TWI429665B - Photosensitive resin and photosensitive composition - Google Patents

Description

感光性樹脂及感光性組成物Photosensitive resin and photosensitive composition

本發明乃有關在結構中具有藉深紫外光、電子束、X光或極紫外光(EUV)等活性輻射線之照射容易產酸之結構及酸解離基，而做為化學放大型之光阻材料為有用之感光性樹脂，以及使用該樹脂之感光性組成物。The invention relates to a structure and an acid dissociation group which are easy to generate acid by irradiation of active radiation such as deep ultraviolet light, electron beam, X-ray or extreme ultraviolet light (EUV) in the structure, and is used as a chemically amplified photoresist. The material is a useful photosensitive resin, and a photosensitive composition using the resin.

例如以DRAM等所代表之高積體電路元件等半導體裝置中，係期待更進一步之高密度化、高積體化或高速化。隨之，各種電子裝置之製造領域中，對於半微米級之微細加工技術之建立、例如形成微細圖案用之光微影(photolithography)技術研發之要求係越加嚴格。光微影技術中，圖謀圖案之微細化之方法之一為形成光阻之圖案之際，縮短所使用活性輻射線(曝光用光)之波長之方法。此處，由於縮小投影曝光裝置之解像度(R)係由雷利氏(Rayleigh)式R＝k．λ/NA(式中，λ示曝光之波長，NA示透鏡孔徑，k示製程因數(process factor))所示，所以可藉由將形成光阻之圖案之際所使用之活性輻射線(曝光用光)之波長λ加以短波長化而改善解像度。For example, in a semiconductor device such as a high-integral circuit device represented by a DRAM or the like, further increase in density, high integration, and high speed are expected. Accordingly, in the field of manufacturing various electronic devices, the requirements for the development of microfabrication technology of a half micron order, for example, the development of photolithography for forming fine patterns, have become stricter. In the photolithography technique, one of the methods for miniaturizing the pattern is to shorten the wavelength of the active radiation (exposure light) used when forming the pattern of the photoresist. Here, the resolution (R) of the reduced projection exposure apparatus is determined by Rayleigh type R=k. λ/NA (where λ indicates the wavelength of the exposure, NA indicates the lens aperture, and k indicates the process factor), so the active radiation used when the pattern of the photoresist is formed can be exposed. The wavelength λ of the light is used to shorten the wavelength to improve the resolution.

適合於短波長之光阻係提議有化學放大型者(參照專利文獻1等)。化學放大型光阻之特徵為，藉由曝光之光照射，而從屬於其所含成份之光產酸劑產生質子酸，該質子酸係藉由曝光後之加熱處理而與具有酸解離性基(因酸而解離．分解之基)之聚合物等發生酸觸媒反應。現已研發之光阻之大半屬於化學放大型。該化學放大型光阻用之光產酸劑已周知有各種鋶鹽(sulfonium)。A photo-resistance system suitable for a short wavelength is proposed to have a chemical amplification type (see Patent Document 1, etc.). The chemically amplified photoresist is characterized in that, by irradiation with exposure light, a protonic acid is generated from a photoacid generator belonging to a component thereof, and the proton acid is subjected to heat treatment after exposure and has an acid dissociable group. An acid catalyst reaction occurs in a polymer such as a polymer which is dissociated by an acid and decomposed. Most of the light barriers that have been developed are chemically amplified. A variety of sulfonium salts are known for the photoacid generators for chemically amplified photoresists.

然而，以往之鋶鹽系光產酸劑係有跟具有屬於光阻之主成份之酸解離基的聚合物之間互溶性不良等缺點。自然地，因該問題，在含有該光產酸劑之光阻上以活性輻射線曝光形成圖案時，會發生所得圖案形狀非為所期待形狀等不良影響之問題。However, conventional bismuth salt photoacid generators have disadvantages such as poor mutual solubility with a polymer having an acid dissociation group which is a main component of a photoresist. Naturally, due to this problem, when the pattern is formed by active radiation exposure on the photoresist containing the photoacid generator, the problem that the obtained pattern shape does not adversely affect the desired shape or the like occurs.

專利文獻1：美國專利第4491628號Patent Document 1: U.S. Patent No. 4,491,628

本發明有鑑於上述情形，以提供一種感光性樹脂及感光性組成物為本發明之課題，該感光性樹脂不會伴隨著產酸劑和具有屬於光阻之主成份之酸解離基的聚合物之間互溶性不良的問題，而可得良好形狀之圖案。The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a photosensitive resin and a photosensitive composition which are not accompanied by an acid generator and a polymer having an acid dissociation group which is a main component of a photoresist. There is a problem of poor mutual solubility, and a pattern of good shape can be obtained.

用於解決上述課題之本發明之第一種方法乃提供一種感光性樹脂，具有下式(1)所示之重複單位、下式(2)所示之重複單位和下式(3)所示之重複單位之至少一方、以及下式(4)所示之重複單位，必要時復可具有下式(5)所示之重複單位。The first method of the present invention for solving the above problems provides a photosensitive resin having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and the following formula (3). At least one of the repeating units and the repeating unit represented by the following formula (4) may have a repeating unit represented by the following formula (5) if necessary.

(式(1)中，R₁ ，表示碳數2至9之直鏈狀或分枝狀之2價之烴基，R₂ 至R₅ 各自獨立地表示氫原子或碳數1至3之直鏈狀或分枝狀之烴基，R₆ 及R₇ 各自獨立地表示有機基，R₆ 及R₇ 可一起形成2價之有機基，X^－ 表示陰離子)(In the formula (1), R ₁ represents a linear or branched divalent hydrocarbon group having 2 to 9 carbon atoms, and R ₂ to R ₅ each independently represent a hydrogen atom or a linear chain having 1 to 3 carbon atoms. a branched or branched hydrocarbon group, R ₆ and R ₇ each independently represent an organic group, R ₆ and R ₇ may together form a divalent organic group, and X ^- represents an anion)

(式(2)中，R₈ 表示碳數2至9之直鏈狀或分枝狀之烴基)(In the formula (2), R ₈ represents a linear or branched hydrocarbon group having 2 to 9 carbon atoms)

本發明之第二種方法如第一種方法所記載之感光性樹脂，其中，X^－ 所示之陰離子係下式(6)所示之陰離子。The second method of the present invention is the photosensitive resin according to the first aspect, wherein the anion represented by X ^- is an anion represented by the following formula (6).

C_k H_m F_n SO₃ ^－ (6)C _k H _m F _n SO ₃ ^- (6)

(式(6)中，k、m及n各自獨立地表示0以上之整數；當m為0時，k為1至8之整數，n為2k＋1，式(6)為全氟烷磺酸鹽離子；當n為0時，k為1至15之整數，m為1以上之整數，式(6)為烷磺酸鹽離子、苯磺酸鹽離子或烷苯磺酸鹽離子；m及n各自獨立地為1以上之整數時，k為1至10之整數，式(6)為經氟取代之苯磺酸鹽離子、經氟取代之烷基苯磺酸鹽離子或經氟取代之烷磺酸鹽離子)(In the formula (6), k, m and n each independently represent an integer of 0 or more; when m is 0, k is an integer of 1 to 8, n is 2k+1, and the formula (6) is a perfluoroalkanesulfonate Ion; when n is 0, k is an integer from 1 to 15, m is an integer of 1 or more, and formula (6) is an alkanesulfonate ion, a besylate ion or an alkylbenzenesulfonate ion; m and n When each is independently an integer of 1 or more, k is an integer of 1 to 10, and the formula (6) is a fluorine-substituted benzenesulfonate ion, a fluorine-substituted alkylbenzenesulfonate ion or a fluorine-substituted alkane. Sulfonate ion)

本發明之第三種方法如第一種方法所記載之感光性樹脂，其中，X^－ 所示之陰離子係下式(7)所示之雙(全氟烷基磺醯)亞胺離子。The third method of the present invention is the photosensitive resin according to the first aspect, wherein the anion represented by X ^- is a bis(perfluoroalkylsulfonyl)imide ion represented by the following formula (7).

(C_p F_2p＋1 SO₂ )₂ N^－ (7)(C _p F _2p+1 SO ₂ ) ₂ N ^- (7)

(式(7)中，p為1至8之整數。)(In the formula (7), p is an integer from 1 to 8.)

本發明之第四種方法如第一種方法所記載之感光性樹脂，其中，X^－ 所示之陰離子係下式(8)所示之陰離子。The fourth method of the present invention is the photosensitive resin according to the first aspect, wherein the anion represented by X ^- is an anion represented by the following formula (8).

本發明之第五種方法如第一種至第四種方法中任一項所記載之感光性樹脂，其中，重量平均分子量在2,000至100,000範圍，上式(1)之重複單位數a、上式(2)之重複單位數b、上式(3)之重複單位數c、上式(4)之重複單位數d、及上式(5)之重複單位數e係滿足a/(a＋b＋c＋d＋e)＝0.001至0.3、(b＋c)/(a＋b＋c＋d＋e)＝0.1至0.5、(d＋e)/(a＋b＋c＋d＋e)＝0.5至0.8、及e/(d＋e)＝0至0.2。The photosensitive resin according to any one of the first to fourth aspect, wherein the weight average molecular weight is in the range of 2,000 to 100,000, and the repeating unit number a of the above formula (1) The number of repetition units b of the formula (2), the number of repetition units c of the above formula (3), the number of repetition units d of the above formula (4), and the number of repetition units e of the above formula (5) satisfy a/(a+b+c+d+e) = 0.001 to 0.3, (b + c) / (a + b + c + d + e) = 0.1 to 0.5, (d + e) / (a + b + c + d + e) = 0.5 to 0.8, and e / (d + e) = 0 to 0.2.

本發明之第六種方法如第一種至第五種方法中任一項所記載之感光性樹脂，其中，主鏈之末端基係氫原子或甲基。The photosensitive resin according to any one of the first to fifth aspect, wherein the terminal of the main chain is a hydrogen atom or a methyl group.

本發明之第七種方法乃提供一種感光性組成物，其為於有機溶劑中溶有如第一種至第六種方法中任一項所記載之感光性樹脂之溶液。The seventh method of the present invention provides a photosensitive composition in which a solution of the photosensitive resin according to any one of the first to sixth methods is dissolved in an organic solvent.

依據本發明可提供具有光產酸劑機能之結構及具有酸解離基之感光性樹脂。該感光性樹脂藉由溶解於溶劑而以不含產酸劑之方式單獨成為化學放大型之感光性組成物，所以不會伴生產酸劑與具有酸解離基之聚合物間之互溶性不良之問題，達到可得良好形狀之圖案之效果。According to the present invention, a structure having a photoacid generator function and a photosensitive resin having an acid dissociation group can be provided. Since the photosensitive resin is a chemically amplified photosensitive composition by being dissolved in a solvent and not containing an acid generator, it is not accompanied by poor mutual solubility between the acid generator and the polymer having an acid dissociation group. The problem is to achieve the effect of a pattern with a good shape.

詳細說明本發明如下。DETAILED DESCRIPTION The present invention is as follows.

本發明之感光性樹脂具有上式(1)所示之重複單位、上式(2)所示之重複單位和上式(3)所示之重複單位之至少一方、以及上式(4)所示之重複單位，必要時尚具有上式(5)所示之重複單位，並具有源自鋶鹽之光產酸劑功能之架構及酸解離基之聚合物。由於本發明之感光性樹脂具有做為光產酸劑功能之架構及酸解離基，故可藉溶解在溶劑，不必含有產酸劑而單獨成為化學放大型之感光性組成物。因此，使用於感光性組成物時，沒有產酸劑及具有酸解離基之聚合物間之互溶性不良問題之伴生，可得形狀良好之圖案。The photosensitive resin of the present invention has at least one of a repeating unit represented by the above formula (1), a repeating unit represented by the above formula (2), and a repeating unit represented by the above formula (3), and the above formula (4). The repeating unit shown is a polymer having a repeating unit represented by the above formula (5) and having a structure derived from the function of a photoacid generator of cerium salt and an acid dissociating group. Since the photosensitive resin of the present invention has a structure and an acid dissociation group as a function of a photoacid generator, it can be a chemically amplified photosensitive composition by dissolving in a solvent without necessarily containing an acid generator. Therefore, when it is used for a photosensitive composition, there is no accompanying problem of miscibility between an acid generator and a polymer having an acid dissociation group, and a pattern having a good shape can be obtained.

具體言之，式(1)所示之重複單位具有曝光於活性輻射線而產酸之做為光產酸劑功能之架構、以及由該產酸劑所產生之酸而可解離之酸解離基。Specifically, the repeating unit represented by the formula (1) has a structure which is exposed to active radiation and which generates acid as a function of a photoacid generator, and an acid dissociable group which is dissociable by an acid generated by the acid generator. .

又，上式(2)所示之重複單位及上式(3)所示之重複單位乃具有以藉由酸就能解離之基來改質上式(4)所示之重複單位中之酚系羥基之架構。上式(4)所示之重複單位及上式(5)所示之重複單位皆為對於鹼顯像液之溶解性有相關者，藉由調整其量就可調整其溶解性。Further, the repeating unit represented by the above formula (2) and the repeating unit represented by the above formula (3) have a phenol which is modified in the repeating unit represented by the above formula (4) by a group which can be dissociated by an acid. The structure of the hydroxyl group. The repeating unit represented by the above formula (4) and the repeating unit represented by the above formula (5) are all related to the solubility of the alkali developing solution, and the solubility can be adjusted by adjusting the amount thereof.

本發明之感光性樹脂本身不溶或極難溶於鹼顯像液中，但是經由活性輻射線曝光，從式(1)所示之重複單位產生酸，由該酸之作用，上式(1)所示之重複單位、上式(2)所示之重複單位及上式(3)所示之重複單位之酸解離基係解離，而增加其對於鹼顯像液之溶解性。The photosensitive resin of the present invention is insoluble or extremely difficult to dissolve in an alkali developing solution, but is exposed to active radiation, and an acid is generated from a repeating unit represented by the formula (1), and the above formula (1) is exerted by the action of the acid. The acid dissociation group of the repeating unit shown, the repeating unit represented by the above formula (2), and the repeating unit represented by the above formula (3) dissociates, and the solubility thereof to the alkali developing solution is increased.

上式(1)中，R₁ 為碳數2至9之二價烴基，可任意為直鏈或分枝狀。R₂ 至R₅ 各自獨立地表示氫原子或碳數1至3之直鏈狀或分枝狀烴基。R₆ 及R₇ 各自獨立地表示有機基。該有機基之例如直鏈、分枝或脂環狀構造之烷基。又，該有機基之例如碳環狀芳基或雜環狀芳基。較佳之有機基為碳環狀芳基，尤以苯基、甲苯基及第三丁基苯基為最佳。上述碳環狀芳基或雜環狀芳基可具有碳數1至30之取代基。該碳數1至30之取代基之例如以碳數1至30之烴基或烷氧基為較佳。該做為取代基之碳數1至30之烴基係例如甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基、己基、庚基、辛基、第三戊基、癸基、十二碳烷基及十六碳烷基等烷基，或環丙基、環戊基、環己基、環辛基、環十二碳烷基、環十六碳烷基及金剛烷基等脂環狀烷基，或苯基及萘基等芳基。又，做為取代基之碳數1至30之烷氧基係例如甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、戊氧基、第三戊氧基、正己氧基、正辛氧基、正癸氧基及1－金剛烷氧基等。In the above formula (1), R ₁ is a divalent hydrocarbon group having 2 to 9 carbon atoms, and may be optionally linear or branched. R ₂ to R ₅ each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 3 carbon atoms. R ₆ and R ₇ each independently represent an organic group. The organic group is, for example, an alkyl group of a linear, branched or alicyclic structure. Further, the organic group is, for example, a carbon cyclic aryl group or a heterocyclic aryl group. Preferred organic groups are carbon cyclic aryl groups, especially phenyl, tolyl and tert-butylphenyl groups. The above carbon cyclic aryl or heterocyclic aryl group may have a substituent having 1 to 30 carbon atoms. The substituent having 1 to 30 carbon atoms is preferably, for example, a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group. The hydrocarbon group having 1 to 30 carbon atoms as a substituent is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, pentyl, hexyl, heptyl, An alkyl group such as octyl, third amyl, decyl, dodecyl or hexadecyl, or cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, or ring An aliphatic cyclic alkyl group such as a hexadecyl group or an adamantyl group; or an aryl group such as a phenyl group or a naphthyl group. Further, the alkoxy group having 1 to 30 carbon atoms as a substituent is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group or a second butoxy group. And a third butoxy group, a pentyloxy group, a third pentyloxy group, a n-hexyloxy group, a n-octyloxy group, a n-decyloxy group, a 1-adamantyloxy group, and the like.

又，R₆ 及R₇ 可互相結合而形成環，此時，可成為包括上述碳架構之2價有機基：－R₆ －R₇ －。該2價之有機基係例如由具有飽和碳架構之R₆ 及R₇ 聯結而成碳數3至9之脂環狀烷基。該脂環狀烷基中之較佳例可列舉如伸丁基及伸戊基等多亞甲基等。一般，2價之有機基－R₆ －R₇ －和硫一起形成之環，以4至8員環為較佳，尤以5至6員環為更佳。Further, R ₆ and R ₇ may be bonded to each other to form a ring, and in this case, may be a divalent organic group including the above carbon skeleton: -R ₆ -R ₇ -. The divalent organic group is, for example, an aliphatic cyclic alkyl group having 3 to 9 carbon atoms bonded by R ₆ and R ₇ having a saturated carbon structure. Preferable examples of the alicyclic alkyl group include polymethylene groups such as a butyl group and a pentyl group. In general, a ring formed by a divalent organic group -R ₆ -R ₇ - and sulfur is preferably a 4- to 8-membered ring, more preferably a 5- to 6-membered ring.

式(1)中，X^－ 所示之陰離子並無特別限制，可採用以往光產酸劑所用之陰離子。該陰離子之例可列舉如式(6)所示之陰離子、上式(7)所示之陰離子及上式(8)所示之陰離子(環1,3－全氟丙烷二磺醯亞胺離子)。In the formula (1), the anion represented by X ^- is not particularly limited, and an anion used in a conventional photoacid generator can be used. Examples of the anion include an anion represented by the formula (6), an anion represented by the above formula (7), and an anion represented by the above formula (8) (cyclo1,3-perfluoropropane disulfonimide ion ).

式(6)中，k、m及n各自獨立地表示0以上之整數。當m為0時，k為1至8之整數，n為2k＋1，式(6)為全氟烷基磺酸鹽離子。較佳之全氟烷基磺酸鹽之例可列舉如CF₃ SO₃ ^－ (三氟甲磺酸鹽離子)、C₄ F₉ SO₃ ^－ (九氟丁烷磺酸鹽離子)及C₈ F₁₇ SO₃ ^－ (十七氟辛烷磺酸鹽離子)等。In the formula (6), k, m and n each independently represent an integer of 0 or more. When m is 0, k is an integer from 1 to 8, n is 2k+1, and formula (6) is a perfluoroalkyl sulfonate ion. Preferred examples of the perfluoroalkyl sulfonate include, for example, CF ₃ SO ₃ ^- (trifluoromethanesulfonate ion), C ₄ F ₉ SO ₃ ^- (nonafluorobutanesulfonate ion), and C ₈ F. ₁₇ SO ₃ ^- (heptadecanofluorooctane sulfonate ion) and the like.

又，式(6)中，n為0時，k為1至15之整數，m為1以上之整數，式(6)為烷磺酸鹽離子、苯磺酸鹽離子或烷苯磺酸鹽離子。當烷磺酸鹽離子時，m為2k＋1。較佳之烷磺酸鹽離子之例可列舉如CH₃ SO₃ ^－ (甲磺酸鹽離子)、C₂ H₅ SO₃ ^－ (乙磺酸鹽離子)、C₉ H₁₉ S0₃ ^－ (1－壬磺酸鹽離子)等、或交聯環狀烷磺酸鹽離子，例如10－樟腦磺酸鹽離子等。較佳之烷苯磺酸鹽離子之例可列舉如4－甲苯磺酸鹽離子或2,4,6－三異丙苯磺酸鹽離子。Further, in the formula (6), when n is 0, k is an integer of 1 to 15, m is an integer of 1 or more, and the formula (6) is an alkanesulfonate ion, a besylate ion or an alkylbenzenesulfonate. ion. When the alkane sulfonate ion, m is 2k+1. Examples of preferred alkane sulfonate ions include, for example, CH ₃ SO ₃ ^- (methanesulfonate ion), C ₂ H ₅ SO ₃ ^- (ethanesulfonate ion), C ₉ H ₁₉ S0 ₃ ^- (1- An oxime sulfonate ion or the like, or a cross-linked cyclic alkane sulfonate ion, for example, a 10-camphorsulfonate ion or the like. Preferred examples of the alkylbenzenesulfonate ion include, for example, 4-toluenesulfonate ion or 2,4,6-triisopropylbenzenesulfonate ion.

又，式(6)中，m及n各自獨立地為1以上之整數時，k為1至10之整數，式(6)為經氟取代之苯磺酸鹽離子、經氟取代之烷苯磺酸鹽離子或經氟取代之烷磺酸鹽離子。較佳之經氟取代之苯磺酸鹽離子之例係如2－氟苯磺酸鹽離子、4－氟苯磺酸鹽離子、2,4－二氟苯磺酸鹽離子及五氟苯磺酸鹽離子等。又，較佳之經氟取代之烷苯磺酸鹽離子之例係如2－三氟甲基苯磺酸鹽離子、4－三氟甲基苯磺酸鹽離子、2,4－雙(三氟甲基)苯磺酸鹽離子及3,5－雙(三氟甲基)苯磺酸鹽離子等。又，較佳之經氟取代之烷磺酸鹽離子之例係如1,1,2,3,3,3－六氟丙磺酸鹽離子。Further, in the formula (6), when m and n are each independently an integer of 1 or more, k is an integer of 1 to 10, and the formula (6) is a fluorine-substituted benzenesulfonate ion, a fluorine-substituted alkenebenzene. a sulfonate ion or a fluorine-substituted alkanesulfonate ion. Preferred examples of the fluorine-substituted besylate ion are, for example, 2-fluorobenzenesulfonate ion, 4-fluorobenzenesulfonate ion, 2,4-difluorobenzenesulfonate ion, and pentafluorobenzenesulfonic acid. Salt ions, etc. Further, preferred examples of the fluorine-substituted alkanesulfonate ion are, for example, 2-trifluoromethylbenzenesulfonate ion, 4-trifluoromethylbenzenesulfonate ion, 2,4-bis(trifluoro Methyl)benzenesulfonate ion and 3,5-bis(trifluoromethyl)benzenesulfonate ion. Further, preferred examples of the fluorine-substituted alkanesulfonate ion are, for example, 1,1,2,3,3,3-hexafluoropropanesulfonate ion.

式(7)所示之陰離子為雙(全氟烷磺醯)亞胺離子，式中，p表示1至8之整數。較佳之雙(全氟烷磺醯)亞胺離子之例係如雙(三氟甲磺醯)亞胺離子及雙(五氟乙磺醯)亞胺離子等。The anion represented by the formula (7) is a bis(perfluoroalkanesulfonyl)imide ion, wherein p represents an integer of 1 to 8. Preferred examples of the bis(perfluoroalkanesulfonyl)imide ion are bis(trifluoromethanesulfonate)imide ion and bis(pentafluoroethanesulfonate)imide ion.

本發明之感光性樹脂，其主鏈之末端為氫原子或甲基為佳。該末端基可依據在合成做為基材之聚合物時之聚合引發劑及終止劑而任意決定。In the photosensitive resin of the present invention, the terminal of the main chain is preferably a hydrogen atom or a methyl group. The terminal group can be arbitrarily determined depending on the polymerization initiator and the terminator in the case of synthesizing the polymer as a substrate.

又，本發明之感光性樹脂，其重量平均分子量以2,000至100,000範圍為佳，其中，以2,000至50,000範圍為較佳。當重量平均分子量小時，曝光感度降低且硬化膜強度亦降低，當重量平均分子量大時，對於基板之黏接性降低而圖案形成不易。又，上述重量平均分子量乃指本發明之感光性樹脂藉由凝膠滲透層析法(GPC)所得之聚苯乙烯換算重量平均分子量(Mw)。Mw和藉GPC所得之聚苯乙烯換算數平均分子量(Mn)之比率(Mw/Mn)，一般以1至3為宜，其中，以1至2.5為較佳。又，式(1)之重複單位數為a，式(2)之重複單位數為b，式(3)之重複單位數為c，式(4)之重複單位數為d，及式(5)之重複單位數為e，以能滿足a/(a＋b＋c＋d＋e)＝0.001至0.3、(b＋c)/(a＋b＋c＋d＋e)＝0.1至0.5、(d＋e)/(a＋b＋c＋d＋e)＝0.5至0.8、及e/(d＋e)＝0至0.2較佳。滿足a/(a＋b＋c＋d＋e)＝0.001至0.3之條件時，式(1)所具有之藉曝光產酸之構造係成為觸媒量，能達成良好的產酸劑之功能。又，當(b＋c)/(a＋b＋c＋d＋e)＝0.1至0.5時，可達成對於鹼顯像液之溶解抑制功能之效果。當滿足(d＋e)/(a＋b＋c＋d＋e)＝0.5至0.8及e/(d＋e)＝0至0.2時，可達成對於基板等塗布對象之黏接性良好及對於鹼顯像液之溶解性良好之效果。Further, the photosensitive resin of the present invention preferably has a weight average molecular weight of from 2,000 to 100,000, more preferably from 2,000 to 50,000. When the weight average molecular weight is small, the exposure sensitivity is lowered and the cured film strength is also lowered. When the weight average molecular weight is large, the adhesion to the substrate is lowered and the pattern formation is not easy. Further, the weight average molecular weight refers to a polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) of the photosensitive resin of the present invention. The ratio (Mw/Mn) of the polystyrene-equivalent number average molecular weight (Mn) obtained by Mw and GPC is generally preferably from 1 to 3, and preferably from 1 to 2.5. Further, the number of repeating units of the formula (1) is a, the number of repeating units of the formula (2) is b, the number of repeating units of the formula (3) is c, the number of repeating units of the formula (4) is d, and the formula (5) The number of repetition units is e, so that a/(a+b+c+d+e)=0.001 to 0.3, (b+c)/(a+b+c+d+e)=0.1 to 0.5, (d+e)/(a+b+c+d+e)=0.5 to 0.8, and e/(d+e) can be satisfied. ) = 0 to 0.2 is preferred. When the condition of a/(a+b+c+d+e)=0.001 to 0.3 is satisfied, the structure of the acid-producing system which is possessed by the formula (1) becomes a catalyst amount, and a good acid generator function can be achieved. Further, when (b + c) / (a + b + c + d + e) = 0.1 to 0.5, the effect of the dissolution inhibiting function on the alkali developing solution can be achieved. When (d+e)/(a+b+c+d+e)=0.5 to 0.8 and e/(d+e)=0 to 0.2 are satisfied, the adhesion to the substrate to be coated or the like is good and the solubility in the alkali developing solution is good.

又，本發明之感光性樹脂，其架構中除式(1)至式(5)所示各重複單元之外，在不影響本發明之效果範圍內，尚可具有其他架構。Further, in the structure of the photosensitive resin of the present invention, in addition to the respective repeating units represented by the formulae (1) to (5), other structures may be provided without affecting the effects of the present invention.

本發明之感光性樹脂之製造方法雖無特別限制，例如在聚羥基苯乙烯或聚(羥基苯乙烯－苯乙烯)之共聚物加成以下式(13)至(15)而製成。The method for producing the photosensitive resin of the present invention is not particularly limited, and for example, a copolymer of polyhydroxystyrene or poly(hydroxystyrene-styrene) is added to the following formulas (13) to (15).

例如可藉下述方法導入式(1)所示重複單位。首先，如下列反應式所示，在甲磺酸(CH₃ SO₃ H)中，以五氧化二磷(P₂ O₅ )為觸媒，使式(9)所示化合物和二烷基亞碸(dialkyl sulfoxide)反應而得式(10)所示化合物(甲磺酸鹽)。又，該二烷基亞碸可由以過氧化氫氧化二烷基硫醚而容易製得。For example, the repeating unit shown in the formula (1) can be introduced by the following method. First, as shown in the following reaction formula, a compound represented by the formula (9) and a dialkyl group are obtained by using phosphorus pentoxide (P ₂ O ₅ ) as a catalyst in methanesulfonic acid (CH ₃ SO ₃ H). Dialkyl sulfoxide is reacted to obtain a compound of the formula (10) (methanesulfonate). Further, the dialkylanthracene can be easily obtained by dialkyl sulfide of hydrogen peroxide.

屬於觸媒之五氧化二磷之用量，相對於式(9)所示化合物1莫耳，以0.1至3.0莫耳為佳，其中，以0.5至1.5莫耳為較佳。又，甲磺酸之用量，相對於式(9)所示化合物1莫耳，以1至10莫耳為佳，其中，以4至6莫耳為較佳。反應溫度一般在0至50℃範圍，其中，以10至30℃為較佳，反應時間一般在1至15小時範圍，其中，以3至8小時為較佳。反應終了後，藉添加水而終止其反應。The amount of phosphorus pentoxide which is a catalyst is preferably 0.1 to 3.0 moles per mole of the compound of the formula (9), and preferably 0.5 to 1.5 moles. Further, the amount of methanesulfonic acid is preferably 1 to 10 moles per mole of the compound of the formula (9), and preferably 4 to 6 moles. The reaction temperature is usually in the range of 0 to 50 ° C, and preferably 10 to 30 ° C, and the reaction time is usually in the range of 1 to 15 hours, with 3 to 8 hours being preferred. After the reaction is completed, the reaction is terminated by the addition of water.

其次，如下列反應式所示，將式(10)所示化合物之甲磺酸離子(CH₃ SO₃ ^－ )以X^－ 進行鹽取代。又，下列反應式中，M^＋ 表示一價之金屬離子。具體言之，於式(10)所示化合物之水溶液中，相對於式(10)所示化合物1莫耳，添加1至2莫耳之X^－ ，例如含式(6)、式(7)或式(8)之各種酸(H^＋ X^－ )或鹽(M^＋ X^－ )為宜，其中，以1.05至1.2莫耳為較佳。反應溶劑可使用例如二氯甲烷、氯仿等氯系溶劑為佳。又，反應溫度一般在10至50℃範圍，其中，以20至30℃為較佳。反應終了後，分離水層，並用水洗淨有機層。洗淨後使用適當再結晶溶劑令其結晶化，而得式(11)所示化合物。又，式(10)所示化合物合成後加入碘化鉀於反應溶液，將式(10)所示化合物藉碘離子進行鹽取代而以固體狀分離，精製後，再用X^－ 進行鹽取代亦行，又，就精製物使用磺酸酯將碘離子進行鹽取代亦可行。Next, the methanesulfonic acid ion (CH ₃ SO ₃ ^- ) of the compound of the formula (10) is substituted with a salt of X ^- as shown in the following reaction formula. Further, in the following reaction formula, M ⁺ represents a monovalent metal ion. Specifically, in the aqueous solution of the compound of the formula (10), with respect to the compound 1 of the formula (10), 1 to 2 mol of X ^{- is added} , for example, containing the formula (6), the formula (7) Or the various acids (H ⁺ X ^- ) or salts (M ⁺ X ^- ) of the formula (8) are preferred, with 1.05 to 1.2 moles being preferred. As the reaction solvent, for example, a chlorine-based solvent such as dichloromethane or chloroform can be used. Further, the reaction temperature is usually in the range of 10 to 50 ° C, and preferably 20 to 30 ° C is preferred. After the end of the reaction, the aqueous layer was separated and the organic layer was washed with water. After washing, it is crystallized by using a suitable recrystallization solvent to obtain a compound of the formula (11). Further, the formula (10) shown in the synthesis of compounds of potassium iodide was added to the reaction solution, the formula (10) compound substituted by an iodide ion and salt to a solid separated, purified, then X ^- line is also substituted by salt, Further, it is also possible to carry out salt substitution of the iodide ion using the sulfonate in the purified product.

之後，如同下列反應式所示，使用式(11)所示之化合物和式(12)所示之化合物進行脫鹵化氫反應而得式(13)所示之鋶鹽。又，下列反應式中，Y表示氯及溴等鹵素原子。具體言之，例如在極性溶劑中，在碳酸鉀(K₂ CO₃ )等鹼性觸媒之存在下，使式(11)所示化合物與式(12)所示化合物反應而達成。反應溫度一般在60至90℃範圍。反應終了後，加入水，用己烷等非極性溶劑洗淨水層後，以氯系溶劑萃取。然後，分離有機層，用水洗淨後，蒸餾去除氯系溶劑，而得式(13)所示鋶鹽。又，式(9)至式(12)所示化合物亦可採用市售物。Thereafter, as shown in the following reaction formula, a compound represented by the formula (11) and a compound represented by the formula (12) are subjected to dehydrohalogenation reaction to obtain an onium salt represented by the formula (13). Further, in the following reaction formula, Y represents a halogen atom such as chlorine or bromine. Specifically, for example, a compound represented by the formula (11) is reacted with a compound represented by the formula (12) in the presence of a basic catalyst such as potassium carbonate (K ₂ CO ₃ ) in a polar solvent. The reaction temperature is usually in the range of 60 to 90 °C. After the completion of the reaction, water is added, and the aqueous layer is washed with a non-polar solvent such as hexane, and then extracted with a chlorine solvent. Then, the organic layer is separated, washed with water, and then the chlorine-based solvent is distilled off to obtain a phosphonium salt represented by the formula (13). Further, a compound represented by the formula (9) to the formula (12) can also be used as a commercially available product.

使該式(13)所示化合物、和聚羥基苯乙烯或聚(羥基苯乙烯－苯乙烯)之共聚物在1,3－二氧雜戊環(dioxolane)等有機溶劑中、在酸性觸媒下反應時，可導入上式(1)所示重複單位。The copolymer of the formula (13) and the polyhydroxystyrene or poly(hydroxystyrene-styrene) are copolymerized in an organic solvent such as 1,3-dioxolane in an acidic catalyst. In the case of the next reaction, a repeating unit represented by the above formula (1) can be introduced.

式(2)所示重複單位可由使羥基苯乙烯或聚(羥基苯乙烯－苯乙烯)之共聚物和下式(14)所示乙烯醚化合物在1,3－二氧雜戊環等有機溶劑中、酸性觸媒之存在下進行加成反應而予以導入。The repeating unit represented by the formula (2) may be a copolymer of hydroxystyrene or poly(hydroxystyrene-styrene) and a vinyl ether compound represented by the following formula (14) in an organic solvent such as 1,3-dioxolane. The addition reaction is carried out in the presence of a medium or acidic catalyst.

(R₈ 表示碳數2至9之直鏈狀或分枝狀之烴基。)(R ₈ represents a linear or branched hydrocarbon group having 2 to 9 carbon atoms.)

式(3)所示重複單位可由下式(15)所示二碳酸二－第三丁酯及聚羥基苯乙烯或聚(羥基苯乙烯－苯乙烯)之共聚物在1,3－二氧雜戊環等有機溶劑中、鹼性觸媒之共存下反應而製成。The repeating unit represented by the formula (3) may be a copolymer of di-tert-butyl dicarbonate and polyhydroxystyrene or poly(hydroxystyrene-styrene) represented by the following formula (15) in the 1,3-dioxan group. It is prepared by reacting in an organic solvent such as a pentacyclic ring in the presence of a basic catalyst.

又，藉由具有式(1)至(5)所示重複單位之聚合物適當反應而製造本發明之感光性樹脂亦行。另外，藉由將式(1)至(5)所示重複單位之單體在有機溶劑中、使用聚合引發劑進行共聚合反應，也能製成本發明之感光性樹脂。該有機溶劑之例如四氫呋喃(THF)、1,3－二氧雜戊環及1,3－二烷(dioxane)等醚類，或丙二醇單甲醚乙酸酯等丙二醇單烷醚類為佳。該聚合引發劑之例如可使用周知之熱聚合引發劑、光聚合引發劑、氧化還原系引發劑等，可考慮處理方便性、反應速度及是否容易調整分子量等而適當選擇決定。Further, the photosensitive resin of the present invention can be produced by appropriately reacting a polymer having a repeating unit represented by the formulas (1) to (5). Further, the photosensitive resin of the present invention can also be produced by copolymerizing a monomer having a repeating unit represented by the formulas (1) to (5) in an organic solvent using a polymerization initiator. The organic solvent such as tetrahydrofuran (THF), 1,3-dioxolane and 1,3-di An ether such as a dioxane or a propylene glycol monoalkyl ether such as propylene glycol monomethyl ether acetate is preferred. For the polymerization initiator, for example, a known thermal polymerization initiator, a photopolymerization initiator, a redox initiator, or the like can be used, and it can be appropriately selected and determined in consideration of handling convenience, reaction rate, and ease of adjustment of molecular weight.

具體的製造方法例舉如下。關於下列表1中所示第1型之感光性樹脂，係例如在上述有機溶劑中、在酸性觸媒之存在下，將式(14)所示化合物及式(13)所示化合物加成至聚羥基苯乙烯中而製成。又，第2型之感光性樹脂可在上述有機溶劑中、在酸性觸媒之存在下，將式(13)所示化合物加成至聚羥基苯乙烯中後，添加鹼性觸媒及式(15)所示化合物經反應而製成。第3型之感光性樹脂可在上述有機溶劑中、在酸性觸媒之存在下，將式(14)所示化合物及式(13)所示化合物加成至聚羥基苯乙烯中之後，添加鹼性觸媒及式(15)所示化合物經反應而製成。第4型之感光性樹脂，可在上述有機溶劑中、在酸性觸媒之存在下，將式(14)所示化合物及式(13)所示化合物加成至聚(羥基苯乙烯－苯乙烯)中而製成。第5型之感光性樹脂，可在上述有機溶劑中、在酸性觸媒之存在下，將式(13)所示化合物加成至聚(羥基苯乙烯－苯乙烯)中後，添加鹼性觸媒及式(15)所示化合物經反應而製成。第6型之感光性樹脂，可在上述有機溶劑中、在酸性觸媒之存在下，將式(14)所示化合物及式(13)所示化合物加成至聚(羥基苯乙烯－苯乙烯)中後，添加鹼性觸媒及式(15)所示化合物經反應而製成。Specific manufacturing methods are exemplified below. The photosensitive resin of the first type shown in the following Table 1 is, for example, added to the compound represented by the formula (14) and the compound of the formula (13) in the presence of an acidic catalyst in the above organic solvent to Made of polyhydroxystyrene. Further, the photosensitive resin of the second type may be added to the polyhydroxystyrene in the presence of an acidic catalyst in the organic solvent in the presence of an acidic catalyst, and then an alkaline catalyst and a formula are added. 15) The compound shown is prepared by reaction. The photosensitive resin of the third type may be obtained by adding a compound represented by the formula (14) and a compound represented by the formula (13) to polyhydroxystyrene in the presence of an acidic catalyst in the organic solvent, and then adding a base. The physiological catalyst and the compound represented by the formula (15) are reacted. In the photosensitive resin of the fourth type, the compound represented by the formula (14) and the compound represented by the formula (13) can be added to the poly(hydroxystyrene-styrene) in the presence of an acidic catalyst in the organic solvent. Made in the middle. The photosensitive resin of the fifth type can be added to the poly(hydroxystyrene-styrene) in the presence of an acidic catalyst in the presence of an acidic catalyst, and then an alkaline contact can be added. The solvent and the compound represented by the formula (15) are reacted. In the photosensitive resin of the sixth type, the compound represented by the formula (14) and the compound represented by the formula (13) can be added to the poly(hydroxystyrene-styrene) in the presence of an acidic catalyst in the organic solvent. After the middle, an alkaline catalyst and a compound represented by the formula (15) are added and reacted.

上述將本發明之感光性樹脂溶解於有機溶劑者，係為本發明之感光性組成物。本發明之感光性樹脂具有做為光產酸劑作用之架構及酸解離基，所以藉由溶解於溶劑，可在不含有產酸劑之情形下，本身單獨成為化學放大型之感光性組成物。因此，不會伴生產酸劑及具有酸解離基之聚合物之間之互溶性不良之問題，可以形成均一溶液之感光性組成物，藉使用此而形成所期待之圖案。The photosensitive resin of the present invention is dissolved in an organic solvent as described above, and is a photosensitive composition of the present invention. The photosensitive resin of the present invention has a structure and an acid dissociation group functioning as a photoacid generator, and therefore, by dissolving in a solvent, it can be a chemically amplified photosensitive composition alone without containing an acid generator. . Therefore, the problem of poor mutual solubility between the acid generating agent and the polymer having the acid dissociating group is not caused, and a photosensitive composition of a uniform solution can be formed, whereby the desired pattern can be formed.

該使用於感光性組成物之有機溶劑，例如乙二醇單烷基醚類、乙二醇單烷基醚乙酸酯類、二乙二醇二烷基醚乙酸酯類、丙二醇單烷基醚類、丙二醇單烷基醚乙酸酯類及丙二醇二烷基醚乙酸酯類。感光性組成物中所含本發明之感光性樹脂之比率，可在感光性樹脂可溶解範圍內適當選擇使用，一般在3至30重量%為佳。The organic solvent used in the photosensitive composition, for example, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether acetate, propylene glycol monoalkyl ether , propylene glycol monoalkyl ether acetates and propylene glycol dialkyl ether acetates. The ratio of the photosensitive resin of the present invention contained in the photosensitive composition can be appropriately selected and used within the range in which the photosensitive resin is soluble, and is usually preferably from 3 to 30% by weight.

於本發明之感光性組成物中，較宜使用能控制藉由曝光而從上式(1)所示重複單位產生之酸在光阻膜中之擴散現象、而具有能抑制在未曝光區域中之不適宜之化學反應之作用等之所謂酸擴散控制劑。該酸擴散控制劑以不會因為曝光或加熱而鹼性發生變化之含氮有機化合物為佳。又，該酸擴散控制劑之使用量，相對於感光性樹脂，一般使用0.005至5重量%。使用量過多時，做為光阻之感度和顯像性有降低之傾向，相反地，過少時，做為光阻之解像度、工序安定性等之改善效果會不足。In the photosensitive composition of the present invention, it is preferred to control the diffusion of the acid generated in the photoresist film by the repeating unit represented by the above formula (1) by exposure, and to suppress the diffusion in the unexposed region. A so-called acid diffusion controlling agent such as an unsuitable chemical reaction. The acid diffusion controlling agent is preferably a nitrogen-containing organic compound which does not change in alkaliity due to exposure or heating. Further, the amount of the acid diffusion controlling agent used is generally 0.005 to 5% by weight based on the photosensitive resin. When the amount of use is too large, the sensitivity and development of the photoresist tend to be lowered. Conversely, when the amount is too small, the effect of improving the resolution of the photoresist and the stability of the process may be insufficient.

又，本發明之感光性組成物中，可因應需要調配界面活化劑、敏化劑、消泡劑等各種添加劑。Further, in the photosensitive composition of the present invention, various additives such as an interface activator, a sensitizer, and an antifoaming agent may be blended as needed.

從本發明之感光性組成物形成光阻圖案時，藉旋轉塗布法、流鑄塗布法等適當塗布方法將感光性組成物塗布在如矽晶片等基板上，形成光阻膜，必要時先行加熱處理後，隔介具有預定圖案之光罩而進行曝光。此時所使用之活性輻射線隨圖案之微細程度、感光性組成物之感度，而從深紫外線、電子束、X光或EUV(極紫外光)等中適當選擇使用。又，曝光量等曝光條件隨組成物之配方組成，各種添加劑之種類等而適當選擇即可。以曝光後進行加熱處理為佳，其加熱條件視組成物之配方組成、各種添加劑之種類等而適當選擇即可。When the photoresist pattern is formed from the photosensitive composition of the present invention, the photosensitive composition is applied onto a substrate such as a tantalum wafer by a suitable coating method such as a spin coating method or a die casting method to form a photoresist film, and if necessary, heated first. After the treatment, exposure is performed by interposing a photomask having a predetermined pattern. The active radiation used at this time is appropriately selected from deep ultraviolet rays, electron beams, X-rays, EUV (extreme ultraviolet light), and the like depending on the degree of fineness of the pattern and the sensitivity of the photosensitive composition. Further, the exposure conditions such as the amount of exposure may be appropriately selected depending on the composition of the composition, the type of various additives, and the like. It is preferable to carry out heat treatment after exposure, and the heating conditions may be appropriately selected depending on the formulation composition of the composition, the type of various additives, and the like.

其次，可將曝光過之光阻膜，藉由鹼顯像液顯像而形成預定之光阻圖案。該鹼顯像液之例如鹼金屬氫氧化物、氨水、單、二或三烷基胺類、氫氧化四烷基銨類、膽鹼等鹼性化合物，且通常溶解成為1至5重量%濃度之鹼性水溶液。又，使用該鹼性水溶液所構成顯像液時，一般在顯像後進行水洗處理。Next, the exposed photoresist film can be developed by an alkali developing solution to form a predetermined photoresist pattern. The alkali developing solution is, for example, an alkali metal hydroxide, ammonia water, a mono-, di- or trialkylamine, a tetraalkylammonium hydroxide or a choline basic compound, and is usually dissolved to a concentration of 1 to 5% by weight. An alkaline aqueous solution. Moreover, when the developing liquid is used to form the developing liquid, the water washing treatment is generally performed after development.

[實施例][Examples]

藉由實施例說明本發明如下，惟本發明不侷限於此等之例。The invention is illustrated by the following examples, but the invention is not limited to such examples.

(合成例1)下式所示化合物(4－乙烯氧基乙氧基苯基二苯基鋶全氟丁烷磺酸鹽)之合成： (Synthesis Example 1) Synthesis of a compound of the formula (4-vinyloxyethoxyphenyldiphenylphosphonium perfluorobutanesulfonate):

溶解52.2g之4－羥基苯基二苯基鋶全氟丁烷磺酸鹽、18.0g之碳酸鉀及1.05g之N,N,N’,N’－四甲基乙二胺於26.1g之二甲亞碸中。之後，添加13.9g之氯乙基乙烯醚，升溫至80℃。攪拌15小時，反應液冷卻至30℃以下。過濾去除固形物後，加入100g之水，使用100g之己烷洗淨水層3次。加入209g之二氯甲烷及260g之水，攪拌後萃取目標物至二氯甲烷層中。用蒸餾水重複洗淨有機層直到分離之水層呈現pH7。用旋轉蒸散器蒸餾去除溶劑而得69.9g之油狀物質。藉¹ H－NMR及離子層析法測定結果，確認該物質為4－乙烯氧基乙氧基苯基二苯基鋶全氟丁烷磺酸鹽。Dissolving 52.2 g of 4-hydroxyphenyldiphenylphosphonium perfluorobutanesulfonate, 18.0 g of potassium carbonate and 1.05 g of N,N,N',N'-tetramethylethylenediamine at 26.1 g In the dimethyl sulfoxide. Thereafter, 13.9 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction liquid was cooled to 30 ° C or lower. After removing the solid matter by filtration, 100 g of water was added, and the aqueous layer was washed three times with 100 g of hexane. 209 g of dichloromethane and 260 g of water were added, and after stirring, the target was extracted into a dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated aqueous layer showed pH 7. The solvent was distilled off by a rotary evaporator to obtain 69.9 g of an oily material. The result of ¹ H-NMR and ion chromatography was confirmed to be 4-vinyloxyethoxyphenyldiphenylphosphonium perfluorobutanesulfonate.

¹ H－NMR(400 MHz,CDCl₃ )δ4.05－4.08(m,3H),4.24(d,J＝7.4,2.4 Hz,1H),4.31－4.33(m,2H),6.49(dd,J＝14.4,7.4 Hz,1H),7.24(d,J＝6.8 Hz,2H),7.64－7.74(m,12H) ¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.05 - 4.08 (m, 3H), 4.24 (d, J = 7.4, 2.4 Hz, 1H), 4.31-4.33 (m, 2H), 6.49 (dd, J =14.4, 7.4 Hz, 1H), 7.24 (d, J = 6.8 Hz, 2H), 7.64 - 7.74 (m, 12H)

(合成例2)下式所示化合物(4－乙烯氧基乙氧基3,5－二甲基苯基二(4－第三丁基苯基)鋶全氟丁烷磺酸鹽)之合成： (Synthesis Example 2) Synthesis of a compound of the formula (4-vinyloxyethoxy 3,5-dimethylphenylbis(4-t-butylphenyl)phosphonium perfluorobutanesulfonate) :

溶解28.6g之4－羥基3,5－二甲基苯基二(4－第三丁基苯基)鋶全氟丁烷磺酸鹽、8.10g之碳酸鉀及0.46g之N,N,N’,N’－四甲基乙二胺於142g之二甲亞碸中。然後，添加6.08g之氯乙基乙烯醚，升溫至80℃。攪拌19小時，反應液冷卻至30℃以下。藉過濾去除固形物後，加入20.9g之水，使用85.1g之己烷洗淨水層3次。加入226g之二氯甲烷及141g之水，攪拌後萃取目標物至二氯甲烷層中。使用蒸餾水重複洗淨有機層直到分離之水呈現pH7為止。用旋轉蒸散器蒸餾去除溶劑，而得27.4g之褐色油狀物。該物質經¹ H－NMR及離子層析法測定結果，確認為4－乙烯氧基乙氧基3,5－二甲苯基二(4－第三丁基苯基)鋶全氟丁烷磺酸鹽。28.6 g of 4-hydroxy 3,5-dimethylphenyl bis(4-t-butylphenyl)phosphonium perfluorobutane sulfonate, 8.10 g of potassium carbonate and 0.46 g of N, N, N were dissolved. ', N'-tetramethylethylenediamine in 142 g of dimethyl hydrazine. Then, 6.08 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 19 hours, the reaction liquid was cooled to 30 ° C or lower. After removing the solid matter by filtration, 20.9 g of water was added, and the aqueous layer was washed 3 times with 85.1 g of hexane. 226 g of dichloromethane and 141 g of water were added, and after stirring, the target was extracted into a dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated water appeared to be pH 7. The solvent was distilled off with a rotary EtOAc to give 27.4 g of brown oil. The substance was identified by ¹ H-NMR and ion chromatography to confirm that 4-vinyloxyethoxy 3,5-dimethylphenyl bis(4-t-butylphenyl)phosphonium perfluorobutanesulfonic acid salt.

¹ H－NMR(400 MHz,CDCl₃ )δ1.35(s,18H),2.36(s,6H),4.02－4.08(m,3H),4.12－4.14(m,2H),4.25(d,J＝14.3,6.1 Hz,1H),6.50(dd,J＝14.3,6.6 Hz,1H),7.35(s,2H),7.59－7.75(m,8H) ¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.35 (s, 18H), 2.36 (s, 6H), 4.02-4.08 (m, 3H), 4.12-4.14 (m, 2H), 4.25 (d, J) =14.3, 6.1 Hz, 1H), 6.50 (dd, J = 14.3, 6.6 Hz, 1H), 7.35 (s, 2H), 7.59-7.75 (m, 8H)

(合成例3)下式所示化合物(4－乙烯氧基辛氧基苯基二苯基鋶全氟丁烷磺酸鹽)之合成： (Synthesis Example 3) Synthesis of a compound of the formula (4-vinyloxyoctyloxyphenyldiphenylphosphonium perfluorobutanesulfonate):

將1.23g之8－氯－1－辛醇、0.47g之碳酸鈉、0.47g之二－μ－氯雙[η－環辛二烯銥(I)]及1.31g之乙酸乙烯酯加入6.15g之甲苯中，在100℃下攪拌4小時。冷卻至室溫後，蒸餾去除溶劑，使用己烷及二氯甲烷之混合溶劑(己烷及二氯甲烷之體積比為2：1)之管柱層析法精製，而得1.16g之無色透明液之8－氯辛基乙烯醚。1.23 g of 8-chloro-1-octanol, 0.47 g of sodium carbonate, 0.47 g of di-μ-chlorobis[η-cyclooctadienefluorene (I)] and 1.31 g of vinyl acetate were added to 6.15 g. The mixture was stirred at 100 ° C for 4 hours. After cooling to room temperature, the solvent was distilled off, and purified by column chromatography using a mixed solvent of hexane and dichloromethane (2:1 ratio of hexane to methylene chloride) to obtain 1.16 g of colorless and transparent. Liquid 8-chlorooctyl vinyl ether.

溶解2.67g之4－羥基苯基二苯基鋶全氟丁烷磺酸鹽、0.78g之碳酸鉀及0.05g之N,N,N’,N’－四甲基乙二胺於13.3g之二甲亞碸中。然後，添加1.05g之8－氯辛基乙烯醚，升溫至80℃。攪拌15小時後，冷卻反應液至30℃以下。藉過濾去除固形物後，加入13.3g之水，用7.96g之己烷洗淨水層3次。加入10.6g之二氯甲烷及水，經攪拌後萃取目標物至二氯甲烷層中。用蒸餾水重複洗淨有機層至分離之水呈現pH7.0為止。利用旋轉蒸散器蒸餾去除溶劑，而得2.53g之褐色油狀物質。該物質藉¹ H－NMR及離子層析法測定結果，確認為4－乙烯氧基辛氧基苯基二苯基鋶全氟丁烷磺酸鹽。2.67 g of 4-hydroxyphenyldiphenylphosphonium perfluorobutanesulfonate, 0.78 g of potassium carbonate and 0.05 g of N,N,N',N'-tetramethylethylenediamine were dissolved in 13.3 g In the dimethyl sulfoxide. Then, 1.05 g of 8-chlorooctyl vinyl ether was added, and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction solution was cooled to 30 ° C or lower. After removing the solid matter by filtration, 13.3 g of water was added, and the aqueous layer was washed three times with 7.96 g of hexane. 10.6 g of dichloromethane and water were added, and the target was extracted with stirring to a dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated water appeared to pH 7.0. The solvent was distilled off using a rotary evacuol to give 2.53 g of a brown oily material. The substance was identified by ¹ H-NMR and ion chromatography to find 4-vinyloxyoctyloxyphenyldiphenylphosphonium perfluorobutanesulfonate.

¹ H－NMR(400 MHz,CDCl₃ )δ1.36－1.47(m,8H),1.64－1.67(m,2H),1.78－1.83(m,2H),3.67(t,J＝6.6 Hz,2H),3.96(dd,J＝6.8,2.0 Hz,1H),4.04(t,J＝6.6 Hz,2H).4.16(dd,J＝14.4,2.0 Hz,1H),6.46(dd,J＝14.4,6.8 Hz,1H),7.16－7.19(m,2H),7.65－7.76(m,12H) ¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.36-1.47 (m, 8H), 1.64-1.67 (m, 2H), 1.78-1.83 (m, 2H), 3.67 (t, J = 6.6 Hz, 2H) ), 3.96 (dd, J = 6.8, 2.0 Hz, 1H), 4.04 (t, J = 6.6 Hz, 2H). 4.16 (dd, J = 14.4, 2.0 Hz, 1H), 6.46 (dd, J = 14.4, 6.8 Hz, 1H), 7.16-7.19 (m, 2H), 7.65-7.76 (m, 12H)

(合成例4)下式所示化合物(4－乙烯氧基乙氧基苯基二苯基鋶環(1,3－全氟丙烷二磺醯)亞胺鹽)之合成： (Synthesis Example 4) Synthesis of a compound of the formula (4-vinyloxyethoxyphenyldiphenylfluorene ring (1,3-perfluoropropanedisulfonyl)imide salt):

溶解4.66g之五氧化二磷及13.3g之二苯亞碸於63.1g之甲磺酸之後，投入9.26g之苯酚，在室溫下攪拌15小時。保持30℃以下溫度下滴入199g之水，用66.4g之第三丁基甲基醚洗淨水層3次之後，再投入120g之二氯甲烷及23.9g之環1,3－全氟丙烷二磺醯亞胺鉀鹽，並攪拌2小時。終止攪拌，去除分離之水層後，加入66.4g之0.1重量%之氨水溶液並攪拌。然後，用蒸餾水洗淨有機層重複至分離之水層呈現pH7.0為止。用旋轉蒸散器蒸餾去除溶劑，而得32.1g之褐色油狀之4－羥基苯基二苯基鋶環(1,3－全氟丙烷二磺醯)亞胺鹽。After dissolving 4.66 g of phosphorus pentoxide and 13.3 g of diphenylargonium in 63.1 g of methanesulfonic acid, 9.26 g of phenol was charged, and the mixture was stirred at room temperature for 15 hours. While maintaining a temperature of 30 ° C or lower, 199 g of water was added dropwise, and after washing the aqueous layer 3 times with 66.4 g of the third butyl methyl ether, 120 g of dichloromethane and 23.9 g of cyclo1,3-1,3-perfluoropropane disulfonate were further charged. Potassium imide potassium salt and stirred for 2 hours. After the stirring was terminated and the separated aqueous layer was removed, 66.4 g of a 0.1% by weight aqueous ammonia solution was added and stirred. Then, the organic layer was washed with distilled water until the aqueous layer was separated to pH 7.0. The solvent was distilled off by a rotary evaporator to give 32.1 g of 4-hydroxyphenyldiphenyl sulfonium (1,3-perfluoropropanedisulfonium)imide salt as a brown oil.

溶解32.1g之4－羥基苯基二苯基鋶環(1,3－全氟丙烷二磺醯)亞胺鹽、11.2g之碳酸鉀及0.67g之N,N,N’,N’－四甲基乙二胺於164g之二甲亞碸中。然後，添加8.65g之氯乙基乙烯醚，升溫至80℃。攪拌15小時，冷卻反應液至30℃以下。藉過濾去除固形物後，加入80g之水，用40g之己烷洗淨水層3次。加入120g之二氯甲烷及260g之水並進行攪拌後，萃取目標物至二氯甲烷層中。用蒸餾水重複洗淨有機層至分離之水呈現pH7為止。以旋轉蒸散器蒸餾去除溶劑，而得29.1g之油狀物質。該物質以¹ H－NMR及離子層析法測定結果，確知係4－乙烯氧基乙氧基苯基二苯基鋶環(1,3－全氟丙烷二磺醯)亞胺鹽。Dissolving 32.1 g of 4-hydroxyphenyldiphenylfluorene ring (1,3-perfluoropropane disulfonium) imide salt, 11.2 g of potassium carbonate and 0.67 g of N, N, N', N'-four Methylethylenediamine was dissolved in 164 g of dimethyl hydrazine. Then, 8.65 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction solution was cooled to 30 ° C or lower. After removing the solid matter by filtration, 80 g of water was added, and the aqueous layer was washed three times with 40 g of hexane. After adding 120 g of dichloromethane and 260 g of water and stirring, the target was extracted into a dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated water appeared to be pH 7. The solvent was distilled off by a rotary evaporator to obtain 29.1 g of an oily substance. This material was analyzed by ¹ H-NMR and ion chromatography to confirm that it was a 4-vinyloxyethoxyphenyldiphenylfluorene ring (1,3-perfluoropropanedisulfonium)imide salt.

¹ H－NMR(400 MHz,CDCl₃ )δ4.05－4.08(m,3H),4.24(d,J＝7.4,2.4 Hz,1H),4.31－4.33(m,2H),6.49(dd,J＝14.4,7.4 Hz,1H),7.24(d,J＝6.8 Hz,2H),7.64－7.74(m,12H) ¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.05 - 4.08 (m, 3H), 4.24 (d, J = 7.4, 2.4 Hz, 1H), 4.31-4.33 (m, 2H), 6.49 (dd, J =14.4, 7.4 Hz, 1H), 7.24 (d, J = 6.8 Hz, 2H), 7.64 - 7.74 (m, 12H)

(合成例5)下式所示化合物(4－乙烯氧基乙氧基苯基二苯基鋶雙(全氟甲烷磺醯)亞胺鹽)之合成： (Synthesis Example 5) Synthesis of a compound of the formula (4-vinyloxyethoxyphenyldiphenylphosphonium bis(perfluoromethanesulfonyl)imide salt):

溶解2.33g之五氧化二磷及6.65g之二苯亞碸於31.5g之甲磺酸後，加入4.80g之苯酚，在室溫下攪拌15小時。保持在30℃以下滴入100g之水，用30g之第三丁基甲基醚洗淨水層3次之後，加入60g之二氯甲烷及11.6g之雙(全氟甲烷磺醯亞胺)鉀鹽，並攪拌2小時。終止攪拌，除去分離之水層後，加入30g之0.1重量%之氨水，並攪拌之。其次，用蒸餾水重複洗淨有機層至分離之水層呈現pH7為止。用旋轉蒸散器蒸餾去除溶劑，而得16.1g之褐色油狀之4－羥基苯基二苯基鋶雙(全氟甲烷磺醯)亞胺鹽。After dissolving 2.33 g of phosphorus pentoxide and 6.65 g of diphenylarylene in 31.5 g of methanesulfonic acid, 4.80 g of phenol was added, and the mixture was stirred at room temperature for 15 hours. While maintaining 100 g of water dropwise at 30 ° C or less, and washing the aqueous layer with 30 g of the third butyl methyl ether three times, 60 g of dichloromethane and 11.6 g of bis(perfluoromethanesulfonimide) potassium salt were added. Stir for 2 hours. After the stirring was terminated and the separated aqueous layer was removed, 30 g of 0.1% by weight aqueous ammonia was added and stirred. Next, the organic layer was repeatedly washed with distilled water until the separated aqueous layer showed pH 7. The solvent was distilled off with a rotary evaporator to give 16.1 g of 4-hydroxyphenyldiphenyl bis(perfluoromethanesulfonyl)imide salt as a brown oil.

溶解16g之4－羥基苯基二苯基鋶雙(全氟甲烷磺醯)亞胺鹽、4.7g之碳酸鉀及0.33g之N,N,N’,N’－四甲基乙二胺於80g之二甲亞碸中。然後，添加3.66g之氯乙基乙烯醚，升溫至80℃。攪拌15小時，冷卻反應液至30℃以下。經過濾去除固形物後，加入40g之水，用30g之己烷洗淨水層3次。加入60g之二氯甲烷及120g之水，攪拌後萃取目標物至二氯甲烷層中。用蒸餾水洗淨有機層重複至分離之水呈現pH7為止。以旋轉蒸散器蒸餾去除溶劑，而得14.4g之油狀物質。該物質藉¹ H－NMR及離子層析法測定結果，確知為4－乙烯氧基乙氧基苯基二苯基鋶二(全氟甲烷磺醯)亞胺鹽。Dissolving 16 g of 4-hydroxyphenyldiphenylphosphonium bis(perfluoromethanesulfonate) imide salt, 4.7 g of potassium carbonate and 0.33 g of N,N,N',N'-tetramethylethylenediamine 80g of dimethyl sulfoxide. Then, 3.66 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction solution was cooled to 30 ° C or lower. After removing the solid matter by filtration, 40 g of water was added, and the aqueous layer was washed three times with 30 g of hexane. 60 g of dichloromethane and 120 g of water were added, and after stirring, the target was extracted into a dichloromethane layer. The organic layer was washed with distilled water until the separated water showed pH 7. The solvent was distilled off by a rotary evaporator to obtain 14.4 g of an oily substance. The substance was determined to be 4-vinyloxyethoxydiphenylphosphonium di(perfluoromethanesulfonate) imide salt by ¹ H-NMR and ion chromatography.

¹ H－NMR(400 MHz,CDCl₃ )δ4.05－4.08(m,3H),4.24(d,J＝7.4,2.4 Hz,1H),4.31－4.33(m,2H),6.49(dd,J＝14.4,7.4 Hz,1H),7.24(d,J＝6.8 Hz,2H),7.64－7.74(m,12H) ¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.05 - 4.08 (m, 3H), 4.24 (d, J = 7.4, 2.4 Hz, 1H), 4.31-4.33 (m, 2H), 6.49 (dd, J =14.4, 7.4 Hz, 1H), 7.24 (d, J = 6.8 Hz, 2H), 7.64 - 7.74 (m, 12H)

(合成例6)4－乙烯氧基乙氧基苯基二(4－第三丁基苯基)鋶2,4,6－三異丙基苯磺酸鹽之合成 (Synthesis Example 6) Synthesis of 4-vinyloxyethoxyphenyl bis(4-t-butylphenyl)phosphonium 2,4,6-triisopropylbenzenesulfonate

溶解5.0g之4－羥基苯基二(4－第三丁基苯基)鋶2,4,6－三異丙基苯磺酸鹽、1.28g之碳酸鉀及0.10g之N,N,N’,N’－四甲基乙二胺於15g之二甲亞碸中。然後，添加0.83g之氯乙基乙烯醚，升溫至80℃。攪拌15小時，冷卻反應液至30℃以下。過濾而去除固形物之後，加入75g之水及44g之二氯甲烷，萃取目標物至二氯甲烷層中。用蒸餾水重複洗淨有機層至分離之水呈現pH7為止。以旋轉蒸散器蒸餾去除溶劑，溶解所得油狀物於20g之乙腈，用15g之己烷洗淨乙腈層5次。再用旋轉蒸散器蒸餾去除溶劑，而得4.64g之褐色油狀物質。該物質藉¹ H－NMR及離子層析法測定結果，確知為4－乙烯氧基乙氧基苯基二(4－第三丁基苯基)鋶2,4,6－三異丙基苯磺酸鹽。Dissolve 5.0 g of 4-hydroxyphenyl bis(4-t-butylphenyl)phosphonium 2,4,6-triisopropylbenzenesulfonate, 1.28 g of potassium carbonate and 0.10 g of N,N,N ', N'-tetramethylethylenediamine in 15 g of dimethyl hydrazine. Then, 0.83 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction solution was cooled to 30 ° C or lower. After filtration to remove the solid matter, 75 g of water and 44 g of dichloromethane were added, and the target was extracted into a dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated water appeared to be pH 7. The solvent was distilled off by a rotary evaporator to dissolve the obtained oil in 20 g of acetonitrile, and the acetonitrile layer was washed 5 times with 15 g of hexane. The solvent was again distilled off with a rotary eva. to give 4.64 g of a brown oil. The substance was determined by ¹ H-NMR and ion chromatography to be 4-vinyloxyethoxyphenyl bis(4-t-butylphenyl)phosphonium 2,4,6-triisopropylbenzene. Sulfonate.

¹ H－NMR(400 MHz,CDCl₃ )δ1.21(d,J＝6.8 Hz,18H),1.32(s,18H),2.83(sep,J＝6.8 Hz,1H),4.02－4.08(m,3H),4.24(dd,J＝14.3,2.4 Hz,1H),4.29－4.31(m,2H),4.73(sep,J＝6.8 H z,2H),6.50(dd,J＝14.4,6.8 Hz,1H),7.02(s,2H),7.24－7.26(m,2H),7.60－7.89(m,10H) ¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.21 (d, J = 6.8 Hz, 18H), 1.32 (s, 18H), 2.83 (sep, J = 6.8 Hz, 1H), 4.02-4.08 (m, 3H), 4.24 (dd, J = 14.3, 2.4 Hz, 1H), 4.29 - 4.31 (m, 2H), 4.73 (sep, J = 6.8 H z, 2H), 6.50 (dd, J = 14.4, 6.8 Hz, 1H), 7.02 (s, 2H), 7.24-7.26 (m, 2H), 7.60-7.89 (m, 10H)

(合成例7)4－乙烯氧基乙氧基苯基二苯基鋶2,4,6－三異丙基苯磺酸鹽之合成： (Synthesis Example 7) Synthesis of 4-vinyloxyethoxyphenyldiphenylphosphonium 2,4,6-triisopropylbenzenesulfonate:

溶解8.00g之4－羥基苯基二苯基鋶2,4,6－三異丙基苯磺酸鹽、2.46g之碳酸鉀及0.16g之N,N,N’,N’－四甲基乙二胺於24.00g之二甲亞碸中。然後，添加1.59g之氯乙基乙烯醚，升溫至80℃。攪拌15小時，冷卻反應液至30℃以下。過濾去除固形物後，加入160g之水及64g之二氯甲烷，萃取目標物至二氯甲烷層中。用蒸餾水重複洗淨有機層至分離之水層呈現pH7為止。藉旋轉蒸散器蒸餾去除溶劑，溶解所得油狀物於32g之乙腈中，使用24g之己烷洗淨乙腈層5次。以旋轉蒸散器蒸餾去除溶劑，而得9.84g之褐色油狀物質。該物質以¹ H－NMR及離子層析法測定結果，確知為4－乙烯氧基乙氧基苯基二苯基鋶2,4,6－三異丙基苯磺酸鹽。Dissolve 8.00 g of 4-hydroxyphenyldiphenylphosphonium 2,4,6-triisopropylbenzenesulfonate, 2.46 g of potassium carbonate and 0.16 g of N,N,N',N'-tetramethyl Ethylenediamine is in 24.00 g of dimethyl hydrazine. Then, 1.59 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction solution was cooled to 30 ° C or lower. After removing the solid matter by filtration, 160 g of water and 64 g of dichloromethane were added, and the target was extracted into a dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated aqueous layer appeared to pH 7. The solvent was distilled off by a rotary ejector, and the obtained oil was dissolved in 32 g of acetonitrile, and the acetonitrile layer was washed 5 times with 24 g of hexane. The solvent was distilled off by a rotary evaporator to give 9.84 g of brown oil. The substance was identified by ¹ H-NMR and ion chromatography to be 4-ethyloxyethoxyphenyldiphenylphosphonium 2,4,6-triisopropylbenzenesulfonate.

¹ H－NMR(400MHz,CDCl₃ )δ1.21(d、18H)、2.83(sep,1H),4.02－4.08(m,3H),4.24(dd,1H),4.29－4.31(m,2H),4.73(sep,2H),6.50(dd,1H),7.02(s,2H),7.24－7.26(m,2H),7.60－7.89z(m,12H) ¹ H-NMR (400MHz, CDCl ₃ ) δ 1.21 (d, 18H), 2.83 (sep, 1H), 4.02-4.08 (m, 3H), 4.24 (dd, 1H), 4.29-4.31 (m, 2H) , 4.73 (sep, 2H), 6.50 (dd, 1H), 7.02 (s, 2H), 7.24-7.26 (m, 2H), 7.60-7.89z (m, 12H)

(合成例8)4－乙烯氧基乙氧基苯基二苯基鋶2－三氟甲基苯磺酸鹽之合成： (Synthesis Example 8) Synthesis of 4-vinyloxyethoxyphenyldiphenylfluorene 2-trifluoromethylbenzenesulfonate:

溶解3.00g之五氧化二磷及8.01g之二苯亞碸於38.11g之甲磺酸之後，加入5.75g之苯酚，在室溫下攪拌15小時。保持在30℃以下滴入120g之水，用40g之第三丁基甲基醚洗淨水層3次後加入80g之二氯甲烷及11.79g之2－三氟甲基苯磺酸鉀鹽，並攪拌2小時。終止攪拌，去除分離之水層後，加入28g之0.1重量%之氨水溶液並攪拌。終止攪拌，去除分離之水層後，重複此步驟至分離之水層呈現pH7為止。用旋轉蒸散器蒸餾去除溶劑，而得10.33g之白色粉末之4－羥基苯基二苯基鋶2－三氟甲基苯磺酸鹽。After 3.00 g of phosphorus pentoxide and 8.01 g of diphenylargonium were dissolved in 38.11 g of methanesulfonic acid, 5.75 g of phenol was added, and the mixture was stirred at room temperature for 15 hours. Keep 120 g of water dropwise below 30 ° C, wash the aqueous layer three times with 40 g of tert-butyl methyl ether, add 80 g of dichloromethane and 11.79 g of potassium 2-trifluoromethylbenzenesulfonate, and stir. 2 hours. After the stirring was terminated and the separated aqueous layer was removed, 28 g of a 0.1% by weight aqueous ammonia solution was added and stirred. After the agitation is terminated and the separated aqueous layer is removed, this step is repeated until the separated aqueous layer exhibits a pH of 7. The solvent was distilled off with a rotary evaporator to give 10.33 g of a white powder of 4-hydroxyphenyldiphenylhydrazine 2-trifluoromethylbenzenesulfonate.

溶解8.01g之4－羥基苯基二苯基鋶2－三氟甲基苯磺酸鹽、2.74g之碳酸鉀及0.18g之N,N,N’,N’－四甲基乙二胺於36g之二甲亞碸中。然後，加入5.31g之氯乙基乙烯醚，升溫至80℃。攪拌15小時，冷卻反應液至30℃以下。過濾去除固形物後，加入40g之水，使用30g之己烷洗淨水層3次。加入30g之二氯甲烷及60g之水，經攪拌後萃取目標物至二氯甲烷層中。使用蒸餾水重複洗淨有機層至分離之水層呈現pH7為止。利用旋轉蒸散器蒸餾去除溶劑而得3.7g油狀物質。該物質以¹ H－NMR及離子層析法測定結果，確知為4－乙烯氧基乙氧基苯基二苯基鋶2－三氟甲基苯磺酸鹽。8.01 g of 4-hydroxyphenyldiphenylfluorene 2-trifluoromethylbenzenesulfonate, 2.74 g of potassium carbonate and 0.18 g of N,N,N',N'-tetramethylethylenediamine were dissolved. 36 g of dimethyl sulfoxide. Then, 5.31 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction solution was cooled to 30 ° C or lower. After removing the solid matter by filtration, 40 g of water was added, and the aqueous layer was washed three times with 30 g of hexane. 30 g of dichloromethane and 60 g of water were added, and the target was extracted into a dichloromethane layer with stirring. The organic layer was washed repeatedly with distilled water until the separated aqueous layer appeared to pH 7. The solvent was distilled off by a rotary evaporator to obtain 3.7 g of an oily substance. The substance was identified by ¹ H-NMR and ion chromatography to be 4-ethyloxyethoxyphenyldiphenylhydrazine 2-trifluoromethylbenzenesulfonate.

¹ H－NMR(400MHz、CDCl₃ )δ4.09－4.05(m、2H)、4.23(d、1H)、4.27(d、1H)、4.36(t、2H)、6.53(q、1H)、7.28(d、2H)、7.41(t、1H)、7.50(t、1H)、7.69－7.64(m、10H)、7.85(d、2H)、8.41(d、2H) ¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.09-4.05 (m, 2H), 4.23 (d, 1H), 4.27 (d, 1H), 4.36 (t, 2H), 6.53 (q, 1H), 7.28 (d, 2H), 7.41 (t, 1H), 7.50 (t, 1H), 7.69-7.64 (m, 10H), 7.85 (d, 2H), 8.41 (d, 2H)

(合成例9)4－乙烯氧基乙氧基苯基二(4－第三丁基苯基)鋶2－三氟甲基苯磺酸鹽之合成： (Synthesis Example 9) Synthesis of 4-vinyloxyethoxyphenylbis(4-t-butylphenyl)fluorene 2-trifluoromethylbenzenesulfonate:

溶解4.51g之4－羥基苯基二(4－第三丁基苯基)鋶2－三氟甲基苯磺酸鹽、5.30g之碳酸鉀及0.53g之N,N,N’,N’－四甲基乙二胺於30g之二甲亞碸中。然後，加入10.03g之氯乙基乙烯醚，升溫至80℃。攪拌15小時，冷卻反應液至30℃以下。過濾去除固形物之後，加入150g之水及93g之二氯甲烷，萃取目標物至二氯甲烷層中。用蒸餾水重複洗淨有機層至分離之水層呈現pH7為止。以旋轉蒸散器蒸餾去除溶劑而得8.57g之紅色粉末。該物質以¹ H－NMR及離子層析法測定結果，確知為4－乙烯氧基乙氧基苯基二(4－第三丁基苯基)鋶2－三氟甲基苯磺酸鹽。Dissolve 4.51 g of 4-hydroxyphenyl bis(4-t-butylphenyl)phosphonium 2-trifluoromethylbenzenesulfonate, 5.30 g of potassium carbonate and 0.53 g of N,N,N',N' - Tetramethylethylenediamine in 30 g of dimethyl hydrazine. Then, 10.03 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction solution was cooled to 30 ° C or lower. After removing the solid matter by filtration, 150 g of water and 93 g of dichloromethane were added, and the target was extracted into a dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated aqueous layer appeared to pH 7. The solvent was distilled off by a rotary evaporator to give 8.57 g of a red powder. The substance was identified by ¹ H-NMR and ion chromatography to find 4-ethyloxyethoxyphenylbis(4-t-butylphenyl)indole 2-trifluoromethylbenzenesulfonate.

¹ H－NMR(400MHz、CDCl₃ )δ1.32(s、18H)、4.09－4.05(m、2H)、4.23(d、1H)、4.27(d、1H)、4.36(t、2H)、6.53(q、1H)、7.28(d、2H)、7.41(t、1H)、7.50(t、1H)、7.69－7.64(m、8H)、7.85(d、2H)、8.41(d、2H) ¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.32 (s, 18H), 4.09-4.05 (m, 2H), 4.23 (d, 1H), 4.27 (d, 1H), 4.36 (t, 2H), 6.53 (q, 1H), 7.28 (d, 2H), 7.41 (t, 1H), 7.50 (t, 1H), 7.69-7.64 (m, 8H), 7.85 (d, 2H), 8.41 (d, 2H)

(實施例1)下式(A)所示感光性樹脂1之合成(即，表1中第1型之感光性樹脂) (Example 1) Synthesis of the photosensitive resin 1 represented by the following formula (A) (that is, the photosensitive resin of the first type in Table 1)

在氮氣環境下，溶解50.0g之以聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯於350ml之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確認反應系統內水分減少到100ppm以下。冷卻反應液至20℃以下，添加62 μ L之35重量%之鹽酸。其次，用1小時滴入28.4g之含有34.6重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻溶液至15℃，以30分鐘滴入8.8g之合成例1所得4－乙烯氧基乙氧基苯基二苯基鋶全氟丁烷磺酸鹽之63.8重量%之1,3－二氧雜戊環溶液之後，在30℃下攪拌2小時。用氨水進行中和，將該溶液滴入在室溫下之1700g之純水中，使固形物析出。濾取固形物後，使用乙腈及純水施予再沈澱，在35℃下乾燥24小時而得53.5g之樹脂。該樹脂以¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為30.6%，式(1)所示單位為1.6%而構成之感光性樹脂。即，各組成為a：b：d＝1.6：30.6：67.8(莫耳%)。50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 was dissolved in 350 ml of 1,3-dioxolane under a nitrogen atmosphere. The 1,3-dioxolane was distilled off under normal pressure, and it was confirmed that the water content in the reaction system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C or lower, and 62 μL of 35 wt% hydrochloric acid was added. Next, 28.4 g of a 1,3-dioxolane solution containing 34.6% by weight of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 8.8 g of 63.8 wt% of 1,3-dioxe of 4-vinyloxyethoxyphenyldiphenylphosphonium perfluorobutanesulfonate obtained in Synthesis Example 1 was added dropwise over 30 minutes. After the heteropentyl ring solution, it was stirred at 30 ° C for 2 hours. Neutralization was carried out with aqueous ammonia, and the solution was dropped into 1700 g of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, reprecipitation was carried out using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 53.5 g of a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 30.6%, and the unit represented by the formula (1) was 1.6%. . That is, each composition is a:b:d=1.6:30.6:67.8 (mole%).

(實施例2)上式(A)所示感光性樹脂2之合成(即，表1中之第1型之感光性樹脂)在氮氣環境下，溶解以聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯50.0g於350mL之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確認反應系統內水分減低至100ppm以下。冷卻反應液至20℃以下，添加62 μL之35重量%之鹽酸。其次，用1小時滴入27.9g之含35.4重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻溶液至15℃，用30分鐘滴入2.8g之含合成例1所得4－乙烯氧基乙氧基苯基二苯基鋶全氟丁烷磺酸鹽之63.8重量%之1,3－二氧雜戊環之後，在30℃下攪拌2小時。以氨水進行中和，滴入該溶液於室溫下之2000g之純水中，使固體析出。濾取固形物，使用乙腈及純水施行再沈澱，在35℃下乾燥24小時，而得52.0g之樹脂。該樹脂以¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為30.8%，式(1)所示單位為0.60%而構成之感光性樹脂。即，各組成為a：b：d＝0.6：30.8：68.6(莫耳%)。(Example 2) The synthesis of the photosensitive resin 2 represented by the above formula (A) (that is, the photosensitive resin of the first type in Table 1) was dissolved in a nitrogen atmosphere to have a molecular weight (Mw) of 16400 in terms of polystyrene. After the molecular weight distribution (Mw/Mn) of polyhydroxystyrene of 1.09 is 50.0 g in 350 mL of 1,3-dioxolane, the 1,3-dioxolane is distilled off under normal pressure to confirm the reaction system. The internal moisture is reduced to less than 100 ppm. The reaction solution was cooled to 20 ° C or lower, and 62 μL of 35 wt% hydrochloric acid was added. Next, 27.9 g of a 1,3-dioxolane solution containing 35.4% by weight of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 2.8 g of 63.8 wt% of 1,3-diethyl 4-vinyloxyethoxyphenyldiphenylphosphonium perfluorobutanesulfonate obtained in Synthesis Example 1 was added dropwise over 30 minutes. After the oxapenic ring, it was stirred at 30 ° C for 2 hours. The mixture was neutralized with aqueous ammonia, and the solution was added dropwise to 2000 g of pure water at room temperature to precipitate a solid. The solid matter was collected by filtration, reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 52.0 g of a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 30.8%, and the unit represented by the formula (1) was 0.60%. . That is, each composition is a:b:d=0.6:30.8:68.6 (mole%).

(實施例3)下式(B)所示感光性樹脂3之合成(即，表1中之第3型之感光性樹脂) (Example 3) Synthesis of photosensitive resin 3 represented by the following formula (B) (that is, photosensitive resin of the third type in Table 1)

在氮氣環境下，溶解50.0g之以聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯於350mL之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確認反應系統內水分減低至100ppm以下。冷卻反應液至20℃以下，添加63 μ L之35重量%之鹽酸。其次，以1小時滴入26.0g之含28.1重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻溶液至15℃，用30分鐘滴入8.8g之含有合成例2所得4－乙烯氧基乙氧基3,5－二甲基苯基二(4－第三丁基苯基)鋶全氟丁烷磺酸鹽之63.8重量%之1,3－二氧雜戊環溶液之後，在30℃下攪拌2小時。然後，添加0.21g之N,N－二甲胺基吡啶，加溫至40℃。用1小時滴入19.5g之含70.0重量%之二碳酸二－第三丁酯之1,3－二氧雜戊環溶液，在相同溫度下攪拌1小時。該溶液滴入於室溫下1700g之純水中，使固形物析出。濾取固形物後，使用二氯甲烷及己烷施行再沈澱，在35℃下乾燥24小時，而得53.1g之樹脂。該樹脂以¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為21.4%，式(1)所示單位為1.7%，第三丁氧基羰基化率為9.2%所構成之感光性樹脂。即，各組成為a：b：c：d＝1.7：21.4：9.2：67.7(莫耳%)。50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 was dissolved in 350 mL of 1,3-dioxolane under a nitrogen atmosphere. The 1,3-dioxolane was distilled off under normal pressure, and it was confirmed that the water content in the reaction system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C or lower, and 63 μL of 35 wt% hydrochloric acid was added. Next, 26.0 g of a 1,3-dioxolane solution containing 28.1% by weight of ethyl vinyl ether was added dropwise thereto over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 8.8 g of 4-vinyloxyethoxy 3,5-dimethylphenyl bis(4-t-butylphenyl)fluorene perfluorochemical obtained in Synthesis Example 2 was added dropwise over 30 minutes. After a 63.8 wt% 1,3-dioxolane solution of butanesulfonate, it was stirred at 30 ° C for 2 hours. Then, 0.21 g of N,N-dimethylaminopyridine was added and the mixture was warmed to 40 °C. 19.5 g of a 1,3-dioxolane solution containing 70.0% by weight of di-tert-butyl dicarbonate was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 1 hour. This solution was dropped into 1700 g of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, reprecipitation was carried out using dichloromethane and hexane, and dried at 35 ° C for 24 hours to obtain 53.1 g of a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 21.4%, and the unit represented by the formula (1) was 1.7%, and the third butoxy group was used. A photosensitive resin composed of a carbonylation ratio of 9.2%. That is, each composition is a:b:c:d=1.7:21.4:9.2:67.7 (mole%).

(實施例4)下式(C)所示感光性樹脂4之合成(即，表1中之第1型之感光性樹脂) (Example 4) Synthesis of the photosensitive resin 4 represented by the following formula (C) (that is, the photosensitive resin of the first type in Table 1)

在氮氣環境下，溶解50.0g之以聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯於350mL之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確認反應系統內水分減低至100ppm以下。冷卻反應液至20℃以下，添加62 μ L之35重量%鹽酸。然後，用1小時滴入27.9g之含35.4重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻溶液至15℃，用30分鐘滴入4.2g之含有合成例3所得4－乙烯氧基辛氧基苯基二苯基鋶全氟丁烷磺酸鹽之63.8重量%之1,3－二氧雜戊環溶液之後，在30℃下攪拌2小時。以氨水進行中和，該溶液滴入在室溫下之2000g之純水中，使固形物析出。濾取固形物後，使用乙腈及純水施予再沈澱，在35℃下乾燥24小時，而得52.0g之樹脂。該樹脂以¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為30.2%，式(1)所示單位為1.0%而構成之感光性樹脂。即，各組成為a：b：d＝1.0：30.2：68.8(莫耳%)。50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 was dissolved in 350 mL of 1,3-dioxolane under a nitrogen atmosphere. The 1,3-dioxolane was distilled off under normal pressure, and it was confirmed that the water content in the reaction system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C or lower, and 62 μL of 35 wt% hydrochloric acid was added. Then, 27.9 g of a 1,3-dioxolane solution containing 35.4% by weight of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 4.2 g of 63.8 wt% of 1,3-diethyl 4-vinyloxyoctyloxydiphenylphosphonium perfluorobutanesulfonate obtained in Synthesis Example 3 was added dropwise over 30 minutes. After the oxacyclopentane solution, it was stirred at 30 ° C for 2 hours. The mixture was neutralized with aqueous ammonia, and the solution was dropped into 2000 g of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, reprecipitation was carried out using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 52.0 g of a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 30.2%, and the unit represented by the formula (1) was 1.0%. . That is, each composition is a:b:d=1.0:30.2:68.8 (mole%).

(實施例5)下式(D)所示感光性樹脂5之合成(即，表1中之第1型之感光性樹脂) (Example 5) Synthesis of the photosensitive resin 5 represented by the following formula (D) (that is, the photosensitive resin of the first type in Table 1)

在氮氣環境下，溶解50.0g之聚苯乙烯換算分子量(Mw)為9000、分子量分布(Mw/Mn)為1.11之聚羥基苯乙烯於400mL之1,3－二氧雜戊環中，確認反應系統內水分減低至100ppm以下。冷卻該溶液至15℃，添加63 μ L之35重量%之鹽酸。其次，以15分鐘滴入28.4g之含35.5重量%之乙基乙烯醚之1,3－二氧雜戊環，在15℃下攪拌60分鐘，繼在30℃下攪拌1.5小時。冷卻該溶液至15℃，用15分鐘滴入8.4g之含合成例4所得4－乙烯氧基乙氧基苯基二苯基鋶環(1,3－全氟丙烷二磺醯)亞胺鹽之35.1重量%之1,3－二氧雜戊環溶液之後，在15℃下攪拌30分鐘，繼在30℃下攪拌2小時。加入172 μ L之28重量%之氨水，攪拌10分鐘以上而進行中和，將該溶液以1小時時間滴入在室溫下之1700g之純水中，使固形物析出。濾取固形物，以乙腈及純水施行再沈澱，在35℃下乾燥24小時而得53.7g之樹脂。該樹脂以¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為31.8%，式(1)所示單位為1.1%而構成之感光性樹脂。即，各組成為a：b：d＝1.1：31.8：67.1(莫耳%)。Under a nitrogen atmosphere, 50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 9000 and a molecular weight distribution (Mw/Mn) of 1.11 was dissolved in 400 mL of 1,3-dioxolane to confirm the reaction. The moisture in the system is reduced to less than 100 ppm. The solution was cooled to 15 ° C, and 63 μL of 35 wt% hydrochloric acid was added. Next, 28.4 g of a 1,3-dioxolane containing 35.5% by weight of ethyl vinyl ether was added dropwise thereto over 15 minutes, and the mixture was stirred at 15 ° C for 60 minutes, followed by stirring at 30 ° C for 1.5 hours. The solution was cooled to 15 ° C, and 8.4 g of the 4-vinyloxyethoxyphenyldiphenylfluorene ring (1,3-perfluoropropane disulfonium) imide salt obtained in Synthesis Example 4 was added dropwise over 15 minutes. After 35.1% by weight of the 1,3-dioxolane solution, the mixture was stirred at 15 ° C for 30 minutes and then at 30 ° C for 2 hours. 172 μL of 28% by weight aqueous ammonia was added, and the mixture was stirred for 10 minutes or more to carry out neutralization, and the solution was dropped into 1700 g of pure water at room temperature over 1 hour to precipitate a solid matter. The solid matter was collected by filtration, reprecipitated with acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 53.7 g of a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 31.8%, and the unit represented by the formula (1) was 1.1%. . That is, each composition is a:b:d=1.1:31.8:67.1 (mole%).

(實施例6)下式(E)所示感光性樹脂6之合成(即，表1中之第1型之感光性樹脂) (Example 6) Synthesis of the photosensitive resin 6 represented by the following formula (E) (that is, the photosensitive resin of the first type in Table 1)

在氮氣環境下，溶解50.0g之聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯於350mL之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確認反應系統內水分減低至100ppm以下。冷卻反應液至20℃以下，添加62 μ L之35重量%之鹽酸。其次，用1小時滴入27.9g之含35.4重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻溶液至15℃，用30分鐘滴入3.4g之含有合成例5所得4－乙烯氧基乙氧基苯基二苯基鋶雙(全氟甲烷磺醯)亞胺鹽之63.8重量%之1,3－二氧雜戊環溶液之後，在30℃下攪拌2小時。用氨水進行中和，將該溶液滴入在室溫下之2000g之純水中，使固形物析出。濾取固形物後，使用乙腈及純水施行再沈澱，在35℃下乾燥24小時而得52.0g之樹脂。該樹脂以¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為30.8%，式(1)所示單位為0.8%而構成之感光性樹脂。即，各組成為a：b：d＝0.8：30.8：68.4(莫耳%)。Under a nitrogen atmosphere, 50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 was dissolved in 350 mL of 1,3-dioxolane. The 1,3-dioxolane was removed by distillation under reduced pressure, and it was confirmed that the water content in the reaction system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C or lower, and 62 μL of 35 wt% hydrochloric acid was added. Next, 27.9 g of a 1,3-dioxolane solution containing 35.4% by weight of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 3.4 g of 63.8 wt% of the 4-vinyloxyethoxyphenyldiphenylphosphonium bis(perfluoromethanesulfonate) imide salt obtained in Synthesis Example 5 was added dropwise over 30 minutes. After the 3-dioxolane solution, it was stirred at 30 ° C for 2 hours. Neutralization was carried out with aqueous ammonia, and the solution was dropped into 2000 g of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, reprecipitation was carried out using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 52.0 g of a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 30.8%, and the unit represented by the formula (1) was 0.8%. . That is, each composition is a:b:d=0.8:30.8:68.4 (mole%).

(實施例7)下式(F)所示感光性樹脂7之合成(即，表1中之第1型之感光性樹脂) (Example 7) Synthesis of photosensitive resin 7 represented by the following formula (F) (that is, photosensitive resin of the first type in Table 1)

在氮氣環境下，溶解50.0g之聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯於350mL之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確知反應系統內水分減低至100ppm以下。冷卻反應液至20℃以下，添加62 μ L之35重量%之鹽酸。其次，用1小時滴入27.2g之含有31.3重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻溶液至15℃，用30分鐘滴入10.1g之含有合成例6所得4－乙烯氧基乙氧基苯基二(4－第三丁基苯基)鋶2,4,6－三異丙基苯磺酸鹽之19.9重量%之1,3－二氧雜戊環溶液之後，在30℃下攪拌2小時。然後，用氨水進行中和，將該溶液滴入在室溫下2500g之純水，使固形物析出。濾取固形物後，用乙腈及純水施行再沈澱，在35℃下乾燥24小時，而得53.7g之樹脂。該樹脂以¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為32.3%，式(1)所示單位為0.6%而構成之感光性樹脂。即，各組成為a：b：d＝0.6：32.3：67.1(莫耳%)。Under a nitrogen atmosphere, 50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 was dissolved in 350 mL of 1,3-dioxolane. The 1,3-dioxolane was removed by distillation, and it was confirmed that the moisture in the reaction system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C or lower, and 62 μL of 35 wt% hydrochloric acid was added. Next, 27.2 g of a 1,3-dioxolane solution containing 31.3 wt% of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 10.1 g of 4-vinyloxyethoxyphenyl bis(4-t-butylphenyl)phosphonium 2,4,6-triisopropyl obtained in Synthesis Example 6 was added dropwise over 30 minutes. After the 19.9 wt% 1,3-dioxolane solution of the benzenesulfonate was stirred at 30 ° C for 2 hours. Then, it was neutralized with aqueous ammonia, and the solution was dropped into 2500 g of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, reprecipitation was carried out with acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 53.7 g of a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 32.3%, and the unit represented by the formula (1) was 0.6%. . That is, each composition is a:b:d=0.6:32.3:67.1 (mole%).

(實施例8)下式(G)所示感光性樹脂8之合成 (Example 8) Synthesis of photosensitive resin 8 represented by the following formula (G)

在氮氣環境下，溶解20.00g之聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯於200mL之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確知反應系統內水分減低至100ppm以下。冷卻反應液至20℃以下，添加25 μ L之35重量%之鹽酸。其次，用1小時滴入11.89g之含37.2重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻該溶液至15℃，用30分鐘滴入1.46g之含有合成例7所得4－乙烯氧基乙氧基苯基二苯基鋶2,4,6－三異丙基苯磺酸鹽之63.8重量%之1,3－二氧雜戊環溶液之後，在30℃下攪拌2小時。用氨水進行中和，將該溶液滴入在室溫下之1000g之純水中，使固形物析出。濾取固形物後，用乙腈及純水施行再沈澱，在35℃下乾燥24小時，而得18.32g之樹脂。該樹脂據¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為33.0%，式(1)所示單位為0.6%而構成之感光性樹脂。即，各組成為a：b：d＝0.6：33.0：66.4(莫耳%)。Under a nitrogen atmosphere, 20.00 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 was dissolved in 200 mL of 1,3-dioxolane. The 1,3-dioxolane was removed by distillation, and it was confirmed that the moisture in the reaction system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C or lower, and 25 μL of 35 wt% hydrochloric acid was added. Next, 11.89 g of a 1,3-dioxolane solution containing 37.2% by weight of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 1.46 g of the 4-vinyloxyethoxyphenyldiphenylphosphonium 2,4,6-triisopropylbenzenesulfonate obtained in Synthesis Example 7 was added dropwise over 30 minutes. After the weight % of the 1,3-dioxolane solution, it was stirred at 30 ° C for 2 hours. Neutralization was carried out with aqueous ammonia, and the solution was dropped into 1000 g of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, reprecipitation was carried out with acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 18.32 g of a resin. According to the results of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 33.0%, and the unit represented by the formula (1) was 0.6%. . That is, each composition is a:b:d=0.6:33.0:66.4 (mol%).

(實施例9)下式(H)所示感光性樹脂9之合成 (Example 9) Synthesis of photosensitive resin 9 represented by the following formula (H)

在氮氣環境下，溶解20.0g之聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯於200mL之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確認反應系統內水分減低至100ppm以下。冷卻反應液至20℃以下，添加25 μ L之35重量%之鹽酸。其次，用1小時滴入12.02g之含有37.8重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻溶液至15℃，用30分鐘滴入1.45g之含有66.0重量%之合成例8所得4－乙烯氧基乙氧基苯基二苯基鋶2－三氟甲基苯磺酸鹽之1,3－二氧雜戊環溶液之後，在30℃下攪拌2小時。用氨水進行中和，將該溶液滴入在室溫下之1000mL之純水中，使固形物析出。濾取固形物後，用乙腈及純水施行再沈澱，在35℃下乾燥24小時而得樹脂。該樹脂以¹ H－NMR測定結果，確知係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為31.5%，式(1)所示單位為1.4%而構成之感光性樹脂。即，各組成為a：b：d＝1.4：31.5：67.1(莫耳%)。20.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 was dissolved in 200 mL of 1,3-dioxolane under a nitrogen atmosphere. The 1,3-dioxolane was removed by distillation under reduced pressure, and it was confirmed that the water content in the reaction system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C or lower, and 25 μL of 35 wt% hydrochloric acid was added. Next, 12.02 g of a 1,3-dioxolane solution containing 37.8% by weight of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 1.45 g of 6-vinyloxyethoxyphenyldiphenylphosphonium 2-trifluoromethylbenzenesulfonate obtained in Synthesis Example 8 was added dropwise over 30 minutes. After the 3-dioxolane solution, it was stirred at 30 ° C for 2 hours. Neutralization was carried out with aqueous ammonia, and the solution was dropped into 1000 mL of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, reprecipitation was carried out with acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 31.5%, and the unit represented by the formula (1) was 1.4%. . That is, each composition is a:b:d=1.4:31.5:67.1 (mole%).

(實施例10)下式(I)所示感光性樹脂10之合成 (Example 10) Synthesis of photosensitive resin 10 represented by the following formula (I)

在氮氣環境下，溶解20.1g之聚苯乙烯換算分子量(Mw)為16400、分子量分布(Mw/Mn)為1.09之聚羥基苯乙烯於200mL之1,3－二氧雜戊環之後，在常壓下蒸餾去除1,3－二氧雜戊環，確認反應系統內水分減低至100ppm以下。冷卻反應液至20℃以下，添加25 μ L之35重量%之鹽酸。其次，以1小時滴入11.84g之含有36.4重量%之乙基乙烯醚之1,3－二氧雜戊環溶液，在30℃下攪拌2小時。冷卻溶液至15℃，用30分鐘滴入1.46g之含有合成例9所得4－乙烯氧基乙氧基苯基二(4－第三丁基苯基)鋶2－三氟甲基苯磺酸鹽之68.8重量%之1,3－二氧雜戊環溶液之後，在30℃下攪拌2小時。用氨水進行中和，該溶液滴入在室溫下之1000mL之純水中，使固形物析出。濾取固形物後，用乙腈及純水施行再沈澱，在35℃下乾燥24小時而得樹脂。該樹脂以¹ H－NMR測定結果，確認係所用聚羥基苯乙烯之羥基之氫原子之乙氧基乙基化率為35.2%，式(1)所示單位為0.6%而構成之感光性樹脂。即，各組成為a：b：d＝0.6：35.2：64.2(莫耳%)。Under a nitrogen atmosphere, 20.1 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 was dissolved in 200 mL of 1,3-dioxolane. The 1,3-dioxolane was removed by distillation under reduced pressure, and it was confirmed that the water content in the reaction system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C or lower, and 25 μL of 35 wt% hydrochloric acid was added. Next, 11.84 g of a 1,3-dioxolane solution containing 36.4% by weight of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The solution was cooled to 15 ° C, and 1.46 g of 4-vinyloxyethoxyphenyl bis(4-t-butylphenyl)fluorene 2-trifluoromethylbenzenesulfonic acid obtained in Synthesis Example 9 was added dropwise over 30 minutes. After a 68.8 wt% 1,3-dioxolane solution of the salt, it was stirred at 30 ° C for 2 hours. Neutralization was carried out with aqueous ammonia, and the solution was dropped into 1000 mL of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, reprecipitation was carried out with acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain a resin. As a result of ¹ H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 35.2%, and the unit represented by the formula (1) was 0.6%. . That is, each composition is a:b:d=0.6:35.2:64.2 (mole%).

<使用氙燈曝光之評估><Evaluation of exposure using xenon lamp>

(調製光阻及測定失效(breakthrough)時間)溶解100重量份之實施例1所得感光性樹脂1、與0.24重量份之三乙醇胺於525重量份之丙二醇單甲基乙酸酯中，用濾器(PTFE濾器)過濾調製得液狀之正型光阻(感光性組成物)。使用旋轉塗布器將該光阻塗布在矽晶片(直徑：4英吋)，在110℃下預烘烤90秒鐘，而得膜厚為500nm之光阻膜。用氙燈(波長為248nm)將該光阻膜曝光，繼在110℃下後烘烤(曝光後加熱)90秒鐘。然後，在23℃下使用顯像液(2.38重量%之氫氧化四甲銨水溶液)，測定失效時間。其中，該失效時間乃指用一定能量照射後，藉顯像使殘膜皆消失所需秒數。(Modulation of photoresist and measurement of breakthrough time) 100 parts by weight of the photosensitive resin 1 obtained in Example 1 and 0.24 parts by weight of triethanolamine in 525 parts by weight of propylene glycol monomethyl acetate were dissolved in a filter ( The PTFE filter was filtered to obtain a liquid positive resist (photosensitive composition). The photoresist was coated on a tantalum wafer (diameter: 4 inches) using a spin coater, and prebaked at 110 ° C for 90 seconds to obtain a photoresist film having a film thickness of 500 nm. The photoresist film was exposed with a xenon lamp (wavelength: 248 nm), followed by post-baking (heating after exposure) at 110 ° C for 90 seconds. Then, the developing time was measured at 23 ° C using a developing solution (2.38 wt% aqueous solution of tetramethylammonium hydroxide). The failure time refers to the number of seconds required for the residual film to disappear after being irradiated with a certain amount of energy.

結果，失效時間當曝光量係100mJ時為12秒鐘，當500mJ時為3秒鐘。因此，實施例1所得感光性樹脂1藉氙燈曝光，從本發明之感光性樹脂中之式(1)所示架構部分產生酸，因該酸而樹脂之酸解離基部分脫離，對於顯像液而言，可知由難溶解性變成可溶性。As a result, the failure time was 12 seconds when the exposure amount was 100 mJ, and 3 seconds when it was 500 mJ. Therefore, the photosensitive resin 1 obtained in Example 1 is exposed by a xenon lamp, and an acid is generated from the structural portion represented by the formula (1) in the photosensitive resin of the present invention, and the acid dissociable radical portion of the resin is detached due to the acid, for the developing solution In other words, it is understood that the solubility is insoluble.

又，替代感光性樹脂1，改用實施例2至10所得各感光性樹脂2至10，按照上述相同方法調製正型光阻，獲得光阻膜，經曝光、預烘烤、後烘烤、顯像、測定其失效時間。結果，失效時間當曝光量100mJ時在12±2秒鐘範圍內，當500mJ時在3±1秒鐘範圍內。因此，可知感光性樹脂2至10也藉氙燈曝光，從本發明之感光性樹脂中式(1)所示架構部分產生酸，因該酸而聚合物之酸解離基部分脫離，對於顯像液而言，由難溶解性變成可溶性。Further, instead of the photosensitive resin 1, the photosensitive resins 2 to 10 obtained in Examples 2 to 10 were used, and a positive photoresist was prepared in the same manner as described above to obtain a photoresist film, which was exposed, prebaked, and post-baked. Visualize and measure the time of failure. As a result, the failure time was in the range of 12 ± 2 seconds when the exposure amount was 100 mJ, and was within the range of 3 ± 1 second at 500 mJ. Therefore, it is understood that the photosensitive resins 2 to 10 are also exposed by a xenon lamp, and an acid is generated from the structural portion represented by the formula (1) in the photosensitive resin of the present invention, and the acid dissociation group of the polymer is partially separated by the acid, and the developing solution is used for the developing solution. Words, from poor solubility to soluble.

<藉極紫外光(EUV)曝光之評估><Evaluation of Extreme Ultraviolet Light (EUV) Exposure>

(光阻之調製及塗布)溶解100重量份之實施例1所得感光性樹脂1、4重量份之三苯基矽烷基胺於2000重量份之丙二醇單甲醚乙酸酯中，用0.2 μm之濾器(PTFE濾器)過濾而調製得正型光阻。用旋轉塗布器將該光阻溶液塗布在使用六甲基二矽氮烷(hexamethyldisilazane)處理之4英吋之矽晶片上，再用加熱板在110℃前後下加熱90秒鐘左右，製作膜厚為0.1 μm之均一之膜。按照相同方法，使用實施例2至10所得感光性樹脂2至10，分別調製正型光阻而製成膜。(Preparation and Coating of Photoresist) 100 parts by weight of the photosensitive resin obtained in Example 1 and 4 parts by weight of triphenylsulfonylalkylamine were dissolved in 2000 parts by weight of propylene glycol monomethyl ether acetate, and 0.2 μm was used. The filter (PTFE filter) is filtered to prepare a positive photoresist. The photoresist solution was coated on a 4 inch crucible wafer treated with hexamethyldisilazane using a spin coater, and then heated at 110 ° C for about 90 seconds using a hot plate to prepare a film thickness. It is a uniform film of 0.1 μm. According to the same method, the photosensitive resins 2 to 10 obtained in Examples 2 to 10 were used to prepare a positive resist to prepare a film.

(感度之測定)使用從大型輻射光設備之Spring－8之直線加速器入射之1GeV之加速電子，在New SUBARU儲存環之偏向電磁鐵所產生之同步加速輻射光，以鉬/矽多層膜反射而單色化成為波長13.5nm之極紫外光(EUV)做為曝光用光。將該EUV照射在上述形成之光阻薄膜上，在90℃上下熱處理60秒鐘左右之後，浸漬30秒鐘在23℃下之氫氧化四甲銨(TMAH)之2.38重量%水溶液中。其次，經水洗，乾燥後藉由非接觸型膜厚測定法測定膜厚。將曝光量之設定水準加以多元化而進行各種之此操作，並將光阻殘膜厚成為零時之曝光量求取做為Eth感度。(Measurement of Sensitivity) Using accelerated electrons of 1 GeV incident from a linear accelerator of a large radiant light device, the synchrotron radiation generated by the biasing electromagnet of the New SUBARU storage ring is reflected by the molybdenum/bismuth multilayer film. Monochromization becomes extreme ultraviolet light (EUV) having a wavelength of 13.5 nm as exposure light. This EUV was irradiated onto the above-formed photoresist film, and heat-treated at 90 ° C for about 60 seconds, and then immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C for 30 seconds. Next, the film thickness was measured by a non-contact type film thickness measurement after washing with water and drying. Various operations were performed by diversifying the exposure level setting level, and the exposure amount when the residual photoresist film thickness was zero was determined as the Eth sensitivity.

結果，就實施例1至10之光阻，Eth分別為0.9至6mJ/cm² 。因此，可知本發明之感光性樹脂之感度優異。As a result, with respect to the photoresists of Examples 1 to 10, Eth was 0.9 to 6 mJ/cm ² , respectively. Therefore, it is understood that the photosensitive resin of the present invention is excellent in sensitivity.

又，藉四極質譜儀測定曝光中從光阻產生之氣體量之結果，實施例1至10時皆少，相較產生氣體量較少之以往之ESCAP型之化學放大系光阻而言，大約僅為其1/2至3/5左右。其中，所產生氣體量越少，影響光罩或光學系等越少而較佳。Further, the results of measuring the amount of gas generated from the photoresist in the exposure by the quadrupole mass spectrometer are small in the examples 1 to 10, and are comparable to the conventional ESCAP type chemically amplified photoresist having a small amount of gas. It is only about 1/2 to 3/5. Among them, the smaller the amount of gas generated, the smaller the effect on the mask or the optical system, and the like.

<藉電子描畫裝置之評估><Evaluation of electronic drawing device>

(光阻之調製及塗布)溶解100重量份之實施例1所得感光性樹脂1及4重量份之三苯基矽烷基胺於2000重量份之丙二醇單甲基醚乙酸酯中，用0.2 μm之濾器(PTFE濾器)過濾而調製得正型光阻。用旋轉塗布器將將該光阻溶液塗布在經六甲基二矽氮烷處理之4英吋之矽晶片上，以加熱板在110℃下加熱90秒鐘而製成膜厚為0.1 μm之均一之膜。按照相同方法，使用實施例2至10所得感光性樹脂2至10分別調製成正型光阻而製膜。(Preparation and Coating of Photoresist) 100 parts by weight of the photosensitive resin 1 obtained in Example 1 and 4 parts by weight of triphenylsulfonylalkylamine were dissolved in 2000 parts by weight of propylene glycol monomethyl ether acetate, and 0.2 μm was used. The filter (PTFE filter) is filtered to prepare a positive photoresist. The photoresist solution was coated on a 4 inch ruthenium wafer treated with hexamethyldiazane by a spin coater, and heated at 110 ° C for 90 seconds to form a film thickness of 0.1 μm. Uniform film. According to the same method, the photosensitive resins 2 to 10 obtained in Examples 2 to 10 were each prepared into a positive resist to form a film.

使用電子束描繪裝置，以加速電壓30keV、電流值50pA左右之條件下，在上述製成之光阻薄膜上，照射期待得100nm之線與間隙(line and space)之圖案。照射後在90℃進行烘烤60秒鐘，在23℃下浸漬於氫氧化四甲銨(TMAH)之2.38重量%之水溶液中30秒鐘，然後用純水淋洗並乾燥。使用下述方法評估所得圖案。An electron beam drawing device was used to irradiate a pattern of lines and spaces expected to have a thickness of 100 nm on the above-mentioned photoresist film under the conditions of an acceleration voltage of 30 keV and a current value of about 50 pA. After the irradiation, baking was carried out at 90 ° C for 60 seconds, and immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C for 30 seconds, followed by rinsing with pure water and drying. The resulting pattern was evaluated using the method described below.

(感度)使用掃描型電子顯微鏡(SEM)觀察所得圖案之剖面。以能解像100nm線條(線與間隙1：1)之最小照射能量做為感度。(Sensitivity) The cross section of the obtained pattern was observed using a scanning electron microscope (SEM). The sensitivity is the minimum illumination energy that resolves the 100 nm line (line and gap 1:1).

(線端粗糙度(line edge roughness))使用掃描型電子顯微鏡(SEM)觀察上述感度下製成之線圖案，求得線端粗糙度(LER)。又，線端粗糙度係沿著所得SEM像之線圖案在1.5 μm長將間隔10nm之各點之分散度之標準偏差乘上3倍而求得。該粗糙度值越小表示越平滑。(Line edge roughness) A line pattern prepared by the above sensitivity was observed using a scanning electron microscope (SEM) to obtain a line end roughness (LER). Further, the line end roughness was obtained by multiplying the standard deviation of the dispersion of each dot at intervals of 10 nm by a factor of 3 along the line pattern of the obtained SEM image by three times. The smaller the roughness value, the smoother it is.

該結果就實施例1至10之光阻而言，感度為6.4至20 μ C/cm² 時，LER顯示2.0至6.0nm，形成良好之圖案。又，就實施例1至10之光阻，藉加速電壓為50keV之電子束描繪裝置，確認可得100nm以下之解像性能。特別在實施例7之光阻，確認具備25nm之解像性能。As a result, with respect to the photoresists of Examples 1 to 10, when the sensitivity was 6.4 to 20 μC/cm ² , the LER showed 2.0 to 6.0 nm, forming a good pattern. Further, with respect to the photoresists of Examples 1 to 10, it was confirmed that the resolution of 100 nm or less was obtained by an electron beam drawing device having an acceleration voltage of 50 keV. In particular, in the photoresist of Example 7, it was confirmed that the resolution of 25 nm was obtained.

因此，確認使用本發明之感光性樹脂可形成良好之圖案。Therefore, it was confirmed that a good pattern can be formed by using the photosensitive resin of the present invention.

Claims (7)

一種感光性樹脂，具有下式(1)所示之重複單位、選自下式(2)所示之重複單位和下式(3)所示之重複單位之至少一方、以及下式(4)所示之重複單位，必要時還具有下式(5)所示之重複單位， (式(1)中，R₁ 表示碳數2至9之直鏈狀或分枝狀之2價之伸烷基，R₂ 至R₅ 各自獨立地表示氫原子或碳數1至3之直鏈狀或分枝狀之烷基，R₆ 及R₇ 表示可經碳數1至6之烷基取代之苯基，X^- 表示下式(6)所示之陰離子、下式(7)所示之雙(全氟烷基磺醯)亞胺離子、下式(8)所示之陰離子) (式(2)中，R₈ 表示碳數2至9之直鏈狀或分枝狀之烴基) C_k H_m F_n SO₃ ^- (6)(式(6)中，k、m及n各自獨立地表示0以上之整數；m為0時，k為1至8之整數，n為2k+1，式(6)為全氟烷基磺酸鹽離子；n為0時，k為1至15之整數，m為1以上之整數，式(6)為烷基磺酸鹽離子、苯磺酸 鹽離子或烷基苯磺酸鹽離子；m及n各自獨立地為1以上之整數時，k為1至10之整數，式(6)為經氟取代之苯磺酸鹽離子、經氟取代之烷基苯磺酸鹽離子或經氟取代之烷基磺酸鹽離子)(C_p F_2p+1 SO₂ )₂ N^- (7)(式中，p表示1至8之整數) A photosensitive resin having a repeating unit represented by the following formula (1), at least one selected from the repeating unit represented by the following formula (2) and the repeating unit represented by the following formula (3), and the following formula (4) The repeating unit shown, if necessary, has a repeating unit as shown in the following formula (5). (In the formula (1), R ₁ represents a linear or branched divalent alkylene group having 2 to 9 carbon atoms, and R ₂ to R ₅ each independently represent a hydrogen atom or a carbon number of 1 to 3 a chain or branched alkyl group, R ₆ and R ₇ represent a phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms, and X ^- represents an anion represented by the following formula (6), and the following formula (7) The bis(perfluoroalkylsulfonyl)imide ion, an anion represented by the following formula (8) (In the formula (2), R ₈ represents a linear or branched hydrocarbon group having 2 to 9 carbon atoms) C _k H _m F _n SO ₃ ^- (6) (In the formula (6), k, m and n each independently represent an integer of 0 or more; when m is 0, k is an integer of 1 to 8, and n is 2k+ 1, (6) is a perfluoroalkyl sulfonate ion; when n is 0, k is an integer from 1 to 15, m is an integer of 1 or more, and formula (6) is an alkylsulfonate ion, benzenesulfonate a salt of an acid salt or an alkylbenzenesulfonate; when m and n are each independently an integer of 1 or more, k is an integer of 1 to 10, and formula (6) is a benzenesulfonate ion substituted by fluorine, and fluorine Substituted alkylbenzene sulfonate ion or fluorine-substituted alkyl sulfonate ion) (C _p F _2p+1 SO ₂ ) ₂ N ^- (7) (wherein p represents an integer from 1 to 8) 如申請專利範圍第1項之感光性樹脂，其中，X^- 所示之陰離子係下式(6)所示之陰離子，C_k H_m F_n SO₃ ^- (6)(式(6)中，k、m及n各自獨立地表示0以上之整數；m為0時，k為1至8之整數，n為2k+1，式(6)為全氟烷基磺酸鹽離子；n為0時，k為1至15之整數，m為1以上之整數，式(6)為烷基磺酸鹽離子、苯磺酸鹽離子或烷基苯磺酸鹽離子；m及n各自獨立地為1以上之整數時，k為1至10之整數，式(6)為經氟取代之苯磺酸鹽離子、經氟取代之烷基苯磺酸鹽離子或經氟取代之烷基磺酸鹽離子)。The photosensitive resin according to claim 1, wherein the anion represented by X ^- is an anion represented by the following formula (6), and C _k H _m F _n SO ₃ ^- (6) (in the formula (6), k, m and n each independently represent an integer of 0 or more; when m is 0, k is an integer of 1 to 8, n is 2k+1, and formula (6) is a perfluoroalkyl sulfonate ion; n is 0. Wherein k is an integer from 1 to 15, m is an integer of 1 or more, and formula (6) is an alkylsulfonate ion, a besylate ion or an alkylbenzenesulfonate ion; m and n are each independently When the integer is 1 or more, k is an integer of 1 to 10, and the formula (6) is a fluorine-substituted benzenesulfonate ion, a fluorine-substituted alkylbenzenesulfonate ion or a fluorine-substituted alkylsulfonate. ion). 如申請專利範圍第1項之感光性樹脂，其中，X^- 所示之陰離子係下式(7)所示之雙(全氟烷基磺醯)亞胺離子，(C_p F_2p+1 SO₂ )₂ N^- (7)(式中，p表示1至8之整數)。The patentable scope of application of the photosensitive resin, Paragraph 1, wherein, X ^- anion of the system shown in formula (7) of bis (perfluoroalkyl sulfonylurea) imide _{ions, (C p F 2p + 1} SO ₂ ) ₂ N ^- (7) (wherein p represents an integer from 1 to 8). 如申請專利範圍第1項之感光性樹脂，其中，X^- 所示之陰離子係下式(8)所示之陰離子， The photosensitive resin according to the first aspect of the invention, wherein the anion represented by X ^- is an anion represented by the following formula (8), 如申請專利範圍第1項之感光性樹脂，其重量平均分子量為2,000至100,000，上式(1)之重複單位數a、上式(2)之重複單位數b、上式(3)之重複單位數c、上式(4)之重複單位數d、及上式(5)之重複單位數e係滿足a/(a+b+c+d+e)=0.001至0.3、(b+c)/(a+b+c+d+e)=0.1至0.5、(d+e)/(a+b+c+d+e)=0.5至0.8、及e/(d+e)=0至0.2。 The photosensitive resin according to the first aspect of the patent application has a weight average molecular weight of 2,000 to 100,000, a repeating unit number a of the above formula (1), a repeating unit number b of the above formula (2), and a repeat of the above formula (3). The number of units c, the number of repeating units d of the above formula (4), and the number of repeating units e of the above formula (5) satisfy a/(a+b+c+d+e)=0.001 to 0.3, (b+c) /(a+b+c+d+e)=0.1 to 0.5, (d+e)/(a+b+c+d+e)=0.5 to 0.8, and e/(d+e)=0 To 0.2. 如申請專利範圍第1項之感光性樹脂，其中，主鏈之末端基為氫原子或甲基。 The photosensitive resin of claim 1, wherein the terminal group of the main chain is a hydrogen atom or a methyl group. 一種感光性組成物，係為使申請專利範圍第1項至第6項中任一項之感光性樹脂溶解於有機溶劑之溶液，該有機溶劑為乙二醇單烷基醚類、乙二醇單烷基醚乙酸酯類、二乙二醇二烷基醚乙酸酯類、丙二醇單烷基醚類、丙二醇單烷基醚乙酸酯類或丙二醇二烷基醚乙酸酯類。 A photosensitive composition which is a solution in which a photosensitive resin according to any one of claims 1 to 6 is dissolved in an organic solvent, which is ethylene glycol monoalkyl ether or ethylene glycol. Monoalkyl ether acetates, diethylene glycol dialkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates or propylene glycol dialkyl ether acetates.