrom). From this point of view, more preferred alkali-soluble resins are ortho-, meta-, para-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly ( Hydroxystyrene), part of poly (hydroxystyrene), o-alkylated or o-halide, styrene-hydroxystyrene copolymer, ex-methylstyrene-hydroxystyrene copolymer, hydrogenated phenolic resin Alkali-soluble resins with structural units such as hydroxystyrene. The component (B) used in the present invention is disclosed in European Patent No. 254853, Japanese Patent Application Laid-Open No. 2-25850, Same No. 223860, Same No. 4-2 5 1 29, etc., and the base obtained by decomposing with an acid in an alkali-soluble resin is disclosed. Precursor reaction, or
-35 - 588218 ____ ___^一 五、發明說明（34 ) 種以酸分解所得基鍵結的鹼可溶性樹脂單體作爲各種單體 共聚合而得。 -—_ 本發明所使用的成分（B)之具體例如下所示，惟不受此 等所限制。 對-第3-丁氧基苯乙烯/對-羥基苯乙烯共聚物， 對-(第3_ 丁氧基羰氧基）苯乙烯/對-羥基苯乙烯共聚物 對-(第3 -丁氧基羰基甲氧基）苯乙烯/對-羥基苯乙烯共 聚物， 4-(第3-丁氧基羰基甲氧基）-3 -甲基苯乙烯/ 4-羥基- 3-甲基苯乙烯共聚物， 對-(第3 -丁氧基羰基甲氧基）苯乙烯/對-羥基苯乙烯 (10%加氫物）共聚物， 間-(第3 -丁氧基羰基甲氧基）苯乙烯/間-羥基苯乙烯共 聚物， 鄰-(第3 -丁氧基羰基甲氧基）苯乙烯/鄰-羥基苯乙烯共 聚物， 對-(枯氧基羰基甲氧基）苯乙烯/對·羥基苯乙烯共聚物 枯基甲基丙烯酸酯/甲基丙烯酸甲酯共聚物， 4-第3-丁氧基羰基苯乙烯/馬來酸二甲酯共聚物， 苯甲基甲基丙烯酸酯/四氫呋喃基甲基丙烯酸酯， 對-(第3 -丁氧基羰基甲氧基）苯乙烯/對-羥基苯乙烯/苯 36- 588218-35-588218 ____ ___ ^ One V. Description of the invention (34) A kind of alkali-soluble resin monomers bonded with a base obtained by acid decomposition is copolymerized as various monomers. ---_ Specific examples of the component (B) used in the present invention are shown below, but are not limited thereto. P-3-butoxystyrene / p-hydroxystyrene copolymer, p- (3-butoxycarbonyloxy) styrene / p-hydroxystyrene copolymer p- (3-butoxy Carbonylmethoxy) styrene / p-hydroxystyrene copolymer, 4- (3-butoxycarbonylmethoxy) -3-methylstyrene / 4-hydroxy-3-methylstyrene copolymer , P- (3-butoxycarbonylmethoxy) styrene / p-hydroxystyrene (10% hydrogenated) copolymer, m- (3-butoxycarbonylmethoxy) styrene / M-hydroxystyrene copolymer, o- (3rd-butoxycarbonylmethoxy) styrene / o-hydroxystyrene copolymer, p- (cumyloxycarbonyl) styrene / p-hydroxyl Styrene copolymer cumyl methacrylate / methyl methacrylate copolymer, 4-three-butoxycarbonyl styrene / dimethyl maleate copolymer, benzyl methacrylate / tetrahydrofuranyl Methacrylate, p- (3-butoxycarbonylmethoxy) styrene / p-hydroxystyrene / benzene 36- 588218
五、發明說明（35 ) 乙烯共聚物， 對-第3-丁氧基苯乙烯/對-羥基苯乙烯/富馬膪共聚較1 ’ 第3-丁氧基苯乙烯/羥基乙基甲基丙烯酸酯共聚％ ’ 苯乙烯/ Ν-(4-羥基苯基）馬來醯亞胺/ Ν-(4-第 羰氧基苯基）馬來醯亞胺共聚物， 對-羥基苯乙烯/第3-丁基甲基丙烯酸酯共聚物’ 苯乙烯/對-羥基苯乙烯/第3 -丁基甲基丙烯酸酯共聚％ y 對-羥基苯乙烯/第3-丁基丙烯酸酯共聚物， 對-(第3-丁氧基羰基甲氧基）苯乙烯/對-羥基苯乙烯/N_ .甲基馬來醯亞胺共聚物， 第3-丁基甲基丙烯酸酯/1-金剛烷基甲基甲基丙烯酸酯 共聚物， 對-羥基苯乙烯/第3-丁基丙烯酸酯/對-乙醯氧基苯乙烯 共聚物， 對-羥基苯乙烯/第3-丁基丙烯酸酯/對-(第3-丁氧基羰 氧基）苯乙烯共聚物， 對-經基苯乙烯/第3-丁基丙烯酸酯/對-(第3-丁氧基羰 基甲氧基）苯乙烯共聚物， -37- 588218 五、發明說明（π)V. Description of the invention (35) Ethylene copolymer, p-3-butoxystyrene / p-hydroxystyrene / fumaridine copolymerization compared with 1 '3-butoxystyrene / hydroxyethyl methacrylic acid Ester copolymerization% 'Styrene / N- (4-hydroxyphenyl) maleimide / N- (4-carbonyloxyphenyl) maleimide copolymer, p-hydroxystyrene / 3rd -Butyl methacrylate copolymer 'styrene / p-hydroxystyrene / 3rd-butyl methacrylate copolymer% y p-hydroxystyrene / 3-butyl acrylate copolymer, p- (3-butylene Oxycarbonylmethoxy) styrene / p-hydroxystyrene / N_. Methylmaleimide copolymer, 3-butyl methacrylate / 1-adamantyl methacrylate copolymer, P-hydroxystyrene / 3-butyl acrylate / p-ethoxylated styrene copolymer, p-hydroxystyrene / 3-butyl acrylate / p- (3-butoxycarbonyloxy) Based) styrene copolymer, p-based styrene / 3-butyl acrylate / p- (3-butoxycarbonylmethoxy) styrene copolymer, -37- 588218 5. Description of the invention ( π)
-38- 588218 五、發明說明（37) 以酸分解所得的基之含率係具有樹脂中之酸分解基數（B) 與不以酸分解的基保護之鹼可溶性基數、以B/(B + S)表示 。含有率以〇.〇1〜0.7較佳、更佳.者爲0.05〜0.50、最佳 者爲0.05〜0.40。 本發明之正型感光性組成物上照射ArF準分子雷射光時 ，（B)成分之樹脂以具有單環或多環脂環烴構造、藉由酸 作用分解、增加對鹼顯像液之溶解度的樹脂較佳。 具有單環或多環之環烴構造、藉由酸作用分解、增加對 鹼顯像液之溶解度的樹脂（以下成爲「脂環烴系酸分解性 樹脂」），以至少含有一種選自於具有含下述通式（PI)〜 P(VI)所示脂環式烴部分構造之重複單位及下述通式（11_ AB)所示重複單位之樹脂較佳。-38- 588218 V. Description of the invention (37) The content of the base obtained by acid decomposition is the number of the base of the acid-decomposable group in the resin (B) and the alkali-soluble base protected by the group not decomposed by the acid. S). The content ratio is preferably from 0.01 to 0.7, more preferably from 0.05 to 0.50, and most preferably from 0.05 to 0.40. When the positive photosensitive composition of the present invention is irradiated with ArF excimer laser light, the resin of component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure, is decomposed by an acid action, and increases the solubility in an alkali developing solution. Is preferred. A resin having a monocyclic or polycyclic cyclic hydrocarbon structure, which is decomposed by an acid to increase the solubility in an alkali developer (hereinafter referred to as "alicyclic hydrocarbon-based acid-decomposable resin"), and contains at least one selected from the group consisting of A resin containing a repeating unit of an alicyclic hydrocarbon moiety structure represented by the following general formulae (PI) to P (VI) and a repeating unit represented by the following general formula (11_AB) is preferable.
-39- 588218 五、發明說明（38) 【化28】 13 / Λ R 1广 id-39- 588218 V. Description of the Invention (38) [化 28] 13 / Λ R 1 广 id
ην πν {p(PI i15ο f 一 ch-r16 (pm) (piv) c ! R21ην πν {p (PI i15ο f a ch-r16 (pm) (piv) c! R21
Rso ^ T23 ?，. •c—ch—e—r24 (pV) R1 〇 ，11 II ，\，c—o—p (pvi) (其中，Ru係表示甲基、乙基、正每基、異丙基、正丁 基、異丁基或，第2_ 丁基， Z係表示碳原子與形成脂環式烴基之必要原子團， R12〜R16係各表示獨立的碳數1〜4個直鏈或支鏈烷基或 -40- 588218 五、發明說明（39 ) 脂環式烴基，惟R i 2〜R i 4中至少一個、或R 1 5、R 1 6中任一 個爲脂環式烴基， Ri 7〜R21係各表示獨立的氫原子、碳數1〜4個直鏈或支 鏈烷基或脂環式烴基，惟R17〜R21中至少一個爲脂環式烴 基，而且R19、R21中一個爲直鏈或支鏈烷基或脂環式烴基 R22〜R25係各表示獨立的碳數1〜4個直鏈或支鏈烷基或 脂環式烴基，惟R22〜R25中至少一個爲脂環式烴基，而且 R23與R24可互相鍵結形成環） 【化29】Rso ^ T23?,. • c—ch—e—r24 (pV) R1 〇, 11 II, \, c—o—p (pvi) (wherein Ru is methyl, ethyl, n-peryl, iso Propyl, n-butyl, isobutyl, or 2-butyl, Z is a carbon atom and an atomic group necessary to form an alicyclic hydrocarbon group, and R12 to R16 each represent an independent carbon number of 1 to 4 straight chains or branches Alkyl or -40-588218 V. Description of the invention (39) Alicyclic hydrocarbon group, but at least one of R 2 to R i 4 or any of R 1 5 and R 1 6 is an alicyclic hydrocarbon group, Ri Each of 7 to R21 represents an independent hydrogen atom, a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, but at least one of R17 to R21 is an alicyclic hydrocarbon group, and one of R19 and R21 is Linear or branched alkyl or alicyclic hydrocarbon groups R22 to R25 each represent an independent carbon number of 1 to 4 linear or branched alkyl or alicyclic hydrocarbon groups, but at least one of R22 to R25 is alicyclic A hydrocarbon group, and R23 and R24 may be bonded to each other to form a ring) [Chem. 29]
(ΙΪ 一AB) (其中，Rll’、r12’係各表示獨立的氫原子、氰基、鹵素 原子、或具有取代基之烷基， Z’係表示包含鍵結的2個碳原子（C-C)、爲形成可具有 取代基之脂環式構造的原子團） 此外，上述通式（II-AB)以下述通式（II-A)或（II-B)更 佳。(ΙΪ-AB) (wherein Rll ′ and r12 ′ each represent an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl group having a substituent, and Z ′ represents two carbon atoms (CC) containing a bond In order to form an atomic group having an alicyclic structure which may have a substituent) The general formula (II-AB) is preferably the following general formula (II-A) or (II-B).
-41 - 588218 五、發明說明（40) 【化30】-41-588218 V. Description of the Invention (40) [化 30]
(其中，r13’〜Ri6’係各表示獨立的氫原子、鹵素原子、 氰基、-COOH、-C00R5、藉由酸作用之基、-C(=0)-X-A，-R17’、或可具取代基之烷基或環狀烴基或下述之-γ基， X係表示氧原子、硫原子、-NH-、-NHS02-或-NHS02NH-， A’係表示單鍵或2價鍵結基， 而且’ Ru，〜R16，中可以至少2個鍵結形成環， n係表示〇或1， Ri7’係表示- COOH-、-C00R6、-CN、羥基、可具取代基之 《完氧基、-C0-NH-R6、-C0-NH-S02-R6 或下述-Y 基， h係表示可具取代基之烷基或環狀烴基， •Y基； 【化3 1】(Wherein, r13 'to Ri6' each represent an independent hydrogen atom, a halogen atom, a cyano group, -COOH, -C00R5, a group acting on an acid, -C (= 0) -XA, -R17 ', or A substituted alkyl group or cyclic hydrocarbon group or the following -γ group, X represents an oxygen atom, a sulfur atom, -NH-, -NHS02-, or -NHS02NH-, and A 'represents a single bond or a divalent bond And 'Ru, ~ R16, at least two bonds may be formed to form a ring, n represents 0 or 1, Ri7' represents-COOH-, -C00R6, -CN, hydroxyl, and "complete oxygen" which may have a substituent. Group, -C0-NH-R6, -C0-NH-S02-R6 or the following -Y group, h is an alkyl group or a cyclic hydrocarbon group which may have a substituent, a Y group; [Chem. 3 1]
-42- 588218-42- 588218
五、發明說明（41 ) 其中，r21’〜 烷基， 1〇’係各表示獨立的氫原子或可具取代基之 a或b係表示1或2) 於通式（pI)〜（pVI)中Ru〜之烷基係表示可經取 代或未經取代的具有碳數丨〜4個之直鏈或支鏈烷基，該 烷基例如甲基、乙基、正丙基、異丙基、正丁基、異丁基 、第2-丁基、第3-丁基等。 另外，上述烷基之另外取代基例如碳數丨〜4個烷氧基 、鹵素原子（氟原子、溴原子、氯原子、碘原子）、醯基、 醯氧基、氰基、經基、殘基、院氧基羰基、硝基等。V. Description of the invention (41) Among them, r21 ′ ~ alkyl, 10 ′ each represents an independent hydrogen atom or a or b which may have a substituent represents 1 or 2) In the general formulae (pI) to (pVI) The alkyl group of Ru ~ means a substituted or unsubstituted linear or branched alkyl group having a carbon number of 1 to 4, such as methyl, ethyl, n-propyl, isopropyl, N-butyl, isobutyl, 2-butyl, 3-butyl and the like. In addition, the other substituents of the above-mentioned alkyl group include, for example, carbon number of ˜4 alkoxy groups, halogen atoms (fluorine atom, bromine atom, chlorine atom, iodine atom), fluorenyl group, fluorenyl group, cyano group, warp group, and residual Radical, oxocarbonyl, nitro, etc.
Ru〜R25之脂環式烴基或Z與形成碳原子之脂環式烴基 可以爲單環式、或多環式。具體例如具有碳數5以上之單 環、二環、三環、四環構造等之基。其碳數以6〜30個較 佳、更佳者爲7〜25個較佳°此等之脂環式烴基亦可具有 取代基。 於下述中，係爲脂環式烴基中脂環式部分之構造例。 -43- 588218 五、發明說明（42 ) 【化32】 〇〇>〇>- W (2) (3) ① CD GO (4) U. (S) , (6) ① CO COO {7) (8) (9) a? 60 ^) (10) (11) (1Z)06^050The alicyclic hydrocarbon group of Ru to R25 or the alicyclic hydrocarbon group of Z and a carbon atom may be monocyclic or polycyclic. Specifically, for example, it has a monocyclic, bicyclic, tricyclic, tetracyclic structure having a carbon number of 5 or more. The alicyclic hydrocarbon group having 6 to 30 carbon atoms, more preferably 7 to 25 carbon atoms, may have a substituent. In the following, it is a structural example of an alicyclic part in an alicyclic hydrocarbon group. -43- 588218 V. Description of the invention (42) [Chem. 32] 〇〇 > 〇 >-W (2) (3) ① CD GO (4) U. (S), (6) ① CO COO {7 ) (8) (9) a? 60 ^) (10) (11) (1Z) 06 ^ 050
(IS) (13) (Μ)(IS) (13) (Μ)
-44- 588218 五、發明說明（43【化33】 (2S) (29)-44- 588218 V. Description of the invention (43 [化 33] (2S) (29)
(3Z) (33) (34) <35)(3Z) (33) (34) < 35)
(40) (41) (42) Λ (43) (44) (45) (46) _·【0.1 1 5】 【化3 4】 .〇 〇 Ο(47) (48) (49)(40) (41) (42) Λ (43) (44) (45) (46) _ · [0.1 1 5] [Chemical 3 4] .〇 〇 〇 (47) (48) (49)
-45- (50) 588218 五、發明說明（44 ) .【化3 .5】.’. ' . ------- (51) 於本發明中，上述脂環式部分之較佳者例如金剛烷基、 正金剛烷基、萘烷殘基、三環癸基、四環十二烷基、原菠 太兀基、雪松嫌醇基、環己基、環庚基、環辛基、環癸基、 環十二烷基等。更佳者爲金剛烷基、萘烷殘基、原菠烷基 、雪松烯醇基、環己基、環庚基、環辛基、環癸基、環十 二烷基。 此等脂環式烴基之取代基例如烷基、取代烷基、鹵素原 子、羥基、烷氧基、羧基、烷氧基羰基。烷基例如甲基、 乙基、丙基、異丙基、丁基等低碳烷基較佳，更佳者爲選 自於甲基、乙基、丙基、異丙基之取代基。取代烷基之取 代基例如羥基、鹵素原子、烷氧基。上述烷氧基例如甲氧 基、乙氧基、丙氧基、丁氧基等碳數1〜4個者。 上述樹脂中通式（pi)〜（pVI)所示構造可使用於保護鹼 可溶性基。鹼可溶性基例如於該技術範圍中有習知之各種 基。 具體例如羧酸基、磺酸基、苯酚基、硫醇基等，較佳者 爲羧酸基、磺酸基。 上述樹脂中以通式（P I )〜（pV I )所示構造保護的鹼可溶 性基以下述通式（PVII)〜（pXI)所示之基較佳。-45- (50) 588218 V. Explanation of the invention (44). [Chem. 3.5]. '.'. ------- (51) In the present invention, the above-mentioned alicyclic part is preferred For example, adamantyl, n-adamantyl, decalinyl residue, tricyclodecyl, tetracyclododecyl, protyl, cedaryl alcohol, cyclohexyl, cycloheptyl, cyclooctyl, ring Decyl, cyclododecyl, etc. More preferred are adamantyl, decalinyl, orthospinyl, cedarenol, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl. The substituents of these alicyclic hydrocarbon groups are, for example, alkyl groups, substituted alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups, and alkoxycarbonyl groups. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, and more preferably a substituent selected from methyl, ethyl, propyl, and isopropyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. The alkoxy group is, for example, one having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The structure represented by the general formulae (pi) to (pVI) in the above resin can be used for protecting alkali-soluble groups. The alkali-soluble group is exemplified by various groups known in the art. Specific examples thereof include a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group. Preferred are a carboxylic acid group and a sulfonic acid group. Among the above resins, it is preferred that the alkali-soluble group protected by a structure represented by the general formulae (P I) to (pV I) be a base represented by the following general formulae (PVII) to (pXI).
-46- 588218 五、發明說明 【化36】 45 )-46- 588218 V. Description of the invention [Chem. 36] 45)
Rn …卿) Ο ^12 ，c-o- (p—r13 R14 …（pVIII)Rn… Qing) 〇 ^ 12, c-o- (p—r13 R14… (pVIII)
.怍i? ? C—O-CH-R (pIX) 16. 怍 i?? C—O-CH-R (pIX) 16
R 18 (px) —C~0一ΌI R21 R20 i? i22.?23 i? 一 C一 O— C—CH — C— R24 (pXI)R 18 (px) —C ~ 0 aΌI R21 R20 i? I22.?23 i? A C one O— C—CH — C— R24 (pXI)
R -47- 588218 五、發明說明（46 ) (其中，RM〜R25及Z係與上述各定義相同者） 上述樹脂中具有以通式（pi)〜（pVI)所示構造保屬的鹼 可溶性基的重複單位以下述通式（pA)所示重複單位較佳。 【化37】 :伽⑽.· A-C-〇-RaR-47- 588218 5. Description of the invention (46) (Among them, RM ~ R25 and Z are the same as the above definitions) The above resin has alkali solubility guaranteed by the structure represented by the general formulae (pi) to (pVI) The repeating unit of the group is preferably a repeating unit represented by the following general formula (pA). [Chem. 37]: Gaya. · A-C-〇-Ra
〇 (其中，R係表示氫原子、鹵素原子或具有1〜4個碳_ 子之取代或未經取代的直鏈或支鏈烷基，數個R可相同$ 各不相同， A係表示單鍵、單獨選自於伸烷基、取代伸烷基、 、硫醚基、羰基、酯基、醯胺基、磺醯胺基、胺甲酸酯基 、或脲基，或2種以上組合之基，〇 (wherein, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted straight or branched chain alkyl group having 1 to 4 carbon atoms, several R may be the same and each may be different, and A is a single The bond is selected from the group consisting of an alkylene group, a substituted alkylene group, a thioether group, a carbonyl group, an ester group, amidino group, a sulfonamido group, a urethane group, or a urea group, or a combination of two or more kinds. base,
Ra係表示上述式（pi)〜（pVI)中任一基）Ra represents any one of the above formulae (pi) to (pVI))
於下述中、係爲通式（pA)所示重複單位之具體例。 -48- 588218The following are specific examples of the repeating unit represented by the general formula (pA). -48- 588218
588218 五、發明說明（48 ) 於上述通式（Π-AB)中，RM’、R12’係各表示獨立的氫原 子、氰基、鹵素原子、或可具取代基之烷基-。- Z’係表示包含鍵結的2個碳原子（C-C)、爲形成可具取 代基之脂環式構造的原子團。 上述Rh’iRu’之鹵素原子例如氯原子、溴原子、氟原 子、碘原子等。 上述Ru’、R12’、 R21’〜R3。’之烷基以碳數1〜10個之直 鏈狀或支鏈狀烷基較佳、更佳者爲碳數1〜6個直鏈狀或 支鏈狀烷基，最佳者爲甲基、乙基、丙基、異丙基、正丁 基、異丁基、第2-丁基、第3-丁基。 上述烷基之另外取代基例如羥基、鹵素原子、羥基、烷 氧基、醯基、氰基、醯氧基等。鹵素原子例如氯原子、溴 原子、氟原子、碘原子等，烷氧基例如甲氧基、乙氧基、 丙氧基、丁氧基等碳數1〜4個者，醯基例如甲醯基、乙 醯基等，醯氧基例如乙醯氧基等。 上述爲形成Z’之脂環式構造的原子團係爲在樹脂中可具 取代基之脂環式烴的重複單位之原子團，其中以爲形成有 橋式脂環式烴重複單位之有橋式脂環式構造的原子團較佳 所形成的脂環式烴之骨架例如與通式（p I )〜（p VI )之R i i 〜R25及通式（II-AB)中Z’之脂環式部分的上述構造例（1) 〜（5 1 )相同者。 較佳的有橋式脂環式烴之骨架，例如上述構造例中（5 )588218 5. Description of the invention (48) In the above general formula (Π-AB), RM 'and R12' each represent an independent hydrogen atom, a cyano group, a halogen atom, or an alkyl- group which may have a substituent. -Z 'represents an atomic group having two carbon atoms (C-C) bonded to form an alicyclic structure having a substituent. Examples of the halogen atom of Rh'iRu 'include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. The above Ru ', R12', R21 'to R3. The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and the most preferable is methyl group. , Ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl. Examples of the other substituents of the alkyl group include a hydroxyl group, a halogen atom, a hydroxyl group, an alkoxy group, a fluorenyl group, a cyano group, and a fluorenyl group. Halogen atom such as chlorine atom, bromine atom, fluorine atom, iodine atom, etc., alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group and the like having 1 to 4 carbon atoms, and fluorenyl group such as formamyl Ethoxyl and the like, and ethoxyl such as ethoxyl and the like. The above-mentioned atomic group forming an alicyclic structure of Z 'is an atomic group of a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, in which a bridged alicyclic group having a bridged alicyclic hydrocarbon repeating unit is considered to be formed The skeleton of the alicyclic hydrocarbon formed by the atomic group structure of the formula is preferably, for example, R ii to R25 of the general formula (p I) to (p VI) and the alicyclic portion of Z 'in the general formula (II-AB). The structural examples (1) to (5 1) are the same. The skeleton of a bridged alicyclic hydrocarbon is preferable, for example, in the above structural example (5)
-50 - 588218 五、發明說明（49 ) 、（6)、 （7)、 （9)、 （10)、 （13)、 （14)、 （15)、 （23)、 （28) 、（36)、（37)、（42)、（47)。 上述脂環式骨架之骨架中亦可具有取代基。該取代基例 如上述通式（II-A)或（II-B)中R13，〜R16，。 於上述具有有橋式脂環式烴之重複單位中，以上述通式 (II-A)或（II-B)所示重複單位更佳。 本發明之脂環烴系酸分解性樹脂中酸分解性可以包含於 上述<(=0)4 4’-17’、亦可以包含作爲通式（1148)中2, 之取代基。 酸分解性基之構造以-(：(=0)41-^表示。 其中，RG例如第3-丁基、第3-戊基等之3級烷基、異 冰片基、1-乙氧基乙基、1-丁氧基乙基、1-異丁氧基乙基 、1-環己氧基乙基等1-烷氧基乙基、1-甲氧基甲基、1-乙 氧基甲基等之烷氧基甲基、3 -羰基烷基、四氫呋喃基、四 氫吡喃基、三烷基甲矽烷酯基、3 -羰基環己酯基、2 -甲基 -2-金剛烷基、戊內酯殘基等。乂1係與上述X同義。 上述R13’〜R16’之鹵素原子例如氯原子、溴原子、氟原 子、捵原子等。 上述R5、R6、R13’〜R16’之烷基以碳數1〜10個直鏈狀或 支鏈狀烷基較佳、更佳者爲碳數1〜6個直鏈狀或支鏈狀 烷基、最佳者爲甲基、乙基、丙基、異丙基、正丁基、異 丁基、第2-丁基、第3-丁基。 上述R5、R6、R13’〜R16’之環狀烴基例如環狀烷基、有橋-50-588218 V. Description of the invention (49), (6), (7), (9), (10), (13), (14), (15), (23), (28), (36 ), (37), (42), (47). The alicyclic skeleton may have a substituent in the skeleton. Examples of the substituent are R13, R16, and R16 in the general formula (II-A) or (II-B). Among the above-mentioned repeating units having a bridged alicyclic hydrocarbon, the repeating unit represented by the above-mentioned general formula (II-A) or (II-B) is more preferable. The acid decomposability in the alicyclic hydrocarbon-based acid-decomposable resin of the present invention may be included in the above < (= 0) 4 4'-17 ', or may include a substituent of 2, in the general formula (1148). The structure of the acid-decomposable group is represented by-(: (= 0) 41- ^. Among them, RG is a tertiary alkyl group such as 3-butyl group, 3-pentyl group, isobornyl group, and 1-ethoxy group. 1-alkoxyethyl, 1-methoxymethyl, 1-ethoxy, such as ethyl, 1-butoxyethyl, 1-isobutoxyethyl, 1-cyclohexyloxyethyl, etc. Alkoxymethyl such as methyl, 3-carbonylalkyl, tetrahydrofuranyl, tetrahydropyranyl, trialkylsilyl ester, 3-carbonylcyclohexyl ester, 2-methyl-2-adamantane Group, valerolactone residue, etc. 乂 1 is synonymous with X. The halogen atoms of R13 ′ to R16 ′ are, for example, chlorine atom, bromine atom, fluorine atom, fluorene atom, etc. R5, R6, R13 ′ to R16 ′ The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably is a linear or branched alkyl group having 1 to 6 carbon atoms. The most preferred group is methyl or ethyl. Group, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, etc. The cyclic hydrocarbon groups of R5, R6, and R13 ′ to R16 ′ are, for example, cyclic alkyl groups, and bridge
-51 - 588218 五、發明說明（5〇 ) 式烴，如環丙基、環戊基、環己基、金剛烷基、2 -甲基-2 -金剛院基、原疲燒基、冰片基、異冰片基、三環癸基、 二環戊基、原菠烷基環氧基、盏基、異盏基、新盏基、四 環十二烷基等。 上述R13’〜R16’中至少2個鍵結形成環例如環戊烷、環 己烷、環庚烷、環辛烷等碳數5〜12之環。 上述R17 ’之烷氧基例如甲氧基、乙氧基、丙氧基、丁氧 基等碳數1〜4個者。 上述烷基、環狀烴基、烷氧基之另外取代基例如羥基、 鹵素原子、羧基、烷氧基、醯基、氰基、醯氧基、烷基、 環狀烴基等。鹵素原子例如氯原子、溴原子、氟原子、碘 原子等。烷氧基例如甲氧基、乙氧基、丙氧基、丁氧基等 之碳數1〜4個者，醯基例如甲醯基、乙醯基等，醯氧基 例如乙醯氧基等。 而且，烷基、環狀烴基例如上述所例舉者。 上述A’之2價鍵結基例如單獨選自於伸烷基、取代伸烷 基、醚基、硫醚基、羰基、酯基、醯胺基、磺醯胺基、胺 甲酸酯基、脲基、或組合2個以上之基。 上述A’之伸烷基、取代伸烷基例如以下述式所示之基。 —C C (R α j(Rb ) D r ~ (其中，Ra、Rb係表示氫原子、烷基、取代烷基、鹵素 原子、羥基、烷氧基，兩者可以相同或不同。烷基以選自 於甲基、乙基、丙基、異丙基、丁基等之低碳烷基較佳，-51-588218 5. Description of the invention (50) hydrocarbons of formula (such as cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, 2-methyl-2-adamantyl, protosyl, borneol, Isobornyl, tricyclodecyl, dicyclopentyl, orthospinyl epoxy, calanyl, isocanyl, neocanyl, tetracyclododecyl and the like. At least two of the above R13 'to R16' are bonded to form a ring such as cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like having 5 to 12 carbon rings. The alkoxy group of the R17 'is, for example, one having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the other substituents of the alkyl group, cyclic hydrocarbon group, and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, a fluorenyl group, a cyano group, a fluorenyl group, an alkyl group, and a cyclic hydrocarbon group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Alkoxy groups such as methoxy, ethoxy, propoxy, butoxy have 1 to 4 carbon atoms, fluorenyl groups such as methylfluorenyl, ethylfluorenyl, etc., fluorenyl groups such as ethanyloxy, etc. . The alkyl group and the cyclic hydrocarbon group are exemplified above. The above-mentioned divalent bonding group of A ′ is independently selected from, for example, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, amidino group, a sulfonamido group, a urethane group, Urea group, or a combination of two or more groups. The alkylene or substituted alkylene of A 'is, for example, a group represented by the following formula. —CC (R α j (Rb) D r ~ (where Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and the two may be the same or different. The alkyl group is selected Lower alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, etc. are preferred,
-52- 588218 五、發明說明（51 ) 更佳者爲甲基、乙基、丙基、異丙基。取代烷基之取代基 例如羥基、鹵素原子、烷氧基。烷氧基例如甲氧基、乙氧 基、丙氧基、丁氧基等之碳數1〜4個者。鹵素原子例如 氯原子、溴原子、氟原子、碘原子等。R係表示1〜1〇之 整數。 本發明之脂環烴系酸分解性樹脂中藉由酸作用分解之基 係至少含有一種具有含上述通式（pi)〜（pVI)所示脂環式 烴之部分構造的重複單位、通式（II-B)所示重複單位、及 下述共聚合成分之重複單位的重複單位。 上述通式（Π-A)或通式（II-B)* R13’〜R16’之各種取代 基係爲形成上述通式（II-AB)中脂環式構造之原子團〜爲 形成有橋式脂環式構造之原子團Z的取代基者。 上述通式（II-A)或通式（Π-Β)所示重複單位之具體例如 下所述，惟本發明不受此等具體例所限制。-52- 588218 V. Description of the invention (51) The more preferable ones are methyl, ethyl, propyl and isopropyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. The alkoxy group is, for example, one having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. R is an integer of 1 to 10. The alicyclic hydrocarbon-based acid-decomposable resin of the present invention contains at least one type of repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulae (pi) to (pVI) above, and a general formula containing a base system decomposed by an acid action. (II-B) The repeating unit shown in the repeating unit and the repeating unit of the copolymerization component described below. The various substituents of the general formula (Π-A) or general formula (II-B) * R13 ′ to R16 ′ are atomic groups forming an alicyclic structure in the general formula (II-AB). Substituents of alicyclic structure group Z. Specific examples of the repeating unit represented by the general formula (II-A) or the general formula (Π-B) are described below, but the present invention is not limited by these specific examples.
-53- 588218 五、發明說明（52 ) 【化39】-53- 588218 V. Description of the Invention (52) [化 39]
-54- 588218 五、發明說明（53 ) 本發明之脂環烴系酸分解性樹脂以具有含下述通式（Lc ) 或下述通式（V-1)〜（V-5)中任一式所示內酯構造基的重複 單位較佳 【化4 0.】-54- 588218 5. Description of the invention (53) The alicyclic hydrocarbon-based acid-decomposable resin of the present invention has any one of the following general formulas (Lc) or (V-1) to (V-5). The repeating unit of the lactone structural group shown in the formula is preferably [Chemical 4 0.]
(Lc) 【0 1.4 5】 【化4 1】(Lc) [0 1.4 5] [Chemical 4 1]
(V-5) R e i係各表 (V-4) (其中，於通式（Lc)、中Ra^Rb^Rc^Rt 示獨立的氫原子或可具取代基之烷基，m、η係各表示獨立 的0〜3之整數，且m + n爲2〜6， 於通式（V-1)〜（V-5)中Rlb〜R5b係各表示獨立的氫原子 、可具取代基之烷基、環烷基、烷氧基、烷氧基羰基、烷 基磺醯基亞胺基或烯基， 〜R5b中有2個可以鍵結形成環） 於通式（Lc)中Ra^Rei之烷基及通式（V-1)〜（V-5)中 Rib〜lb之院基、院氧基、院氧基鑛基、院基礦釀基亞月女 基之烷基例如直鏈狀、支鏈狀烷基，可具有取代基。 直鏈狀、支鏈狀烷基以碳數1〜12個直鏈狀或支鏈狀或 -55- 588218 五、發明說明（54 ) 支鏈狀烷基較佳、更佳者爲碳數1〜1 0個直鏈狀或支鏈狀 烷基，最佳者爲甲基、Ζτ基〜、丙基、異丙基、正丁基、異 丁基、第2-丁基、第3-丁基、戊基、己基、庚基、辛基 、壬基、癸基。 Rlb〜R5b之環烷基以環丙基、環戊基、環己基、環庚基 、環辛基等之碳數3〜8個者較佳。 Rlb〜R5b之烯基以乙烯基、丙烯基、丁烯基、己烯基等 碳數2〜6個者較佳。 而且，Rlb〜R5b中有2個鍵結形成環例如環丙烷環、環 丁烷環、環戊烷環、環己烷環、環辛烷環等3〜8碳環。 此外，通式（V-1)〜（V-5)中Rlb〜R5b亦可以鍵結於構成 環狀骨架之任一碳原子上。 Rai-Rei之烷基及Rlb〜R5b之烷基、環烷基、烷氧基、 烷氧基羰基、烷基磺醯基亞胺基、烯基可具有的較佳取代 基例如碳數1〜4個烷氧基、鹵素原子（氟原子、氯原子、 溴原子、碘原子）、碳數2〜5之醯基、碳數2〜5之醯氧 基、氰基、羥基、羧基、碳數2〜5之烷氧基羰基、硝基 通式（Lc)或通式（V-1)〜（V-5)中任一所示具有內酯構造 之重複單位例如上述通式（II-A)或（114)之R13,〜R16，中 至少一個爲具有通式（Lc)或通式（V-1)〜（V-5)所示基者（ 例如- COOR5之r6係表示通式（Lc)或通式（V-1)〜（V-5)所示 之基）' 或下述通式（AI)所示重複單位等。(V-5) Rei is each table (V-4) (wherein Ra ^ Rb ^ Rc ^ Rt in the general formula (Lc) represents an independent hydrogen atom or an alkyl group which may have a substituent, m, η Each represents an independent integer of 0 to 3, and m + n is 2 to 6, in the general formulae (V-1) to (V-5), Rlb to R5b each represent an independent hydrogen atom and may have a substituent Alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylsulfoimino or alkenyl, ~ 2 of R5b can be bonded to form a ring) Ra ^ in the general formula (Lc) Rei's alkyl group and the general formula (V-1) ~ (V-5) of Rib ~ lb's courtyard, courtyard oxygen, courtyard oxygen-based, courtyard-based ore group and alkylene group The linear or branched alkyl group may have a substituent. Linear or branched alkyl groups have 1 to 12 carbons, straight or branched or -55- 588218 5. Description of the invention (54) Branched alkyl groups are preferred, more preferably carbon number 1 ~ 10 linear or branched alkyl groups, the most preferred are methyl, Zτ ~, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl Base, pentyl, hexyl, heptyl, octyl, nonyl, decyl. The cycloalkyl group of Rlb ~ R5b is preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like having 3 to 8 carbon atoms. The alkenyl groups of Rlb to R5b are preferably vinyl, propenyl, butenyl, hexenyl and the like having 2 to 6 carbon atoms. In addition, Rlb to R5b have 2 to 8 carbon rings such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. In addition, Rlb to R5b in the general formulae (V-1) to (V-5) may be bonded to any carbon atom constituting a cyclic skeleton. Rai-Rei alkyl group and Rlb ~ R5b alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, alkylsulfoimino group, alkenyl group may have preferable substituents such as carbon number 1 ~ 4 alkoxy groups, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), fluorenyl group having 2 to 5 carbon atoms, fluorenyl group having 2 to 5 carbon atoms, cyano group, hydroxyl group, carboxyl group, carbon number A repeating unit having a lactone structure shown in any of 2 to 5 alkoxycarbonyl, nitro general formula (Lc), or general formula (V-1) to (V-5), such as the general formula (II-A ) Or (114), at least one of R13 and R16 is a group represented by the general formula (Lc) or (V-1) to (V-5) (for example, r6 of COOR5 represents the general formula ( Lc) or a group represented by general formulae (V-1) to (V-5)) or a repeating unit represented by the following general formula (AI).
-56- 588218 五、發明說明（55 ) 【化42】 .寸 042-丫十· _ (AI) 、 o=c _ ·. I ·· 0 ,· _ I . A 丨一B2 (其中，Rb〇係表示氫原子、鹵素原子、或碳數1〜4個 經取代或未經取代的烷基。Rb。之烷基可具有的較佳取代 基例如上述通式（V- 1 )〜（V-5)之Rlb的烷基可具有的取代 基例如上述所例示者。-56- 588218 V. Description of the invention (55) [化 42]. Inch 042-Ya ·· (AI), o = c_ .. I ·· 0, · _ I. A 丨 A B2 (where Rb The 〇 series represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Rb. The alkyl group may have a preferable substituent such as the above-mentioned general formula (V-1) to (V -5) The substituent which the alkyl group of Rlb may have is, for example, those exemplified above.
Rb0之鹵素原子例如氟原子、氯原子、溴原子、碑原子 。Rb〇以氫原子較佳。 A’係表示單鍵、醚基、酯基、羰基、伸烷基、或組合此 等之2價基。 B2係表示通式（Lc)或通式（V-1)〜（V-5)中任—所示之基 。A’中該組合的2價基例如下述式者。 -57- 588218 五、發明說明（56 ) 【化43】Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and a monument atom. Rb0 is preferably a hydrogen atom. A 'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group in combination of these. B2 represents a group represented by any one of the general formula (Lc) or (V-1) to (V-5). The divalent base of this combination in A 'is, for example, the following formula. -57- 588218 V. Description of the Invention (56) [化 43]
於上述式中，Rab、Rbb係表示氫原子、烷基、取代院基 、鹵素原子、經基、院氧基，兩者可相同或不同。 烷基以甲基、乙基、丙基、異丙基、丁基等低碳烷基較 佳，更佳者爲選自於甲基、乙基、丙基、異丙基。取代院 基之取代基例如羥基、鹵素原子、碳數i〜4之院氧基。 烷氧基例如甲氧基、乙氧基、丙氧基、丁氧基等碳數1 〜4個者。鹵素原子例如氯原子、溴原子、氟原子、碘原 子等。rl爲1〜1〇之整數、較佳者爲1〜4之整數。^爲1 • 58- 588218 五、發明說明（57 ) 〜3之整數、較佳者爲1或2。 於下述中係爲通式（AI )所示重複單位之具體例，惟本發 明之內容不受此等所限制。 -59- 588218 五、發明說明（58 ) 【化44】(其中，Rx係表〜示Η或CH3) G=0In the above formulas, Rab and Rbb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a mesogenic group, or an oxygen group, and the two may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, and more preferably selected from methyl, ethyl, propyl, and isopropyl. Examples of the substituents for the substituted group include a hydroxyl group, a halogen atom, and a grouped oxygen group having 4 to 4 carbon atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. rl is an integer of 1 to 10, more preferably an integer of 1 to 4. ^ Is 1 • 58- 588218 V. Description of the invention (57) An integer of 3 to 3, preferably 1 or 2. The following are specific examples of repeating units represented by the general formula (AI), but the content of the present invention is not limited by these. -59- 588218 V. Description of the invention (58) [化 44] (where Rx is shown in the table or shown as CH or CH3) G = 0
0*0 (1V-3) (IV4) (ΠΜ)0 * 0 (1V-3) (IV4) (ΠΜ)
、汁 CH厂 ^r. • f=〇, Juice CH Plant ^ r. • f = 〇
(TV-7) ψ-0(TV-7) ψ-0
(IV-Il) o =〇 0(IV-Il) o = 〇 0
(IV42) (IV4)(IV42) (IV4)
(JV-15) (IV-16), 60- 588218 五、發明說明（59 ) 【化45】 (其中，Rx係表示Η或CH3)(JV-15) (IV-16), 60- 588218 V. Description of the invention (59) [Chemical 45] (where Rx represents 系 or CH3)
-61 - 588218 五、發明說明（6〇) 【化46】 (其中-〜Rx係表示Η或CH3)-61-588218 V. Description of the invention (60) [Chemical 46] (where-~ Rx means Η or CH3)
本發明之脂環式烴系酸分解性樹脂亦可含有具下述通式 (VIII)所示基的重複單位。 【化47】.The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may contain a repeating unit having a group represented by the following general formula (VIII). [Hua 47].
-62- 588218 五、發明說明（61 ) (其中’ R2e〜R4。係各表示獨立的氫原子或羥基，惟R2c 〜r4c中至少一個表示經基） ------------- 通式（VII )所示之基以二羥基體、單羥基體較佳，更佳 者爲二羥體。 具有通式（VII)所示基之重複單位例如上述通式（II-A) 或（II-B)之R13’〜R16’中至少一個爲具有上述通式（VII)所 示基者（例如- COOR5之R5係表示通式（VII)所示之基）、或 下述通式（All)所示之重複單位等。 【化48】-62- 588218 V. Description of the invention (61) (wherein 'R2e ~ R4. Each represents an independent hydrogen atom or hydroxyl group, but at least one of R2c ~ r4c represents a meridian group) ----------- -The group represented by the general formula (VII) is preferably a dihydroxy body or a monohydroxy body, and more preferably a dihydroxy body. A repeating unit having a group represented by the general formula (VII), for example, at least one of R13 ′ to R16 ′ of the general formula (II-A) or (II-B) is a group having the group represented by the general formula (VII) (for example, -R5 of COOR5 represents a group represented by the general formula (VII)), or a repeating unit represented by the following general formula (All). [Chemical 48]
c=o 0 (All.) R3c 通式（All)中，Ric表不氣原子或甲基。 R2e〜R4c各自獨立地表示氫原子或羥基。但，〜R4C中至 少一個表示經基。 於下述中係爲通式（All )所示重複單位之具體例，惟本 發明之內容不受此等所限制。 -63 - 588218 五、發明說明（62 ) 【化49】c = o 0 (All.) R3c In the general formula (All), Ric represents no gas atom or methyl group. R2e to R4c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of ~ R4C represents a meridian. In the following, specific examples of the repeating unit represented by the general formula (All) are shown, but the content of the present invention is not limited by these. -63-588218 V. Description of the Invention (62) [化 49]
本發明之脂環烴系酸分解性樹脂亦可含有下_ s $ (VI 11 )所示重複單位。 【化50】 —CH-CH—The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may contain a repeating unit represented by _s $ (VI 11). [Chem. 50] —CH-CH—
上述通式（VIII)中，Z2係表示-0-、或- N(R4I)-。此處’ R41係表示氫原子、羥基、烷基、鹵化烷基、或-〇S〇2-R42 。r42係表示烷基、鹵化烷基、環烷基或樟腦殘基。 上述R41及R42之烷基以碳數1〜10個直鏈狀或支鏈狀烷 基較佳、更佳者爲碳數1〜6個直鏈狀或支鏈狀院基、最 佳者爲甲基、乙基、丙基、異丙基、正丁基、異丁基、第 2-丁基、第3-丁基。 上述R41及R42之鹵化烷基例如三氟甲基、九氟丁基、十 五氟辛基、三氯甲基等。上述R42之環烷基例如環戊基、 -64- 588218 五、發明說明（63 ) 環己基、環辛基等。 及R42之院基及鹵化烷基、R42之環烷基或樟g腦殘基 可具有取代基。該取代基例如羥基、羧基、氰基、鹵素原 子（例如氯原子、溴原子、氟原子、碘原子）、烷氧基（較 佳者爲碳數1〜4，例如甲氧基、乙氧基、丙氧基、丁氧基 等）、醯基（較佳者碳數爲2〜5，例如甲醯基、乙醯基等） 、醯氧基（較佳者碳數爲2〜5，例如乙醯氧基）、芳基（較 佳者碳數6〜1 4，例如苯基）等。 上述通式（VI I I )所示重複單位之具體例如下述[I ’ -1 ]〜 [Γ-7] ’惟本發明不受此等具體例所限制。【化51】 [r-j] *In the general formula (VIII), Z2 represents -0 or -N (R4I)-. Here, 'R41' represents a hydrogen atom, a hydroxyl group, an alkyl group, a halogenated alkyl group, or -0SO2-R42. The r42 series represents an alkyl group, a halogenated alkyl group, a cycloalkyl group or a camphor residue. The above-mentioned alkyl groups of R41 and R42 are preferably straight or branched alkyl groups having 1 to 10 carbon atoms, more preferably 1 to 6 linear or branched alkyl groups having carbon atoms, and the most preferable Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl. Examples of the halogenated alkyl group of R41 and R42 include trifluoromethyl, nonafluorobutyl, pentafluorooctyl, and trichloromethyl. Examples of the above cycloalkyl group of R42 are cyclopentyl group, -64-588218, etc. 5. Description of the invention (63) cyclohexyl group, cyclooctyl group and the like. And R42 may have a substituent and a halogenated alkyl group, a cycloalkyl group of R42, or a camphor residue. The substituent is, for example, a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), an alkoxy group (preferably a carbon number of 1 to 4, such as a methoxy group, an ethoxy group, etc.). , Propoxy, butoxy, etc.), fluorenyl (preferably carbon number is 2 to 5, such as methyl fluorenyl, ethyl fluorenyl, etc.), fluorenyl (preferably carbon number is 2 to 5, such as Acetyloxy), aryl (preferably 6 to 14, carbon, such as phenyl) and the like. Specific examples of the repeating unit represented by the general formula (VI I I) are, for example, the following [I'-1] to [Γ-7] ', but the present invention is not limited to these specific examples. [Chem. 51] [r-j] *
'η 卞Η—广vc in- [Γ-4] CH3 【化52】'η 卞 Η— 广 vc in- [Γ-4] CH3 【化 52】
-65 - 588218 五、發明說明（64 ) 本發明之脂環烴系酸分解性樹脂係除上述之重覆構造單 --一位外，以調節乾式蝕刻耐性或標準顯像液適性、基板密接 性、光阻劑外型、以及光阻劑之一般必要特性的解像力、 耐熱性、感度等爲目的時，可含有各種重覆構造單位。 該重複構造單位例如下述單體之重複構造單位，惟不受 此等所限制。 藉此可微調整脂環烴系酸分解性樹脂所要求的性能，尤 其是 (1)對塗覆溶劑之解性、 (2 )製膜性（玻璃轉移溫度）、 (3)鹼顯像性、 (4 )膜邊緣（親疏水性、鹼可溶性基選擇）、 (5 )對未曝光部基板之密接性、 (6 )乾式蝕刻耐性、 等之微調整。 該單體例如有選自於丙烯酸酯類、甲基丙烯酸酯類、丙 烯酸醯胺類、甲基丙烯酸醯胺類、烯丙基化合物、乙烯醚 類、乙烯酯類等具一個加成聚合性不飽和鍵之化合物等。 其他爲上述各種重複單位之單體與可共聚合的加成聚合 性不飽和化合物時，亦可以共聚合。 於脂環烴系酸分解性樹脂中各重複構造單位之含有莫耳 比，爲調節乾式蝕刻耐性或標準顯像液適性、基板密接性 、光阻劑外型、以及光阻劑之一般必要特性的解像力、耐-65-588218 5. Description of the invention (64) The alicyclic hydrocarbon acid-decomposable resin of the present invention is in addition to the above-mentioned repeating structure sheet-one bit, in order to adjust the dry etching resistance or the standard developing solution suitability, and the substrate is tightly attached. For the purpose of resolution, appearance of the photoresist, and general necessary characteristics of the photoresist, heat resistance, sensitivity, etc., various overlapping structural units may be included. The repeating structural unit is, for example, a repeating structural unit of the following monomers, but is not limited thereto. This allows fine adjustment of properties required for alicyclic hydrocarbon acid-decomposable resins, in particular (1) its solubility in coating solvents, (2) film-forming properties (glass transition temperature), and (3) alkali developability. (4) Fine adjustment of film edges (hydrophilicity, alkali-soluble group selection), (5) adhesion to the substrate of the unexposed part, (6) dry etching resistance, and so on. This monomer is, for example, selected from acrylates, methacrylates, ammonium acrylates, ammonium methacrylates, allyl compounds, vinyl ethers, vinyl esters, etc. Compounds with saturated bonds, etc. When other monomers of the above-mentioned various repeating units and copolymerizable addition polymerizable unsaturated compounds are copolymerized, they may be copolymerized. The molar ratio of each repeating structural unit in the alicyclic hydrocarbon acid-decomposable resin is for adjusting dry etching resistance or standard developing solution suitability, substrate adhesion, photoresist appearance, and general necessary characteristics of photoresist Resolution
-66- 588218 五、發明說明（65 ) 熱性、感度等予以適當設定。 本發明脂環烴系酸分解性樹脂之較佳形態例〜如τ述者。 (1) 含有具含上述通式（pi)〜（pVI)所示脂環式烴之部分 構造的重複單位者（側鏈型） (2) 含有通式（II-AB)所示重複單位者（主鏈型），惟於（2) 中更例如下述者。 (3 )具有通式（11-AB)所示重複單位、馬來酸酐衍生物及 (甲基）丙烯酸酯構造者（混雜型） 脂環烴系酸分解性樹脂中具有含通式（PI )〜（P VI )所示 脂環式烴部分構造之重複單位含量，在全部重複構造單位 中以30〜70莫耳％較佳、更佳者爲35〜65莫耳％、最佳者 爲40〜60莫耳％。 脂環烴系酸分解性樹脂中通式（Π - AB)所示重複單位之 含有量，在全部重複構造單位中以1〇〜60莫耳％較佳、更 佳者爲15〜55莫耳％、最佳者爲20〜50莫耳％。 而且’以上述另外共聚合成分的單體爲基準、重複構造 單位之樹脂中含量可視企求的光阻劑性能而定予以適當設 定’惟~般而言具有含上述通式（pi)〜（PVI)所示脂環式 烴之部分構造的重複構造單位與上述通式（I丨_ AB)所示重 複單位之合計總莫耳數而言以99莫耳％以下較佳、更佳者 爲9 0莫耳％以下、最佳者爲8〇莫耳％以下。 本發明之組成物爲ArF曝光用時，就對ArF光之透明性 而言樹脂以不具芳香族基者較佳。 -67- 588218 五、發明說明（66 ) 另外’在本發明正型感光性組成物上照射f2準分子雷射 光時’（B )成分之樹脂以在聚合物骨架之主鏈及/或側鏈上 具有取代的構造、且藉由酸作用分解、增大對鹼顯像液之 溶解度的樹脂（以下稱爲含氟基之樹脂）較佳，更佳者係爲 在聚合物骨架之主鏈上至少具有一個選自於全氟伸烷基、 全氟伸芳基之部位，或在聚合物骨架之側鏈上至少具有一 個選自於保護全氟·院基、全氟芳基、六氟-2-丙醇基、及 六氟-2 -丙醇基之0H基部位的含氟基樹脂。 含氟基之樹脂例如至少具有一個下述通式（IR)〜（XR)所 示重複單位之樹脂較佳。 -68- 588218 五、發明說明（67 【化53】 R〇 \ R〇 〇-R2 Rs-O O-R4 〇η2〇ρ3 ; ^P〇_R‘5 cf3 (IVR) m -R2 Ρ?3-0 0—R4 (HR) 师）-66- 588218 V. Description of the Invention (65) The heat and sensitivity should be set appropriately. Examples of preferred embodiments of the alicyclic hydrocarbon-based acid-decomposable resin of the present invention are as described in τ. (1) Those containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulae (pi) to (pVI) (side chain type) (2) Those containing a repeating unit represented by the general formula (II-AB) (Main chain type), except for the following in (2). (3) Those having a repeating unit represented by the general formula (11-AB), a maleic anhydride derivative, and a (meth) acrylate structure (hybrid type) The alicyclic hydrocarbon-based acid-decomposable resin contains the general formula (PI) The content of the repeating unit of the partial structure of the alicyclic hydrocarbon shown in (P VI) is preferably 30 to 70 mol%, more preferably 35 to 65 mol%, and most preferably 40 ~ 60 mol%. The content of the repeating unit represented by the general formula (Π-AB) in the alicyclic hydrocarbon acid-decomposable resin is preferably 10 to 60 mol%, and more preferably 15 to 55 mol in all the repeating structural units. %, The best is 20 to 50 mole%. In addition, the content of the repeating structural unit resin based on the monomer of the other copolymerization component as a reference may be appropriately set depending on the desired photoresist performance. However, it generally contains the general formula (pi) to (PVI) The repeating unit of the partial structure of the alicyclic hydrocarbon shown by) and the repeating unit shown by the general formula (I 丨 _ AB) above is preferably 99 mol% or less, more preferably 9 0 mole% or less, the best is 80 mole% or less. When the composition of the present invention is for ArF exposure, it is preferred that the resin has no aromatic group in terms of transparency of ArF light. -67- 588218 V. Description of the invention (66) In addition, 'When the f2 excimer laser light is irradiated on the positive-type photosensitive composition of the present invention', the resin of the (B) component is added to the main chain and / or side chain of the polymer skeleton. A resin (hereinafter referred to as a fluorine-containing resin) having a substituted structure and being decomposed by an acid to increase the solubility in an alkali developing solution is more preferable, and the more preferable is a polymer backbone backbone. At least one site selected from the group consisting of perfluoroalkylenes and perfluoroarylenes, or at least one selected from the group consisting of protected perfluorinyl, perfluoroaryl, hexafluoro- Fluorine-based resin in the 0H group of 2-propanol group and hexafluoro-2 -propanol group. The fluorine-containing resin is preferably, for example, a resin having at least one repeating unit represented by the following general formulae (IR) to (XR). -68- 588218 V. Description of the invention -0 0—R4 (HR) division)
a2_a2_
(VR) 0、 CF3 R10 -4ch2-c^ R K11 II 」 CF3 R7 Re Αιη-°~r5 cf3 "V— CF R5 R12 0-R5 cf3 f3c-c-cf3 〇. cvm) R13 jR14 -fci(VR) 0, CF3 R10 -4ch2-c ^ R K11 II '' CF3 R7 Re Αιη- ° ~ r5 cf3 " V— CF R5 R12 0-R5 cf3 f3c-c-cf3 〇. Cvm) R13 jR14 -fci
RisRis
Ris^/ 1^=0 R17R18l (vmK) (IXR) (VDR)Ris ^ / 1 ^ = 0 R17R18l (vmK) (IXR) (VDR)
(其中，R。、Rl係表示氫原子、氟原子、可具取代基之 烷基、全氟烷基、環烷基或芳基，R2〜R4係表示可具取代基之烷基、全氟烷基、環烷基或 芳基，且R〇與Ri、R〇與R2、R3與R4可鍵結形成環， -69- 588218 五、發明說明（68 ) I係表不可具取代基之烷基、全氟烷基、單環或多環環 烷基、醯基、烷氧基羰基， I、R?、R8係表示相同或不同的氫原子、鹵素原子、可 具取代基之烷基、全氟烷基、烷氧基， b係表示相同或不同的氫原子、鹵素原子、氰基、 可具取代基之烷基或鹵化烷基， Ru、R1S係表示相同或不同的氫原子、羥基、鹵素原子 、氰基、烷氧基、醯基或可具取代基之烷基、環烷基、烯 基、芳烷基或芳基， h 3、R14係表示相同或不同的氫原子、鹵素原子、氰基 、可具取代基之烷基或鹵化烷基， R15係表示具有氟原子之烷基、單環或多環之環烷基、 稀基、芳烷基或芳基， Ru、R17、R18係表示相同或不同的氫原子、鹵素原子、 氰基、可具取代基之烷基、全氟烷基、烷氧基、-C0-0- R 1 5 ’ Ri9、R2Q、R21係表示相同或不同的氫原子、氟原子、具 有氟原子之烷基、單環或多環之環烷基、烯基、芳烷基、 芳基或烷氧基，惟R19、R2。、R21中至少一個爲氫原子以外 之基， Μ、A2係表示可具取代基之2價伸烷基、烯基、環伸院 基或伸芳基、或-O-CO-R22-、_C0-0-R23-、-C0-N(R24)-R25 -，(Wherein R. and R1 represent a hydrogen atom, a fluorine atom, an alkyl group which may have a substituent, a perfluoroalkyl group, a cycloalkyl group, or an aryl group, and R2 to R4 represent an alkyl group which may have a substituent, a perfluoro group Alkyl, cycloalkyl or aryl, and R0 and Ri, R0 and R2, R3 and R4 can be bonded to form a ring, -69- 588218 V. Description of the invention (68) I is a non-substitutable alkane Group, perfluoroalkyl group, monocyclic or polycyclic cycloalkyl group, fluorenyl group, alkoxycarbonyl group, I, R ?, R8 represent the same or different hydrogen atom, halogen atom, alkyl group which may have a substituent, Perfluoroalkyl group and alkoxy group, b represents the same or different hydrogen atom, halogen atom, cyano, optionally substituted alkyl or halogenated alkyl group, and Ru and R1S represent the same or different hydrogen atom and hydroxyl group , Halogen atom, cyano, alkoxy, fluorenyl or substituted alkyl, cycloalkyl, alkenyl, aralkyl or aryl, h 3 and R14 represent the same or different hydrogen atom, halogen Atom, cyano, optionally substituted alkyl or halogenated alkyl, R15 represents an alkyl group having a fluorine atom, a monocyclic or polycyclic cycloalkyl, a dilute group, an aromatic group Or aryl, Ru, R17, and R18 represent the same or different hydrogen atom, halogen atom, cyano group, optionally substituted alkyl group, perfluoroalkyl group, alkoxy group, -C0-0- R 1 5 'Ri9, R2Q, R21 represent the same or different hydrogen atom, fluorine atom, alkyl group having fluorine atom, monocyclic or polycyclic cycloalkyl, alkenyl, aralkyl, aryl or alkoxy group, but At least one of R19, R2, and R21 is a group other than a hydrogen atom, and M and A2 represent a divalent alkylene group, an alkenyl group, a cycloalkylene group, or an arylene group, or -O-CO-, which may have a substituent. R22-, _C0-0-R23-, -C0-N (R24) -R25-,
-70 - 588218 五、發明說明（69 ) R23、R24、R25係表示相同或不同的單鍵、或可具醚基、 酯基、醯胺基、胺甲酸酯基或脲·基之2價伸烷基、烯基、 環伸烷基或伸芳基， R24係表示氫原子、可具取代基之烷基、環烷基、芳烷 基或芳基， N係表示0或1，X、y、z係表示0〜4之整數） 含氟基之樹脂例如以至少具有一個下述通式（FA)〜（FF) 所示重複單位的樹脂較佳。 【化54】-70-588218 V. Description of the invention (69) R23, R24, R25 represent the same or different single bonds, or may have divalence of ether group, ester group, amido group, urethane group or urea · group Alkylene, alkenyl, cycloalkylene or aryl, R24 represents a hydrogen atom, an alkyl group which may have a substituent, cycloalkyl, aralkyl or aryl, N represents 0 or 1, X, y and z represent integers of 0 to 4) The fluorine-containing resin is preferably a resin having at least one repeating unit represented by the following general formulae (FA) to (FF), for example. [Chem. 54]
CO^Rio^ (FC) (Rh6R,15Rih)C 〇Χ· (FA)CO ^ Rio ^ (FC) (Rh6R, 15Rih) C 〇Χ · (FA)
(其中’ R1()1、R1()2係表示氫原子、氟原子、氯原子、溴 原子、氰基、三氟甲基， x係表示氫原子或藉由酸作用分解之基，(Wherein R1 () 1 and R1 () 2 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, and a trifluoromethyl group, and x represents a hydrogen atom or a group decomposed by the action of an acid,
Ri〇3、R1()4係表示氫原子、可具取代基之烷基、芳基、芳 院基’該烷基、該芳烷基係各在途中可具有_〇·、-S-、- -71 - 588218 五、發明說明（70) C02-、-C0-、-S02-、-S0-， η係表示1〜5之整數， Rlll 〜R116、Rl21 〜Rl32、R141 〜R148、Rl51 〜R158 係各表示 氫原子、氟原子、可具取代基之院基，至少一個爲戴原子） X中藉由酸作用分解之基例如使0X基酸分解、生成0H 基之基，縮醛基（例如1-烷氧基乙基、四氫呋喃基、第3-丁氧基羰基）、3級烷醚基（例如第3 - 丁醚基）。 本發明中含氟基之樹脂以另至少具有一個下述通式（XIR) 〜（XniR)所示重複單位較佳。 【化55】Ri〇3 and R1 () 4 represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group, an aromatic group, and the alkyl group and the aralkyl group may each have _〇 ·, -S-, --71-588218 V. Description of the invention (70) C02-, -C0-, -S02-, -S0-, η is an integer of 1 to 5, Rlll to R116, Rl21 to Rl32, R141 to R148, Rl51 to R158 each represents a hydrogen atom, a fluorine atom, or a substituent that may have a substituent, at least one of which is a Dai atom.) In X, a group decomposed by the action of an acid, such as a group that decomposes a 0X acid to form a 0H group, an acetal group ( Examples include 1-alkoxyethyl, tetrahydrofuranyl, 3-butoxycarbonyl), and tertiary alkyl ether groups (such as 3-butyl ether). The fluorine-containing resin in the present invention preferably has at least one repeating unit represented by the following general formulae (XIR) to (XniR). [Chem 55]
(其中，R26、R27、R32係表示相同或不同的氫原子、鹵素 原子、氰基、可具取代基之烷基或鹵化院基， 只28、R33 係表示- C(R36) (R37) (R38)、-C(R36) (R37) (〇R39)、 或下述通式（XIVR)之基，(Wherein R26, R27, and R32 represent the same or different hydrogen atom, halogen atom, cyano, optionally substituted alkyl or halogenated alkyl group, and only 28 and R33 represent -C (R36) (R37) ( R38), -C (R36) (R37) (〇R39), or the following general formula (XIVR),
-72- 588218 五、發明說明（71 ) 【化56】 —>〇八.AJ、(XTVR) 1 r29、r3。、R”係表示相同或不同的氫原子、鹵素原子' 氰基、可具取代基之院基、_化院基、院氧基、·⑶-οι R34、R35係表不相同或不同的氫原子、羥基、鹵素原子 、氰基、烷氧基、醯基、或可具取代基之烷基、環烷基、 烯基、芳烷基或芳基， R36、R37、R38、R39係表示相同或不同的可具取代基之烷 基、環烷基、烯基、炔基、芳烷基或芳基，r36、、R38 中有2個、或R36、r37、r39中有2個可鍵結形成環，且所 形成的環中亦可含有羰基， 尺4〇係表示可具取代基之烷基、環烷基、烯基、炔基、 芳烷基或芳基， Μ〜A4係表示單鍵、可具取代基之2價伸烷基、烯基、 環伸烷基或伸芳基、或_〇_co_R22_、-C0-0-R23-、-C0-N(R24)-R25*·， R22〜R25係與上述同義， z係表不碳原子與構成單環或多環脂環式基的原子團， n係表示0或1 )-72- 588218 V. Description of the invention (71) [Chem. 56] —> 08. AJ, (XTVR) 1 r29, r3. "R" represents the same or different hydrogen atom, halogen atom 'cyano group, chemical group which may have a substituent, chemical compound, chemical group, · 34-R35 are different or different hydrogen Atom, hydroxyl, halogen atom, cyano, alkoxy, fluorenyl, or optionally substituted alkyl, cycloalkyl, alkenyl, aralkyl, or aryl, R36, R37, R38, R39 represent the same Or different substituted alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl or aryl groups, two of r36, r38, or two of r36, r37, r39 can be bonded Forms a ring, and the formed ring may also contain a carbonyl group. The rule 40 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group, and M ~ A4 represents a single group. Bond, divalent alkylene, alkenyl, cycloalkylene or arylene, or _〇_co_R22_, -C0-0-R23-, -C0-N (R24) -R25 *, which may have a substituent R22 ~ R25 are synonymous with the above, z represents a carbon atom and an atomic group constituting a monocyclic or polycyclic alicyclic group, and n represents 0 or 1)
-73· 588218 五、發明說明（72 ) 而且，於本發明中爲控制含氟基樹脂的疏水性、玻璃轉 移溫度、-對曝光光源之透過率等物性時、或爲控制聚合物 合成時之聚合性時，可以至少具有一個下述通式（XVR)〜 (XV IIR)所示馬來酸酐、乙烯醚或含氰基之乙烯化合物由 來的重複單位。 【化5 7】。坎 (XVR) (其中，R41係表示可具取代基之烷基、環烷基、芳烷基 或芳基， R42係表示氫原子、鹵素原子、氰基、可具取代基之烷 基或鹵化垸基， A5係表示單鍵、可具取代基之2價伸烷基、烯基、環伸 烷基或伸芳基、或-〇-CO-R22-、-co-o-r23-、-co-n(r24)-R25 - ’ r22〜R25係與上述同義） 另外’本發明中更佳含氟基之樹脂例如至少具有一個下 述通式（IA)及（IIA)所示重複單位之樹脂、以及各至少具 有一個下述通式（IIA)及（VIA)所示重複單位之樹脂。 此等各至少具有一個下述通式（IA)及（IIA)所示重複單 尸42 VC、十-73 · 588218 V. Description of the invention (72) Furthermore, in the present invention, when controlling the physical properties such as the hydrophobicity of the fluorine-containing resin, the glass transition temperature,-the transmittance to the exposure light source, or when controlling the polymer synthesis In the case of polymerizability, it may have at least one repeating unit derived from maleic anhydride, vinyl ether, or a cyano-containing vinyl compound represented by the following general formulae (XVR) to (XV IIR). [Chemical 5 7]. XVR (where R41 represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group which may have a substituent, and R42 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, or halogenation Fluorenyl, A5 represents a single bond, a divalent alkylene group which may have a substituent, an alkenyl group, a cycloalkylene group or an arylene group, or -0-CO-R22-, -co-o-r23-,- co-n (r24) -R25-'r22 ~ R25 are synonymous with the above.) In addition, the more preferable fluorine-containing resin in the present invention has at least one repeating unit represented by the following general formulae (IA) and (IIA). A resin and a resin each having at least one repeating unit represented by the following general formulae (IIA) and (VIA). Each of these has at least one repeating unit represented by the following general formulae (IA) and (IIA).
十 CH；s O-R41 A5 — CN (XVIR) (XVM) -74- 588218 五、發明說明（73 ) 位之樹脂、以及各至少具有一個下述通式（IIA)及（VIA)所 示重複單位之樹脂，另可具有上述通式（IR )〜（VR )所示.重 複單位。 【化58】Ten CH; s O-R41 A5 — CN (XVIR) (XVM) -74- 588218 V. Resin of the invention (73) position, and each having at least one of the following formulae (IIA) and (VIA) is repeated The unit of the resin may further have the above-mentioned general formulae (IR) to (VR). Repeating units. [Chemical] 58
(其中，ha及R5a係表示相同或不同的氫原子、鹵素原 子、氰基或可具取代基之烷基， R2a、R3a、R6a及R7a係表示相同或不同的氫原子、鹵素 原子、氰基、羥基或可具取代基之烷基、環烷基、烷氧基 、醯基、醯氧基、烯基、芳基或芳烷基， Loa〜R55a係表示相同或不同的氫原子、氟原子或可具取 代基之烷基，惟R5Qa〜R55a中至少一個爲氟原子或至少一 個氫原子以氟原子取代的烷基， R56a係表示氫原子或可具取代基之烷基、環烷基、醯基 或烷氧基羰基，以氫原子較佳， R4a係表示下述通式（IVA)或（VA)之基， -75- 588218 五、發明說明（74 【化5 9】 f?11a(Wherein ha and R5a represent the same or different hydrogen atom, halogen atom, cyano or alkyl group which may have a substituent, and R2a, R3a, R6a and R7a represent the same or different hydrogen atom, halogen atom, cyano group , Hydroxy or optionally substituted alkyl, cycloalkyl, alkoxy, fluorenyl, fluorenyl, alkenyl, aryl or aralkyl, Loa ~ R55a represents the same or different hydrogen atom, fluorine atom Or an alkyl group which may have a substituent, but at least one of R5Qa to R55a is an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and R56a represents a hydrogen atom or an alkyl group which may have a substituent, a cycloalkyl group, A fluorenyl group or an alkoxycarbonyl group is preferably a hydrogen atom, R4a represents a group of the following general formula (IVA) or (VA), -75- 588218 5. Description of the invention (74 [Chem. 5 9] f? 11a
I ~C-R12a fw (IVA3 ^14a r°^6a (VA) 於通式（IVA)中，Rlla、Rl2a及R 体 、1 θ a 1糸袠不相同或不同的 可具取代基之烷基、環烷基、烯基、I ~ C-R12a fw (IVA3 ^ 14a r ° ^ 6a (VA) In the general formula (IVA), Rlla, Rl2a and R body, 1 θ a 1 糸 袠 are different or different alkyl groups which may have substituents , Cycloalkyl, alkenyl,
万屍基或芳基， 方< 通式（VA)中，RMa及R1Sa係表示相 怕问或不同的氫原子 、或可具取代基之烷基，Manganyl or aryl, in the formula (VA), RMa and R1Sa represent hydrogen atoms which may be different or different, or an alkyl group which may have a substituent,
Rua係表示可具取代基之烷基、環户I 孩如基、芳烷基或芳基 j RMa〜R16a中有2個可以鍵結形成， 【化60】Rua is an alkyl group, a cyclic group I, such as an aryl group, an aralkyl group, or an aryl group which may have a substituent. Two of R Ma ~ R16a can be bonded to form [Chem. 60]
(via) • ^ ♦ . 其中，Rual及係表示相同或不同的氫原子、鹵素 原子、氰基或可具取代基之烷基，(via) • ^ ♦. Among them, Rual and represent the same or different hydrogen atom, halogen atom, cyano group or alkyl group which may have a substituent,
Rl8a 係表不- C(R18ai)(Rl8a2)(Rl8a3)或- C(R18a 丨）（R18a2) (R 1 8 a 1 )， 〜Rum係表示相同或不同的氫原子或可具取代基之 -76- 588218 五、發明說明（75 ) 烷基、環烷基、烯基、芳烷基或芳基， Rl8al、Rl8a2、中至少一個可鍵結形成環， A〇係表示單鍵或可具取代基之2價鍵結基，以單鍵較佳） 此等含氟基之樹脂中通式（VIA)中R18a以下述通式（VIA-A)或通式（VIA-B)所示之基較佳。而且，此等含氟基之樹 脂（A)係以通式（IA)之Rla、通式（IIA)中R5a、及通式（VIA) 中R17a2中至少一個爲三氟甲基較佳。 【化6 1】Rl8a means-C (R18ai) (Rl8a2) (Rl8a3) or-C (R18a 丨) (R18a2) (R 1 8 a 1), ~ Rum means the same or different hydrogen atom or may have a substituent- 76-588218 V. Description of the invention (75) Alkyl, cycloalkyl, alkenyl, aralkyl or aryl, at least one of R18a, R18a2 may be bonded to form a ring, A0 means a single bond or may be substituted This is a divalent bond group, preferably a single bond.) These fluorine-containing resins have a group represented by the following general formula (VIA-A) or (VIA-B) in R18a in general formula (VIA). Better. In addition, it is preferred that these fluorine-containing resins (A) have at least one of Rla in general formula (IA), R5a in general formula (IIA), and R17a2 in general formula (VIA) be a trifluoromethyl group. 【Chemical 6 1】
(νίΛ-Λ) . (VIA-B) (於通式（VIA-A)中，R18a5及R18a6係表示相同或不同的 可具取代基之烷基， Rl8a7係表不可具取代基之環院基’ 於通式（VIA-B)中，R18a8係表示可具取代基之烷基、烯 基、炔基、芳烷基或芳基） 另外，各至少具有一個上述通式（IA)及（ΠΑ)所示重複 單位之樹脂、以及各至少具有一個上述通式（IIA)及（VIA) 所示重複單位之樹脂，另可至少具有一個下述通式（ΠΙΑ) 或（VIIA)所示重複單位。 -77- 588218 五、發明說明（76 ) 【化62】(νίΛ-Λ). (VIA-B) (In the general formula (VIA-A), R18a5 and R18a6 represent the same or different alkyl groups which may have a substituent, and Rl8a7 is a cycloalkyl group which cannot have a substituent. 'In the general formula (VIA-B), R18a8 represents an alkyl group, alkenyl group, alkynyl group, aralkyl group, or aryl group which may have a substituent. In addition, each of them has at least one of the general formula (IA) and (ΠΑ). The resin having the repeating unit represented by) and the resin having at least one repeating unit represented by the above-mentioned general formulae (IIA) and (VIA) may each have at least one repeating unit represented by the following general formula (IIIA) or (VIIA) . -77- 588218 V. Description of the invention (76) [化 62]
> ,^19a ^2Ga>, ^ 19a ^ 2Ga
^21a ArCN (VIIA) (於通式（ΙΠΑ)中’ R5a係表示氫原子、鹵素原子、氰基 或可具取代基之烷基， R9a及RlOa係表不相同或不同的氫原子、鹵素原子、氰 基或可具取代基之院基、環院基、垸氧基、醯基、醯氧基 、烯基、芳基或芳烷基， 於通式（VIIA)中，R.l9a及R2Qa係表示相同或不同的氫原 子、鹵素原子、氰基或可具取代基之烷基， R2la係表示氫原子、鹵素原子、可具取代基之烷基或-ArCN 基， Ai係表示單鍵或2價鍵結基） 上述烷基例如碳數1〜8個烷基，具體例如甲基、乙基 、丙基、正丁基、第2-丁基、己基、2-乙基己基、辛基較 佳。 環烷基可以爲單環型、或多環型。單環型係爲碳數3〜8 個者，例如環丙基、環戊基、環己基、環庚基、環辛基較 佳。多環型係爲碳數6〜20個者，例如金剛烷基、原菠烷 基、異冰片基、苯醯甲基、二環戊基、α-蒎烯基、三環癸^ 21a ArCN (VIIA) (In the general formula (ΙΠΑ) 'R5a represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent, and R9a and R10a represent different or different hydrogen atoms and halogen atoms , Cyano, or optionally substituted, cycloalkyl, fluorenyl, fluorenyl, fluorenyl, fluorenyl, alkenyl, aryl, or aralkyl, in general formula (VIIA), R.19a and R2Qa Represents the same or different hydrogen atom, halogen atom, cyano group or alkyl group which may have a substituent, R2la represents hydrogen atom, halogen atom, alkyl group which may be substituted or -ArCN group, and Ai represents a single bond or Divalent bonding group) The alkyl group is, for example, 1 to 8 carbon atoms, and specific examples are methyl, ethyl, propyl, n-butyl, 2-butyl, hexyl, 2-ethylhexyl, and octyl Better. The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type is one having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Polycyclic systems are those with 6 to 20 carbon atoms, such as adamantyl, orthospinyl, isobornyl, benzamyl, dicyclopentyl, α-pinenyl, and tricyclodecyl
-78 - 588218 五、發明說明（77 ) 基、四環十二烷基、雄烷基等較佳。爲上述單環或多環之 環烷基中碳原子亦可以氧原子等雜原子取代 全氟烷基例如碳數4〜12個者，具體例如全氟丁基、全 氟己基、全氟辛基、全氟辛基乙基、全氟十二烷基等較佳 氟化烷基例如碳數1〜4個者，具體例如氯甲基、氯乙 基、氯丙基、氯丁基、溴甲基、溴乙基等較佳。 芳基例如碳數6〜15個芳基，具體例如苯基、甲苯基、 二甲基苯基、2,4,6-三甲基苯基、萘基、蒽基、9, 10-二 甲氧基蒽基等較佳。 芳烷基例如碳數7〜1 2個芳烷基，具體例如苯甲基、苯 乙基、萘甲基等較佳。 烯基例如碳數2〜8個烯基，具體例如乙烯基、烯丙基 、環己烯基較佳。 烷氧基例如碳數1〜8個烷氧基，具體例如甲氧基、乙 氧基、正丙氧基、異丙氧基、丁氧基、戊氧基、烯丙氧基 、辛氧基等較佳。 醯基例如碳數1〜10個醯基，具體例如甲醯基、乙醯基 、丙醯基、丁醯基、戊醯基、辛醯基、苯甲醯基等較佳。 醯氧基例如碳數2〜12個醯氧基，具體例如乙醯氧基、 丙醯氧基、苯甲醯氧基等、 炔基例如碳數2〜5〜之炔基，具體例如乙炔基、丙炔基 、丁炔基等。-78-588218 V. Description of the invention (77) group, tetracyclododecyl group, androstyl group are preferred. In the above monocyclic or polycyclic cycloalkyl group, a carbon atom may be substituted with a heteroatom such as an oxygen atom, for example, a perfluoroalkyl group having 4 to 12 carbon atoms. Specific examples include perfluorobutyl, perfluorohexyl, and perfluorooctyl. Preferred fluorinated alkyl groups such as perfluorooctylethyl, perfluorododecyl, such as those having 1 to 4 carbon atoms, specific examples include chloromethyl, chloroethyl, chloropropyl, chlorobutyl, bromomethyl And bromoethyl are preferred. Aryl is, for example, 6 to 15 carbons, specifically, phenyl, tolyl, dimethylphenyl, 2,4,6-trimethylphenyl, naphthyl, anthracenyl, 9, 10-dimethyl Oxanthracene and the like are preferred. The aralkyl group is, for example, 7 to 12 carbon atoms, and specific examples thereof include benzyl, phenethyl, and naphthylmethyl. The alkenyl group is, for example, an alkenyl group having 2 to 8 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a cyclohexenyl group. Examples of the alkoxy group include 1 to 8 carbon atoms, and specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentoxy, allyloxy, and octyloxy And so on. The fluorenyl group is, for example, 1 to 10 carbon atoms, and specific examples include methyl fluorenyl, ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, pentyl fluorenyl, octyl fluorenyl, benzyl fluorenyl and the like. The alkoxy group is, for example, 2 to 12 carbon atoms, specifically, ethoxyl, propionyl, benzyloxy, etc., and the alkynyl group is, for example, an alkynyl group, having 2 to 5 carbons, specifically, for example, an ethynyl group , Propynyl, butynyl and the like.
-79- 588218 五、發明說明（78 ) 烷氧基羰基例如異-丙氧基羰基、第3-丁氧基羰基、第 3 -戊氧基羰基、1-甲基-1-環己氧基羰基等，較佳者爲2 碳、更佳者爲3碳烷氧基羰基。 鹵素原子例如氟原子、氯原子、溴原子、碘原子等。 伸院基以可具取代基之伸甲基、伸乙基、伸丙基、伸丁 基、伸戊基、伸己基、伸辛基等之碳數1〜8個者較佳。 伸烯基以可具取代基之伸乙烯基、伸丙烯基、伸丁烯基 等之碳數2〜6個者較佳。 環伸烷基以可具取代基之環伸戊基、環伸己基等碳數5 〜8個者較佳。 伸芳基以可具取代基之伸苯基、伸甲苯基、伸萘基等之 碳數6〜15個者較佳。 2價鍵結基係表示可具取代基之2價伸烷基、環伸烷基 、伸烯基或伸芳基或0-(：0-1?2221-、-(：0-04233-、-(：0-N(R24a) -R25a-。R22a、R23a及R25a係表示相同或不同的單鍵 或具有醚基、酯基、醯胺基、胺甲酸酯基或脲基之2價伸 院基、伸烯基、環伸烷基或伸芳基。R24a係表示氫原子或 可具取代基之烷基、環烷基、芳烷基或芳基。 R〇與R!、R。與r2、r3與R4鍵結形成環例如有5〜7碳環 ’具體而言有3〜8碳環，具體例如取代氟之戊烷環、己 院環、呋喃環、二喏嚕環、1，3 -二矽氧烷等。 R36〜R38中有2個、或r36〜r37與r38中有2個鍵結形成 環例如3〜8碳環，具體而言環丙烷環、環戊烷環、環己-79- 588218 V. Description of the invention (78) Alkoxycarbonyl group such as iso-propoxycarbonyl group, 3-butoxycarbonyl group, 3-pentyloxycarbonyl group, 1-methyl-1-cyclohexyloxy group As the carbonyl group, a 2-carbon group is preferred, and a 3-carbon alkoxycarbonyl group is more preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Shenyuanji is preferably 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl, which may have a substituent. As the alkenyl group, those having 2 to 6 carbon atoms, such as vinylidene, acrylyl, and buteneyl, which may have a substituent, are preferred. Cycloalkylene is preferably 5 to 8 carbon atoms, such as cyclopentyl and cyclohexyl, which may have a substituent. The arylene is preferably 6 to 15 carbon atoms, such as phenylene, tolyl, and naphthyl, which may have a substituent. The divalent bonding group means a divalent alkylene group, a cycloalkylene group, an alkenyl group, or an arylene group or 0-(: 0-1? 2221-,-(: 0-04233-, -(: 0-N (R24a) -R25a-. R22a, R23a and R25a represent the same or different single bond or have a divalent extension of ether group, ester group, amido group, urethane group or urea group Nominal, alkenyl, cycloalkylene, or arylene. R24a represents a hydrogen atom or an alkyl, cycloalkyl, aralkyl, or aryl group that may have a substituent. R0 and R !, R. and R2, r3 and R4 are bonded to form a ring. For example, there are 5 to 7 carbon rings. Specifically, there are 3 to 8 carbon rings. Specifically, for example, a fluorine-substituted pentane ring, a tetrad ring, a furan ring, a difluorene ring, 1, 3-disiloxane, etc. Two of R36 to R38 or two of r36 to r37 and r38 form a ring such as a 3 to 8 carbocyclic ring, specifically a cyclopropane ring, a cyclopentane ring, a ring already
- 80- 588218 五、發明說明（79 ) 院環、呋喃環、吡喃環等較佳。 R1“〜R16a中有2個、R18al〜R18a3|有2個或R18al〜 R18a2與Ri 8a4中有2個鍵結形成環例如3〜8碳環，具體而 言環丙烷環、環戊烷環、環己烷環、四環氧化伸甲基、氧 化五伸甲基、氧化六伸甲基、呋喃環、吡喃環、二喏嚕環 、1，3 -二矽氧烷類等較佳。 Z係表示單環或多環之構成脂環式基之原子團，所形成 的脂環式基，單環型時爲碳數3〜8個者例如環丙基、環 戊基、環己基、環庚基、環辛基較佳。多環型時爲碳數6 〜20個者例如金剛烷基、正冰片基、異冰片基、苯醯甲基 、二環戊基、α_蒎烯基、三環癸基、四環十二烷基、雄烷 等較佳。 而且’取代此等基之取代基例如院基、環院基、芳基、 胺基、醯胺基、脲基、胺甲酸酯基、羥基羧基等具有活性 氫者、或鹵素原子（氟原子、氯原子、溴原子、碘原子）、 烷氧基（甲氧基、乙氧基、丙氧基、丁氧基等）、硫醚基、 醯基（乙醯基、丙醯基、苯甲醯基等）、醯氧基（乙醯氧基 、丙醯氧基、苯甲醯氧基等）、烷氧基羰基（甲氧基羰基、 乙氧基羰基、丁氧基羰基等）、氰基、硝基等。 此處’ 基、環院基、芳基例如上述所示者，院基可另 以氟原子、環烷基取代。 本發明含氟基之樹脂中所包含的藉由酸作用分解、具有 驗可彳谷丨生之基例如-0 - C ( R 3 6) ( R 3 7 M U、. q 3 6 η u-80- 588218 V. Description of the invention (79) The courtyard ring, furan ring and pyran ring are preferred. There are 2 in R1 "~ R16a, 2 in R18al ~ R18a3 | or 2 in R18al ~ R18a2 and Ri 8a4 to form a ring such as a 3 to 8 carbocyclic ring, specifically, a cyclopropane ring, a cyclopentane ring, Cyclohexane ring, tetraepoxymethyl, pentaoxymethyl, hexamethyloxy, furan ring, pyran ring, difluorene ring, 1,3-disilaxane, etc. are preferred. Z It is a monocyclic or polycyclic atomic group constituting an alicyclic group. The alicyclic group formed is a monocyclic type having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, and cycloheptyl. And cyclooctyl are preferred. In the polycyclic type, those having 6 to 20 carbon atoms are, for example, adamantyl, n-bornyl, isobornyl, benzamyl, dicyclopentyl, α-pinenyl, Cyclodecyl, tetracyclododecyl, androstane, etc. are preferred. Further, the substituents which substitute these groups are, for example, noctyl, cyclonosyl, aryl, amino, amido, urea, and carbamate. Ester groups, hydroxycarboxyl groups and other active hydrogen, or halogen atoms (fluorine, chlorine, bromine, iodine), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), Sulfide , Fluorenyl (ethenyl, propionyl, benzamyl, etc.), fluorenyl (ethynyl, propionyl, benzyl, etc.), alkoxycarbonyl (methoxycarbonyl , Ethoxycarbonyl, butoxycarbonyl, etc.), cyano, nitro, etc. Here, the 'group, cycloalkyl, and aryl are as shown above, and the alkyl may be substituted with a fluorine atom or cycloalkyl. The fluorine-containing resin contained in the present invention is decomposed by the action of acid, and has a testable group such as -0-C (R 3 6) (R 3 7 MU,. Q 3 6 η u
-81 - 588218 五、發明說明（so) (R39) ' -〇-COO-C(R36) (R37) (R38) ' -〇-C(R01)(R02)COO-C ( R36) ( R37) ( R38) ' - COO - C ( R36) ( R37) ( R3g) ' -COO-C(R36) (R37)(R39)寺。 R3 6〜R38係與上述同義，Rm、r〇2係表示氫原子、可具有 上述所示取代基之烷基、環烷基、烯基、芳烷基、或芳基 〇 較佳的具體例如第3-丁基、第3-戊基、1-烷基-1-環己 基、2 -院基-2-金剛院基、2-金剛院基-2-丙基、2-(4 -甲 基環己基）-2 -丙基等3級烷基之醚基或酯基、1-烷氧基-1-乙氧基、四氫呋喃基等之縮醛基或縮醛酯基、第3 -烷基 碳酸酯基、第3-烷基羰基甲氧基等較佳。 通式（IR)〜（XR)所示重複單位之含量合計，於全部聚合 物組成物中一般爲10〜80莫耳％、較佳者爲30〜70莫耳％ 、更佳者爲35〜65莫耳％。 通式（XIR)〜（XIIIR)所示重複單位之含量，於全部聚合 物組成中一般爲0〜70莫耳％、較佳者爲10〜60莫耳％、 更佳者爲20〜50莫耳％。 通式（XVR)〜（XVIIR)所示重複單位之含量，於全部聚合 物組成中一般爲0〜70莫耳％、較佳者爲10〜60莫耳％、 更佳者爲20〜50莫耳％。 本發明（B )樹脂以至少具有一種通式（I R )〜（11 I R )所示 重複單位、與至少具有一種通式（IVR)〜（VIR)所示重複單 位較佳。 -82- 588218 五、發明說明（81 ) 而且，本發明（B)樹脂以至少具有一種通式（IVR)〜（VIR) 所示重複單位、與至少具有一種〜通式（VIIIR)〜（XR)所示 重複單位，與上述相同地較佳。 此外，本發明（B)樹脂以至少具有一種通式（IVR)〜 (VI IR)所示重複單位、與至少具有一種通式（XVR)〜 (XVI IR)所示重複單位，與上述相同地較佳。 藉此可充分提高樹脂在157nm之透過性、且可抑制耐乾 式蝕刻性降低情形。 本發明（B)樹脂爲至少具有一種通式（IR)〜（IIIR)所示 重複單位、與至少具有一種通式（IVR)〜（VIR)所示重複單 位時，通式（IVR)〜（IIIR)所示重複單位之含量合計，於 全部聚合物組成中一般爲0〜70莫耳％、較佳者爲10〜6.0 莫耳％、更佳者爲20〜50莫耳％。 通式（IVR)〜（VIR)所示重複單位之含量，於全部聚合物 組成中一般爲0〜80莫耳％、較佳者爲30〜70莫耳％、更 佳者爲3 5〜6 5莫耳％。 本發明（B)樹脂爲至少具有一種通式（IVR)〜（VIR)所示 重複單位、與至少具有一種通式（VIIIR)〜（XR)所示重複 單位，通式（IVR)〜（VIR)所示重複單位之含量，於全部聚 合物組成中一般爲〇〜80莫耳％、較佳者爲30〜70莫耳％ 、更佳者爲35〜65莫耳％。 通式（VIIIR)〜（XR)所示重複單位之含量，於全部聚合 物組成中一般爲〇〜70莫耳％、較佳者爲10〜60莫耳％、-81-588218 V. Description of the Invention (so) (R39) '-〇-COO-C (R36) (R37) (R38)' -〇-C (R01) (R02) COO-C (R36) (R37) (R38) '-COO-C (R36) (R37) (R3g)' -COO-C (R36) (R37) (R39) Temple. R3 6 to R38 are synonymous with the above, and Rm and r〇2 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group which may have a substituent as shown above. 3-butyl, 3-pentyl, 1-alkyl-1-cyclohexyl, 2-noryl-2-adamantyl, 2-adamantyl-2-propyl, 2- (4-methyl Cyclohexyl) ether group or ester group of tertiary alkyl group such as 2-propyl group, acetal group or acetal ester group of 1-alkoxy-1-ethoxy group, tetrahydrofuryl group, etc. Carbonyl carbonate, 3-alkylcarbonylmethoxy, and the like are preferred. The total content of repeating units represented by the general formulae (IR) to (XR) is generally 10 to 80 mol%, preferably 30 to 70 mol%, and more preferably 35 to mol in all polymer compositions. 65 mol%. The content of the repeating units represented by the general formulae (XIR) to (XIIIR) is generally 0 to 70 mole%, preferably 10 to 60 mole%, and more preferably 20 to 50 moles in the total polymer composition ear%. The content of the repeating units represented by the general formulae (XVR) to (XVIIR) is generally 0 to 70 mole%, preferably 10 to 60 mole%, and more preferably 20 to 50 moles in the total polymer composition ear%. The resin (B) of the present invention preferably has at least one repeating unit represented by the general formulae (I R) to (11 I R) and at least one repeating unit represented by the general formulae (IVR) to (VIR). -82- 588218 V. Description of the invention (81) Furthermore, the resin of the present invention (B) has at least one repeating unit represented by the general formulae (IVR) to (VIR) and at least one of the general formulae (VIIIR) to (XR) The repeating unit shown by) is the same as described above. In addition, the resin of the present invention (B) has at least one repeating unit represented by the general formulae (IVR) to (VI IR) and at least one repeating unit represented by the general formulae (XVR) to (XVI IR). Better. This makes it possible to sufficiently improve the transmittance of the resin at 157 nm and to suppress the decrease in dry etching resistance. When the resin (B) of the present invention has at least one repeating unit represented by the general formulae (IR) to (IIIR) and at least one repeating unit represented by the general formulae (IVR) to (VIR), the general formulae (IVR) to ( The total content of the repeating units shown in IIIR) is generally 0 to 70 mole%, preferably 10 to 6.0 mole%, and more preferably 20 to 50 mole% in the total polymer composition. The content of the repeating units represented by the general formulae (IVR) to (VIR) is generally 0 to 80 mole%, preferably 30 to 70 mole%, and more preferably 3 to 5 to 6 in the total polymer composition. 5 mole%. The resin (B) of the present invention has at least one repeating unit represented by the general formulae (IVR) to (VIR), and at least one repeating unit represented by the general formulae (VIIIR) to (XR), and the general formulae (IVR) to (VIR) The content of the repeating unit shown) is generally 0 to 80 mol%, preferably 30 to 70 mol%, and more preferably 35 to 65 mol% in the total polymer composition. The content of the repeating units represented by the general formulae (VIIIR) to (XR) is generally 0 to 70 mol%, preferably 10 to 60 mol%,
-83- 588218 五、發明說明（82 ) 更佳者爲20〜50莫耳％。 本發明（B)樹脂爲至少具有一種通式（IVR)〜（VIIR)所示 重複單位、與至少具有一種通式（XVR)〜（XVIIR)所示重複 單位，通式（IVR)〜（VI IR)所示重複單位之含量，於全部 聚合物組成中一般爲10〜80莫耳％、較佳者爲30〜70莫 耳％、更佳者爲35〜65莫耳％。-83- 588218 V. Description of the invention (82) The better is 20 ~ 50 mole%. The resin (B) of the present invention has at least one repeating unit represented by the general formulae (IVR) to (VIIR), and at least one repeating unit represented by the general formulae (XVR) to (XVIIR), and the general formulae (IVR) to (VI The content of the repeating unit shown in IR) is generally 10 to 80 mol%, preferably 30 to 70 mol%, and more preferably 35 to 65 mol% in the total polymer composition.
通式（XVR)〜（XVIIR)所示重複單位之含量，於全部聚合 物組成中一般爲〇〜70莫耳％、較佳者爲10〜60莫耳％、 更佳者爲20〜50莫耳％。 於各至少具有一種通式（IA)與（IIA)所示重複單位之含 基的樹脂中，以通式（I A )所示重複單位之含量一般爲5 〜80莫耳％、較佳者爲〜75莫耳％、更佳者爲20〜70莫 耳％。 於各至少具有一種通式（IA)與（IIA)所示重複單位之含 氟基的樹脂中，以通式（IIA)所示重複單位之含量一般爲5The content of the repeating units represented by the general formulae (XVR) to (XVIIR) is generally 0 to 70 mole%, preferably 10 to 60 mole%, and more preferably 20 to 50 moles in the total polymer composition. ear%. In the group-containing resin each having at least one repeating unit represented by the general formulae (IA) and (IIA), the content of the repeating unit represented by the general formula (IA) is generally 5 to 80 mol%, preferably the repeating unit is ~ 75 mole%, more preferably 20 ~ 70 mole%. The content of the repeating unit represented by the general formula (IIA) in the fluorine-containing resin each having at least one repeating unit represented by the general formulae (IA) and (IIA) is generally 5
8〇吳耳％、較佳者爲1〇〜70吴耳％、更佳者爲20〜65吴 耳％ 〇 於各至少具有一種通式（ΠΑ)與（VIA)所示重複單位之含 氣基的樹脂中，以通式（IIA)所示重複單位之含量一般爲5 〜80奠耳％、較佳者爲10〜70莫耳％、更佳者爲20〜65莫 耳％ 〇 方々各至少具有一種通式（ΠΑ)與（VIA)所示重複單位之含 氯基的樹脂中，以通式（VIA)所示重複單位之含量一般爲5 -84- 588218 五、發明說明（83 ) 〜80莫耳％、較佳者爲1〇〜70莫耳％、更佳者爲20〜65莫 耳 ％ 〇 一 —— 此等含氟基的樹脂中，以通式（IIIA)所示重複單位之含 量一般爲1〜40莫耳％、較佳者爲3〜35莫耳％、更佳者爲 5〜3 0莫耳％。 此等含氟基的樹脂中，以通式（VIIA)所示重複單位之含 量一般爲1〜40莫耳％、較佳者爲3〜35莫耳％、更佳者爲 5〜3 0莫耳％。 本發明（B)樹脂除上述重複構造單位外，另爲提高本發 明正型感光性之性能爲目的時可使其他聚合物單體共聚合 〇 可使用共聚合單體包含下述所示者。例如具有1個除上 述外選自於丙烯酸酯類、丙烯酸醯胺類、甲基丙烯酸酯類 、甲基丙烯酸醯胺類、烯丙基化合物、乙烯醚類、乙烯酯 類 '苯乙烯類、檸檬酸酯類等之加成聚合性不飽和鍵的化 合物。 於下述中係爲通式（IR)〜（XR)所示重複構造單位之具體 例’惟本發明不受此等限制。 -85- 588218 五、發明說明（84 ) 【化63】 (F-1) 4-c-c-f P C5F11 (F-5) (F-2)命參F^cvF F F (F-6) (F-3) (卜4) F OCaFs F 〇C3F7 (F-?) (F-8) 存一谷奋-存 -^c-〇4- F OC5F11 F OCH2CH2C8F17 F OCH2CF-OC3F7 CF3 (F-ll) (F-9) (F-10) >v F F (F-12) -fCH〇CH4-80%, preferably 10% to 70%, and more preferably 20% to 65%, each having at least one repeating unit represented by the general formula (ΠA) and (VIA) The content of the repeating unit represented by the general formula (IIA) in the base resin is generally 5 to 80 mol%, preferably 10 to 70 mol%, and more preferably 20 to 65 mol%. The content of the repeating unit represented by the general formula (VIA) in the chlorine-containing resin having at least one repeating unit represented by the general formula (ΠA) and (VIA) is generally 5 -84- 588218 5. Explanation of the invention (83) ~ 80 mole%, preferably 10 ~ 70 mole%, and more preferably 20 ~ 65 mole% 〇—These fluorine-containing resins are repeated as shown by the general formula (IIIA) The content of the unit is generally 1 to 40 mole%, preferably 3 to 35 mole%, and more preferably 5 to 30 mole%. In these fluorine-containing resins, the content of the repeating unit represented by the general formula (VIIA) is generally 1 to 40 mole%, preferably 3 to 35 mole%, and more preferably 5 to 30 mole%. ear%. In addition to the repeating structural unit described above, the resin of the present invention (B) can copolymerize other polymer monomers for the purpose of improving the performance of the positive-type photosensitivity of the present invention. The copolymerizable monomers include those shown below. For example, there is one selected from the group consisting of acrylates, ammonium acrylates, methacrylates, ammonium methacrylates, allyl compounds, vinyl ethers, vinyl esters, styrenes, and lemons. Compounds with addition polymerizable unsaturated bonds such as acid esters. In the following, specific examples of repeating structural units represented by the general formulae (IR) to (XR) 'are used, but the present invention is not limited to these. -85- 588218 V. Description of the invention (84) [Chem. 63] (F-1) 4-ccf P C5F11 (F-5) (F-2) F ^ cvF FF (F-6) (F-3) ) (Bu 4) F OCaFs F 〇C3F7 (F-?) (F-8) Save Yigufen-save- ^ c-〇4- F OC5F11 F OCH2CH2C8F17 F OCH2CF-OC3F7 CF3 (F-ll) (F- 9) (F-10) > v FF (F-12) -fCH〇CH4-
I 4CH^CH-)~ -fCH2CH^· CH2 ?F3 6h2〇F3. ch3 CH29F3 '9 ' C~OH 'C~0—C—CH3 'C^〇-CH2~C—〇—C—CH3 cp3 CF3 ch3 cf3 * ch3 (F-13) (F-14) (F-15) -fCH2，〒H+ _ ch2 9f3 4-CH2CH-)- -fCH2CH2) ch2?F3 ch3 ch2?f3 o ch3 0、 彳一 o - c-oc2h5 o-o-c^o-c-ch3 cf3 (F-16)I 4CH ^ CH-) ~ -fCH2CH ^ · CH2? F3 6h2〇F3. Ch3 CH29F3 '9' C ~ OH 'C ~ 0-C-CH3' C ^ 〇-CH2 ~ C-〇-C-CH3 cp3 CF3 ch3 cf3 * ch3 (F-13) (F-14) (F-15) -fCH2, 〒H + _ ch2 9f3 4-CH2CH-)--fCH2CH2) ch2? F3 ch3 ch2? f3 o ch3 0, 彳 1o -c-oc2h5 ooc ^ oc-ch3 cf3 (F-16)
cf3 h (T-17) cf3 (f-18) ch3cf3 h (T-17) cf3 (f-18) ch3
w ; w w gh^F〇h chJF〇-c^ch3 CH^〇r〇. ^chJF〇-ch2'0-o-0Hch3 .CF3 cf3 ch3 . cf3 LJ . cf3 ch3 (F-19) (F-20) (F-21) (F-22) -86- 588218 五 明說 明化發 ί 4 6 c 3 2 F- 5 8w; ww gh ^ F〇h chJF〇-c ^ ch3 CH ^ 〇r〇. ^ chJF〇-ch2'0-o-0Hch3 .CF3 cf3 ch3. cf3 LJ. cf3 ch3 (F-19) (F-20 ) (F-21) (F-22) -86- 588218 Wu Ming Explained 4 6 c 3 2 F- 5 8
Η3ch3 CC-丨 c I 0 9C 1 . 3 0 -3 F 1 F C*9CΗ3ch3 CC- 丨 c I 0 9C 1. 3 0 -3 F 1 F C * 9C
、?f3 ch3 丫 ch2c-o*choc2h5 J. CFa (F-26),? F3 ch3 ah ch2c-o * choc2h5 J. CFa (F-26)
9^3 9η3 η ch2-c-o-cho*ch2ch2_^^ ,(F_27.)9 ^ 3 9η3 η ch2-c-o-cho * ch2ch2 _ ^^, (F_27.)
cf3 o ch3 CH2C-〇-CH2-C-〇-C-CH3 cf3 ch3 〇2S) CHg ch3 十 ch2.c-)-o=c -fCH： 0 汗3 ch2-c-oh cf3 · 巧十 =：c ch3 o=c cf3 . ch2-c-0^0^ CH2eC'-.0-CH*〇C2H5 cf3 (F-29) (F-30) (F-31)cf3 o ch3 CH2C-〇-CH2-C-〇-C-CH3 cf3 ch3 〇2S) CHg ch3 ten ch2.c-)-o = c -fCH: 0 Khan 3 ch2-c-oh cf3 · Qiao ten =: c ch3 o = c cf3. ch2-c-0 ^ 0 ^ CH2eC '-. 0-CH * 〇C2H5 cf3 (F-29) (F-30) (F-31)
ox Hs十 vy CICICIO v = CHO c Η H c — c - F3-0F3 CICIC I H2 ς> H3十 cl-c--c 丨 o H2= a H3 H3-CH3 c»cic 0 1 one I H2 c F3'?P3 c 丨 c<c (F-32) (F-33) CH3 十CH2_(p十 .0 = C 1 0 . .cf3 ch3 CH2CH2CH2-C-〇-C-：CH3 OH CF3 CH3 (F-34)ox Hs ten vy CICICIO v = CHO c Η H c — c-F3-0F3 CICIC I H2 & > H3 ten cl-c--c 丨 o H2 = a H3 H3-CH3 c »cic 0 1 one I H2 c F3 '? P3 c 丨 c < c (F-32) (F-33) CH3 ten CH2_ (p ten .0 = C 1 0. .Cf3 ch3 CH2CH2CH2-C-〇-C-: CH3 OH CF3 CH3 (F- 34)
CH2-C - OH cf3 (F-35) 0^0 ch3CH2-C-OH cf3 (F-35) 0 ^ 0 ch3
-87- 588218 五、發明說明（86 ) 【化65】 ch3 •+CH2€f ?h3 十 CHfi-87- 588218 V. Description of the invention (86) [化 65] ch3 • + CH2 € f? H3 Ten CHfi
cf3 ch3 'CH2-C-0-C-CH3 cf3 ch3 (F〇7) 4〇H2€Hf 4ch2ch 异 4ch2ch)- (F-38) 4CH2CHf- Γcf3 ch3 'CH2-C-0-C-CH3 cf3 ch3 (F〇7) 4〇H2 € Hf 4ch2ch iso 4ch2ch)-(F-38) 4CH2CHf- Γ
4ch2ohL F3C-C"CF3 OH (F-39) F3C~C-CF3 o h3c-c-ch3 CH, (F40) F3C-C-CF3.όΟ (F-4】） F3C-C-CF3 q . ch*oc2h5 ch3 (F^2). F3C-C-CF3 Q · CH3 (F-43) 4ch2-ch}- F3OC-CF3 0、 CH3 1 yC-〇-C-CH3 o ch3 .(F-44) 4ch2〇h)- -fCH2CH^ F3C"C-CF3 f3c-c-cf30、 ?h3 6 . ch3 CH2.C-〇-9-CH3 vc-0-C-CH3 .o ch3 6: ch3 ch3 fCH彳十 .o=c I · 0 1 ch2ch2-c6f13 (F^47) (F-45) (F46) 〒h3 fCH2f 十.o=c 1 9 CHsCHg-CgFiy :.(F-4S) ch3 十c.h2·^十 o=c Ό 、 ch2ch^c10f21 • (F-49) ch3 +CH巧十 0=C· I .9 CHS 十 CH^+ o=c 9ρ3 ό cf3 ch2ch2 令 cf3 ch2ch2-cfc2fs cf3. (F-50 ) (下·51 ) -88- 588218 五、發明說明（87 )【化66】 ch3 气CH-CH卜. 0-C I .〇 ch3 · *^fCH2*C-h o^c 9^3 ό CF3 cf3 CH2CHrCF2CF2CFCF3 (F-52) CH2-CF-O-CFCF3 (F-53) ?h3 -fCH2'C-)- O^C 1 . 9 - ,. 0H2CHCHrO-CHr(CF2)7-CHF2 'OH • (F-54)4ch2ohL F3C-C " CF3 OH (F-39) F3C ~ C-CF3 o h3c-c-ch3 CH, (F40) F3C-C-CF3.ό〇 (F-4)) F3C-C-CF3 q. Ch * oc2h5 ch3 (F ^ 2). F3C-C-CF3 Q · CH3 (F-43) 4ch2-ch}-F3OC-CF3 0, CH3 1 yC-〇-C-CH3 o ch3. (F-44) 4ch2〇 h)--fCH2CH ^ F3C " C-CF3 f3c-c-cf30,? h3 6 .ch3 CH2.C-〇-9-CH3 vc-0-C-CH3 .o ch3 6: ch3 ch3 fCH 彳 十 .o = c I · 0 1 ch2ch2-c6f13 (F ^ 47) (F-45) (F46) 〒h3 fCH2f ten. o = c 1 9 CHsCHg-CgFiy:. (F-4S) ch3 ten c.h2 · ^ ten o = c Ό, ch2ch ^ c10f21 • (F-49) ch3 + CHCH10 0 = C · I .9 CHS ten CH ^ + o = c 9ρ3 cf3 ch2ch2 Let cf3 ch2ch2-cfc2fs cf3. (F-50) (Next · 51) -88- 588218 V. Description of the invention (87) [Chem 66] ch3 gas CH-CH Bu. 0-CI .〇ch3 · * ^ fCH2 * Ch o ^ c 9 ^ 3 CF3 cf3 CH2CHrCF2CF2CFCF3 ( F-52) CH2-CF-O-CFCF3 (F-53)? H3 -fCH2'C-)-O ^ C 1. 9-,. 0H2CHCHrO-CHr (CF2) 7-CHF2 'OH • (F-54 )
c=o I •9 CH2CH2-C8F17 (F-55)c = o I • 9 CH2CH2-C8F17 (F-55)
C=0 I 9 CH2CH2~C^〇F2i (F-56 )C = 0 I 9 CH2CH2 ~ C ^ 〇F2i (F-56)
cf3· v 0 CH2CH2-CF2CF2CFCF3 . · 00 9F3 ch2ch2-c.cf3 cf3cf3 · v 0 CH2CH2-CF2CF2CFCF3. · 00 9F3 ch2ch2-c.cf3 cf3
(F-57) ( F-5S〇 .(F-57) (F-5S〇.
(F-59)(F-59)
(F-60 ) CH2CH2-C6F17 (F-61 )(F-60) CH2CH2-C6F17 (F-61)
V (HhV (Hh
c=o ? 9^3 CH2CH2-CF2CF2CFCF3 (F‘62)· n=8 (F-63) (F-64)c = o? 9 ^ 3 CH2CH2-CF2CF2CFCF3 (F‘62) n = 8 (F-63) (F-64)
而且，係爲通式（XIR)〜（XIIIR)所示重複構造單位之具 體例，惟本發明不受此等所限制。Moreover, it is a specific example of a repeating structural unit represented by the general formulae (XIR) to (XIIIR), but the present invention is not limited by these.
-89- 588218 發明說明（88) 【化67】 CH3 o=c ch3 十CH:〒十 O-C - 9H3 •十CH2〒十 ./"Λ 〇==? I 0 . H3C-C-CH3 ch3 〇、ch^〇_CH2CH2- ch3 〇 ? H3C-C - CH: ' ch3 . (B-1) (B-2) (B-3) .(B-4); ch3 -{CH-CH) o«c όχ!) ch3 . 十CH2?十 D ch3 十ch2^十 0=?ch3 :°i0 十CH2〒十 0=? ch3 (B-5) (B-6) (B-7)-89- 588218 Description of the invention (88) CH3 o = c ch3 TenCH: 〒 十 OC-9H3 • Ten CH2〒ten ./" Λ 〇 ==? I 0. H3C-C-CH3 ch3 〇 , Ch ^ 〇_CH2CH2- ch3 〇? H3C-C-CH: 'ch3. (B-1) (B-2) (B-3). (B-4); ch3-(CH-CH) o « c όχ!) ch3. Ten CH2? Ten D ch3 Ten ch2 ^ Ten 0 =? ch3: ° i0 Ten CH2〒 Ten 0 =? ch3 (B-5) (B-6) (B-7)
ch3 -fCH-CH)-0=C ch3 十ch2〒十 o=c ch3 c-o=c 十CH2<p十 CH3 0ch3 -fCH-CH) -0 = C ch3 ten ch2〒ten o = c ch3 c-o = c ten CH2 < p ten CH3 0
>ch3> ch3
(B-10 )(B-10)
ch3 (B-9) <B-8)ch3 (B-9) < B-8)
ch3 -fCH2-Cf- OC 6 ch3H〆 ch3 寸CHr^十 o=c ,ch3 h3c h3cch3 -fCH2-Cf- OC 6 ch3H〆 ch3 inch CHr ^ ten o = c, ch3 h3c h3c
(B-14) CH3 寸ch2_9十o=c(B-14) CH3 inch ch2_9 ten o = c
H.cr H3CH.cr H3C
CHi c;〇 I o H3C-C-CH3 ch3CHi c; 〇 I o H3C-C-CH3 ch3
c=o 9;o ch3 { B-18) ch3 (B-15)c = o 9; o ch3 {B-18) ch3 (B-15)
(B-16) 1(B-16) 1
C:0 0_CH3 气 (S-19) · c=oC: 0 0_CH3 gas (S-19) c = o
(B-20 ) -90 588218(B-20) -90 588218
588218 五、發明說明（9〇)【化6 9】 -fCH2-CH-)- ch3(C，1) -(όη2 ch4~ c2h5 (C-2) 如 h2-?.h+588218 V. Description of the invention (9〇) [化 6 9] -fCH2-CH-)-ch3 (C, 1)-(όη2 ch4 ~ c2h5 (C-2) such as h2-?. h +
如〜〒斗 °\ 1 • c4iV (C-3)-fcH2，?H4- _ 〇、ch2 (C-6) ~(-CH2-CH 士K?H^ (C-9)Such as ~ 〒 ° ° \ 1 • c4iV (C-3) -fcH2,? H4- _〇, ch2 (C-6) ~ (-CH2-CH 士 K? H ^ (C-9)
. ch3 十ch2·〒十 CN ch2ci十(3Η2·〒十ch3 十 ch2 · 〒 十 CN ch2ci 十 (3Η2 · 〒 十
CN (C-10) (C-ll) CH2F十CHq十 CN (C-12) H3十 CICIGIO H2*o= N c .2 H 2C H cCN (C-10) (C-ll) CH2F ten CHq ten CN (C-12) H3 ten CICIGIO H2 * o = N c. 2 H 2C H c
4ch2-&4ch2- &
CN (C-15) 3 il C- 4 1 0 2 9 588218 五、發明說明（91 ) 於下述中係爲通式（I A)所示重複構造單位之具體例 本發明不受此等所限制。 【化70】 惟CN (C-15) 3 il C- 4 1 0 2 9 588218 V. Description of the invention (91) The following are specific examples of repeating structural units represented by the general formula (IA). The present invention is not limited by these. . [Chem 70] only
、a γ, A γ
(Α-6) (A]) (A-2) (A-3) (Α-4) ·, (Α-5)(Α-6) (A)) (A-2) (A-3) (Α-4) ·, (Α-5)
0 2 5 2] 【化7 1】0 2 5 2] 【化 7 1】
Et (Α-3/ 。丫 '(A-3,）. 0 2 5 3 ] -93 - 588218 五、發明說明（92 ) 【化72】Et (Α-3 /. Ah '(A-3,). 0 2 5 3] -93-588218 V. Description of the invention (92) [化 72]
(A-I8) 【0 2 5 4】 •【化7 3】(A-I8) [0 2 5 4] • [Chemical 7 3]
(A-20)(A-20)
(A-20')(A-20 ')
-94 - 588218 五、發明說明（93) 【化74】-94-588218 V. Description of the Invention (93) [化 74]
〇 (A-25)〇 (A-25)
(A-30)(A-30)
GH3 CF〇 φ : φ + (A^35) (Α-36)GH3 CF〇 φ: φ + (A ^ 35) (Α-36)
(Α-37)(Α-37)
(Α-38) 於下述中係爲通式（I I A)所示重複構造單位之具體例 惟本發明不受此等所限制。 -95 - 588218 五、發明說明（94 ) 【化75】(A-38) The following are specific examples of the repeating structural unit represented by the general formula (I I A), but the present invention is not limited thereto. -95-588218 V. Description of the Invention (94) [化 75]
(lla-1) (lla-2) (lla-3) (H^) ch3 o FCH2-C—Cf3 f3c- -cf3 OH (lla-^5) OH (lla^)(lla-1) (lla-2) (lla-3) (H ^) ch3 o FCH2-C—Cf3 f3c- -cf3 OH (lla- ^ 5) OH (lla ^)
(lla-7)(lla-7)
另外，通式（ΠΑ)所示重複單位之具體例如上述例式的 (F-40)〜（F-45)。 於下述中係爲通式（VIA)所示重複構造單位之具體例， 惟本發明不受此等所限制。Further, specific examples of the repeating unit represented by the general formula (ΠA) include (F-40) to (F-45) of the above-mentioned examples. In the following, specific examples of the repeating structural unit represented by the general formula (VIA) are used, but the present invention is not limited thereto.
-96- 588218 五、發明說明（95 )、【、化76】 ch3 . CH3 .ch3 . -{ch2-c}- iCjv 汁 -fcH2-CH)- o=c o=c o=c __ o=c • 1 0 1 'Vi 〇^ch^-ch2ch2-/) 1 0 ] H3C-C-CH3 1 · • | ^-’ ch3 H3C-C-CH3 ch3 _ ch3 (β-υ (B-2) • (B-3) (B4)-96- 588218 V. Description of the invention (95), [, Chemical 76] ch3. CH3 .ch3.-{Ch2-c}-iCjv juice-fcH2-CH)-o = co = co = c __ o = c • 1 0 1 'Vi 〇 ^ ch ^ -ch2ch2- /) 1 0] H3C-C-CH3 1 · • | ^-' ch3 H3C-C-CH3 ch3 _ ch3 (β-υ (B-2) • (B -3) (B4)
-97 588218 五、發明說明（96 )另外，通式（VIA)所示重複單位之具體例如上述例式的 (F-29)〜（F-38)及（F-47)〜（F-54) 〇----於下述中係爲通式（IIIA)所示重複構造單位之具體例， 惟本發明不受此等所限制。【化7 8】-97 588218 V. Description of the invention (96) In addition, specific examples of the repeating unit represented by the general formula (VIA) are (F-29) to (F-38) and (F-47) to (F-54) ) ○-The following are specific examples of the repeating structural unit represented by the general formula (IIIA), but the present invention is not limited thereto. [Chemical 7 8]
於下述中係爲通式（VIIA)所示重複構造單位之具體例， 惟本發明不受此等所限制。 【化79ΪIn the following, specific examples of the repeating structural unit represented by the general formula (VIIA) are used, but the present invention is not limited thereto.化 79Ϊ
-CH2—CH: CN (VIM)' pv (CH2-C7- CN (VII-2).-CH2--CH: CN (VIM) 'pv (CH2-C7- CN (VII-2).
CH2CI ch2f ~(ch2-汁卡h2 一十乡 CN · CN (Vll-3) CN+¾-汁 CN ..0/1 卜5〉CH2CI ch2f ~ (ch2-Juice h2 Yishixiang CN · CN (Vll-3) CN + ¾-Juice CN ..0 / 1 bu 5>
NC CN (Vll^) 〇h3(CH广汁· .o=c ch2ch2~cn (VII-7) CN (VI!，S) (VIM) ^ch2-ch·)-NC CN (Vll ^) 〇h3 (CH Guang Ju. .O = c ch2ch2 ~ cn (VII-7) CN (VI !, S) (VIM) ^ ch2-ch ·)-
本發明所使用的（B)酸分解性樹脂可以常法（例如游離子 聚合）合成。例如，一般合成方法係使單體種一次或在反 -98 - 588218 五、發明說明（97 ) 應途中加入反應容器中、使其視其所需例如使本發明組成 物溶解於如四氫呋喃、1，4 -二噁烷、二異丙醚等之醚類或 甲基乙酮、甲基異丁酮之酮類、醋酸乙酯之酯溶劑、以及 下述之丙二醇單甲醚乙酸酯之反應溶劑中予以均勻溶解後 ，在氮氣氣氛或氬氣等惰性氣體氣氛下視其所需加熱、使 用市售的自由基起始劑（偶氮系起始劑、過氧化物等）以開 始聚合。藉此追加起始劑、或分批添加、反應終了後，投 入溶劑、以粉體或固體回收等方法回收企求的聚合物。 反應之濃度爲20重量％以上、較佳者爲30重量％以上、 更佳者爲40重量％以上。反應溫度爲10°C〜150°C、較佳 者爲30°C〜120°C、更佳者爲50°C〜100°C。 以上述具體例所示重複構造單位各使用1種、亦可數種 混合使用。 而且，於本發明中（B)成分可以使用1種、亦可以數種 倂用。 本發明之（B)樹脂的重量平均分子量藉由GPC法苯乙烯 換算値爲1，〇〇〇〜200,000、更佳者爲3,000〜20,000。若 重量平均分子量小於1，〇〇〇時由於耐熱性或乾式蝕刻耐性 會惡化、故不爲企求，而若大於2 0 0，0 0 0時顯像性惡化、 且黏度極高，故製膜性惡化等，產生不爲企求的結果。 分子量分布爲1〜10、較佳者爲1〜5、更佳者爲1〜4。 分子量愈小者，解像度、光阻劑形狀、及光阻劑圖樣之側 壁愈平滑、粗糙性愈優異。 -99- 588218 五、發明說明（98 ) 於本發明之正型感光性組成物中，本發明全部樹脂在組 成物全體中之配合量爲全部組--成〜物之固成分中以40〜 99.99重量％較佳、更佳者爲50〜99.97重量％。 [3 ]藉由酸作用分解、增大對鹼顯像液之溶解度、分子 量3 000以下之阻溶性化合物（以下稱爲「酸分解性阻溶性 化合物」） 藉由酸作用分解、增大對鹼顯像液之溶解度、分子量 3 000以下之阻溶性化合物，由於不會降低220nm以下之透 過性，以含有如 Proceeding of SPIE，2724，355 ( 1 996 ) 記載的酸分解性基之膽酸衍生物之含酸分解性基之脂環族 或脂肪族化合物較佳。酸分解性基、脂環式構造例如說明 上述脂環烴系酸分解性樹脂相同者。 本發明酸分解性阻溶性化合物之分子量爲3000以下、 較佳者爲300〜3000、更佳者爲500〜2500。 酸分解性阻溶性化合物之添加量，對全部組成物之固成 分而言以3〜50重量％較佳、更佳者爲5〜40重量％。 於下述中係爲酸分解性阻溶性化合物之具體例，惟不受 此等所限制。 -100- 588218 五、發明說明（"） 【化80】The (B) acid-decomposable resin used in the present invention can be synthesized by a conventional method (for example, free ion polymerization). For example, the general synthesis method is to make the monomer species once or in trans-98-588218 V. Description of the invention (97) should be added to the reaction vessel on the way, so that it can be dissolved according to its needs, for example, the composition of the present invention is dissolved in tetrahydrofuran, 1 , 4-Dioxane, diisopropyl ether and other ethers or methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate ester solvent, and the following propylene glycol monomethyl ether acetate reaction After uniformly dissolving in a solvent, it is heated under an inert gas atmosphere such as a nitrogen atmosphere or argon as needed, and a commercially available radical initiator (azo-based initiator, peroxide, etc.) is used to start polymerization. In this way, an additional starter is added or added in batches. After the reaction is completed, a solvent is added, and the desired polymer is recovered by a method such as powder or solid recovery. The reaction concentration is 20% by weight or more, preferably 30% by weight or more, and more preferably 40% by weight or more. The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, and more preferably 50 ° C to 100 ° C. The repeating structural units shown in the above specific examples may be used either individually or in combination. In the present invention, the component (B) may be used singly or in combination. The weight average molecular weight of the (B) resin of the present invention is 10,000 to 200,000, more preferably 3,000 to 20,000, in terms of styrene by GPC method. If the weight-average molecular weight is less than 1,000, heat resistance or dry etching resistance will be deteriorated, so it is not desirable. If it is greater than 200,000, the developability will be deteriorated, and the viscosity will be extremely high, so the film will be formed. Sexual deterioration, etc., produces unintended results. The molecular weight distribution is from 1 to 10, preferably from 1 to 5, and more preferably from 1 to 4. The smaller the molecular weight, the smoother the resolution and the side wall of the photoresist pattern, and the more excellent the roughness. -99- 588218 V. Description of the invention (98) In the positive-type photosensitive composition of the present invention, the compounding amount of all the resins in the entire composition of the present invention is the entire group-the solid content of the product is 40 ~ 99.99% by weight is preferable, and more preferably 50 to 99.97% by weight. [3] Decomposition by acid action, increase solubility in alkali developing solution, and insoluble compounds with molecular weight below 3,000 (hereinafter referred to as "acid-decomposable inhibitor compound") Decomposition by acid action, increase alkali resistance Soluble compounds with a solubility in the developing solution and a molecular weight of less than 3,000 do not reduce the permeability below 220 nm, so they are bile acid derivatives containing acid-decomposable groups as described in Proceeding of SPIE, 2724, 355 (1 996) The alicyclic or aliphatic compound containing an acid-decomposable group is preferable. The acid-decomposable group and the alicyclic structure will be explained, for example, by the same alicyclic hydrocarbon-based acid-decomposable resin. The molecular weight of the acid-decomposable and insoluble compound of the present invention is 3,000 or less, preferably 300 to 3000, and more preferably 500 to 2500. The addition amount of the acid-decomposable and insoluble compound is preferably 3 to 50% by weight, and more preferably 5 to 40% by weight, based on the solid content of the entire composition. The following are specific examples of acid-decomposable and insoluble compounds, but they are not limited thereto. -100- 588218 5. Description of the invention
-101 - 588218 五、發明說明（1〇〇 ) [4 ] ( D )鹼可溶性樹脂 鹼可溶性樹脂之鹼溶解-速〜度係以0.261N四甲銨氫氧化 物（TMAH)測定（23°C)爲20A/秒以上較佳。更佳者爲200人/ 秒以上（A爲埃）。 本發明所使用的鹼可溶性樹脂酚醛淸漆樹脂、氫化酚醛 淸漆樹脂、丙酮-焦培酚樹脂、鄰-聚羥基苯乙烯、間-聚 羥基苯乙烯、對-聚羥基苯乙烯、氫化聚羥基苯乙烯、鹵 素或烷基取代聚羥基苯乙烯、羥基苯乙烯-N-取代馬來醯 亞胺共聚物、鄰/對-及間/對-羥基苯乙烯共聚物、對聚羥 基苯乙烯之羥基而言部分鄰-烷基化物（例如5〜30莫耳％之 鄰-甲基化物、鄰- (1-甲氧基）乙基化物、鄰- (1-乙氧基）） 乙基化物、鄰-2-四氫吡喃化物、鄰-(第3-丁氧基羧基）甲 基化物等）或鄰-醯基化物（例如5〜30莫耳％之鄰-醯基化物 、鄰-(第3 -丁氧基）醯基化物等）、苯乙烯-馬來酸酐共聚 物、苯乙烯·羥基苯乙烯共聚物、α -甲基苯乙烯-羥基苯 乙烯共聚物、含羧基之甲基丙烯酸系樹脂及其衍生物、聚 乙二醇衍生物，惟不受此等所限制。 更佳的鹼可溶性樹脂係爲酚醛淸漆樹脂、鄰·聚羥基苯 乙烯、間-聚羥基苯乙烯、對-羥基苯乙烯及此等之共聚物 、烷基取代的聚羥基苯乙烯、部分聚羥基苯乙烯鄰-烷基 化、或α -甲基苯乙烯-羥基苯乙烯共聚物。 該酚醛淸漆樹脂以下述所定單體爲主成分、在酸性觸媒 存在下與醛類加成縮合所得者。-101-588218 V. Description of the invention (100) [4] (D) Alkali-soluble resins Alkali-soluble resins Alkali-dissolved resins-The speed is determined by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C) ) Is preferably 20 A / second or more. More preferably, it is 200 people / second or more (A is Angstrom). Alkali soluble resin phenolic resin, hydrogenated phenolic resin, acetone-pyrophenol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxy Styrene, halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, ortho / para- and meta / para-hydroxystyrene copolymer, hydroxyl of para-polyhydroxystyrene In terms of partial ortho-alkylate (for example, 5 to 30 mole% of ortho-methylate, ortho- (1-methoxy) ethylate, ortho- (1-ethoxy)) ethylate, Ortho-2-tetrahydropyranide, ortho- (3-butoxycarboxy) methylate, etc.) or ortho-fluorenyl compound (eg, 5 to 30 mole% of ortho-fluorenyl compound, ortho- ( 3rd-butoxy) fluorenated compounds, etc.), styrene-maleic anhydride copolymer, styrene · hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl-containing methacrylic acid Resins, their derivatives, and polyethylene glycol derivatives are not limited by these. More preferred alkali-soluble resins are phenolic resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-hydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially polymerized Hydroxystyrene is ortho-alkylated, or alpha-methylstyrene-hydroxystyrene copolymer. This phenolic lacquer resin is obtained by adding and condensing aldehydes in the presence of an acidic catalyst with a monomer as the main component described below.
-102- 588218 五、發明說明（1〇1 ) 而且，所得的鹼可溶性樹脂之重量平均分子量爲2000 以上、較佳者爲5,000〜200000、更佳者爲5000〜1 00000 〇 其中，重量平均分子量以凝膠滲透色層分析法之聚苯乙 嫌換算値予以定義。 本發明中此等（D)鹼可溶性樹脂可以2種以上混合使用 〇 鹼可溶性樹脂之使用量，對各全部組成物之固成分而言 以40〜97重量％較佳、更佳者爲60〜90重量％。 [5 ]( C )藉由酸作用與上述鹼可溶性樹脂交聯的酸交聯劑 (以下稱爲「交聯劑」） 交聯劑可使用苯酚衍生物。較佳者例如分子量爲1 200 以下、分子內含有3〜5個苯環、以及具有2個以上組合 羥基甲基或烷氧基甲基、至少使該羥基甲基、烷氧基甲基 集中於任一苯環上、或分開鍵結所成的苯酚衍生物。 藉由使用該苯酚衍生物，可更爲顯著本發明之效果。 鍵結於苯環之烷氧基甲基以碳數6個以下者較佳。具體 而言以甲氧基甲基、乙氧基甲基、正丙氧基甲基、異丙氧 基甲基、正丁氧基甲基、異丁氧基甲基、第2-丁氧基甲基 、第3-丁氧基甲基較佳。更佳者爲如2-甲氧基乙氧基、 及2-甲氧基-1-丙基之烷氧基取代的烷氧基。 於此等之苯酚衍生物中更佳者如下所述。 -103- 588218-102- 588218 V. Description of the invention (101) In addition, the weight-average molecular weight of the obtained alkali-soluble resin is 2,000 or more, preferably 5,000 to 200,000, and more preferably 5,000 to 1,000,000. Among them, the weight average molecular weight It is defined by the conversion of polystyrene to gel permeation chromatography. In the present invention, these (D) alkali-soluble resins may be used in combination of two or more kinds. The amount of the alkali-soluble resin is 40 to 97% by weight, and 60 to 60% by weight of the solid content of each composition is more preferred. 90% by weight. [5] (C) An acid cross-linking agent (hereinafter referred to as a "cross-linking agent") which is an acid-cross-linking agent which cross-links the alkali-soluble resin with an acid, and a phenol derivative can be used as the cross-linking agent. Preferably, for example, the molecular weight is 1 200 or less, the molecule contains 3 to 5 benzene rings, and there are two or more combined hydroxymethyl or alkoxymethyl groups, and at least the hydroxymethyl and alkoxymethyl groups are concentrated in A phenol derivative formed by bonding to or separating from any benzene ring. By using this phenol derivative, the effect of this invention can be more remarkable. The alkoxymethyl group bonded to a benzene ring preferably has 6 or less carbon atoms. Specifically, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, and 2-butoxy Methyl and 3-butoxymethyl are preferred. More preferred are alkoxy-substituted alkoxy groups such as 2-methoxyethoxy and 2-methoxy-1-propyl. Among these phenol derivatives, the following are more preferable. -103- 588218
五、發明說明（1〇2) 【化8 1】 0HV. Description of the invention (102) [化 8 1] 0H
0H0H
-104- 588218 五、發明說明（1〇3) 【化82】 …-104- 588218 V. Description of the Invention (103) [化 82]…
-105- 588218 五、發明說明（1〇4) 【化83】-105- 588218 V. Description of the Invention (104) [化 83]
-106- 588218 五、發明說明（1〇5 【化84】-106- 588218 V. Description of the invention (105)
L4 OHL4 OH
-107- 588218 五、發明說明（1〇6) 【化85】’-107- 588218 V. Description of the invention (106) [化 85] ’
(其中，L1〜L8係表示相同或不同的羥基甲基、甲氧基 甲基或乙氧基甲基） -108- 588218 五、發明說明（1〇7 ) 具有羥基甲基之苯酚衍生物可藉由不具對應羥基甲基之 苯酌化合物（其中，L1〜L8爲氫原子之化合物）與甲醛在鹼 觸媒下反應予以製得。此時，爲防止樹脂化或凝膠化時， 以在反應溫度爲60°C以下進行較佳。具體而言可以如特開 平6 - 282067號、特開平7 - 64285號等記載的方法予以合 成。 具有烷氧基甲基之苯酚衍生物可藉由具有對應的羥基甲 基之苯酚衍生物與醇在酸觸媒存在下予以製得。此時，爲 防止樹脂化或凝膠化時，以在反應溫度爲1 〇〇°C以下進行 較佳。具體而言可以如歐洲專利EP632003A1號等記載的 方法予以合成。 該合成的具有羥基甲基或烷氧基甲基之苯酚衍生物、就 保存時之安定性而言較佳，就保存時之安定性而言以具有 烷氧基甲基之苯酚衍生物更佳。 具有組合2個以上羥基甲基或烷氧基甲基、且集中於任 一苯環上、或分開鍵結所成的苯酚衍生物可以單獨使用、 或組合2種以上使用。 除上述苯酚衍生物外，下述（i )、（ i i )之化合物可使用 作爲（E )交聯劑。 (i)具有N-羥基甲基、N-烷氧基甲基、或N-乙醯氧基甲 基之化合物 (i i )環氧化合物 於本發明中，上述交聯劑以苯酚衍生物較佳。而且，亦 -109- 588218 五、發明說明（1〇8) 可組合2種以上上述交聯劑使用。 倂用上述交聯劑時之苯酚衍生物與（i )或（i i )之交聯劑 比例，以莫耳比爲100/0〜0/100、較佳者爲 90/10〜 20/80、更佳者爲 90/10〜50/ 50。 (i) 具有N-羥基甲基、N-烷氧基甲基、或N-醯氧基甲基 之化合物例如歐洲專利公開（以下記載爲「EP-A」）第 0,133,216 號、西德專利第 3,634,67 1號、同第 3, 711，264號揭示的單體及寡聚物-蜜胺-甲醛縮合物以及 尿素-甲醛、EP-A第0,2 1 2,482號揭示的烷氧基取代化合 物等所揭示的苯并鳥糞胺-甲醛縮合物等。 更佳例如至少具有2個游離N-羥基甲基、N-烷氧基甲基 、或N-醯氧基甲基之蜜胺-甲醛衍生物，尤以N-烷氧基甲 基衍生物最佳。 (ii) 環氧化合物例如含有一個以上環氧基、單體、二聚 物、寡聚物、聚合物狀環氧化合物。例如雙酚與環氧氯丙 烷之反應生成物、低分子量苯酚與甲醛樹脂與環氧氯丙烷 之反應生成物等。其他力如美國專利第4,01 6, 705號公報 、英國專利第1，539, 1 92號公報記載、使用的環氧樹脂。 交聯劑在全部組成物固成分中使用3〜70重量％、較佳 者爲5〜50重量％。 若交聯劑之添加量小於3重量％時殘膜率較低，而若大 於70重量％時解像力降低、且就感光性組成物保存時之安 定性而言不爲企求。 -110- 588218 五、發明說明（1〇9 ) <本發明感光性組成物所使用的其他成分> [6 ]鹼性化合物 含氮鹼性化合物可使用有機胺、鹼性銨鹽、鹼性毓鹽等 ’不會使昇華性或光阻性能惡化者。 此等之含氮鹼性化合物中，有機胺就畫像性能優異而言 較佳。例如特開昭63 - 1 49640號、特開平5 -249662號、 特開平5 - 1 27369號、特開平5 - 289322號、特開平5-249863號、特開平5-289340號、特開平5-232706號、特 開平5-257282號、特開平6- 24 2605號、特開平6 -2426 0 6 號、特開平6 - 266 1 00號、特開平5 - 266 1 1 0號、特開平6-3 1 7902號、特開平7- 120929號、特開平7 - 146558號、特 開平7-319163號、特開平7 - 508440號、特開平7 - 3 3 388.4 號、特開平7-219217號、特開平7 - 92678號、特開平7-28247號、特開平8-22120號、特開平8- 1 10638號、特開 平8 - 1 23030號、特開平9 - 2743 1 2號、特開平9 - 1 6687 1 號、特開平9-292708號、特開平9-325496號、特表平7-508840 號、USP5525453 號、USP5629134 號、USP5667938 號等記載的鹼性化合物。 鹼性化合物具體例如下述（A)〜（E)所示構造。 【化86】 子251 _ r254 r255 K250-N^ «C-N^C- R253r^N-C-R256 (A) (Bj (C) (D) CB) · . . * · 、 -111- 588218 五、發明說明（110) (其中，R25()、R251及R252可爲相同或不同的碳原子、碳 數1〜6之烷基、碳數1〜6之胺基烷基、碳數1〜6之羥 基或碳數6〜20之經取代或未經取代之芳基，且R251與 R252可互相鍵結形成環， 其中，R253、R254、R255及R256可爲相同或不同的碳數1 〜6之烷基） 較佳的化合物係爲一分子中具有2個以上不同化學環境 之氮原子的含氮鹼性化合物、或脂肪族3級胺。 較佳的含氮鹼性化合物例如1，5 -二偶氮二環[4 · 3 . 0 ] - 5 -壬烯、1，8-二偶氮二環[5·4·0]-7-十一烯（DBU)、1，4-二 偶氮二環[2 . 2 . 2 ]辛烷、4 -二甲基胺基吡啶、1 -萘胺、哌 啶類、六亞甲基四胺、咪唑類、羥基吡啶類、吡啶類、苯 胺類、羥基烷基苯胺類、4,4’-二胺基苯醚、吡錠基對-甲 苯磺酸酯、2,4,6-三甲基吡錠基對-甲苯磺酸酯、四甲銨 對-甲苯磺酸酯、及四丁銨內酯、三乙胺、三丁胺、三苯 甲胺、三正辛胺、三異辛胺、參（乙基己基）胺、三癸胺、 三十二烷胺等。 其中以1，5 -二偶氮二環[4.3·0]-5 -壬烯、1，8 -二偶氮二 環[5·4·0]-7 -十一烯、1，4 -二偶氮二環[2.2.2]辛烷、4 -二 甲基胺基吡啶、1-萘胺、4-羥基噠畊、2,2,6,6-四甲基- 4-羥基吡啶類、吡啶類、4,4’·二胺基二苯醚、三乙胺、三丁 胺、三戊胺、三正辛胺、參（乙基己基）胺、三十二烷胺、 Ν，Ν-二-羥基乙基苯胺、Ν-羥基乙基·Ν_乙基苯胺等之有機 -112- 588218 五、發明說明（111 ) 胺較佳。 此等之鹼性化合物可單獨使用或2種以上組合使用。鹼 性化合物之使用量對感光性組成物之全部固成分而言通常 爲0.001〜10重量份、較佳者爲0.01〜5重量份。若小於 0.001重量份時無法得到上述鹼性化合物之添加效果。另 外，大於10重量份時會有感度降低且非曝光部之顯像性 惡化的傾向。 [7]氟系及/矽系界面活性劑 本發明之感光性組成物係以氟系及/或矽系界面活性劑（ 氟系界面活性劑、矽系界面活性劑、及含有氟原子與矽原 子兩者之界面活性劑）中任一種或含有2種以上較佳。 藉由含有本發明感光性組成物與上述界面活性劑.，使用 250nm以下、尤其是220nm以下之曝光光源時，可得良好 感度及解像力、密接性、及很少會有顯像缺點之光阻劑圖 此等之界面活性劑例如有特開昭62 - 36663號、特開昭 6 1 - 226746 號、特開昭 6 1 - 226745 號、特開昭 62 - 1 70950 號、特開昭63 - 34540號、特開平7 - 2301 65號、特開平8-62834號、特開平9 - 54432號、特開平9 - 5988號、特開 2002 - 277862號、美國專利第 5405720號說明書、同 5 3 60692號說明書、同552988 1號說明書、同52963 30號 說明書、同5436098號說明書、同5576 1 43號說明書、同 52945 1 1號說明書、同582445 1號說明書所記載的界面活 -113- 588218 五、發明說明（112 ) 性劑，亦可直接使用下述市售的界面活性劑。 可使用的市售界面活性劑例如有耶夫頓部（譯音）EF301 、EF303 (新秋田化成（股）製）、夫蘿拉頓（譯音）FC430、 431(住友史里耶姆（股）製）、梅卡法克（譯音）F171、F173 、F176、F189、R0 8(大日本油墨（股）製）、撒夫龍（譯音 )S-3 82、SC101、102、103、104、105、106(旭玻璃（股） 製）、頓龍衣羅魯（譯音）S- 366(頓龍衣（譯音）化學（股）製） 等氟系界面活性劑或矽系界面活性劑。聚矽氧烷聚合物 KP-341(信越化學工業（股）製）亦可使用作爲矽系界面活性 劑。 而且，界面活性劑除上述所示習知者外，可使用藉由調 .節聚合法（調聚法）或寡聚法（稱爲寡聚物法）所製造的氟化 脂肪族化合物衍生的具有氟化脂肪族基之聚合物的界面活 性劑。氟化脂肪族化合物可藉由特開2002 - 9099 1號公報 記載的方法合成。 具有氟化脂肪族基之聚合物以具有氟化脂肪族基之單體 (聚（環氧烷基））丙烯酸酯及/或（聚（環氧烷基））甲基丙烯 酸酯之共聚物較佳，可以不規則分布者、亦可以嵌段共聚 合。另外，聚（環氧烷基）例如聚（環氧乙烷）基、聚（環氧 丙烷）基、聚（環氧丁烷）基等，此外，亦可以聚（環氧乙烷 與環氧丙烷與環氧乙烷之嵌段鍵結物）或（環氧乙烷與環氧 丙烷之嵌段鍵結物）基等相同鏈長內具有不同鏈長之伸烷 基的單位。此外，具有氟化脂肪族基之單體（聚（環氧烷基 -114· 588218 五、發明說明（1彳3 ) ))丙烯酸酯（或甲基丙烯酸酯）之共聚物不僅爲2元共聚物 、具有2種以上氟化脂肪族基之單體、或同時使2種以上 不同的（聚（環氧烷基））丙烯酸酯（或甲基丙烯酸酯）等共聚 合的2元系以上之共聚物。 例如市售的界面活性劑例如梅卡法克？178、？-470、卜 473、F-475、F-476、F-472(大日本油墨化學工業（股）製） 。另外，具有C6F13基之丙烯酸酯（或甲基丙烯酸酯）與（聚 (環氧烷基））丙烯酸酯（或甲基丙烯酸酯）之共聚物、具有 C6F13基之丙烯酸酯（或甲基丙烯酸）與（聚（環氧乙烷））丙烯 酸酯（或甲基丙烯酸酯）與（聚（環氧丙烷））丙烯酸酯（或甲 基丙烯酸酯）之共聚物、具有C8F17基之丙烯酸酯（或甲基 丙烯酸）與（聚（環氧乙烷））丙烯酸酯（或甲基丙烯酸酯）與（ 聚（環氧丙烷））丙烯酸酯（或甲基丙烯酸酯）之共聚物、具 有C8F17基之丙烯酸酯（或甲基丙烯酸）與（聚（環氧乙烷）） 丙烯酸酯（或甲基丙烯酸酯)與（聚（環氧丙烷））丙烯酸酯（ 或甲基丙烯酸酯）之共聚物、等。 界面活性劑之使用量對感光性組成物全量（除溶劑外）而 言，以0.0001重量％〜2重量％較佳、更佳者爲0.001重量 %〜1重量％ 0 [8 ]有機溶劑 本發明之感光性組成物係使用使上述各成分溶解於有機 溶劑中。所使用的有機溶劑係以二氯化乙烯、環己酮、環 戊酮、2 -庚酮、7 -丁內酯、甲基乙酮、乙二醇單甲醚、 -115- 588218 五、發明說明（114 ) 乙二醇單乙醚、2-甲氧基乙基乙酸酯、乙二醇單乙醚乙酸 酯、丙二醇單甲醚、丙二醇單甲醚乙酸酯、甲苯、醋酸乙 酯、乳酸甲酯、乳酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸 乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、N，N-二甲 基甲醯胺、二甲基亞楓、N -甲基吡咯烷酮、四氫呋喃。 於本發明中有機溶劑可以單獨使用、亦可以混合使用， 以使用混合於構造中含有羥基之溶劑、與不含羥基之溶劑 的混合溶劑較佳。藉此可減輕感光性組成物保存時之粒子 產生情形。 含有羥基之溶劑例如乙二醇、乙二醇單甲醚、乙二醇單 乙醚、丙二醇、丙二醇單甲醚、丙二醇單乙醚、乳酸乙酯 等，於此等之中乙丙二醇單甲醚、乳酸乙酯較佳。 不含羥基之溶劑例如丙二醇單甲醚乙酸酯、乙基乙氧基 丙酸酯、2-庚酮、γ-丁內酯、環己酮、醋酸丁酯、N-甲基 吡咯烷酮、Ν，Ν-二甲基乙烯醯胺、二甲基亞楓等，於此等 之中以丙二醇單甲醚乙酸酯、乙基乙氧基丙酸酯、2 -庚酮 、γ-丁內酯、環己酮、醋酸丁酯較佳，更佳者爲丙二醇單 甲醚乙酸酯、乙基乙氧基丙酸酯、2 -庚酮。 含羥基之溶劑與不含羥基之溶劑的混合比（重量）爲1/99 〜99/1、較佳者爲 10/90〜90/10、更佳者爲 20/80〜 60 /40。含有50重量％不含羥基之溶劑的混合溶劑就塗覆 均勻性而言較佳。 <其他添加劑> -116- 588218 五、發明說明（115 ) 本發明之正型感光性組成物，視其所需另可含有染料、 可塑劑、上述外之界面活性劑、光增感劑、及對顯像液而 言促進溶解性的化合物等。 本發明可使用的對顯像液而言溶解促進性化合物係爲具 有2個以上〇H基、或具有1個以上羧基之分子量爲1〇〇〇 以下之低分子化合物較佳。 此等溶解促進性化合物之較佳添加量對（B)樹脂或（D)樹 脂而言爲2〜50重量％、更佳者爲5〜30重量％。若大於50 重量％時，顯像殘渣惡化、且於顯像時圖樣變形之新缺點 產生故不爲企求。 該分子量1 000以下之苯酚化合物例如參照特開平4-1 22938號、特開平2 - 2853 1號、美國專利第491 621 0號、 歐洲專利第2 1 9294號等記載的方法，爲該業者可容易地 予以合成。 具有羧基之脂環族、或脂肪族化合物的具體例如辛二酸 、脫氧膽酸、石膽酸等具有膽固醇構造之羧酸衍生物、金 剛烷基羧酸衍生物、金剛烷基二羧酸衍生物、環己烷羧酸 、環己烷二羧酸等，惟不受此等所限制。 於本發明中，亦可倂用氟系及/或矽系界面活性劑以外 之其他界面活性劑。 具體例如聚環氧乙烷月桂醚、聚環氧乙烷硬脂醚、聚環 氧乙烷十六烷醚、聚環氧乙烷油醚等之聚環氧乙烷烷醚類 ，聚環氧乙烷辛基苯酚醚、聚環氧乙烷壬基苯酚醚等之聚 -117- 588218 五、發明說明（116) 環氧乙烷烷基芳醚類、聚環氧乙烷•聚環氧丙醚嵌段共聚 物類’山梨糖醇單月桂酸酯、山梨糖醇單棕櫚酸酯、山梨 糖醇單硬脂酸酯、山梨糖醇單油酸酯、山梨糖醇三油酸酯 、山梨糖醇單硬脂酸酯等之山梨糖醇脂肪酸酯類、聚環氧 乙院山梨糖醇單月桂酸酯、聚環氧乙烷山梨糖醇單棕櫚酸 酯、聚環氧乙烷山梨糖醇單硬脂酸酯、聚環氧乙烷山梨糖 醇三油酸酯、聚環氧乙烷山梨糖醇三硬脂酸酯等之聚環氧 基山梨糖醇脂肪酸酯類等之非離子系界面活性劑等。 此等界面活性劑可以單獨添加、或幾種組合添加。 <<使用方法>> 本發明之感光性組成物係使上述成分溶解於所定有機溶 劑、較佳者爲上述混合溶劑中，如下述塗覆於所定載體上 使用。 換言之，使上述感光性組成物藉由旋轉器、滾筒等之適 當塗覆方法塗覆於製造精密積體電路元件時所使用的基板 (例如矽/二氧化矽被覆）上。 塗覆後通過所定光罩予以曝光，進行烘烤、顯像。如此 可得良好的光阻圖樣。 此處，曝光光源爲2 50nm以下、較佳者爲220nm以下波 長之紫外光線。具體例如KrF準分子雷射光（ 248nm)、ArF 準分子雷射光（193nm)、F2準分子雷射光（157nm)、 EUV(13nm)、X光線、電子束等，以ArF準分子雷射光 (193nm)、F2準分子雷射光（157nm)較佳。 -118- 588218 五、發明說明（117) 於顯像工程中使用如下述之鹼顯像液。感光性組成物之 鹼顯像液可使用氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、 甲基矽酸鈉、銨水等無機鹼類，乙胺、正丙胺等一級胺， 二乙胺、二正丙胺等二級胺，三乙胺、甲基二乙胺等三級 胺，二甲基乙醇胺、三乙醇胺等醇胺類，四甲銨氫氧化物 、四乙銨氫氧化物等四級銨鹽，吡咯、？啶等環狀胺類等 之鹼性水溶液。 另外，在上述鹼性水溶液中亦可添加適量的醇類、界面 活性劑。 鹼顯像液之鹼濃度通常爲0.1〜20重量％、較佳者爲0.2 〜15重量％、更佳者爲0.5〜10重量％。 鹼顯像液之pH値通常爲10〜15、較佳者爲10.5〜14.5 、更佳者爲1 1〜1 4。 【實施例】 於下述中藉由實施例具體地說明本發明，惟本發明之範 圍不受實施例所限制。 <酸發生劑之合成例> 合成例（1 ) 化合物（I - 2 )之合成 使10克異丙叉丙酮溶解於100mlN，N-二甲基甲醯胺中， 於其中加入50ml三乙胺。於該溶液中加入22. 1克三甲基 甲矽烷基氯化物、在100°C下反應2小時。放冷後，加入 300m 1己烷、以飽和的碳酸氫鈉水溶液洗淨2次、以蒸餾 水洗淨2次。使有機相濃縮後，製得粗生成物。使該物在(Wherein L1 to L8 represent the same or different hydroxymethyl, methoxymethyl, or ethoxymethyl) -108- 588218 5. Description of the invention (107) A phenol derivative having a hydroxymethyl group may be It is prepared by reacting a benzene compound without a corresponding hydroxymethyl group (wherein L1 to L8 are compounds of hydrogen atom) with formaldehyde under a base catalyst. In this case, in order to prevent resinization or gelation, the reaction temperature is preferably 60 ° C or lower. Specifically, it can be synthesized by the methods described in JP-A-6-282067 and JP-A-7-64285. A phenol derivative having an alkoxymethyl group can be prepared by using a phenol derivative having a corresponding hydroxymethyl group and an alcohol in the presence of an acid catalyst. In this case, in order to prevent resinization or gelation, the reaction is preferably performed at a reaction temperature of 100 ° C or lower. Specifically, it can be synthesized by a method described in European Patent EP632003A1 and the like. The synthesized phenol derivative having a hydroxymethyl group or an alkoxymethyl group is more preferable in terms of stability during storage, and more preferably a phenol derivative having an alkoxymethyl group in terms of stability during storage. . A phenol derivative having two or more hydroxymethyl or alkoxymethyl groups in combination, concentrated on any benzene ring, or separated and bonded can be used alone or in combination of two or more. In addition to the above phenol derivatives, the following compounds (i) and (i i) can be used as the (E) crosslinking agent. (i) Compound having N-hydroxymethyl, N-alkoxymethyl, or N-ethoxymethyl (ii) epoxy compound In the present invention, the above-mentioned crosslinking agent is preferably a phenol derivative . Moreover, also -109- 588218 5. Description of the invention (108) Two or more of the above-mentioned crosslinking agents can be used in combination.比例 The ratio of the phenol derivative to the crosslinking agent of (i) or (ii) when the above-mentioned crosslinking agent is used, the molar ratio is 100/0 ~ 0/100, preferably 90/10 ~ 20/80, More preferably, it is 90/10 ~ 50/50. (i) Compounds having N-hydroxymethyl, N-alkoxymethyl, or N-fluorenylmethyl, for example, European Patent Publication (hereinafter referred to as "EP-A") No. 0,133,216, West German Patent No. 3,634,67 No. 1, same as the monomer and oligomer-melamine-formaldehyde condensate disclosed in No. 3, 711,264 and urea-formaldehyde, alkoxy substitution of EP-A No. 0,2 1 2,482 Compounds and the like disclosed by benzoguanosine-formaldehyde condensates and the like. More preferably, for example, a melamine-formaldehyde derivative having at least two free N-hydroxymethyl, N-alkoxymethyl, or N-fluorenylmethyl groups, most preferably an N-alkoxymethyl derivative good. (ii) The epoxy compound contains, for example, one or more epoxy groups, monomers, dimers, oligomers, and polymer-like epoxy compounds. For example, the reaction product of bisphenol and epichlorohydrin, the reaction product of low molecular weight phenol and formaldehyde resin and epichlorohydrin. Other forces are epoxy resins described and used in U.S. Patent No. 4,01 6,705 and British Patent No. 1,539,192. The crosslinking agent is used in an amount of 3 to 70% by weight, and more preferably 5 to 50% by weight, based on the total solid content of the composition. If the amount of the cross-linking agent is less than 3% by weight, the residual film ratio is low, and if it is more than 70% by weight, the resolution is lowered, and the stability of the photosensitive composition during storage is not desirable. -110- 588218 V. Description of the invention (109) < Other components used in the photosensitive composition of the present invention > [6] Basic compounds Nitrogen-containing basic compounds can use organic amines, basic ammonium salts, alkalis Sexual salt, etc. 'will not degrade sublimation or photoresistance. Among these nitrogen-containing basic compounds, organic amines are preferred in terms of excellent image performance. For example, JP-A No. 63-1 49640, JP-A No. 5-249662, JP-A No. 5-1-27369, JP-A No. 5-289322, JP-A No. 5-249863, JP-A No. 5-289340, JP-A No. 5- No. 232706, No. Hei 5-257282, No. 6- 24 2605, No. 6-2426 0 No. 6, No. 6-266 1 00, No. 5-266 1 1 0, No. 6-260 3 1 7902, JP-A 7-120929, JP-A 7-146558, JP-A 7-319163, JP-A 7-508440, JP-A 7- 3 3 388.4, JP-A 7-219217, special Kaiping 7-92678, JP 7-28247, JP 8-22120, JP 8-1 10638, JP 8-1 23030, JP 9-2743 1 2 and JP 9-1 Basic compounds described in 6687 No. 1, JP-A-9-292708, JP-A-9-325496, JP-A-7-508840, USP5525453, USP5629134, USP5667938, etc. Specific examples of the basic compound include structures shown in the following (A) to (E). [Chem. 86] 251 _ r254 r255 K250-N ^ «CN ^ C- R253r ^ NC-R256 (A) (Bj (C) (D) CB) ·.. * ·, -111- 588218 V. Description of the invention (110) (wherein R25 (), R251 and R252 may be the same or different carbon atoms, alkyl groups having 1 to 6 carbon atoms, amino alkyl groups having 1 to 6 carbon atoms, hydroxyl groups having 1 to 6 carbon atoms or A substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R251 and R252 may be bonded to each other to form a ring, wherein R253, R254, R255, and R256 may be the same or different alkyl groups having 1 to 6 carbon atoms ) A preferred compound is a nitrogen-containing basic compound or an aliphatic tertiary amine having two or more nitrogen atoms in different chemical environments in one molecule. Preferred nitrogen-containing basic compounds such as 1,5-diazobicyclo [4.3.0] -5-nonene, 1,8-diazobicyclo [5 · 4 · 0] -7- Undecene (DBU), 1,4-diazobicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidines, hexamethylenetetramine , Imidazoles, hydroxypyridines, pyridines, anilines, hydroxyalkylanilines, 4,4'-diaminophenyl ethers, pyridyl p-toluenesulfonate, 2,4,6-trimethyl Pyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, and tetrabutylammonium lactone, triethylamine, tributylamine, tribenzylamine, tri-n-octylamine, triisooctylamine, Refer to (ethylhexyl) amine, tridecylamine, dodecylamine, etc. Among them, 1,5-diazobicyclo [4.3 · 0] -5-nonene, 1,8-diazobicyclo [5 · 4 · 0] -7-undecene, 1,4-diene Azobicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, 4-hydroxypyridine, 2,2,6,6-tetramethyl-4-hydroxypyridine, Pyridines, 4,4 '· diaminodiphenyl ether, triethylamine, tributylamine, tripentylamine, tri-n-octylamine, ginsyl (ethylhexyl) amine, dodecylamine, Ν, Ν- Organic-112-588218 such as di-hydroxyethylaniline, N-hydroxyethyl · N-ethylaniline, etc. 5. Description of the invention (111) Amine is preferred. These basic compounds can be used alone or in combination of two or more. The amount of the basic compound used is usually 0.001 to 10 parts by weight, and preferably 0.01 to 5 parts by weight, based on the total solid content of the photosensitive composition. If it is less than 0.001 parts by weight, the effect of adding the above-mentioned basic compound cannot be obtained. In addition, if it is more than 10 parts by weight, the sensitivity tends to decrease and the developability of the non-exposed portion tends to deteriorate. [7] Fluorine-based and / silicon-based surfactants The photosensitive composition of the present invention is based on fluorine-based and / or silicon-based surfactants (fluorine-based surfactants, silicon-based surfactants, and containing fluorine atoms and silicon). Any one of the two surfactants) or two or more of them are preferred. By containing the photosensitive composition of the present invention and the above-mentioned surfactant, when using an exposure light source of 250 nm or less, especially 220 nm or less, good sensitivity and resolution, adhesion, and photoresist with few developmental defects can be obtained. Examples of such surfactants include JP-A-Sho 62-36663, JP-A-Sho 6 1-226746, JP-A-Sho 6 1-226745, JP-A-Sho 62-1 70950, JP-A-Sho 63- No. 34540, JP-A 7-2301 65, JP-A 8-62834, JP-A 9-54432, JP-A 9-9988, JP-A 2002-277862, US Patent No. 5405720, same as 5 3 60692 No. 552988 No. 1, No. 52963 No. 30, No. 5436098, No. 5576 1 No. 43, No. 52945 No. 1 No. 1, and No. 582445 No. 1 Instruction No. -113- 588218 V. DESCRIPTION OF THE INVENTION (112) As the surfactant, the following commercially available surfactants can also be used directly. Commercially available surfactants can be used, for example, Gefton Department (Transliteration) EF301, EF303 (Sin Akita Kasei Co., Ltd.), Floraton (Transliteration) FC430, 431 (Sumitomo Shreem Co., Ltd.) ), Mekafak (transliteration) F171, F173, F176, F189, R0 8 (made by Dainippon Ink), Safran (transliteration) S-3 82, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Dun Long Yiluolu (transliteration) S-366 (don Long Yi (transliteration) chemistry (shares)) and other fluorine-based surfactants or silicon-based surfactants. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. In addition, the surfactant may be derived from a fluorinated aliphatic compound produced by a telomerization method (telomerization method) or an oligomerization method (referred to as an oligomer method) in addition to those shown in the above. Surfactant for polymers with fluorinated aliphatic groups. The fluorinated aliphatic compound can be synthesized by the method described in JP 2002-9099A. A polymer having a fluorinated aliphatic group is a copolymer of a monomer (poly (alkylene oxide)) acrylate and / or (poly (alkylene oxide)) methacrylate having a fluorinated aliphatic group. It can be irregularly distributed or block copolymerized. In addition, poly (alkylene oxide) is, for example, poly (ethylene oxide) -based, poly (propylene oxide) -based, poly (butylene oxide) -based, etc. In addition, poly (ethylene oxide and epoxy Units with different chain lengths in the same chain length, such as propane and ethylene oxide block bond) or (block oxide of ethylene oxide and propylene oxide) groups. In addition, fluorinated aliphatic radical-containing monomers (poly (alkylene oxide-114 · 588218, fifth, description of the invention (1 彳 3))) acrylate (or methacrylate) copolymers are not only two-component copolymers. Products, monomers having two or more fluorinated aliphatic groups, or two- or more-membered systems that copolymerize two or more different (poly (alkylene oxide)) acrylates (or methacrylates) at the same time Copolymer. For example, a commercially available surfactant such as Mekafak? 178 、? -470, Bu 473, F-475, F-476, F-472 (made by Dainippon Ink Chemical Industry Co., Ltd.). In addition, a copolymer of an acrylate (or methacrylate) having a C6F13 group and a (poly (alkylene oxide)) acrylate (or a methacrylate), an acrylate (or a methacrylic acid) having a C6F13 group Copolymer with (poly (ethylene oxide)) acrylate (or methacrylate) and (poly (propylene oxide)) acrylate (or methacrylate), acrylate (or formic acid) with C8F17 group Copolymer of acrylic acid) and (poly (ethylene oxide)) acrylate (or methacrylate) and (poly (propylene oxide)) acrylate (or methacrylate), acrylate with C8F17 group (Or methacrylic acid) and (poly (ethylene oxide)) copolymers of acrylate (or methacrylate) and (poly (propylene oxide)) acrylate (or methacrylate), etc. The amount of the surfactant used is 0.0001% to 2% by weight, and more preferably 0.001% to 1% by weight of the total amount of the photosensitive composition (excluding the solvent). [8] Organic solvent The present invention As the photosensitive composition, each of the above components is dissolved in an organic solvent. The organic solvents used are ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, 7-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, -115- 588218 Explanation (114) Ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, lactic acid Methyl ester, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl Methylsulfenyl, N-methylpyrrolidone, tetrahydrofuran. In the present invention, the organic solvents may be used singly or in combination. It is preferable to use a mixed solvent mixed with a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group in the structure. This can reduce the occurrence of particles during storage of the photosensitive composition. Hydroxyl-containing solvents such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, etc. Among these, ethylene propylene glycol monomethyl ether, lactic acid Ethyl ester is preferred. Hydroxyl-free solvents such as propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethyl vinylammonium amine, dimethyl sulfene, and the like, among them propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, Cyclohexanone and butyl acetate are preferred, and more preferred are propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, and 2-heptanone. The mixing ratio (weight) of the hydroxyl-containing solvent and the non-hydroxyl-containing solvent is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. A mixed solvent containing 50% by weight of a non-hydroxyl-containing solvent is preferred in terms of coating uniformity. < Other additives > -116- 588218 V. Description of the invention (115) The positive photosensitive composition of the present invention may further contain dyes, plasticizers, surfactants other than the above, and photosensitizers as required. And compounds that promote solubility in the developer. The dissolution-promoting compound that can be used in the developing solution of the present invention is preferably a low-molecular compound having two or more 0H groups or one or more carboxyl groups and having a molecular weight of 1,000 or less. The preferable addition amount of these dissolution promoting compounds is 2 to 50% by weight, and more preferably 5 to 30% by weight for the (B) resin or (D) resin. If it is more than 50% by weight, development residues are deteriorated, and new disadvantages of pattern deformation during development are not desirable. The phenol compounds having a molecular weight of 1,000 or less are referred to, for example, the methods described in Japanese Patent Application Laid-Open No. 4-1 22938, Japanese Patent Application Laid-Open No. 2-2853, US Patent No. 491 6212 0, European Patent No. 2 1294, and the like. Easily synthesized. Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a cholesterol structure such as suberic acid, deoxycholic acid, and lithocholic acid, adamantyl carboxylic acid derivatives, and adamantyl dicarboxylic acid derivatives. Substances, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, etc., but are not limited by these. In the present invention, a surfactant other than a fluorine-based and / or silicon-based surfactant may be used. Specific examples are polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide cetane ether, polyethylene oxide oleyl ether, etc. Ethyl octyl phenol ether, polyethylene oxide nonyl phenol ether, etc. -117- 588218 V. Description of the invention (116) Ethylene oxide alkyl aryl ethers, polyethylene oxide • polypropylene oxide Ether block copolymers' sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbose Sorbitol fatty acid esters such as alcohol monostearate, polyethylene oxide sorbitol monolaurate, polyethylene oxide sorbitol monopalmitate, polyethylene oxide sorbitol mono Non-ionic interfacial activity of polyepoxy sorbitol fatty acid esters such as stearates, polyethylene oxide sorbitol trioleate, polyethylene oxide sorbitol tristearate, and the like Agent. These surfactants can be added individually or in combination. < < Method of use > > The photosensitive composition of the present invention is made by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, and coating it on a predetermined carrier as described below. In other words, the photosensitive composition is applied to a substrate (such as a silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by a suitable coating method such as a spinner or a roller. After coating, it is exposed through a predetermined mask, and baked and developed. In this way, a good photoresist pattern can be obtained. Here, the exposure light source is ultraviolet light having a wavelength of 2 50 nm or less, preferably 220 nm or less. Specific examples include KrF excimer laser light (248nm), ArF excimer laser light (193nm), F2 excimer laser light (157nm), EUV (13nm), X-ray, electron beam, etc., and ArF excimer laser light (193nm) , F2 excimer laser light (157nm) is better. -118- 588218 V. Description of the invention (117) In the development process, an alkali developing solution as described below is used. As the alkali developing solution of the photosensitive composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, and ammonium water, primary amines such as ethylamine and n-propylamine, and diethyl ether can be used. Secondary amines such as amines and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. Quaternary ammonium salt, pyrrole,? Aqueous alkaline solutions such as cyclic amines such as pyridine. In addition, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution. The alkali concentration of the alkali developing solution is usually 0.1 to 20% by weight, preferably 0.2 to 15% by weight, and more preferably 0.5 to 10% by weight. The pH of the alkali developing solution is usually 10 to 15, preferably 10.5 to 14.5, and more preferably 1 1 to 14. [Examples] The present invention will be specifically described in the following examples, but the scope of the present invention is not limited by the examples. < Synthesis example of acid generator > Synthesis example (1) Synthesis of compound (I-2) 10 g of isopropylidene acetone was dissolved in 100 ml of N, N-dimethylformamide, and 50 ml of triethyl was added thereto. amine. To this solution was added 22.1 g of trimethylsilyl chloride, and the mixture was reacted at 100 ° C for 2 hours. After leaving to cool, 300 m of 1 hexane was added, washed twice with a saturated aqueous sodium hydrogen carbonate solution, and washed twice with distilled water. After concentrating the organic phase, a crude product was obtained. Make the thing in
-119- 588218 五、發明說明（118 ) 減壓蒸餾（78°C/15mmHg)下生成後，製得異丙叉丙酮之甲 政丈兀基稀醇醚。使5克所得的甲砂院基嫌醇醚、3 . 1克四 甲基儲烴亞碾溶解於50ml氯仿中，使該溶液冷卻至_ 3 ot： 。於其中在30分鐘內滴入9.9克三氟醋酸酐。反應2小 時後’使1 0克九氟磺酸鉀溶解於乙臆/水中。使混合液水 洗、且使氯仿相濃縮。使所得粗生成物以二異丙醚洗淨， 製得4 · 2克化合物（I - 2 )。 300MHz 'H-NMRCCDC^) Sl.95(s，3H) 、 52.2(s，3H) 、 δ2·2〜2.5(m，4H) 、 δ3·5〜 3.7(m，4H) 、 54.75(s，2H) 、 δ6·2(ί，1Η) 合成例（2) 化合物（1-26)之合成 使20克2-環己烯-1-酮溶解於300mlN，N-二甲基甲醯胺 中，於其中加入150ml三乙胺。於該溶液中加入45克三 甲基甲矽烷基氯化物、在100°C下反應2小時。放冷後， 加入500m 1己烷、以飽和的碳酸氫鈉水溶液洗淨2次、以 蒸餾水洗淨2次。使該物在減壓蒸餾（86°C/15mmHg)下生 成後，製得2 -環己烯-1-酮之甲矽烷基烯醇醚。使5克所 得的2-環己烯-1-酮之甲矽院基烯醇醚、3.1克四甲基烯 烴亞碾溶解於100ml氯仿中，使該溶液冷卻至-3(TC。於 其中在30分鐘內滴入6.24克三氟醋酸酐。反應2小時後 ，使1 0克九氟磺酸鉀溶解於乙腈/水中。使混合液水洗、 且使氯仿相濃縮。使所得粗生成物再醋酸乙酯/二異丙醚 (40/60)中再結晶，製得3.7克化合物（1-26)。 -120- 588218 五、發明說明（119 ) 300MHz 'H-NMRCCDCls) δ2·1 〜2·3(ιώ，3Η)、δ2·5 〜2.8(s,4H)、δ3·05(ηι，1Η)、 δ3.45(ηι，1Η)、δ3·8(πι，2Η)、δ3.9(πι，1Η)、δ5·3(ιη，1Η) 56.2(dd,lH) ' 67.25 (d,lH) 合成例（3 ) 化合物（I A - 3 2 )之合成 使23.8克異佛爾酮溶解於100ml乙醯腈中，於其中加 入20 · 9克三乙胺、3 1 . 0克碘化鈉。於該溶液中加入22 · 5 克三甲基甲矽烷基氯化物、在6(TC下反應2小時。放冷後 ，使反應液注入冰中、以二異丙醚萃取、使有機相以飽和 的碳酸氫鈉水溶液洗淨2次、以蒸餾水洗淨2次。使有機 相濃縮後，製得粗生成物。使該物在減壓蒸餾（1 08 °C /15mmHg)下精製後，製得異佛爾酮之烯丙基位上的氫脫離 的烯醇甲矽烷醚。使1 5克所得的烯醇甲矽烷醚、7 · 5克四 甲基烯烴亞碾溶解於100ml氯仿中，使該溶液冷卻至 -30°C。於其中在30分鐘內滴入15.0克三氟醋酸酐。反 應2小時後，使24克九氟磺酸鉀溶解於乙腈/水中。使混 合液水洗、且使氯仿相濃縮。使所得粗生成物以二異丙醚 洗淨，製得粉體。使該物在醋酸乙酯/二異丙醚中再結晶 ，製得20克化合物（IA-32)。 300MHz ^-NMRCCDCls) 5l.2(s,6H) > 6l.75(s,3H) ' 52.3(s,2H) ' 52.4(s,2H) 、δ2·3 〜2.6(m，4H)、δ3.4 〜3.8(m，4H)、S4.2(s，2H)、 δ6·2(s，1H)-119- 588218 V. Description of the invention (118) After formation under reduced pressure distillation (78 ° C / 15mmHg), methyl isopropylidene ether is obtained. Dissolve 5 grams of the obtained methanilide base ether and 3.1 grams of tetramethylhydrocarbon storage in 50 ml of chloroform, and cool the solution to _ 3 ot:. 9.9 g of trifluoroacetic anhydride was added dropwise thereto over 30 minutes. After 2 hours of reaction ', 10 g of potassium nonafluorosulfonate was dissolved in acetamidine / water. The mixture was washed with water and the chloroform phase was concentrated. The obtained crude product was washed with diisopropyl ether to obtain 4.2 g of a compound (I-2). 300MHz 'H-NMRCCDC ^) Sl.95 (s, 3H), 52.2 (s, 3H), δ2 · 2 ~ 2.5 (m, 4H), δ3 · 5 ~ 3.7 (m, 4H), 54.75 (s, 2H ), Δ6.2 · (1, 1Η) Synthesis Example (2) Synthesis of Compound (1-26) 20 g of 2-cyclohexen-1-one was dissolved in 300 ml of N, N-dimethylformamide, in To this was added 150 ml of triethylamine. To this solution was added 45 g of trimethylsilyl chloride, and the mixture was reacted at 100 ° C for 2 hours. After allowing to cool, 500 m of 1 hexane was added, washed twice with a saturated aqueous sodium hydrogen carbonate solution, and washed twice with distilled water. This was produced under reduced pressure distillation (86 ° C / 15 mmHg) to obtain a silyl enol ether of 2-cyclohexen-1-one. 5 grams of the obtained 2-cyclohexen-1-one silylsenolenol ether and 3.1 grams of tetramethylolefin were triturated in 100 ml of chloroform, and the solution was cooled to -3 ° C. 6.24 g of trifluoroacetic anhydride was added dropwise within 30 minutes. After 2 hours of reaction, 10 g of potassium nonafluorosulfonate was dissolved in acetonitrile / water. The mixed solution was washed with water and the chloroform phase was concentrated. The resulting crude product was re-acetic acid Recrystallize from ethyl acetate / diisopropyl ether (40/60) to obtain 3.7 g of compound (1-26). -120- 588218 V. Description of the invention (119) 300MHz 'H-NMRCCDCls) δ2 · 1 ~ 2 · 3 (ιώ, 3Η), δ2.5 · ~ 2.8 (s, 4H), δ3 · 05 (ηι, 1Η), δ3.45 (ηι, 1Η), δ3.8 · (2 (, 2 ，), δ3.9 (πι , 1Η), δ5.3 · 3 (ιη, 1Η) 56.2 (dd, lH) '67.25 (d, lH) Synthesis Example (3) Synthesis of Compound (IA-3 2) 23.8 g of isophorone was dissolved in 100 ml of ethyl To acetonitrile, 20.9 g of triethylamine and 3 1.0 g of sodium iodide were added. To this solution was added 22.5 g of trimethylsilyl chloride, and the mixture was reacted at 60 ° C. for 2 hours. After cooling, the reaction solution was poured into ice, extracted with diisopropyl ether, and the organic phase was saturated. The sodium bicarbonate aqueous solution was washed twice and washed twice with distilled water. After concentrating the organic phase, a crude product was obtained. The product was purified by distillation under reduced pressure (1 08 ° C / 15mmHg) to obtain Isolone hydrolyzed enol silyl ether at the allyl position. 15 g of the obtained enol silyl ether and 7.5 g of tetramethyl olefin were triturated and dissolved in 100 ml of chloroform. The solution was cooled to -30 ° C. 15.0 g of trifluoroacetic anhydride was added dropwise thereto within 30 minutes. After 2 hours of reaction, 24 g of potassium nonafluorosulfonate was dissolved in acetonitrile / water. The mixture was washed with water and chloroform The phases were concentrated. The obtained crude product was washed with diisopropyl ether to obtain a powder. The substance was recrystallized from ethyl acetate / diisopropyl ether to obtain 20 g of a compound (IA-32). 300MHz ^ -NMRCCDCls) 5l.2 (s, 6H) > 6l.75 (s, 3H) '52.3 (s, 2H)' 52.4 (s, 2H), δ2 · 3 ~ 2.6 (m, 4H), δ3.4 ~ 3.8 (m, 4H), S4.2 (s, 2H), 6 · 2 (s, 1H)
-121 - 588218 五、發明說明（12〇) 其他化合物亦使用相同的方法合成。 <樹脂之合成例> 合成例（1 )樹脂（1 )之合成（側鏈型） 使2 -乙基-2 -金剛烷基甲基丙烯酸酯、丁內酯甲基丙燃 酸酯以55 / 45之比例加入溶解於甲基乙酮/四氫呋喃=5/5 中，調製lOOmL固成分濃度20%之溶液。在該溶液中加入 2莫耳％和光純藥製V-65，使其在氮氣氣氛下、在4小時 內滴入加熱至60°C之甲基乙酮。滴完後，使反應液加熱4 小時，再度添加1莫耳％ V - 6 5、攪拌4小時。於反應終了 後，使反應液冷卻至室溫，在3L蒸餾水/1 SO丙醇=1 /1之 混合溶劑中晶析，回收結晶白色粉末之樹脂（丨）。 自C13NMR求得的聚合物組成比爲46/54。而且，藉由 GPC測定求得的標準聚苯乙烯換算的重量平均分子量爲 10700 〇 以與上述合成例（1)相同的操作合成樹脂（2)〜（15)。 下述係表示上述樹脂（2)〜（15)之組成比、分子量。（重 複單位1、2、3、4係爲構造式自左而右的順序）。 -122- 588218 五、發明說明（121 ) 表 樹脂 重複單位1 重複單位2 重複單位3 重複單位4 分子量 (莫耳％) (莫耳％) (莫耳％) (莫耳％) 2 53 40 7 13400 3 46 34 20 9400 4 42 31 27 8300 5 49 42 9 9900 6 42 30 28 10300 7 39 35 26 8900 8 46 22 30 2 12900 9 42 20 32 6 11600 10 46 42 12 9200 11 40 20 40 11000 12 42 18 38 2 13800 13 38 31 29 2 11100 14 50 31 19 11700 15 40 20 40 9000 另外，下述中係爲上述樹脂（1)〜（15)之構造。-121-588218 V. Description of the invention (12) Other compounds were also synthesized by the same method. < Synthesis example of resin > Synthesis example (1) Synthesis of resin (1) (side chain type) 2-ethyl-2 -adamantyl methacrylate, butyrolactone methyl propionate was A ratio of 55/45 was added to methyl ethyl ketone / tetrahydrofuran = 5/5 to prepare 100 mL of a 20% solids solution. To this solution was added 2 mole% of V-65 manufactured by Wako Pure Chemical Industries, Ltd., and methyl ethyl ketone heated to 60 ° C was added dropwise under a nitrogen atmosphere over 4 hours. After the dropping was completed, the reaction solution was heated for 4 hours, and 1 mole% V-6 was added again, followed by stirring for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and crystallized in a mixed solvent of 3 L of distilled water / 1 SO propanol = 1/1, and the resin (丨) was recovered as a crystalline white powder. The polymer composition ratio obtained from C13NMR was 46/54. The weight average molecular weight in terms of standard polystyrene obtained by GPC measurement was 10,700. The resins (2) to (15) were synthesized in the same manner as in the above-mentioned Synthesis Example (1). The following shows composition ratios and molecular weights of the resins (2) to (15). (Repeating units 1, 2, 3, and 4 are the structural formulas from left to right). -122- 588218 5. Description of the invention (121) Table resin repeating unit 1 Repeating unit 2 Repeating unit 3 Repeating unit 4 Molecular weight (mole%) (mole%) (mole%) (mole%) 2 53 40 7 13400 3 46 34 20 9400 4 42 31 27 8300 5 49 42 9 9900 6 42 30 28 10300 7 39 35 26 8900 8 46 22 30 2 12900 9 42 20 32 6 11600 10 46 42 12 9200 11 40 20 40 11000 12 42 18 38 2 13800 13 38 31 29 2 11100 14 50 31 19 11700 15 40 20 40 9000 In addition, the following are structures of the resins (1) to (15).
-123- 588218 五、發明說明（122) 【化87】 .卜. *—CH2一C- Ic:〇-123- 588218 V. Description of the invention (122) [Chem. 87]. Bu. * —CH2—C- Ic: 〇
•CH,• CH,
•CH• CH
COOCOO
(2 3 ο Η 一一 Η CICIC ——ο •c一 Ic=o ?h3(2 3 ο Η 一 一 IC CICIC ——ο • c I Ic = o? H3
ch3 1_c 一 I , c=〇 I〇 (3)ch3 1_c-I, c = 〇 I〇 (3)
OHOH
OHOH
3 Η C丨clGlo 人 一 C3 1 V。 ΗΗ2 c3 Η C 丨 clGlo People One C3 1 V. ΗΗ2 c
一2 COne 2 C
Hi c——clcl〇Hi c-clcl〇
OH 4) /1\ -124- 588218 五、發明說明（]23 【化88】 .CH3I ch2—c— •t 0=0 〒h3 "CH2一c — Ic=o ch3 I CH2一C~" ! c=oOH 4) / 1 \ -124- 588218 V. Description of the invention [] 23 [化 88] .CH3I ch2—c— • t 0 = 0 〒h3 " CH2—c — Ic = o ch3 I CH2—C ~ "! c = o
(5) NH[ CH(CH3)2(5) NH [CH (CH3) 2
•125- 588218• 125- 588218
588218 五、發明說明（！25 •【化9 1】·588218 V. Description of the invention (! 25 • [化 9 1] ·
ch3 I CH, CH, CH^ h3c—6—ch3ch3 I CH, CH, CH ^ h3c—6—ch3
’ch2—c- ch2-c——ch2—C--CH2—c— c=o ▲ c=o c=；〇’Ch2—c- ch2-c——ch2—C--CH2—c— c = o ▲ c = o c =; 〇
ch2och3ch2och3
(12) -0〜0H 〔0 3 2 7.】 【化.9 2】 ch3 CH, CH, CH, •ch2-c--ch2—C— 一 CH2—c c=o c=〇 0 CH2CH3 o -CH2—o(12) -0 ~ 0H [0 3 2 7.] [Chem. 9 2] ch3 CH, CH, CH, • ch2-c--ch2—C— One CH2—cc = oc = 〇0 CH2CH3 o -CH2 —O
c=o I o c=o C13) i&〇H°c = o I o c = o C13) i & 〇H °
'NH 2 H c'NH 2 H c
CH3-?-c=olo H2cCH3-?-C = olo H2c
o i=Hfc·丨c=Ioo i = Hfc 丨 c = Io
7 2 588218 五、發明說明（126) .【化93】7 2 588218 V. Description of the invention (126). [化 93]
合成例（2 ) 樹脂（1 6 )之合成（主鏈型） 在分離燒瓶中加入原菠烯基羧酸第3 -丁酯、原菠烯基羧 酸丁內酯與馬來酸酐（莫耳比40/ 1 0 / 50 )及THF(反應溫度 60重量％)，在氮氣氣流下加熱至6(TC。於反應溫度安定 時加入2莫耳％和光純藥公司製自由基起始劑V-601以開 始反應。加熱1 2小時。使所得反應混合物以2倍四氫呋 喃稀釋後，投入己烷/異丙醇=1 / 1之混合溶液中以析出白 色粉末。過濾取出結晶的粉體、予以乾燥，製得目的物之 樹脂（1 6 )。 使所得樹脂（1 6 )藉由GPC進行分子量分析時，以聚苯乙 烯換算爲8300 (重量平均）。而且，藉由NMR光譜可確認樹 脂（1 )之原菠烯基羧酸第3 - 丁酯/原菠烯基羧酸丁內酯/馬 來酸酐重複單位之莫耳比爲42 / 8 / 50。 以與合成例（2 )相同的方法合成樹脂（1 7 )〜（27 )。下述 係表示上述樹脂（1 7 )〜（27 )之組成比、分子量。（脂環烯 烴單位1、2、3係爲構造式自左而右的順序）。 -128- 588218 五、發明說明（彳27) 表2 樹脂 脂環烴單位1 (莫耳％) 脂環烴單位2 (莫耳％) 脂環烴單位3 (莫耳％) 馬來酸酐 (莫耳％) 分子量 17 35 15 50 8200 18 20 30 50 8600 19 36 14 50 9100 20 31 19 50 7900 21 35 5 10 50 8300 22 33 17 50 8500 23 38 12 50 8900 24 31 6 13 50 8100 25 33 7 10 50 9100 26 40 10 50 9300 27 34 16 50 8800 另外，下述中係爲上述樹脂（16)〜（27)之構造。 -129- 588218 五、發明說明（^28 【化94】Synthesis example (2) Synthesis of resin (16) (main chain type) In a separate flask, orthospinylcarboxylic acid 3 -butyl ester, orthospinylcarboxylic acid butyrolactone, and maleic anhydride (Mole Ratio 40/1 0/50) and THF (reaction temperature 60% by weight), and heated to 6 (TC under nitrogen flow). 2 mol% of radical initiator V- manufactured by Wako Pure Chemical Industries was added at a constant temperature. Start the reaction with 601. Heat for 12 hours. Dilute the obtained reaction mixture with 2 times tetrahydrofuran and put it into a mixed solution of hexane / isopropanol = 1/1 to precipitate a white powder. The crystal powder is taken out by filtration and dried. A target resin (16) was obtained. When the obtained resin (16) was subjected to molecular weight analysis by GPC, the polystyrene conversion was 8300 (weight average). Further, the resin (1) was confirmed by NMR spectrum. The molar ratio of the repeating unit of ortho-spinyl carboxylic acid 3-butyl ester / ortho-spinyl carboxylic acid butyrolactone / maleic anhydride is 42/8 / 50. In the same manner as in Synthesis Example (2) Synthetic resins (1 7) to (27). The following shows the composition ratio and molecular weight of the resins (1 7) to (27). Cyclic olefin units 1, 2, and 3 are in the order of the structural formula from left to right.) -128- 588218 V. Description of the invention (彳 27) Table 2 Resin alicyclic hydrocarbon unit 1 (mole%) Alicyclic hydrocarbon unit 2 (Mol%) Alicyclic hydrocarbon unit 3 (mol%) Maleic anhydride (mol%) Molecular weight 17 35 15 50 8200 18 20 30 50 8600 19 36 14 50 9100 20 31 19 50 7900 21 35 5 10 50 8300 22 33 17 50 8500 23 38 12 50 8900 24 31 6 13 50 8100 25 33 7 10 50 9100 26 40 10 50 9300 27 34 16 50 8800 In addition, the following are the structures of the above resins (16) to (27) -129- 588218 V. Description of the Invention (^ 28 [化 94]
coo-coo-
0^0^-° (16) (17) C00— cr (18) coo0 ^ 0 ^-° (16) (17) C00— cr (18) coo
COO、:t) (pQQCH2CH2COOC(CH3)3COO,: t) (pQQCH2CH2COOC (CH3) 3
O (19). OCOCH3 CH3 CH3 。乂 〇乂。 COO—coo-c—ch2-c—ch3 CH3 o (20).O (19). OCOCH3 CH3 CH3.乂 〇 乂. COO—coo-c—ch2-c—ch3 CH3 o (20).
COQCH2CH2〇CH2CH2OCH3vCOQCH2CH2〇CH2CH2OCH3v
O 又0^0 coo- OCOCH3 -130- (21) 588218 五、發明說明 【化95】 129O and 0 ^ 0 coo- OCOCH3 -130- (21) 588218 V. Description of the invention [Chem 95] 129
0 〇Α〇α〇 (22) (23) coo- ~b "cooT^)~ o0 〇Α〇α〇 (22) (23) coo- ~ b " cooT ^) ~ o
QH COO (24) COO- O-QH COO (24) COO- O-
COO OCH2CH3 coo：--cooCOO OCH2CH3 coo: --coo
O 〇 w . (.26) coo-O 〇 w. (.26) coo-
o 乂。&〇 OCOCH3 -13 1- (27) 588218 五、發明說明（1 30 ) 合成例（3 ) 樹脂（28 )之合成（混雜型） 在反應容器中加入原菠烯、馬來酸酐、丙烯酸第3-丁酯 、2-甲基環己基-2-丙基丙烯酸酯（莫耳比35/ 35 / 20 / 1 0 )， 溶解於四氫呋喃中，調製固成分60%之溶液。使其在氮氣 氣流下加熱至6 51。於反應溫度安定時加入1莫耳％和光 純藥公司製自由基起始劑V-601以開始反應。加熱8小時 。使所得反應混合物以2倍四氫呋喃稀釋後，投入反應混 合液之5倍容量之己烷中以析出白色粉末。過濾取出結晶 的粉體溶解於甲基乙酮、再沉於5倍容量之己烷/第3 - 丁 基甲醚=1/1混合溶劑，使析出的白色粉體濾取、乾燥，製 得目的物之樹脂（28)。 使所得樹脂（28)藉由GPC進行分子量分析時，以聚苯乙 烯換算爲12100(重量平均）。而且，藉由NMR光譜可確認 樹脂（1)之原菠烯/馬來酸酐/丙烯酸第3 -丁酯/ 2-甲基環己 基-2-丙基丙烯酸酯之莫耳比爲3 2 / 3 9 / 1 9 / 1 0。 以與合成例（3 )相同的方法合成樹脂（29 )〜（4 1 )。下述 係表示上述樹脂（29 )〜（4 1 )之組成比、分子量。o 乂. & 〇OCOCH3 -13 1- (27) 588218 V. Description of the invention (1 30) Synthesis example (3) Synthesis of resin (28) (hybrid) Add orthospinene, maleic anhydride, acrylic acid to the reaction vessel 3-Butyl ester and 2-methylcyclohexyl-2-propyl acrylate (Molar ratio 35/35/20/10) were dissolved in tetrahydrofuran to prepare a solution of 60% solid content. It was heated to 6 51 under a stream of nitrogen. To the reaction temperature was added 1 mol% of free radical starter V-601 manufactured by Wako Pure Chemical Industries, Ltd. at a constant temperature to start the reaction. Heat for 8 hours. The obtained reaction mixture was diluted with 2 times tetrahydrofuran, and then charged into 5 times the capacity of hexane in the reaction mixture to precipitate a white powder. The crystalline powder was taken out by filtration, dissolved in methyl ethyl ketone, and then settled in a mixed solvent of hexane / 3rd-butyl methyl ether = 1/1 with a capacity of 5 times, and the precipitated white powder was filtered and dried to obtain the target substance. Of resin (28). When the obtained resin (28) was subjected to molecular weight analysis by GPC, it was 12100 (weight average) in terms of polystyrene. Furthermore, it was confirmed from the NMR spectrum that the molar ratio of orthospinene / maleic anhydride / 3-butyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of resin (1) was 3 2/3 9/1 9/1 0. Resins (29) to (4 1) were synthesized in the same manner as in Synthesis Example (3). The following represents composition ratios and molecular weights of the resins (29) to (4 1).
-132- 588218 五、發明說明（131 ) 表3 樹脂 原菠烯類 酸酐 (甲基）丙烯酸酯 Mw 29 20/15 40 15/10 11900 30 32 37 20/8/3 10500 31 16 21 36/27 13900 32 15 22 34/29 12300 33 17 20 33/30 12400 34 18 24 32/26 1 3000 35 15 19 36/30 12700 36 15 20 29/10/26 13100 37 17 21 31/31 12800 38 18 17/3 30/32 13300 39 16 19 31/12/11/11 12600 40 20 22 58 14700 41 23 28 35/14 1 3300 另外，下述中係爲上述樹脂（28)〜（41)之構造。 -133- 588218 五、發明說明（13 2 【化96】 —CH-CH— -CH2^CH—* CH3 C 一Ο—C—CH3 II I 0 CH3 (28) * —-132- 588218 V. Description of the invention (131) Table 3 Resin orthospinic anhydride (meth) acrylate Mw 29 20/15 40 15/10 11900 30 32 37 20/8/3 10500 31 16 21 36/27 13900 32 15 22 34/29 12300 33 17 20 33/30 12400 34 18 24 32/26 1 3000 35 15 19 36/30 12700 36 15 20 29/10/26 13100 37 17 21 31/31 12800 38 18 17 / 3 30/32 13300 39 16 19 31/12/11/11 12600 40 20 22 58 14700 41 23 28 35/14 1 3300 In addition, the following are the structures of the resins (28) to (41). -133- 588218 V. Description of the invention (13 2 [化 96] —CH-CH— -CH2 ^ CH— * CH3 C—O—C—CH3 II I 0 CH3 (28) * —
-CH-CH---CH2一CH — * CH3Ί 乂 _ 、0 Ό OCOCH3 • C—O——C~rCH^CH3 II I 0 · · CH3 .(29) * ch2-ch— c一 0 II o CH3-〇 -CH-CH- g ，CH2—CH— * CH3 C—〇—C一CH2CH3 (30) II Io ch3 * —ch2~ch-CH-CH --- CH2 一 CH — * CH3Ί 乂 _, 0 Ό OCOCH3 • C—O——C ~ rCH ^ CH3 II I 0 · · CH3. (29) * ch2-ch— c 一 0 II o CH3-〇-CH-CH- g, CH2—CH— * CH3 C—〇—C—CH2CH3 (30) II Io ch3 * —ch2 ~ ch
CH2一CH- c—o—(CH2CH20)2CH3o CH—CH· -CHa—CH— ch3 CH2—CH_CH2—CH- c—o— (CH2CH20) 2CH3o CH—CH · -CHa—CH— ch3 CH2—CH_
O o—o—^T^Pd 〇 o=c I 0O o—o— ^ T ^ Pd 〇 o = c I 0
〇 0 -134- (31) 588218 五、發明說明（133【化97】〇 0 -134- (31) 588218 V. Description of the invention (133 [Chem. 97]
-CH-CN* -ch2-〒h—* CH2CH3 c—〇-il.0 一-CH2 一 CH- io=c CH3 (32)-CH-CN * -ch2-〒h— * CH2CH3 c—〇-il.0 a-CH2 a CH- io = c CH3 (32)
、ch3 -ch2—ch—；* ch3, Ch3 -ch2—ch—; * ch3
COOCOO
00
C——0——C II | 0 CH * —CH?_CHC——0——C II | 0 CH * —CH? _CH
3 _ (33) c—o 〇3 _ (33) c—o 〇
OH -7~V— —CH-CH —◦人。义〇 -CH2—CH—^ CH3OH -7 ~ V— —CH-CH —◦ people.义 〇 -CH2—CH— ^ CH3
CH-CH· II0 •ch2-ch—* ch3 .· . I . 八 o—o—yT^\CH-CH · II0 • ch2-ch— * ch3. ·. I. Eight o—o—yT ^ \
-135- (35) 588218 五、發明說明（1 34 【化9 8】 -CH—CH- ?H3 dc——* ch2ch3 c—ο ..(36)-135- (35) 588218 V. Description of the invention (1 34 [Chem. 9 8] -CH—CH-? H3 dc —— * ch2ch3 c—ο .. (36)
—CH-CH— —CH-CH---CH2-CH—.*CH2CH3 \Z/ O^o^OO^n^O—CH-CH— —CH-CH --- CH2-CH —. * CH2CH3 \ Z / O ^ o ^ OO ^ n ^ O
Γ°·® * —CH2—CH- I 八 0一 0- II ο "Λ- (38) -136- 588218Γ ° · ® * —CH2—CH- I eight 0 one 0- II ο " Λ- (38) -136- 588218
588218 五、發明說明（136) 合成例（4) 樹脂（FII-1)之合成 使20克α-三氟甲基丙烯酸第3-丁酯及20-克一3-(2-羥基 甲基-2, 2 -雙三氟甲基乙基）原疲嫌如溶解於4〇克THF，在 氮氣氣流下加熱至70°C。於其中加入2 . 〇克聚合起始劑 V-65(和光純藥工業製）、直接攪拌6小時。放置於室溫後 在反應液中添加300ml己烷，回收析出的樹脂。使所得的 樹脂溶解於丙酮後，再度添加於己烷中除去未反應單體及 寡聚物成分，製得本發明所使用的樹脂（FI I -1 )。 以合成例（4)相同的方法合成下述樹脂（FII-1)〜（FII-24 )。有關所得樹脂以GPC進行分子量測定’可得下述結 果。 -138- 588218 五、 發明說明（137 【化100】 CFn588218 V. Description of the invention (136) Synthesis example (4) Synthesis of resin (FII-1) 20 grams of α-trifluoromethacrylic acid 3-butyl ester and 20-gram of 3- (2-hydroxymethyl- 2,2-Bistrifluoromethylethyl) was dissolved in 40 g of THF and heated to 70 ° C under a stream of nitrogen. 2.0 g of polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by stirring for 6 hours. After standing at room temperature, 300 ml of hexane was added to the reaction solution, and the precipitated resin was recovered. The obtained resin was dissolved in acetone, and then added to hexane to remove unreacted monomers and oligomer components to obtain a resin (FI I -1) used in the present invention. The following resins (FII-1) to (FII-24) were synthesized in the same manner as in Synthesis Example (4). The obtained resin was measured for molecular weight by GPC, and the following results were obtained. -138- 588218 V. Description of the invention (137 [Chem. 100] CFn
Ά2 756 .CF3 k>CF3 F〇C OH F3cr〇CH2〇C2Hs (F1M) ，45 -cf3 C〇2C(CH3)a (FJI-5)Ά2 756 .CF3 k > CF3 F〇C OH F3cr〇CH2〇C2Hs (F1M), 45 -cf3 C〇2C (CH3) a (FJI-5)
CHa 七γ~Λ—_#CH 广?V C〇2C(CH^ (F1I4)CHa VII γ ~ Λ —_ # CH 广? V C〇2C (CH ^ (F1I4)
CN #32 ^ · •Γ3 co2ch3 C02C(CH3>3 (FII-7)CN # 32 ^ · • Γ3 co2ch3 C02C (CH3 > 3 (FII-7)
-CF3, F3cT〇H-CF3, F3cT〇H
(FIM4) ΐν. cf3(FIM4) ΐν. Cf3
OH cf3 cf3 £ · c〇ii^Hiofioe • (FII-15) * CO, co2- 139 588218OH cf3 cf3 £ · c〇ii ^ Hiofioe • (FII-15) * CO, co2- 139 588218
588218 五、發明說明（139) 表4 樹脂 重量平均分子量 Mw 分散度 分子量1000以下之 寡聚物含率 (FII-1) 15200 1.45 5 (FII-2) 24000 1.75 8 (FII-3) 18200 1.85 7 (FII-4) 18500 1.46 6 (FII-5) 9500 1.58 8 (FII-6) 19500 2.02 8 (FII-7) 8500 1.85 7 (FII-8) 28400 1.68 9 (FII-9) 28600 1.44 5 (FII-10) 12800 1.65 8 (FII-11) 16800 1.68 9 (FII-12) 28400 1.58 6 (FII-13) 19800 1.69 8 (FII-14) 8700 1.95 8 (FII-15) 15200 1.46 7 (FII-16) 19500 1.65 4 (FII-17) 16900 1.42 8 (FII-18) 15900 1.85 9 (FII-19) 15000 1.55 4 (FII-10) 12500 1.88 8 (FII-21) 25000 1.68 9 (FII-22) 16000 1.54 7 (FII-23) 14600 1.95 5 (FII-24) 17500 1.48 5 -141- 588218 ------— ^^ 五、發明說明（14〇) 合成例（5) 樹脂（k-1)之合成 在燒瓶中溶解日本曹達製vpl 5000( 1 00克）與丙二醇單 甲醚乙酸酯（PGMEA) ( 400克），進行減壓蒸餾’共沸餾去水 予 PGMEA 〇 確認含水分充分降低後，添加乙基乙烯醚（25 · 0克）與對 -甲苯磺酸（0.02克），在室溫下攪拌1小時。 在反應液中添加三乙胺（〇 · 03克）、使反應停止、添加水 (40ml)與醋酸乙酯（ 800ml)予以分液，另外水洗後，藉由 減壓餾去醋酸乙酯、水、共沸份之PGMEA，製得本發明具 有取代基之樹脂k-l(30% PGMEA 溶液）。 以合成例（5)相同的方法合成表2所示樹脂（k-2)〜（k-15) ° 於下述中表示上述樹脂（k-Ι)〜（k-15)之組成比、分子 量。 -142- 588218 五、發明說明（14〇 表5 樹脂 分子量 組成比 (單位係對由於化18) k-1 17,000 40/60 k-2 17,000 27/73 k-3 17,000 23/77 k-4 17,000 35/65 k-5 17,000 20/80 k-6 17,000 35/55/10 k-7 17,000 27/63/10 k-8 17,000 18/72/10 k-9 17,000 30/60/10 k-10 17,000 20/75/5 k-11 12,000 70/30 k-12 13,000 10/60/30 k-13 14,000 15/60/25 k-14 17,000 35/65 k-15 17,000 30/10/60 <鹼可溶性樹脂（D)> 於下述中係爲實施例所使用的鹼可溶性樹脂（D)之構造 、分子量及分子量分布。 -143- 588218588218 V. Description of the invention (139) Table 4 Resin weight average molecular weight Mw Dispersion oligomer content below 1000 molecular weight (FII-1) 15200 1.45 5 (FII-2) 24000 1.75 8 (FII-3) 18200 1.85 7 (FII-4) 18500 1.46 6 (FII-5) 9500 1.58 8 (FII-6) 19500 2.02 8 (FII-7) 8500 1.85 7 (FII-8) 28400 1.68 9 (FII-9) 28600 1.44 5 (FII -10) 12800 1.65 8 (FII-11) 16800 1.68 9 (FII-12) 28400 1.58 6 (FII-13) 19800 1.69 8 (FII-14) 8700 1.95 8 (FII-15) 15200 1.46 7 (FII-16 ) 19500 1.65 4 (FII-17) 16900 1.42 8 (FII-18) 15900 1.85 9 (FII-19) 15000 1.55 4 (FII-10) 12500 1.88 8 (FII-21) 25000 1.68 9 (FII-22) 16000 1.54 7 (FII-23) 14600 1.95 5 (FII-24) 17500 1.48 5 -141- 588218 -------- ^^ V. Description of the invention (14) Synthesis example (5) Resin (k-1) The synthesis dissolves vpl 5000 (100 g) manufactured by Soda Japan and propylene glycol monomethyl ether acetate (PGMEA) (400 g) in a flask, and performs distillation under reduced pressure to azeotropically distill water to PGMEA. ○ Confirm that the moisture content is sufficiently reduced. After that, ethyl vinyl ether (25.0 g) and p-toluenesulfonate were added (0.02 g) was stirred at room temperature for 1 hour. Triethylamine (0.03 g) was added to the reaction solution to stop the reaction. Water (40 ml) and ethyl acetate (800 ml) were added for liquid separation. After washing with water, the ethyl acetate and water were distilled off under reduced pressure. And azeotrope of PGMEA to obtain the resin kl (30% PGMEA solution) having a substituent of the present invention. The resins (k-2) to (k-15) shown in Table 2 were synthesized in the same manner as in Synthesis Example (5). The composition ratio and molecular weight of the resins (k-1) to (k-15) are shown below. . -142- 588218 V. Description of the invention (14〇 Table 5 Resin molecular weight composition ratio (unit system vs. chemical 18) k-1 17,000 40/60 k-2 17,000 27/73 k-3 17,000 23/77 k-4 17,000 35/65 k-5 17,000 20/80 k-6 17,000 35/55/10 k-7 17,000 27/63/10 k-8 17,000 18/72/10 k-9 17,000 30/60/10 k-10 17,000 20/75/5 k-11 12,000 70/30 k-12 13,000 10/60/30 k-13 14,000 15/60/25 k-14 17,000 35/65 k-15 17,000 30/10/60 < alkali soluble Resin (D) > The structure, molecular weight, and molecular weight distribution of the alkali-soluble resin (D) used in the examples are as follows. -143- 588218
588218 五、發明說明（143 ) <交聯劑（c)> 於下述中係表示實施例所使用的交聯劑之構造。 【化103】588218 V. Description of the invention (143) < Crosslinking agent (c) > In the following, the structure of the crosslinking agent used in the examples is shown. 【Chemical 103】
(pH2OMe 〇Η2〇Μθ(pH2OMe 〇Η2〇Μθ
CH2OMeCH2OMe
N/leOH2C’NN / leOH2C’N
ch2om« MqOH2C" ' CH2OMe CL-5 _XV〇ch2om «MqOH2C " 'CH2OMe CL-5 _XV〇
MeCT 0Η20Μθ .CL-6 ι2ς ph2cMeCT 0Η20Μθ .CL-6 ι2ς ph2c
MeOH2Q pH2OMe =0 MeOH2C CH2OMe CL-7 Μ eO /C H；2〇 Me Η ^ p CL-8 -145 - 588218 五、發明說明（144 ) 實施例1〜50及比較例丨〜3 <光阻劑調整 > ——一__ 使下述表6〜9所示原料調整爲溶解的固成分濃度1 2重 量％之溶液，且使其以〇·ΐμιη之鐵氟隆過濾器或聚乙烯過 濾器過濾，調製感光性組成物。以下述方法使調製的組成 物進行評估，結果如下述表10〜1 3所示。而且，比較例1 、2、3中除使用不具共軛雙鍵之毓鹽外，使用與實施例1 、16、28相问的成分。 -146- 588218 五、發明說明（145 )表6 樹脂 (10 克） 酸發生劑 (克） 鹼性化合物 (克） 界面活性劑 (0.08 克） 溶劑 (重量比） 其他 (克） 實施例1 樹脂（1) 1-2(0.8) DBN (0.02) W-l Al=100 實施例2 樹脂（2) 1-2(0.3) Ζ33Γ0.075) ΤΡΙ (0.03) W-l Al=100 實施例3 樹脂（3) 1-1(0.3) Z6(0.15) TPSA (0.02) W-2 Al=100 實施例4 樹脂（4) 1-3(0.3) z3(0.1) HEP (0.01) W-2 A3/Bl=80/20 實施例5 樹脂（5) Ml(l) DIA (0.02) W-3 A2/B1=90/10 實施例6 樹脂（6) 1-17(0.3) Ζ22(0·2) DIA (0.03) W-3 A4/B1=90/10 LCB (1) 實施例7 樹脂（7) 1-18(0.6) Ζ12(0·05) TPA (0.007) W-4 Al/Bl=50/50 實施例8 樹脂（8) 1-25(0.2) Ζ5(0.1) DBN (0.02) W-4 A1/B1=90/10 實施例9 樹脂（9) 1-33(0.3) ζ34(0.1) TP I (0.03) W-l A5/B2=90/10 實施例10 樹脂（10) 1-36(0.4) ζ30(0.2) TP I (0.02) W-l Al/Bl=95/5 實施例11 樹脂（11) 1-40(0.4) ζ35(0·4) TP I (0.08) W-2 A1/B1=90/10 實施例12 樹脂（12) 1-45(0.3) Ζ6(0·1) TP I (0.03) W-2 Al/Bl=95/5 實施例13 樹脂（13) 1-46(0.6) TP I (0.03) W-3 Al/Bl=95/5 實施例14 樹脂（14) 1-53(0.1) ζ32(0.1) DBN (0.02) W-3 Al/Bl=95/5 實施例15 樹脂（15) 1-26(0.3) ζ33(0.075) TPI (0.03) W-4 Al/Bl=80/20 -147- 588218 五、發明說明（146 )表7 樹脂 (10 克） 酸發生劑 (克） 鹼性化合物 (克） 界面活性劑 (0.08 克） 溶劑 (重量比） 其他 (克） 實施例16 樹脂Π6Η52) (15)(52) 1-1(0.2) z32(0.3) ΤΡΑ (0.01) W-4 Al=100 實施例17 樹脂（17) 1-26(0.3) z33(0.075) ΤΡΙ (0.03) W-4 Al=100 實施例18 樹脂（18) 1-60(0.5) z26(0.5) DCMA (0.01) W-4 Al=100 實施例19 樹脂（19) 1-54(0.3) ζ16(0·15) ΤΡΙ (0.02) W-4 Al/Bl=95/5 實施例20 樹脂（20) 1-26(0.2) a28(0.2) ΤΡΙ (0.03) W-4 Al/Bl=95/5 實施例21 樹脂（21) 1-2(0.6) DBN (0.02) W-l Al/Bl=95/5 實施例22 樹脂（22) 1-2(0.3) ζ33(0.075) ΤΡΙ (0.03) W-l Al/Bl=80/20 實施例23 樹脂（23) 1-1(0.1) ζ6(0.15) TPSA (0.02) W-2 A1/B1=90/10 實施例24 樹脂（24) 1-3(0.3) ζ3(0.1) ΗΕΡ (0.01) W-2 A3/B2=80/20 實施例25 樹脂（25)) 1-11(0.5) DIA (0.02) W-3 A2/B1=90/10 實施例26 樹脂（26) Μ7(0.3) ζ22(0.2) DIA (0.03) W-3 A4/B1=90/10 實施例27 樹脂（27) 1-18(0.6) ζ12(0.05) ΤΡΑ (0.007) W-4 Al/Bl=50/50 LCB (1) 實施例28 樹脂（28) 1-25(0.2) ζ5(0.1) DBN (0.02) W-4 A1/B1=90/10 實施例29 樹脂（29) 1-33(0.3) ζ34(0.1) ΤΡΙ (0.03) W-l A5/B2=90/10 實施例30 樹脂（30) 1-36(0.4) ζ30(0·2) ΤΡΙ (0.02) W-l Al/Bl=95/5MeOH2Q pH2OMe = 0 MeOH2C CH2OMe CL-7 Μ eO / CH; 2Me Η ^ p CL-8 -145-588218 V. Description of the invention (144) Examples 1 to 50 and Comparative Examples 丨 to 3 < Photoresist Adjustment > —— __ The raw materials shown in the following Tables 6 to 9 were adjusted to a solution with a dissolved solid content concentration of 12% by weight, and a Teflon filter or a polyethylene filter of 0 · ΐμιη was used. Filtration to prepare a photosensitive composition. The prepared composition was evaluated in the following manner, and the results are shown in Tables 10 to 13 below. In addition, in Comparative Examples 1, 2, and 3, in addition to using a salt without a conjugated double bond, the components related to Examples 1, 16, and 28 were used. -146- 588218 5. Description of the invention (145) Table 6 Resin (10 g) Acid generator (g) Basic compound (g) Surfactant (0.08 g) Solvent (weight ratio) Other (g) Example 1 Resin (1) 1-2 (0.8) DBN (0.02) Wl Al = 100 Example 2 resin (2) 1-2 (0.3) Z33Γ0.075) TPI (0.03) Wl Al = 100 Example 3 resin (3) 1 -1 (0.3) Z6 (0.15) TPSA (0.02) W-2 Al = 100 Example 4 Resin (4) 1-3 (0.3) z3 (0.1) HEP (0.01) W-2 A3 / Bl = 80/20 Example 5 Resin (5) Ml (l) DIA (0.02) W-3 A2 / B1 = 90/10 Example 6 Resin (6) 1-17 (0.3) Z22 (0 · 2) DIA (0.03) W- 3 A4 / B1 = 90/10 LCB (1) Example 7 Resin (7) 1-18 (0.6) Z12 (0 · 05) TPA (0.007) W-4 Al / Bl = 50/50 Example 8 Resin ( 8) 1-25 (0.2) Z5 (0.1) DBN (0.02) W-4 A1 / B1 = 90/10 Example 9 Resin (9) 1-33 (0.3) ζ34 (0.1) TP I (0.03) Wl A5 / B2 = 90/10 Example 10 Resin (10) 1-36 (0.4) ζ30 (0.2) TP I (0.02) Wl Al / Bl = 95/5 Example 11 Resin (11) 1-40 (0.4) ζ35 (0.4) TP I (0.08) W-2 A1 / B1 = 90/10 Example 12 Resin (12) 1-45 (0.3) Z6 (0 · 1) TP I (0.03) W-2 Al / Bl = 95/5 Example 13 Resin (13) 1-46 (0.6) TP I (0.03) W-3 Al / Bl = 95/5 Example 14 Resin (14) 1-53 (0.1 ) ζ32 (0.1) DBN (0.02) W-3 Al / Bl = 95/5 Example 15 Resin (15) 1-26 (0.3) ζ33 (0.075) TPI (0.03) W-4 Al / Bl = 80/20 -147- 588218 V. Description of the invention (146) Table 7 Resin (10 g) Acid generator (g) Basic compound (g) Surfactant (0.08 g) Solvent (weight ratio) Other (g) Example 16 Resin Π6Η52) (15) (52) 1-1 (0.2) z32 (0.3) TPA (0.01) W-4 Al = 100 Example 17 Resin (17) 1-26 (0.3) z33 (0.075) TPI (0.03) W -4 Al = 100 Example 18 Resin (18) 1-60 (0.5) z26 (0.5) DCMA (0.01) W-4 Al = 100 Example 19 Resin (19) 1-54 (0.3) ζ16 (0 · 15 ) TPI (0.02) W-4 Al / Bl = 95/5 Example 20 Resin (20) 1-26 (0.2) a28 (0.2) TPI (0.03) W-4 Al / Bl = 95/5 Example 21 Resin (21) 1-2 (0.6) DBN (0.02) Wl Al / Bl = 95/5 Example 22 Resin (22) 1-2 (0.3) ζ33 (0.075) TPI (0.03) Wl Al / Bl = 80/20 Example 23 Resin (23) 1-1 (0.1) ζ6 (0.15) TPSA (0.02) W-2 A1 / B1 = 90/10 Example 24 Resin (24) 1-3 (0.3) ζ3 (0.1) ZEP (0.01) W-2 A3 / B2 = 80/20 Example 25 Resin (25)) 1-11 (0.5) DIA (0.02) W-3 A2 / B1 = 90/10 Example 26 Resin (26) M7 (0.3) ζ22 (0.2) DIA (0.03) W-3 A4 / B1 = 90/10 Example 27 Resin (27) 1-18 (0.6) ζ12 (0.05) TPA (0.007) W-4 Al / Bl = 50/50 LCB (1) Example 28 Resin (28) 1-25 (0.2) ζ5 (0.1) DBN (0.02) W-4 A1 / B1 = 90 / 10 Example 29 Resin (29) 1-33 (0.3) ζ34 (0.1) TPI (0.03) Wl A5 / B2 = 90/10 Example 30 Resin (30) 1-36 (0.4) ζ30 (0 · 2) ΤΡΙ (0.02) Wl Al / Bl = 95/5
-148- 588218 五、發明說明（147 )表8 樹脂 (10 克） 酸發生劑 (克） 鹼性化合物 (克） 界面活性劑 (0.08 克） 溶劑 (重量比） 其他 (克） 實施例31 樹脂（31) 1-40(0.6) Z35(0.4) TP I (0.03) W-2 A1/B1=90/10 實施例32 樹脂（32) 1-45(0.3) z6(0.1) TP I (0.03) W-2 Α1/Β1=95/5 實施例33 樹脂（33) 1-46(1.5) TP I (0.03) W-3 Al/Bl=95/5 實施例34 樹脂（34) 1-53(0.1) ζ32(0·1) DBN (0.02) W-3 Al/Bl=95/5 實施例35 樹脂（35) 1-26(0.3) ζ33(0.075) TP I (0.03) W-4 Al/Bl=80/20 實施例36 樹脂（36) 1-1(0.2) ζ32(0.3) TPI (0.01) W-4 Al/Bl=80/20 實施例37 樹脂（37) 1-26(0.3) ζ33(0.075) TPI (0.03) W-4 Al/Bl=95/5 實施例38 樹脂（38) 1-60(0.5) ζ26(0·2) DCMA (0.01) W-4 Al/Bl=95/5 實施例39 樹脂（39) 1-54(0.3) ζ16(0.15) TPI (0.02) W-4 Al/Bl=95/5 實施例40 樹脂（40) 1-26(0.6) ζ28(0.2) TPI (0.03) W-4 Al/Bl=95/5 實施例41 樹脂（41)(52) (11)(52) 1-26(0.3). ζ33(0.075) DBN (0.02) W-l Al/Bl=95/5-148- 588218 V. Description of the invention (147) Table 8 Resin (10 g) Acid generator (g) Basic compound (g) Surfactant (0.08 g) Solvent (weight ratio) Other (g) Example 31 Resin (31) 1-40 (0.6) Z35 (0.4) TP I (0.03) W-2 A1 / B1 = 90/10 Example 32 Resin (32) 1-45 (0.3) z6 (0.1) TP I (0.03) W-2 Α1 / Β1 = 95/5 Example 33 Resin (33) 1-46 (1.5) TP I (0.03) W-3 Al / Bl = 95/5 Example 34 Resin (34) 1-53 (0.1 ) ζ32 (0 · 1) DBN (0.02) W-3 Al / Bl = 95/5 Example 35 Resin (35) 1-26 (0.3) ζ33 (0.075) TP I (0.03) W-4 Al / Bl = 80/20 Example 36 Resin (36) 1-1 (0.2) ζ32 (0.3) TPI (0.01) W-4 Al / Bl = 80/20 Example 37 Resin (37) 1-26 (0.3) ζ33 (0.075 ) TPI (0.03) W-4 Al / Bl = 95/5 Example 38 Resin (38) 1-60 (0.5) ζ26 (0 · 2) DCMA (0.01) W-4 Al / Bl = 95/5 Example 39 Resin (39) 1-54 (0.3) ζ16 (0.15) TPI (0.02) W-4 Al / Bl = 95/5 Example 40 Resin (40) 1-26 (0.6) ζ28 (0.2) TPI (0.03) W-4 Al / Bl = 95/5 Example 41 Resin (41) (52) (11) (52) 1-26 (0.3). Ζ33 (0.075) DBN (0.02) Wl Al / Bl = 95/5
-149- 588218 五、發明說明（148 )表9 樹脂 (1◦克） 酸發生劑 (克） 鹼性化合物 (克） 界面活性劑 (0.08 克） 溶劑 (重量比） 其他 (克） 實施例42 樹脂（11) 1-69(0.5) Z35(0.2) ΤΡΙ (0.03) W-2 A1/BU90/10 — 實施例43 樹脂（12) 1-70(0.7) Ζ6(0·1) ΤΡΙ (0.03) W-2 Α1/Β1=95/5 — 實施例44 樹脂（13) ΙΑ-44(0.7) Ζ36(0·5) ΤΡΙ (0.03) W-3 Α1/Β1=95/5 - 實施例45 樹脂（14) ΙΑ-14(0·6) Ζ32(0.1) DBN (0.02) W-3 Al/Bl=95/5 — 實施例46 樹脂（15) ΙΑ-32(0.4) Ζ33(0·2) ΤΡΙ (0.03) W-4 Al/Bl=80/20 一 實施例47 樹脂（16)(5g) (15)(5g) ΙΑ-55(0.3) Ζ32(0.3) ΤΡΙ (0.01) W-4 Al=100 — 實施例48 樹脂（17) ΙΑ-52(0.3) Ζ33(0.075) ΤΡΙ (0.03) W-4 Al=100 — 實施例49 樹脂（40) ΙΑ-63(0.8) Ζ28(0.2) ΤΡΙ (0.03) W-4 Al/Bl=95/5 — 實施例50 樹脂（41)(5g) (ll)(5g) ΙΑ-32(0·5) Ζ33(0.075) DBN (0.02) W-l Al/Bl=95/5 — 比較例1 樹脂（1) Ζ38(0.8) DBN (0.02) W-l Al=100 — 比較例2 樹脂（16) Z2K0.2) Ζ32(0.3) ΤΡΑ (0.01) W-4 Al=100 — 比較例3 樹脂（28) Z2K0.2) Ζ5(0·1) DBN (0.02) W-4 A1/B1=90/10 —-149- 588218 V. Description of the invention (148) Table 9 Resin (1◦g) Acid generator (g) Basic compound (g) Surfactant (0.08g) Solvent (weight ratio) Other (g) Example 42 Resin (11) 1-69 (0.5) Z35 (0.2) TPI (0.03) W-2 A1 / BU90 / 10 — Example 43 Resin (12) 1-70 (0.7) Z6 (0 · 1) TPI (0.03) W-2 Α1 / Β1 = 95/5 — Example 44 Resin (13) IA-44 (0.7) Z36 (0 · 5) TPI (0.03) W-3 Α1 / Β1 = 95/5-Example 45 Resin ( 14) IA-14 (0 · 6) Zn32 (0.1) DBN (0.02) W-3 Al / Bl = 95/5 — Example 46 Resin (15) IA-32 (0.4) Zn33 (0 · 2) ΤΡΙ ( 0.03) W-4 Al / Bl = 80/20 Example 47 Resin (16) (5g) (15) (5g) IA-55 (0.3) Zn32 (0.3) TPI (0.01) W-4 Al = 100 — Example 48 Resin (17) IA-52 (0.3) Z33 (0.075) TPI (0.03) W-4 Al = 100 — Example 49 Resin (40) IA-63 (0.8) Z28 (0.2) TPI (0.03) W -4 Al / Bl = 95/5 — Example 50 Resin (41) (5g) (ll) (5g) ΙΑ-32 (0 · 5) Zn33 (0.075) DBN (0.02) Wl Al / Bl = 95/5 — Comparative Example 1 Resin (1) Z38 (0.8) DBN (0.02) Wl Al = 100 — Comparative Example 2 Grease (16) Z2K0.2) Z32 (0.3) TPA (0.01) W-4 Al = 100 — Comparative Example 3 Resin (28) Z2K0.2) Z5 (0 · 1) DBN (0.02) W-4 A1 / B1 = 90/10 —
-150- 588218 五、發明說明（149 ) 表中之簡稱係如下所述。 DBN ; 1，5_二偶氮二環[4· 3 · 〇]壬-5-烯 —— TPI ; 2,4,5-三苯基咪唑 TPSA ;三苯基銃基乙酸酯 HEP ; N-羥基乙基哌啶 ; 2,6-二異丙基苯胺 ， DCMA ;二環己基甲胺 TPA ;三苯甲胺 TOA ;三正辛胺 HAP ;羥基安替比林 TBAH ;四丁銨氫氧化物 TMEA;參（甲氧基乙氧基乙基）胺 LCB ;石膽酸第3-丁酯 W-1;梅卡法克（譯音）F176(大日本油墨（股）製）（藥系） W-2;梅卡法克（譯音）R08(大日本油墨（股）製）（氟系及 矽系） W-3;聚矽氧烷聚合物KP- 341(信越化學工業（股）製） W-4 ;頓龍衣索魯（譯音）S- 366 (頓龍衣（譯音）化學（股） 製） 有關溶劑之簡稱如下所述。而且，表中數次使用之比爲 重量比。 A1 ;丙二醇甲醚乙酸酯 A2 ; 2-庚酮 -151- 588218 五、發明說明（15〇 ) A3;乙基乙氧基丙酸酯 Α4^τ- 丁內酯 Α5 ;環己酮 Β1 ;丙二醇單甲醚 Β2 ;乳酸乙酯 (Π感度及解像力之評估 在旋轉塗覆器中使布里瓦賽恩斯（譯音）公司製反射防止 膜ARC25以600埃均勻地塗覆於施有六甲基二矽烷處理的 矽基版上，在100°C下熱板上乾燥90秒後，在190°C下進 行加熱乾燥處理240秒。然後，使各感光性樹脂組成物以 旋轉塗覆器塗覆、在120 °C下進行乾燥90秒以形成 〇·30μιη光阻膜。對該光阻膜而言，通過光罩以ArF準分子 雷射分檔曝光器（ISI公司製、NA = 0.6)曝光，於曝光後直 接在120°C下、熱板上加熱90秒鐘。另外，以2.38%四甲 銨氫氧化物水溶液、在231下顯像60秒，以純水洗淨30 秒後、予以乾燥，製得線圖樣。 [感度]感度係以使0.16μιη之光罩圖樣再現的曝光量表 示0 [解像力]解像力係以0·16μπι之光罩圖樣再現的曝光量 之臨界解像力表示。 152- 588218 五、發明說明（151 )表10 感度（mJ /cm2) 解像力（μιη) 實施例1 12.5 0.10 實施例2 13.6 0.10 實施例3 10.2 0.10 實施例4 11.1 0.10 實施例5 10.4 0.10 實施例6 13.5 0.10 實施例7 14.3 0.10 實施例_8 11.5 0.10 實施例9 12.3 0.10 實施例1.0 10.9 0.10 實施例11 11.8 0.10 實施例12 11.1 0.10 實施例13 13.6 0.10 實施例14 14.3 0.10 實施例15 11.8 0.10 -153- 588218 五、發明說明（152 ) 表11 感度（mJ/cm2) 解像力（μη〇 實施例16 18.5 0.105 實施例17 15.1 0.105 實施例18 17.3 0.105 實施例19 19.3 0.105 實施例20 16.7 0.105 實施例21 18.3 0.105 實施例22 15.7 0.105 實施例23 16.2 0.105 實施例24 15.9 0.105 實施例25 16.5 0.105 實施例26 18.1 0.105 實施例27 19.5 0.105 實施例28 16.1 0.105 實施例29 15.4 0.105 實施例30 18.8 0.105 -154- 588218 五、發明說明（153 ) 表12 感度（nJ / cm2) 解像力（μπ〇 實施例31 16.6 0.105 實施例32 17.1 0.105 實施例33 15.3 0.105 實施例34 16.9 0.105 實施例35 17.5 0.105 實施例36 19.1 0.105 實施例37 16.8 0.105 實施例38 17.3 0.105 實施例39 15.8 0.105 實施例40 .17.4 0.105 實施例41 18.8 0.105 -155- 588218 五、發明說明（154 ) 表13 感度（nJ /cm2) 解像力（μιη) 42 13.5 0.100 施例43 10.8 0.100 _實施例44 14.2 0.100 實施例45 11.6 0. loo _實施例46 12.3 0.100 .實施例47 17.8 0.105 _實施例48 19.2 0.105 實施例49 16.5 ——0.105 實施例50 17.2 0.105 比較例1 64.2 0.13 比較例2 53.5 0.12 比較例3 59.5 0.12 由表1 0〜1 3可知，實施例1〜5 〇之正型感光性組成物 具有優異的感度、及解像力。 實施例51〜62及比較例4 <光阻劑調製> 使下述表1 4所示之成分溶解於表1 4所示之溶劑中，使 其以0 · 1 μπι鐵氛隆過濾器過濾；，調製成固成分濃度1 4重 量％之正型光阻劑組成物。 有關所調製的正型感光性組成物係以下述方法進行評估 ，結果如表1 5所示。 •156- 588218 五、發明說明（155 ) 表14 酸發生劑 (克） 樹脂（10克） (重量比） 鹼性化合 物（克） 界面活性劑 (0.08 克） 溶劑 (重量比） 阻溶性化合 物（克） 實施例51 1-2(0.4) K-2 DBN (0.02) W-l Al=100 — 實施例52 1-3(0.3) Z5(0.1) Κ-7 TP I (0.03) W-l Al=100 — 實施例53 1-6(0.3) Z4(0.1) Κ-8 TPSA (0.01) W-2 Al=100 — 實施例54 1-11(0.4) ZK0.05) Κ-9 HEP (0.02) W-2 A3/Bl=80/20 — 實施例55 1-32(0.6) Z15(0.2) Κ-13 DIA (0.05) W-3 A2/B1=90/10 — 實施例56 1-42(0.4) Z12(0.3) Κ-15 DCMA (0.03) W-4 A4/B1=90/10 — 實施例57 1-59(0.3) Z33(0.1) Κ-12 TPA (0.01) W-4 Al/Bl=50/50 — 實施例58 IA-32(0.3) Z22(0.1) Κ-1/Κ-3 =50/50 TOA (0.005) W-4 A1/B1=90/10 — 實施例59 1-35(0.3) Z13(0.1) Z29(0.2) Κ-15/Κ-2 =30/70 TBAH (0.0015) W-4 A5/B2=90/10 實施例60 IA-18(0.2) Z26(0.5) Κ-13/Κ-15 =50/50 TMEA (0.02) W-4 Al/Bl=95/5 — 實施例61 IA-57(0.39) PHS HAP (0.01) W-l A1/B1=90/10 C-l (2) 實施例62 IA-62(0.2) Κ-2 DBN (0.002) W-2 Al/Bl=95/5 C-2 (1) 比較例4 Z38(0.4) Κ-2 DBN (0.02) W-l Al=100 — PHS:聚羥基苯乙烯（日本曹達公司製 VP- 8000 ) 表14之阻溶性化合物、（C-l)、（C-2)之構造係如下述 所示。 -157- 588218 五、發明說明（156 ) 【化104】-150- 588218 V. Description of Invention (149) The abbreviations in the table are as follows. DBN; 1,5-diazobicyclo [4 · 3 · 〇] non-5-ene——TPI; 2,4,5-triphenylimidazole TPSA; triphenylfluorenyl acetate HEP; N -Hydroxyethylpiperidine; 2,6-Diisopropylaniline, DCMA; Dicyclohexylmethylamine TPA; Tribenzylamine TOA; Tri-n-octylamine HAP; Hydroxyantipyrine TBAH; Tetrabutylammonium hydroxide Material TMEA; ginseng (methoxyethoxyethyl) amine LCB; 3-butyl lithocholic acid W-1; mekafak (transliteration) F176 (made by Dainippon Ink Co., Ltd.) (pharmaceutical) W-2; Mekafak (transliteration) R08 (made by Dainippon Ink Co., Ltd.) (fluorine-based and silicon-based) W-3; polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) W-4; Dunlong Yisuolu (Transliteration) S-366 (Don Longyi (Transliteration) Chemical Co., Ltd.) The abbreviations of the solvents are as follows. In addition, the ratio used several times in the table is the weight ratio. A1; propylene glycol methyl ether acetate A2; 2-heptanone-151-588218 5. Description of the invention (15) A3; ethyl ethoxypropionate A4 ^ τ-butyrolactone A5; cyclohexanone B1; Propylene Glycol Monomethyl Ether B2; Ethyl Lactate (II Sensitivity and Resolution Evaluation In a spin coater, the anti-reflection film ARC25 manufactured by Brivasion Co., Ltd. was uniformly applied at 600 angstroms to Rokko On a silicon-based plate treated with disilane, it was dried on a hot plate at 100 ° C for 90 seconds, and then heat-dried at 190 ° C for 240 seconds. Then, each photosensitive resin composition was applied with a spin coater Cover and dry at 120 ° C for 90 seconds to form a 0.30μm photoresist film. For this photoresist film, an ArF excimer laser stepped exposure device (manufactured by ISI, NA = 0.6) was passed through a photomask. After exposure, heat directly on a hot plate at 120 ° C for 90 seconds after exposure. In addition, develop with 2.38% tetramethylammonium hydroxide aqueous solution at 231 for 60 seconds, and wash with pure water for 30 seconds. It is dried to obtain a line pattern. [Sensitivity] The sensitivity is represented by the exposure amount which reproduces a mask pattern of 0.16 μm. 0 [resolution] The resolution is based on The critical resolution of the exposure amount reproduced by the mask pattern of 0 · 16μπι is expressed. 152- 588218 V. Description of the invention (151) Table 10 Sensitivity (mJ / cm2) Resolution (μιη) Example 1 12.5 0.10 Example 2 13.6 0.10 Example 3 10.2 0.10 Example 4 11.1 0.10 Example 5 10.4 0.10 Example 6 13.5 0.10 Example 7 14.3 0.10 Example_8 11.5 0.10 Example 9 12.3 0.10 Example 1.0 10.9 0.10 Example 11 11.8 0.10 Example 12 11.1 0.10 Example Example 13 13.6 0.10 Example 14 14.3 0.10 Example 15 11.8 0.10 -153- 588218 V. Description of the invention (152) Table 11 Sensitivity (mJ / cm2) Resolution (μη〇 Example 16 18.5 0.105 Example 17 15.1 0.105 Example 18 17.3 0.105 Example 19 19.3 0.105 Example 20 16.7 0.105 Example 21 18.3 0.105 Example 22 15.7 0.105 Example 23 16.2 0.105 Example 24 15.9 0.105 Example 25 16.5 0.105 Example 26 18.1 0.105 Example 27 19.5 0.105 Example 28 16.1 0.105 Example 29 15.4 0.105 Example 30 18.8 0.105 -154- 588218 V. Description of the invention (153) Table 12 Sensitivity (nJ / cm2) Resolution (μπ〇 Example 31 16.6 0.105 Example 32 17.1 0.105 Example 33 15.3 0.105 Example 34 16.9 0.105 Example 35 17.5 0.105 Example 36 19.1 0.105 Example 37 16.8 0.105 Example 38 17.3 0.105 Example 39 15.8 0.105 Example 40 .17.4 0.105 Example 41 18.8 0.105 -155- 588218 V. Description of the invention (154) Table 13 Sensitivity (nJ / cm2) Resolution (μιη) 42 13.5 0.100 Example 43 10.8 0.100 _ Example 44 14.2 0.100 Example 45 11.6 0. loo _ Example 46 12.3 0.100. Example 47 17.8 0.105 _ Example 48 19.2 0.105 Example 49 16.5-0.105 Example 50 17.2 0.105 Comparative Example 1 64.2 0.13 Comparative Example 2 53.5 0.12 Comparative Example 3 59.5 0.12 As can be seen from Tables 10 to 13, the positive-type photosensitive compositions of Examples 1 to 50 have excellent sensitivity and resolution. Examples 51 to 62 and Comparative Example 4 < Preparation of photoresist > The components shown in Table 14 below were dissolved in the solvent shown in Table 14 so that they were filtered with a 0. 1 μm iron atmosphere filter. Filtration; a positive photoresist composition having a solid content concentration of 14% by weight was prepared. The prepared positive-type photosensitive composition was evaluated in the following manner. The results are shown in Table 15 below. • 156-588218 5. Description of the invention (155) Table 14 Acid generator (g) Resin (10 g) (weight ratio) Basic compound (g) Surfactant (0.08 g) Solvent (weight ratio) Insoluble compound ( G) Example 51 1-2 (0.4) K-2 DBN (0.02) Wl Al = 100 — Example 52 1-3 (0.3) Z5 (0.1) K-7 TP I (0.03) Wl Al = 100 — Implementation Example 53 1-6 (0.3) Z4 (0.1) K-8 TPSA (0.01) W-2 Al = 100 — Example 54 1-11 (0.4) ZK0.05) K-9 HEP (0.02) W-2 A3 / Bl = 80/20 — Example 55 1-32 (0.6) Z15 (0.2) K-13 DIA (0.05) W-3 A2 / B1 = 90/10 — Example 56 1-42 (0.4) Z12 (0.3 ) K-15 DCMA (0.03) W-4 A4 / B1 = 90/10 — Example 57 1-59 (0.3) Z33 (0.1) K-12 TPA (0.01) W-4 Al / Bl = 50/50 — Example 58 IA-32 (0.3) Z22 (0.1) K-1 / K-3 = 50/50 TOA (0.005) W-4 A1 / B1 = 90/10 — Example 59 1-35 (0.3) Z13 ( 0.1) Z29 (0.2) KK-15 / Κ-2 = 30/70 TBAH (0.0015) W-4 A5 / B2 = 90/10 Example 60 IA-18 (0.2) Z26 (0.5) KK-13 / κ- 15 = 50/50 TMEA (0.02) W-4 Al / Bl = 95/5 — Example 61 IA-57 (0.39) PHS HAP (0.01) Wl A1 / B1 = 90/10 Cl (2) Example 62 IA -62 (0.2) K-2 DBN (0.002) W-2 Al / Bl = 95/5 C-2 (1) Comparative Example 4 Z38 (0.4) K-2 DBN (0.02) Wl Al = 100 — PHS: Polyhydroxystyrene (Japan VP-8000 manufactured by Caoda Co., Ltd.) The structure of the anti-solubilizing compound (Cl) and (C-2) in Table 14 is shown below. -157- 588218 V. Description of the Invention (156) [化 104]
RORO
Ο II R：—CH2-C-0-- (G - 2), <光阻劑評估> 、 在旋轉塗覆器中使經調製的正型感光性組成物塗覆於施 有六甲基二矽烷處理的矽基板上，在120°C下熱板上乾燥 90秒後，形成0.5μηι光阻膜。 -158- 588218〇 II R: —CH2-C-0-- (G-2), < Evaluation of photoresist >, Applying the prepared positive-type photosensitive composition to Rokko in a spin coater A 0.5 μm photoresist film was formed on the disilane-treated silicon substrate and dried on a hot plate at 120 ° C for 90 seconds. -158- 588218
五、發明說明（157 ) 對該光阻膜而言，通過光罩以KrF準分子雷射分檔曝光 器（NA = 〇 · 63)、線與間隙用光罩予以圖樣囑-光，於曝光後 直接在110°C下、熱板上加熱90秒鐘。另外，以2. 38%四 甲銨氫氧化物水溶液、在23°C下顯像60秒，以純水洗淨 30秒後、予以乾燥，形成線圖樣，與實施例1相同地評估 感度及解像力。 -159- 588218 五、發明說明（158) 表15 感度（nJ/cm2) 解像力（_) 實施例51 26 0.14 實施例52 22 0.14 實施例53 28 0.13 實施例54 27 0.14 實施例55 23 0.14 實施例56 27 0.13 實施例57 29 0.13 實施例58 21 0.14 實施例59 25 0.13 實施例60 29 0.13 實施例61 28 0.13 實施例62 24 0.14 比較例4 78 0.18 藉由表1 5可知，實施例5 1〜62之正型感光性組成物具 有優異的感度及解像力。 實施例6 3〜7 4及比較例5 <感光性組成物調製> 混合下述表1 6所示之組成物，且藉由〇 ·丨μπι鐵氟隆過 濾器過濾、以調製固成分濃度12重量％負型感光性組成物。 有經調製的負型感光性組成物與實施例51相同的方法 進行評估，結果如表1 7所示。 -160- 588218 五、發明說明（159)表1 6 酸發生劑 (克） 樹脂（10克） (重量比） 鹼性化合 物（克） 界面活性劑 ----— (0.08 克） 溶劑 (重量比） 阻溶性化合 物(克） 實施例63 1-2(0.4) P-1 DIA (0.05) W-l Al=100 CL-1 (2) 實施例64 1-3(0.3) Z5(0.1) P-2 ΤΡΙ (0.03) W-l Al=100 CL-2 (3) 實施例65 1-6(0.3) Ζ4(0·1) P-3 TOA (0.005) W-2 Al=100 CI-3 (2.5) 實施例66 1-11(0.4) Zl(0.05) P-4 HEP (0.02) W-2 A3/Bl=80/20 CL-4 (3) 實施例67 1-32(0.6) Ζ15(0.2) P-5 DBN (0.03) W-3 A2/B1=90/10 CL-5 (1.5) 實施例68 1-42(0.4) Ζ12(0.3) P-6 DCMA (0.03) W-4 A4/B1=90/10 CL-6 (3) 實施例69 1-9(0.3) Ζ33(0·1) P-1 TPA (0.01) W-4 Al/Bl二50/50 CL-7 (2.5) 實施例70 ΙΑ·32(0·3) Ζ22(0·1) P-l/P-6 (80/20) TPSA (0.1) W-4 A1/B1=90/10 CL-8 (2.5) 實施例71 1-35(0.3) Ζ13(0·1) P-3 TBAH (0.015) W-4 A5/B2=90/10 CL-1(2) CL-5(2) 實施例72 ΙΑ-18(0·2) Ζ26(0.5) P-4 TMEA (0.02) W-4 Al/Bl=95/5 CL-2(1) CL-7(2) 實施例73 ΙΑ-57(0.39) P-5 HAP (0.01) W-l A1/B1=90/10 CL-1 (2.5) 實施例74 ΙΑ-62(0.2) P-6 DBN (0.002) W-2 Al/Bl=95/5 CL-2 (2.5) 比較例5 Ζ38(0.4) P-1 DIA (0.05) W-l Al=100 CL-1 (2) -161 - 588218 五、發明說明（16〇 ) 表17 感度（mJ /cm2) 解像力（μπ〇 實施例63 28 0.13 實施例64 23 0.13 實施例65 26 0.14 實施例66 29 0.13 實施例67 27 0.14 實施例68 27 0.13 實施例69 21 0.14 實施例70 22 0.14 實施例71 29 0.13 實施例72 27 .0.14 實施例73 21 0.14 實施例74 26 0.13 比較例5 72 0.18 藉由表17可知，實施例63〜74之負型感光性組成物具 有優異的感度及解像力。 實施例75〜86及比較例6 <光阻劑調製> 與實施例5 1〜62及比較例4相同地使表1 4所示之成分 溶解於溶劑，且使其藉由〇 · 1 μιτι鐵氟隆過濾器過濾、以言周 製固成分濃度1 2重量％正型感光性組成物。 18 有經調製的正型感光性組成物進行評估，結果如袠 -162- 588218 五、發明說明（161 ) 所示。 <光阻劑評估> -------------^ 在旋轉塗覆器中使經調製的正型感光性組成物塗覆於施 有六甲基二矽烷處理的矽基版上，在！2〇°C下熱板上乾燥 60秒後，形成0.3μηι光阻膜。 對該光阻膜而言，以理光（譯音）公司製電子線噴射微影 術裝置（加速電壓lOOkeV)照射，照射後直接在110°C下、 熱板上加熱90秒鐘。 另外，以2.38%四甲銨氫氧化物水溶液、在23°C下顯像 60秒，以純水洗淨30秒後、予以乾燥’形成線圖樣’除 感度、解像力作爲〇 . 1 〇μηι之1 /1線與間隙外’與實施例1 相同地評估感度、解像力及外型。 -163- 588218 五、發明說明（162 ) 感度（rrJ / cm2) 實施例75 2.8 0.10 ------匕―。___ 實施例76 3.5 0.11 _ 實施例77 4.8 0.11 實施例78 4.3 0.11 實施例79 2.7 0.10 實施例80 4.3 0.10 實施例81 3.8 0.11 實施例82 3.3 0.10 實施例83 4.2 0.11 實施例84 2.8 0.10 實施例85 4.2 0.11 實施例86 3.7 0.11 比較例6 9.8 0.14 藉由表1 8可知，實施例75〜86之正型感光性組成物具 有優異的感度及解像力。 實施例87〜98及比較例7 <感光性組成物調製> 與實施例63〜74及比較例5相同地，使上述表1 6所示 之成分溶解於溶劑中，且藉由0 . 1 μιη鐵氟隆過濾器過濾、 以調製固成分濃度1 2重量％負型感光性組成物。 有經調製的負型感光性組成物與實施例7 5相同的方法 進行評估，結果如表1 9所示。-164- 588218 五、發明說明（163 ) 表19 感度（mj / cm2~)~ ------- 角華像力（μπ〇 實施例87 4.7 0.10 實施例88 3.3 —-—- 0.10 實施例89 2.8 ---- 0.11 實施例90 4·7 0.10 實施例91 2.7 0.10 實施例92 3.3 0.11 實施例93 4.3 0.10 實施例94 2.3 0.10 實施例95 3.8 0.10 實施例96 4.5 0.11 實施例97 2.6 0.10 實施例98 3.4 0.11 比較例7 9.8 0.14 藉由表19可知，實施例87〜98之負型感光性組成物具 有優異的感度及解像力。 實施例99〜122及比較例8 <感光性組成物調製> 使下述表20所示之成份溶解於表20所示之溶劑中’且 使其藉由〇 . 1 μιη鐵氟隆過濾器過濾、以調製固成分濃度1 〇 重量％正型感光性組成物。 有經調製的正型感光性組成物以下述方法進行評估’結 果如表21所示。 -165- 588218 五、發明說明（164 ) 表20 酸發生劑 (克） 樹脂（10克） (重量比） 鹼性化合物 (克） 界面活性劑 (〇·〇8 克） 溶劑 (重量比） 實施例99 1-2(0.4) (FII-1) DIA (0.02) W-l Al=100 實施例100 1-3(0.3) Z5(0.1) (FII-2) ΤΡΙ (0.01) W-l Al=100 實施例101 1-6(0.3) Ζ4(0·1) (FII-3) TOA (0.005) W-2 Al=100 實施例102 1-11(0.4) Zl(0.05) (FII-4) HEP (0.02) W-2 A3/Bl=80/20 實施例103 1-32(0.6) Ζ15(0·2) (FII-5) DBN (0.02) W-3 A2/B1=90/10 實施例104 1-42(0.4) Ζ12(0.3) (FII-6) DCMA (0.03) W-4 A4/B1=90/10 實施例105 1-59(0.3) Ζ33(0.1) (FII-7) TPA (0.01) W-4 Al/Bl=50/50 實施例106 ΙΑ-32(0.3) Ζ22(0.1) (FII-8) TPSA (0.1) W-4 A1/B1=90/10 實施例107 1-35(0.3) Ζ13(0·1) Ζ29(0·2) (FII-9) TBAH (0.015) W-4 A5/B2=90/10 實施例108 ΙΑ-18(0·2) Ζ26(0.5) (FII-10) TMEA (0.02) W-4 Al/Bl=95/5 實施例109 ΙΑ-57(0.39) (FII-11) HAP (0.01) W-l A1/B1=90/10 實施例110 ΙΑ-62(0.2) (FII-12) DBN (0.015) W-2 Al/Bl=95/5 實施例111 1-33(0.3) Ζ14(0.1) (FII-13) DIA (0.02) W-l Al/Bl=95/5 -166- 588218 五、發明說明（165) 實施例112 1-54(0.3) Z2K0.3) Ζ33(0.075) (FII-14) ΤΡΙ (0.01) W-1 Al/Bl=95/5 實施例113 1-56(0.2) (FII-15) ΤΟΑ W>2 Al/Bl=80/20 Ζ7(0·05) (0.005) Ζ2(0·1) 實施例114 1-64(0.1) (FII-16) ΗΕΡ W-2 Al=100 Ζ33(0·2) (0.02) 實施例115 1-63(0.3) (FII-17) DBN W-3 Al=100 Ζ33(0.1) (0.02) 實施例116 ΙΑ-2(0.2) (FII-18) DCMA W-4 Al=100 Ζ22(0.2) (0.03) 實施例117 LA-55(0.1) (FII-19) ΤΡΑ W-4 Al/Bl=95/5 Ζ12(0·1) (0.01) 實施例118 1-63(0.2) (FII-20) TPSA W-4 Al/Bl=95/5 Ζ17(0.2) (0.1) 實施例119 1-65(0.2) (FII-21) ΤΒΑΙ-1 W-4 Al/Bl=95/5 Ζ32(0.2) (0.015) 實施例120 1-41(0.5) (FII-22) ΤΜΕΑ W-4 Al/Bl=80/20 Ζ8(0.1) (0.02) 實施例121 1-35(0.4) (FII-23) ΗΑΡ W-ll A1/B1=90/10 Ζ33(0.15) (0.01) 實施例122 1-38(0.3) (FII-24) DBN W-2 A3/B2=80/20 Ζ5(0.05) (0.015) 比較例8 Z3K0.4) (FII-1) DIA W-1 Al=100 (0.02) <光阻劑評估> 在旋轉塗覆器中使經調製的正型感光性組成物塗覆於施 有六甲基二矽烷處理的矽基版上，在120t下熱板上乾燥 90秒後，形成Ο.ίμιτι光阻膜。 -167- 588218 五、發明說明（166 ) 對該光阻膜而言，使用157nm雷射曝光·溶解舉動解析 裝置VUVES- 4500 (微影日本製）曝光，於曝光後直接在 120°C下、熱板上加熱90秒鐘。另外，以2.38%四甲銨氫 氧化物水溶液、在23 °C下顯像60秒，以純水洗淨30秒後 、予以乾燥，以使大圖樣解像的曝光量作爲感度。 -168- 588218 五、發明說明（167 ) 表21 — _ 感度 mJ/cm2 實施例99 2 實施例100 1 實施例101 3 實施例102 3 實施例103 2 實施例104 4 實施例105 1 實施例106 3 實施例107 2 實施例108 2 實施例109 3 實施例110 3 實施例111 4 實施例112 2 實施例113 1 實施例114 4 實施例115 3 實施例116 4 實施例117 2 實施例118 1 實施例119 2 實施例120 2 實施例121 3 實施例122 4 比較例8 6 -169- 588218 五、發明說明（168 ) 藉由表21可知，實施例99〜122之正型感光性組成物 具有優異的感度。 而且，本發明感光性組成物不僅可以上述實施例所記載 的曝光光源、且可發揮與EUV( 13nm)相同的效果。 【發明效果】 藉由本發明可提供一種感度及解像力優異的感光性組成 物。 -170-V. Description of the invention (157) For this photoresist film, a KrF excimer laser stepped exposure device (NA = 0.63) is used to pattern the photoresist film through a photomask, and the line and gap are patterned with a photomask. After that, heat directly on a hot plate at 110 ° C for 90 seconds. In addition, a 2.38% tetramethylammonium hydroxide aqueous solution was developed at 23 ° C. for 60 seconds, washed with pure water for 30 seconds, and dried to form a line pattern. The sensitivity and the same were evaluated as in Example 1. Resolution. -159- 588218 5. Description of the invention (158) Table 15 Sensitivity (nJ / cm2) Resolution (_) Example 51 26 0.14 Example 52 22 0.14 Example 53 28 0.13 Example 54 27 0.14 Example 55 23 0.14 Example 56 27 0.13 Example 57 29 0.13 Example 58 21 0.14 Example 59 25 0.13 Example 60 29 0.13 Example 61 28 0.13 Example 62 24 0.14 Comparative Example 4 78 0.18 According to Table 1 5 it can be seen that Example 5 1 ~ The positive photosensitive composition of 62 has excellent sensitivity and resolution. Example 6 3 to 7 4 and Comparative Example 5 < Preparation of photosensitive composition > The compositions shown in the following Table 16 were mixed, and filtered through a 0.1 μm Teflon filter to prepare a solid component. Negative photosensitive composition at a concentration of 12% by weight. The prepared negative-type photosensitive composition was evaluated in the same manner as in Example 51. The results are shown in Table 17 below. -160- 588218 V. Description of the invention (159) Table 1 6 Acid generator (g) Resin (10 g) (weight ratio) Basic compound (g) Surfactant ----— (0.08 g) Solvent (weight Ratio) Insoluble compound (g) Example 63 1-2 (0.4) P-1 DIA (0.05) Wl Al = 100 CL-1 (2) Example 64 1-3 (0.3) Z5 (0.1) P-2 TPI (0.03) Wl Al = 100 CL-2 (3) Example 65 1-6 (0.3) Zn4 (0 · 1) P-3 TOA (0.005) W-2 Al = 100 CI-3 (2.5) Example 66 1-11 (0.4) Zl (0.05) P-4 HEP (0.02) W-2 A3 / Bl = 80/20 CL-4 (3) Example 67 1-32 (0.6) Z15 (0.2) P-5 DBN (0.03) W-3 A2 / B1 = 90/10 CL-5 (1.5) Example 68 1-42 (0.4) Z12 (0.3) P-6 DCMA (0.03) W-4 A4 / B1 = 90/10 CL-6 (3) Example 69 1-9 (0.3) Z33 (0 · 1) P-1 TPA (0.01) W-4 Al / Bl 50/50 CL-7 (2.5) Example 70 IA · 32 (0 · 3) Z22 (0 · 1) Pl / P-6 (80/20) TPSA (0.1) W-4 A1 / B1 = 90/10 CL-8 (2.5) Example 71 1-35 (0.3) Z13 (0 · 1) P-3 TBAH (0.015) W-4 A5 / B2 = 90/10 CL-1 (2) CL-5 (2) Example 72 ΙΑ-18 (0 · 2) Z26 (0.5) P-4 TMEA (0.02) W-4 Al / Bl = 95/5 CL-2 (1) CL-7 (2) Example 73 IA-57 (0.39) P-5 HAP (0. 01) Wl A1 / B1 = 90/10 CL-1 (2.5) Example 74 IA-62 (0.2) P-6 DBN (0.002) W-2 Al / Bl = 95/5 CL-2 (2.5) Comparative example 5 Z38 (0.4) P-1 DIA (0.05) Wl Al = 100 CL-1 (2) -161-588218 V. Description of the invention (16) Table 17 Sensitivity (mJ / cm2) Resolution (μπ〇 Example 63 28 0.13 Example 64 23 0.13 Example 65 26 0.14 Example 66 29 0.13 Example 67 27 0.14 Example 68 27 0.13 Example 69 21 0.14 Example 70 22 0.14 Example 71 29 0.13 Example 72 27 .0.14 Example 73 21 0.14 Example 74 26 0.13 Comparative Example 5 72 0.18 As can be seen from Table 17, the negative photosensitive compositions of Examples 63 to 74 have excellent sensitivity and resolution. Examples 75 to 86 and Comparative Example 6 < Photoresist Preparation > In the same manner as in Examples 5 to 62 and Comparative Example 4, the components shown in Table 14 were dissolved in a solvent, and passed through 0.1 A μm teflon filter was used to filter the positive photosensitive composition with a solid content concentration of 12% by weight. 18 A modulated positive-type photosensitive composition was evaluated, and the results are shown in 袠 -162- 588218 V. Invention description (161). < Evaluation of photoresist > ------------- ^ The prepared positive-type photosensitive composition was applied to a hexamethyldisilanes-treated film in a spin coater. On the silicon version, here! After drying on a hot plate at 20 ° C. for 60 seconds, a 0.3 μm photoresist film was formed. This photoresist film was irradiated with an electron beam lithography apparatus (acceleration voltage 100keV) manufactured by Ricoh, and was heated at 110 ° C directly on a hot plate for 90 seconds after the irradiation. In addition, a 2.38% tetramethylammonium hydroxide aqueous solution was developed at 23 ° C. for 60 seconds, and washed with pure water for 30 seconds, and then dried to form a line pattern. In addition, the sensitivity and resolution were 0.1 to 10 μm. 1/1 Line and Out of Gap 'The sensitivity, resolution, and appearance were evaluated in the same manner as in Example 1. -163- 588218 V. Description of the invention (162) Sensitivity (rrJ / cm2) Example 75 2.8 0.10 ------ Dagger. ___ Example 76 3.5 0.11 _ Example 77 4.8 0.11 Example 78 4.3 0.11 Example 79 2.7 0.10 Example 80 4.3 0.10 Example 81 3.8 0.11 Example 82 3.3 0.10 Example 83 4.2 0.11 Example 84 2.8 0.10 Example 85 4.2 0.11 Example 86 3.7 0.11 Comparative Example 6 9.8 0.14 As can be seen from Table 18, the positive-type photosensitive compositions of Examples 75 to 86 have excellent sensitivity and resolution. Examples 87 to 98 and Comparative Example 7 < Preparation of photosensitive composition > In the same manner as in Examples 63 to 74 and Comparative Example 5, the components shown in Table 16 above were dissolved in a solvent and passed through 0. A 1 μm Teflon filter was used to filter the negative photosensitive composition with a solid content concentration of 12% by weight. The prepared negative-type photosensitive composition was evaluated in the same manner as in Example 75. Table 19 shows the results. -164- 588218 V. Description of the invention (163) Table 19 Sensitivity (mj / cm2 ~) ~ ------ Angle image power (μπ〇 Example 87 4.7 0.10 Example 88 3.3 —-—- 0.10 Implementation Example 89 2.8 ---- 0.11 Example 90 4 · 7 0.10 Example 91 2.7 0.10 Example 92 3.3 0.11 Example 93 4.3 0.10 Example 94 2.3 0.10 Example 95 3.8 0.10 Example 96 4.5 0.11 Example 97 2.6 0.10 Example 98 3.4 0.11 Comparative Example 7 9.8 0.14 As can be seen from Table 19, the negative photosensitive composition of Examples 87 to 98 has excellent sensitivity and resolution. Examples 99 to 122 and Comparative Example 8 < Photosensitive composition Preparation> The components shown in Table 20 below were dissolved in the solvent shown in Table 20 'and filtered through a 0.1 μm Teflon filter to adjust the solid content concentration to 10% by weight of a positive-type photosensitive agent. The composition was evaluated with the positive photosensitive composition prepared in the following manner. The results are shown in Table 21. -165- 588218 V. Description of the invention (164) Table 20 Acid generator (g) Resin (10 g ) (Weight ratio) basic compound (g) surfactant (〇 · 〇8 G) Solvent (weight ratio) Example 99 1-2 (0.4) (FII-1) DIA (0.02) Wl Al = 100 Example 100 1-3 (0.3) Z5 (0.1) (FII-2) TPI (0.01 ) Wl Al = 100 Example 101 1-6 (0.3) Z4 (0 · 1) (FII-3) TOA (0.005) W-2 Al = 100 Example 102 1-11 (0.4) Zl (0.05) (FII -4) HEP (0.02) W-2 A3 / Bl = 80/20 Example 103 1-32 (0.6) Z15 (0 · 2) (FII-5) DBN (0.02) W-3 A2 / B1 = 90 / 10 Example 104 1-42 (0.4) Z12 (0.3) (FII-6) DCMA (0.03) W-4 A4 / B1 = 90/10 Example 105 1-59 (0.3) Z33 (0.1) (FII-7 ) TPA (0.01) W-4 Al / Bl = 50/50 Example 106 IA-32 (0.3) Z22 (0.1) (FII-8) TPSA (0.1) W-4 A1 / B1 = 90/10 Example 107 1-35 (0.3) Zn13 (0 · 1) AZ29 (0 · 2) (FII-9) TBAH (0.015) W-4 A5 / B2 = 90/10 Example 108 IA-18 (0 · 2) Z26 ( 0.5) (FII-10) TMEA (0.02) W-4 Al / Bl = 95/5 Example 109 IA-57 (0.39) (FII-11) HAP (0.01) Wl A1 / B1 = 90/10 Example 110 ΙΑ-62 (0.2) (FII-12) DBN (0.015) W-2 Al / Bl = 95/5 Example 111 1-33 (0.3) Z14 (0.1) (FII-13) DIA (0.02) Wl Al / Bl = 95/5 -166- 588218 V. Description of the invention (165) Example 112 1-54 (0.3) Z2K0.3) Z33 (0.075) (FII-14 ) ΤΡΙ (0.01) W-1 Al / Bl = 95/5 Example 113 1-56 (0.2) (FII-15) ΤΟΑ W > 2 Al / Bl = 80/20 Z7 (0 · 05) (0.005) Z2 (0.1) Example 114 1-64 (0.1) (FII-16) HPE W-2 Al = 100 Z33 (0.2) (0.02) Example 115 1-63 (0.3) (FII-17) DBN W-3 Al = 100 Z33 (0.1) (0.02) Example 116 IA-2 (0.2) (FII-18) DCMA W-4 Al = 100 Z22 (0.2) (0.03) Example 117 LA-55 (0.1) (FII-19) TPA W-4 Al / Bl = 95/5 Z12 (0 · 1) (0.01) Example 118 1-63 (0.2) (FII-20) TPSA W-4 Al / Bl = 95/5 Z17 (0.2) (0.1) Example 119 1-65 (0.2) (FII-21) TBAI-1 W-4 Al / Bl = 95/5 Z32 (0.2) (0.015) Example 120 1-41 (0.5) (FII-22) TMEA W-4 Al / Bl = 80/20 Z8 (0.1) (0.02) Example 121 1-35 (0.4) (FII-23) ΗΑΡ W-ll A1 / B1 = 90/10 Z33 ( 0.15) (0.01) Example 122 1-38 (0.3) (FII-24) DBN W-2 A3 / B2 = 80/20 Z5 (0.05) (0.015) Comparative Example 8 Z3K0.4) (FII-1) DIA W-1 Al = 100 (0.02) < Evaluation of photoresist > In a spin coater, a prepared positive-type photosensitive composition was coated on a hexamethyldisilanes-treated On the base plate, the hot plate and dried at 120t for 90 seconds to form a resist film Ο.ίμιτι. -167- 588218 V. Description of the Invention (166) For this photoresist film, exposure was performed using a 157nm laser exposure and dissolution behavior analysis device VUVES- 4500 (Made by Nippon Film Japan), and after exposure, directly at 120 ° C, Heat on the hot plate for 90 seconds. In addition, a 2.38% tetramethylammonium hydroxide aqueous solution was developed at 23 ° C for 60 seconds, washed with pure water for 30 seconds, and then dried, so that the exposure amount for large pattern resolution was used as the sensitivity. -168- 588218 V. Description of the invention (167) Table 21 — _ Sensitivity mJ / cm2 Example 99 2 Example 100 1 Example 101 3 Example 102 3 Example 103 2 Example 104 4 Example 105 1 Example 106 3 Example 107 2 Example 108 2 Example 109 3 Example 110 3 Example 111 4 Example 112 2 Example 113 1 Example 114 4 Example 115 3 Example 116 4 Example 117 2 Example 118 1 Example Example 119 2 Example 120 2 Example 121 3 Example 122 4 Comparative Example 8 6 -169- 588218 5. Explanation of the invention (168) As can be seen from Table 21, the positive photosensitive composition of Examples 99 to 122 has excellent Sensitivity. In addition, the photosensitive composition of the present invention can exhibit the same effects as EUV (13 nm) not only as the exposure light source described in the above embodiment. [Effects of the Invention] The present invention can provide a photosensitive composition excellent in sensitivity and resolution. -170-
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| JP2001250451 | 2001-08-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2964990B2 (en) * | 1997-05-07 | 1999-10-18 | 日本電気株式会社 | Photosensitive resin composition containing photoacid generator having cross-linked cyclic alkyl group, and pattern forming method using the same |
| JPH11228534A (en) * | 1998-02-12 | 1999-08-24 | Sanwa Chemical:Kk | New sulfonium salt compound having oxycarbonylmethyl group |
| JP3961139B2 (en) * | 1998-12-24 | 2007-08-22 | 富士フイルム株式会社 | Positive photosensitive composition |
| SG76651A1 (en) * | 1999-03-31 | 2000-11-21 | Sumitomo Chemical Co | Chemical amplification type positive resist |
| JP2001056555A (en) * | 1999-08-20 | 2001-02-27 | Tokyo Ohka Kogyo Co Ltd | Negative type resist composition and photosensitive material using same |
| JP3711230B2 (en) * | 1999-08-25 | 2005-11-02 | 東京応化工業株式会社 | Multi-layer type photosensitive material |
| JP3989149B2 (en) * | 1999-12-16 | 2007-10-10 | 富士フイルム株式会社 | Chemical amplification negative resist composition for electron beam or X-ray |
| JP4161497B2 (en) * | 1999-12-24 | 2008-10-08 | Ｊｓｒ株式会社 | Negative radiation sensitive resin composition |
| JP2001215709A (en) * | 2000-02-07 | 2001-08-10 | Fuji Photo Film Co Ltd | Positive resist composition |
| JP2001222110A (en) * | 2000-02-10 | 2001-08-17 | Fuji Photo Film Co Ltd | Positive photoresist composition |
| JP4378872B2 (en) * | 2000-11-15 | 2009-12-09 | 日本電気株式会社 | Photoacid generator, chemically amplified resist composition, and pattern formation method using the same |
| JP2002156750A (en) * | 2000-11-20 | 2002-05-31 | Sumitomo Chem Co Ltd | Chemical amplification type positive resist composition |
| KR100796585B1 (en) * | 2001-02-08 | 2008-01-21 | 후지필름 가부시키가이샤 | Radiation sensitive resist composition |
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| KR100897292B1 (en) | 2009-05-14 |
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