TW200832068A - Positive radiation-sensitive resin composition and pattern forming method - Google Patents

Abstract

Disclosed is a positive radiation-sensitive resin composition which is excellent in nano edge roughness, etching resistance, sensitivity and resolution, and enables to stably form a high-precision fine pattern. Specifically disclosed is a positive radiation-sensitive resin composition containing a radiation-sensitive acid generator (A) and an acid-cleavable group-containing resin (B). The radiation-sensitive acid generator (A) is a mixed acid generator containing an acid generator (A1) and another acid generator (A2), and the acid generator (A1) and the acid generator (A2) have a same cation. The acid generator (A1) is represented by the formula (1) below and generates a carboxylic acid having a boiling point at atmospheric pressure of not less than 150 DEG C when irradiated with radiation. The acid generator (A2) is represented by the formula (2) below and generates an acid other than carboxylic acids when irradiated with radiation. The resin (B) contains the repeating unit (I) below, the repeating unit (ii) below and the repeating unit (iii) below. M<+>RCOO<-> (1) M<+>X<-> (2) In the above formulae, M<+> represents a monovalent onium cation; R represents a monovalent organic group; and X<-> represents a monovalent anion.

Description

200832068 九、發明說明 【發明所屬之技術領域】 本發明關於適合於使用電子線、X射線、極紫外線等 的微細圖型形成之正型敏輻射線性樹脂組成物及圖型形成 方法。 【先前技術】 • 於積體電路元件之製造所代表的微細加工領域中，爲 了得到積體電路的更高積體度，急速進行微影術的設計規 則之微細化，可安定地進行微細加工的微影術製程之開發 係被強烈推進著。然而，於習知的使用KrF、ArF準分子 雷射的方法中’由於以局精度來形成1 〇 〇 n m以下的微細 圖型係困難的，故有提案使用電子線（以下亦稱爲「EB 」）、極紫外線（以下亦稱爲「EUV」）的超微細化工。 作爲如此的超微細加工中所使用的EB或EUV用正型 ® 光阻材，即正型敏輻射線性樹脂組成物，有提案（1 ) PMMA (聚甲基丙烯酸酯）等的甲基丙烯酸系主鏈切斷型 敏輻射線性樹脂組成物，（2 )含有經酸解離性官能基所 部分保護的聚羥基苯乙烯系樹脂（KrF準分子用樹脂）、 ' 酚醛清漆（i線用樹脂）、及酸產生劑的化學增幅型敏輻 射線性樹脂組成物等。 上述（1 )甲基丙烯酸系主鏈切斷型敏輻射線性樹脂 組成物，一般顯示優異的解像度，但會有蝕刻耐性、感度 等不充分等的問題。作爲用於消除如此問題的關聯技術， -5- 200832068 可舉出解像度與感度的平衡優異之聚第三丁基α -苯乙烯（例如參照專利文獻1 )，於樹脂末端導入 子線可容易切斷的氮原子、氧原子、硫原子者（例 專利文獻2)等。然而，現狀爲一方面雖然感度確 善，但另一方面其水平與鈾刻耐性係尙未達到實用 圍。 又，上述（2 )化學增幅型敏輻射線性樹脂組 φ 一般係感度、解像度、及蝕刻耐性的平衡優異者。 聯的先前技術，可舉出部分縮醛保護聚羥基苯乙烯 酸產生劑的組合（例如參照專利文獻3 )，各種酸 部分保護聚羥基苯乙烯樹脂與含氟的芳香族磺酸發 及氟系或矽系界面活性劑的組合（例如參照專利文 ，具有至少一個吸電子基（氟原子、氰基、硝基） 離子部的取代基之鑰鹽（例如參照專利文獻5 )， 磺醯基的樹脂（例如參照專利文獻6)，具有Ν -• 胺基磺醯基的樹脂（例如參照專利文獻7)等。然 使爲此等專利文獻所揭示的樹脂等，在微細圖型形 實際的線寬與設計線寬的尺寸差異（以下亦稱爲「 ^ 緣粗糙度」）、感度、及解像度的方面，現狀爲尙 ' 實用化水平。 專利文獻1 :特開2000- 1 47777號公報 專利文獻2 :特開平1 1 - 2 9 6 1 2號公報 專利文獻3 :特開平6-1 94842號公報 專利文獻4:特開2000-187330號公報 氯甲基 有以電 如參照 實有改 化的範 成物， 作爲關 樹脂與 解離性 生鑰鹽 獻4 ) 當作陽 具有二 氧基亞 而，即 成中， 奈米邊 未達到 200832068 專利文獻5 :特開200 1 -075283號公報 專利文獻6 :特開2002-072483號公報 專利文獻7 :特開2002-1 07920號公報 【發明內容】 發明所欲解決的問題 本發明係鑒於如此的先前技術所具有的問題點而完成 # 者，其課題爲提供奈米邊緣粗糙度、蝕刻耐性、感度、及 解像度優異，可安定地形成高精度的微細圖型之正型敏輻 射線性樹脂組成物以及圖型形成方法。 解決問題的手段 本發明人們爲了達成上述課題，經過精心檢討’結果 發現藉由組合作爲敏輻射線性酸產生劑的指定鐵鹽、與鹼 不溶性或難溶性的指定樹脂成分，可達成上述課題，終於 ® 完成本發明。 即，本發明的正型敏輻射線性樹脂組成物之特徵爲含 有以下的敏輻射線性酸產生劑（A )、及藉由樹脂中所含 &quot; 有的酸解離性基之解離而成爲鹼可溶性之鹼不溶性或難溶 ' 性的樹脂（B )。特徵爲：上述敏輻射線性酸產生劑係含 酸產生劑（A 1 )與酸產生劑（A2 )的混合酸產生劑，酸 產生劑（A1)與酸產生劑（A2)具有相同的陽離子，上 述酸產生劑（A 1 )係經由輻射線照射而產生常壓之沸點 爲150 °C以上的羧酸，且由下述式（Ο所表示，上述酸產 200832068 生劑（A2 )係經由輻射線照射而產生羧酸以外的酸，J 由下述式（2 )所表示，上述樹脂（B )係含有下述重複單 位（i)、下述重複單位（ii)及下述重複單位（Hi)的胃 ， 脂。 酸產生劑（A 1 ): [化7] φ M + RCOCT (1) 酸產生劑（A2 ): [化8] Μ + Χ· (2) 式（1 )及式（2 )中，Μ +係下述式（6 )或下述式（ 7 )所表示的1價鐵陽離子。 • [化 9] R16 RI9[Technical Field] The present invention relates to a positive-type radiation-sensitive linear resin composition and a pattern forming method which are suitable for forming a fine pattern using an electron beam, an X-ray, an extreme ultraviolet ray or the like. [Prior Art] In the field of microfabrication represented by the manufacture of integrated circuit components, in order to obtain a higher integration of the integrated circuit, the design rule of the lithography is rapidly refined, and the microfabrication can be performed stably. The development of the lithography process was strongly promoted. However, in the conventional method using KrF and ArF excimer lasers, it is difficult to form a fine pattern of 1 〇〇 nm or less with local precision. Therefore, it is proposed to use an electron beam (hereinafter also referred to as "EB". ") Ultra-fine chemicals of extreme ultraviolet rays (hereinafter also referred to as "EUV"). As a positive-type radiation-resistant linear resin composition for EB or EUV used in such ultrafine processing, there is a proposal for (1) methacrylic acid such as PMMA (polymethacrylate). a main chain-cut type sensitive radiation linear resin composition, (2) a polyhydroxystyrene resin (KrF excimer resin) partially protected by an acid-dissociable functional group, a 'novolak resin (i-line resin), And a chemically amplified type sensitive radiation linear resin composition of an acid generator. The above (1) methacrylic-based main chain-cut type radiation sensitive linear resin composition generally exhibits excellent resolution, but has problems such as insufficient etching resistance and sensitivity. As a related art for eliminating such a problem, -5-200832068 is a polybutylene-α-styrene excellent in the balance between resolution and sensitivity (see, for example, Patent Document 1), and the introduction of a strand at the end of the resin can be easily cut. A nitrogen atom, an oxygen atom or a sulfur atom (for example, Patent Document 2). However, the status quo is that on the one hand, although the sensitivity is good, on the other hand, its level and uranium tolerance system have not reached a practical level. Further, the above (2) chemically amplified type radiation sensitive linear resin group φ is generally excellent in the balance of sensitivity, resolution, and etching resistance. The prior art of the combination may be a combination of a partial acetal-protected polyhydroxystyrene acid generator (for example, refer to Patent Document 3), and various acid portions protect the polyhydroxystyrene resin, the fluorine-containing aromatic sulfonic acid, and the fluorine-based compound. Or a combination of a lanthanide surfactant (for example, refer to the patent, a key salt having a substituent of at least one electron-withdrawing group (fluorine atom, cyano group, nitro group) ion moiety (for example, refer to Patent Document 5), sulfonyl group Resin (for example, refer to Patent Document 6), a resin having an oxime-aminosulfonyl group (for example, see Patent Document 7), etc., and the resin disclosed in the patent documents, etc. The difference between the width and the design line width (hereinafter also referred to as "^ edge roughness"), sensitivity, and resolution is the current level of practicality. Patent Document 1: JP-A-2000- 1 47777 (2) Unexamined Patent Publication No. JP-A No. Hei. No. Hei. No. 2000-187330. Fan Cheng, as a resin And dissociative key salt 4) as a cation with a dioxy group, in the middle, the nano side does not reach 200832068 Patent Document 5: JP-A-200 1 -075283 Patent Document 6: Special opening 2002-072483 SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The present invention has been made in view of the problems of the prior art, and the problem is to provide a rough edge of the nanometer. Excellent in degree, etching resistance, sensitivity, and resolution, and it is possible to stably form a highly accurate micro-pattern positive positive radiation linear resin composition and pattern forming method. Means for Solving the Problems In order to achieve the above-mentioned problems, the present inventors have made a careful review. As a result, it has been found that the above-mentioned problems can be attained by combining a specified iron salt as a linear radiation generator for a radiation radiation, and a specified resin component which is insoluble or poorly soluble in alkali. ® completed the invention. That is, the positive-sensitive radiation linear resin composition of the present invention is characterized in that it contains the following radiation-sensitive linear acid generator (A) and is dissociated by the acid dissociation group contained in the resin to become alkali-soluble. An alkali-insoluble or poorly soluble resin (B). The above-mentioned sensitive radiation linear acid generator is a mixed acid generator containing an acid generator (A 1 ) and an acid generator (A2 ), and the acid generator (A1) has the same cation as the acid generator (A2). The acid generator (A 1 ) is a carboxylic acid having a boiling point of 150 ° C or higher at normal pressure by irradiation with radiation, and is represented by the following formula (Ο, the above-mentioned acid production 200832068 (A2) is via radiation The line is irradiated to generate an acid other than a carboxylic acid, and J is represented by the following formula (2), and the resin (B) contains the following repeating unit (i), the following repeating unit (ii), and the following repeating unit (Hi) The stomach, fat. Acid generator (A 1 ): [Chem. 7] φ M + RCOCT (1) Acid generator (A2 ): [Chemical 8] Μ + Χ · (2) Formula (1) and formula ( 2), Μ + is a monovalent iron cation represented by the following formula (6) or the following formula (7): • [Chemical 9] R16 RI9

I II I

Rn_ 矿 ι+ I ! R18 R20 (6) (7) 式（6)及式（7)中，R16、R17、R18、R19 及 R2G 互相獨 立地係取代或未取代的碳數1〜1 0的直鏈狀或支鏈狀的烷 基、或碳數6〜18的芳基，R16、R17及R18中的二個以上 可互相鍵結而與式中的硫原子一起形成環，R19與r2G可 -8-Rn_ 矿+ I ! R18 R20 (6) (7) In the formula (6) and (7), R16, R17, R18, R19 and R2G are independently substituted or unsubstituted carbon numbers 1 to 1 0 a linear or branched alkyl group or an aryl group having 6 to 18 carbon atoms; two or more of R16, R17 and R18 may be bonded to each other to form a ring together with a sulfur atom in the formula, and R19 and r2G may be used. -8-

200832068 互相鍵結而與式中的碘原子一起形成環。 式（1)的R表示碳數5〜20的直鏈狀、支鏈狀 狀的烷基、碳數5〜2 0的直鏈狀、支鏈狀或環狀的烯 _ 碳數5〜20的直鏈狀、支鏈狀或環狀的炔基、碳數f 的直鏈狀、支鏈狀或環狀的烷氧基、上述烷基的氫原 至少一部分經鹵素原子及/或羥基取代的基、上述烯 氫原子之至少一部分經鹵素原子及/或羥基取代的基 • 碳數6〜20的取代或未取代的芳基。 式（2)的X表示取代或未取代的碳數1〜20的 狀、支鏈狀或環狀的烷基、或取代或未取代的碳數6 的具有芳基的磺酸陰離子，上述烷基的氫原子之至少 分經鹵素原子及/或羥基取代的基、或碳數6〜18的 或未取代的芳基。 重複單位（i ):下述式（3 )所示的重複單位 [化 10] R] 式（3 )中，R1係氫原子或甲基，R2係1價有機基 r2以複數存在時，該複數的R2可互相相同或不同， 〇〜3的整數，q係1〜3的整數。 重複單位（Π ) ··下述式（4 )所示的重複單位 或環 基、 〜20 子之 基的 、或 直鏈 〜1 8 一部 取代 ，於 P係 -9- 200832068 [化 11]200832068 Bonds to each other to form a ring together with the iodine atom in the formula. R in the formula (1) represents a linear or branched alkyl group having 5 to 20 carbon atoms, a linear, branched or cyclic alkene having 5 to 20 carbon atoms, and a carbon number of 5 to 20 a linear, branched or cyclic alkynyl group, a linear, branched or cyclic alkoxy group having a carbon number f, and at least a part of the hydrogen atom of the above alkyl group substituted by a halogen atom and/or a hydroxyl group And a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, at least a part of which is substituted by a halogen atom and/or a hydroxyl group. X of the formula (2) represents a substituted or unsubstituted carbon number of 1 to 20, a branched or cyclic alkyl group, or a substituted or unsubstituted sulfonic acid anion having an aryl group having 6 carbon atoms, the above alkane The hydrogen atom of the group is substituted with at least a halogen atom and/or a hydroxyl group, or a carbon number of 6 to 18 or an unsubstituted aryl group. Repeating unit (i): a repeating unit represented by the following formula (3) [Chemical Formula 10] R] In the formula (3), when R1 is a hydrogen atom or a methyl group, and R2 is a monovalent organic group r2, it is present in a plural number. The plural R2s may be the same or different from each other, 整数~3 integers, and q are integers of 1 to 3. Repeating unit (Π) · Repeating unit or ring group represented by the following formula (4), base of ~20 subunit, or straight chain ~1 8 part substitution, in P system -9- 200832068 [Chem. 11]

(R4)r (〇R5)2 式（4 )中，R3係氫原子或甲基，R4係1價有機基（但是 ，相當於-OR5的基係除外），R5係從1-支鏈烷基、三有 機矽烷基、及三有機甲鍺烷基所組成族群所選出的1價酸 解離性基，於R4及R5各以複數存在時，該複數的R4及 R5各可互相相同或不同，r係0〜3的整數、s係1〜3的 整數。 重複單位（iii):從下述式（5-1)〜式（5-4)所組 成族群所選出的至少1個重複單位 [化 12](R4)r (〇R5)2 In the formula (4), R3 is a hydrogen atom or a methyl group, R4 is a monovalent organic group (except for a group corresponding to -OR5), and R5 is a 1-branched alkane. a monovalent acid dissociable group selected from the group consisting of a triorganoalkylene group and a triorganomylalkyl group; when R4 and R5 are each present in plural, the plural R4 and R5 may be the same or different from each other, r is an integer of 0 to 3, and an integer of s is 1 to 3. Repeating unit (iii): at least one repeating unit selected from the group consisting of the following formulas (5-1) to (5-4) [Chemical 12]

式（5-1)〜式（5-4)中、rIrIrM'R11 及 R14 各自 獨立地係氫原子或甲基，R7係1價有機基（但是’相當 -10- 200832068 於式（4 )的-OR5之基係除外），於r7以複數存在時， 該複數的R7可互相相同或不同，t係0〜3的整數，r9係 2價的酸解離性之有機基，R12係碳數1〜4的烷基， ^ 係氫原子、甲基、或乙基，R15係3級烷基。 本發明的正型敏輻射線性樹脂組成物之特徵爲上述輻 射線係電子線或極紫外線，由樹脂組成物所得到的被膜係 被電子線或極紫外線所圖型化。 • 本發明的圖型形成方法之特徵爲使用上述本發明的正 型敏輻射線性樹脂組成物，藉由電子線或極紫外線來曝光 發明的效果 本發明的正型敏輻射線性樹脂組成物，由於含有上述 敏輻射線性酸產生劑（A )及上述含酸解離性的樹脂（B )，故奈米邊緣粗糙度、飩刻耐性、感度、及解像度優異 ，可安定地形成高精度的微細圖型。 【實施方式】 實施發明的最佳形態 &lt;敏輻射線性酸產生劑（A ) &gt; 本發明所可使用的敏輻射線性酸產生劑（A )係含有 上述式（1)所示的酸產生劑（A1)及上述式（2)所示 的酸產生劑（A2 )之混合酸產生劑。 式（1 )及式（2 )中，M +係相同的1價鑰陽離子。 -11 - 200832068 作爲1價鍚陽離子的合適例，可舉出Ο、S、Se、N、P、 As、Sb、Cl、Br、I等的鑰陽離子。其中，更佳爲S、I 的鑰陽離子。 作爲M +所表示的1價鑰陽離子之具體例子，可舉出 下述式（6)或式（7)所表示的鑰陽離子。 [化 13] R16 R19In the formulae (5-1) to (5-4), rIrIrM'R11 and R14 are each independently a hydrogen atom or a methyl group, and R7 is a monovalent organic group (but 'equivalent to -10-200832068 to the formula (4)) Except for the base of -OR5), when r7 is present in a complex number, the plural R7 may be the same or different from each other, t is an integer of 0 to 3, r9 is a divalent acid dissociable organic group, and R12 is a carbon number of 1 ～4 alkyl, ^ is a hydrogen atom, a methyl group, or an ethyl group, and R15 is a tertiary alkyl group. The positive-type radiation-sensitive linear resin composition of the present invention is characterized by the above-mentioned radiation-based electron beam or extreme ultraviolet ray, and the film obtained from the resin composition is patterned by electron rays or extreme ultraviolet rays. • The pattern forming method of the present invention is characterized in that the positive-sensitive radiation linear resin composition of the present invention is used to expose the effect of the invention by electron beam or extreme ultraviolet ray, and the positive-sensitive radiation linear resin composition of the present invention is The above-mentioned sensitive radiation linear acid generator (A) and the above-mentioned acid-dissociable resin (B) are excellent in nanometer edge roughness, etch resistance, sensitivity, and resolution, and can stably form a high-precision fine pattern. . [Embodiment] The best mode for carrying out the invention &lt;sensitive radiation linear acid generator (A) &gt; The radiation sensitive linear acid generator (A) usable in the present invention contains the acid produced by the above formula (1) A mixed acid generator of the acid generator (A2) represented by the agent (A1) and the above formula (2). In the formulae (1) and (2), the M + is the same monovalent cation. -11 - 200832068 A suitable example of the monovalent phosphonium cation is a key cation such as ruthenium, S, Se, N, P, As, Sb, Cl, Br, or I. Among them, the key cations of S and I are more preferable. Specific examples of the monovalent cation represented by M + include a key cation represented by the following formula (6) or (7). [Chem. 13] R16 R19

⑹ ⑺ 式（6)中，R16、R17及R18係互相獨立地的取代或未取 代的碳數1〜1 〇的直鏈狀或支鏈狀的烷基、或係互相獨立 的取代或未取代的碳數6〜18的芳基。再者，R1 6、Ri7及 R18中的二個以上可互相鍵結而與式中的硫原子一起形成 環。 式（7)中，R1 9與R2G係互相獨立的取代或未取代的 碳數1〜10的直鏈狀或支鏈狀的烷基、或互相獨立的取代 或未取代的碳數6〜18的芳基。再者，R19與互相鍵 結而與式中的碘原子一起形成環。 式（1 )及（2 )中，M +所表示的1價鐵陽離子之部 分，例如可依照 Advances in Polymer Sciences，Vol (7-41 ρ·1 -48 ( 1 984 )所記載的眾所周知方法來製造。作爲丨價 鑰陽離子之更合適的具體例子，可舉出下述式（64)〜 (6-63 )所表示的锍陽離子、及下述式（π ) -12 - 200832068 )所表示的碘鑰陽離子等。 [化 14](6) (7) In the formula (6), R16, R17 and R18 are each independently substituted or unsubstituted, linear or branched alkyl group having 1 to 1 carbon number, or substituted or unsubstituted independently of each other. The carbon number is 6 to 18 aryl groups. Further, two or more of R1 6, Ri7 and R18 may be bonded to each other to form a ring together with a sulfur atom in the formula. In the formula (7), R1 9 and R2G are independently substituted or unsubstituted, linear or branched alkyl groups having 1 to 10 carbon atoms, or independently substituted or unsubstituted carbon numbers 6 to 18; Aryl. Further, R19 is bonded to each other to form a ring together with the iodine atom in the formula. In the formulae (1) and (2), the moiety of the monovalent iron cation represented by M + can be, for example, according to a well-known method described in Advances in Polymer Sciences, Vol (7-41 ρ·1 -48 (1 984)). Specific examples of the valence cation of the valence are exemplified by the phosphonium cation represented by the following formulas (64) to (6-63) and the following formula (π) -12 - 200832068). Iodine cations and the like. [Chem. 14]

(6-3)(6-3)

C：H3C:H3

ch3 -13- 200832068Ch3 -13- 200832068

CHj CH3CHj CH3

ch3Ch3

(6-10)(6-10)

〇CH3〇CH3

-14 - 200832068-14 - 200832068

O (CH2)3CH3O (CH2)3CH3

〇C(CHj)3〇C(CHj)3

och2cooc(ch3)3Och2cooc(ch3)3

(6-22) 200832068(6-22) 200832068

(CH3&gt;jCOOCCH20(CH3&gt;jCOOCCH20

-16- 200832068-16- 200832068

OHOH

OCOCH3OCOCH3

(6-33)(6-33)

(6-34) -17- 200832068 α(6-34) -17- 200832068 α

(6-35)(6-35)

CH3CH3

(6-39)(6-39)

HjC — S — CH3 (6-40)HjC — S — CH3 (6-40)

(6-41)(6-41)

CHj H3C—S+—CH2COCHj H3C—S+—CH2CO

(6-42) (CH2)3CH3(6-42) (CH2)3CH3

I CH3(CH2)3— s+—ch2co (6-43)I CH3(CH2)3— s+—ch2co (6-43)

ch3Ch3

-18- 200832068-18- 200832068

(6 一45) (6-46) 0-0 .&quot;。仆0 (6-47) (6-48)(6-45) (6-46) 0-0 .&quot;. Servant 0 (6-47) (6-48)

(6-50)(6-50)

CH3CH3

CH3 CH3CH3 CH3

-19- 200832068-19- 200832068

FF

(6-62)(6-62)

[化 15] 〇-ι+Ό (7·1) -20- 200832068 Ο^^Ό-013 , Hic^O^i+O~cH3 (7-2) (7-3)[化15] 〇-ι+Ό (7·1) -20- 200832068 Ο^^Ό-013 , Hic^O^i+O~cH3 (7-2) (7-3)

(7-4) (7_5)(7-4) (7_5)

0~i+~0^QHi, HiC2O~i+^O^c2Hs (7-6) (7-7) 〇-i+-〇-ch(ch3)2 (7-8) CH(€H3)2 ™-^ι+-〇- (7-9) ^,+-〇-c(cuj)3 (7-10) C(CH5b (ch3),c^O&quot;i+O^ (7-11) 200832068 /N〇2 . 〇·ι+·〇 (7-12) CM3) /Ν〇2 〇ζν^^ι+Ό^ν〇2 , ^&quot;ι+_η0 ο2ν7 (7-14) (7-15)0~i+~0^QHi, HiC2O~i+^O^c2Hs (7-6) (7-7) 〇-i+-〇-ch(ch3)2 (7-8) CH(€H3)2 TM-^ ι+-〇- (7-9) ^,+-〇-c(cuj)3 (7-10) C(CH5b (ch3),c^O&quot;i+O^ (7-11) 200832068 /N〇 2 . 〇·ι+·〇(7-12) CM3) /Ν〇2 〇ζν^^ι+Ό^ν〇2 , ^&quot;ι+_η0 ο2ν7 (7-14) (7-15)

〇-i+-^〇cHi, cHj〇-〇-i+-〇-〇c^ (7-16) (7-17) 0&quot;ι+_0^α . α^Ο~ι+Ό&quot;σ (7-18) (7-19)〇-i+-^〇cHi, cHj〇-〇-i+-〇-〇c^ (7-16) (7-17) 0&quot;ι+_0^α . α^Ο~ι+Ό&quot;σ (7- 18) (7-19)

(7-20) (7-21)(7-20) (7-21)

(7-22) (7-23) -22- 200832068(7-22) (7-23) -22- 200832068

Qt'O 以.CF3 π_ν/_Ι_ν/_€Γ3 (7-24) (7-25)Qt'O to .CF3 π_ν/_Ι_ν/_€Γ3 (7-24) (7-25)

Qt令、Qt order,

COOCHj -cooch3\UI (7-26) (7-27) OCH2COOC(CH3&gt;3 (7-28) 〇-i+-〇-°· o -c—〇—C(CH3)3 (7-29) 0C(CH3)3 (7-30)COOCHj -cooch3\UI (7-26) (7-27) OCH2COOC(CH3&gt;3 (7-28) 〇-i+-〇-°· o -c—〇—C(CH3)3 (7-29) 0C (CH3)3 (7-30)

ClfcOOC COOCH3 (7-31) -23- 200832068ClfcOOC COOCH3 (7-31) -23- 200832068

(CHj)jCOOCCH20 OCH2COOC(CH3)3 (7-33)(CHj)jCOOCCH20 OCH2COOC(CH3)3 (7-33)

Ο (CH3 )3 c —ο—c — ο 仆·仆丄。— c(ch3)3 (7-34)Ο (CH3 ) 3 c — ο — c — ο servant servant. — c(ch3)3 (7-34)

(CH3)3CO OC(CHj)3 (7-35)(CH3)3CO OC(CHj)3 (7-35)

(7-36) (7-37)(7-36) (7-37)

-24- 200832068 (7-40) (7-41) 於上述1價鑰陽離子之中，較佳爲式（6-i )、式（ 6-2)、式（6-6)、式（6-8)、式（6-12)、式（6-13) 、式（6-18)、式（6-19)、式（6-27)、式（6-28)、 鲁式（6-29)、式（6-33)、式（6-54)、式（6-62)、式 (6-63)所表示的锍陽離子、式（7-1)、式（7-3)、式 (7-5)、式（7-11)、式（7-12)、式（7_15)、式（7-16 )、式（7-19 )、式（7-25 )、式（7-36 )、式（7-40 )、式（7-41 )所表示的碘鑰陽離子，特佳爲式（6-1 ) 、式（6-2)、式（6-6)、式（6-29)、式（6-62)、式 (7-1 )的鑰陽離子。 作爲式（1)所表示的酸產生劑（A1)之藉由曝光而 ® 產生常壓之沸點爲1 5 0 °C以上的羧酸，例如可舉出飽和脂 肪族羧酸、不飽和脂肪族羧酸、含鹵素原子的脂肪族羧酸 、含羥基的脂肪族羧酸、含烷氧基的脂肪族羧酸、含酮基 的脂肪族羧酸、含醛基的脂肪族羧酸、含脂環式骨架的脂 ' 肪族羧酸、含芳香環的共軛羧酸、含芳香環的非共軛羧酸 等。含芳香環的共軛羧酸係指羧基的c = o基與芳香環中 的雙鍵成共軛關係的羧酸。 本發明所可使用的酸產生劑，係藉由組合上述產生常 壓的沸點爲150 °c以上的羧酸之酸產生劑（A1 )、與陽離 -25- 200832068 子部相同的產生其它酸的酸產生劑（A2 ) | 到能形成奈米邊緣粗糙度及感度優異的光阻 線性樹脂組成物。 ^ 作爲式（1)中的RCOO·，可舉出下述ϊ 1 9 )所表示的構造。 [化 16] R21COO- (8) R21表示碳數5〜20的直鏈狀、支鏈狀 '碳數5〜20的直鏈狀、支鏈狀或環狀的烯 20的直鏈狀、支鏈狀或環狀的炔基、碳數 ^ $鏈狀或環狀的烷氧基、上述烷基的氫 經鹵素原子及/或羥基取代的基、上述 t S β —部分經鹵素原子及/或羥基取代的 〜20的取代或未取代的芳基。 _ [化 17] [化 17] (CH2)h CHCOCT (9) 式（9)中，h係2〜6的整數。 fii使用，而得 圖型之敏輻射 ：；(8 )〜式（ 或環狀的院基 基、碳數5〜 5〜2 0的直鏈 原子之至少一 基的氫原子 基、或碳數6 -26- 200832068 [化 18] Ο r-c-r-coo' ⑽ R~C-R~C-R—coo~ (”) 式（10)及式（11)中，R22係與式（8)的R21同義 ，R23係亞甲基、碳數2〜20的直鏈狀、支鏈狀或環狀的 伸烷基、碳數1〜2 0的直鏈狀、支鏈狀或環狀的伸烯基、 上述伸院基的氫原子之至少一部分經鹵素原子及/或經基 取代的基、上述伸烯基的氫原子之至少一部分經鹵素原子 取代的基、或碳數2〜20的烷氧基伸烷基，複數存在的 R23可互相同或不同。 [化 19]-24- 200832068 (7-40) (7-41) Among the above 1-valent key cations, preferred are formula (6-i), formula (6-2), formula (6-6), and formula (6). -8), formula (6-12), formula (6-13), formula (6-18), formula (6-19), formula (6-27), formula (6-28), Lu (6 -29), an anthracene cation represented by formula (6-33), formula (6-54), formula (6-62), formula (6-63), formula (7-1), formula (7-3) , formula (7-5), formula (7-11), formula (7-12), formula (7_15), formula (7-16), formula (7-19), formula (7-25), formula ( 7-36), the iodine cation represented by the formula (7-40), and the formula (7-41), particularly preferably the formula (6-1), the formula (6-2), the formula (6-6), and the formula (6-29), key cation of formula (6-62), formula (7-1). The acid generator (A1) represented by the formula (1) is a carboxylic acid having a boiling point of 150 ° C or higher at normal pressure by exposure, and examples thereof include a saturated aliphatic carboxylic acid and an unsaturated aliphatic group. Carboxylic acid, halogen atom-containing aliphatic carboxylic acid, hydroxyl group-containing aliphatic carboxylic acid, alkoxy group-containing aliphatic carboxylic acid, keto group-containing aliphatic carboxylic acid, aldehyde group-containing aliphatic carboxylic acid, fat-containing a cyclic skeleton of a fatty carboxylic acid, an aromatic ring-containing conjugated carboxylic acid, an aromatic ring-containing non-conjugated carboxylic acid, and the like. The aromatic ring-containing conjugated carboxylic acid means a carboxylic acid in which a c = o group of a carboxyl group is conjugated to a double bond in an aromatic ring. The acid generator which can be used in the present invention is produced by combining the above-mentioned acid generator (A1) which produces a normal temperature of a carboxylic acid having a boiling point of 150 ° C or more, and the same acid as the cation -25-200832068 sub-portion. Acid generator (A2) | To a photoresist linear resin composition that can form nano-edge roughness and sensitivity. ^ As the RCOO· in the formula (1), the structure represented by the following ϊ 1 9 ) can be cited. R21COO-(8) R21 represents a linear or branched linear or branched chain of a linear, branched or cyclic alkene 20 having a carbon number of 5 to 20 and having a carbon number of 5 to 20 a chain or cyclic alkynyl group, a carbon number of a chain or a cyclic alkoxy group, a group in which a hydrogen of the above alkyl group is substituted with a halogen atom and/or a hydroxyl group, and the above t S β — partially passed through a halogen atom and/or Or a hydroxy substituted -20 substituted or unsubstituted aryl group. _ [Chem. 17] (CH2)h CHCOCT (9) In the formula (9), h is an integer of 2 to 6. Fii is used, and the sensitivity of the pattern is: (8)~ (or a circular base group, a hydrogen atom group of at least one of the linear atoms having a carbon number of 5 to 5 to 2 0, or a carbon number 6 -26- 200832068 化 rcr-coo' (10) R~CR~CR-coo~ (") In equations (10) and (11), R22 is synonymous with R21 of formula (8), R23 a methylene group, a linear, branched or cyclic alkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkenyl group having 1 to 20 carbon atoms, and the above-mentioned extension a group in which at least a part of a hydrogen atom of a group is substituted with a halogen atom and/or a group substituted with a group, a hydrogen atom of at least a part of the above-mentioned alkenyl group, a group substituted with a halogen atom, or an alkoxy group having a carbon number of 2 to 20 alkyl group, plural The existing R23 may be the same or different from each other.

式（12 )及式（13 )中，R22係與式（8 )的r21同義 ，複數存在的R22可互相同或不同，R23係與式（1〇 )的 R23同義，R24表示羥基或鹵素原子，複數存在的R24可互 相同或不同，m及n係〇〜3的整數，m + ng5。 -27- 200832068 [化 20]In the formulae (12) and (13), R22 is synonymous with r21 of the formula (8), and R22 of the plural number may be the same or different, R23 is synonymous with R23 of the formula (1〇), and R24 represents a hydroxyl group or a halogen atom. The plural R24s may be the same or different, m and n are integers of 〇~3, m + ng5. -27- 200832068 [Chem. 20]

式（14)中，R22係與式（8)的R21同義，複數存在 # 的R22可互相同或不同，R23係與式（10 )的R23同義， R24係與式（12 )的R24同義，複數存在的R24可互相同 或不同，m、n、m，及 η’係 0〜3 的整數，m + nS5及 m5+n，€ 5。 [化 21] N〇2 (R22)mIn the formula (14), R22 is synonymous with R21 of the formula (8), R22 of the plural number # may be the same or different, R23 is synonymous with R23 of the formula (10), and R24 is synonymous with R24 of the formula (12). The plural R24s present may be the same or different, m, n, m, and η' are integers of 0 to 3, m + nS5 and m5+n, € 5. [化 21] N〇2 (R22)m

coo (15)Coo (15)

式（15 )中，R22係與式（8 )的R21同義，m係0〜3 的整數。 [化 22]In the formula (15), R22 is synonymous with R21 of the formula (8), and m is an integer of 0 to 3. [化22]

(R23)厂 COO_ (16) 式（16)中，R22係與式（8)的R21同義，複數存在 -28- 200832068(R23) Plant COO_ (16) In formula (16), R22 is synonymous with R21 of formula (8), and plural is present -28- 200832068

(18) 的 R22可互相同或不 同 ，R23 係 與 式 ( 10) 的R23同 義 R1 4係與式（12 )的 R1 複 R24可互 rv 问義 y 數 存 在的 相 同 或 不同，m、η、m， 及 η，係 0 3 的 整數 ，m + n ^ 4 及 πΓ + n’ $ 3，z 係 〇 或 1 ° [化 23] m、η、m,及 的 R同義’複數存在的R2 3可互相同或不同， η’係0〜3的整數，m + n^5及m，+n，$4， [化 24]R18 of (18) may be the same or different, R23 is synonymous with R23 of formula (10) R1 4 is different from R1 of formula (12) R24 can be the same or different from y number, m, η, m, and η, an integer of 0 3 , m + n ^ 4 and πΓ + n' $ 3, z system 〇 or 1 ° [23] m, η, m, and R synonymous 'complex R2 3 Can be the same or different, η' is an integer of 0~3, m + n^5 and m, +n, $4, [24]

(19) 式（19 )中’：^^係與式^:的尺^同義 R22可互相同或不同，R23係與式（1〇)的 ，複數存在 R23同義， -29- 1 係0或1。 200832068 R24係與式（l2 )的R24同義，複數存在的R24可互相同 或不同，m及η係0〜3的整數，m + n$4，z係0或1。 作爲特佳的RC00_之例子，可舉出下述。 [化 25](19) In the formula (19), the '^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ 1. 200832068 R24 is synonymous with R24 of formula (l2), and R24 of plural number may be the same or different, m and η are integers of 0~3, m + n$4, z is 0 or 1. As an example of the particularly preferable RC00_, the following is mentioned. [Chem. 25]

COO· ch2- coo-,COO· ch2- coo-,

作爲上述式（1 )所表示的酸產生劑（A 1 )之具體例 子，可舉出三苯基锍水楊酸鹽、4 -羥苯基二苯基毓水楊 酸鹽、三（4 一氟苯基）鏡水楊酸鹽、4 一甲基苯基二苯基 鏡1 -金剛烷羧酸鹽、2,4,6三甲基苯基二苯基毓水楊酸 鹽、雙（4 一氟苯基）碘鑰水楊酸鹽、三（4 一氟苯基）鏡 1 一金剛烷羧酸鹽、（4 一氟苯基）碘鑰水楊酸鹽、雙（4 一氟苯基）碘鏺1 一金剛烷羧酸鹽、2,4,6 -三甲基苯基二 苯基毓1 一金剛烷羧酸鹽、4-第三丁氧羰基甲基氧基苯 基二苯基锍水楊酸鹽等。 又，上述式（1)所表示的酸產生劑（A1)可爲單獨 或混合2種以上使用。 另外，經由輻射線照射而產生羧酸以外的酸之式（2 -30- 200832068 )所表示的酸產生劑（A2 ) ’例如是鑰鹽化合物。作爲 鑰鹽化合物，可舉出锍鹽、碘鐵鹽等。 作爲式（2 )所表示的鑰鹽化合物之具體例子’可舉 出以下的例子。 * 作爲式（6-1)所表示的毓陽離子之鹽，可舉出三苯 * 基毓三氟甲烷磺酸鹽、三苯基鏡九氟正丁烷磺酸鹽、三苯 基毓全氟正辛烷磺酸鹽、三苯基毓對甲苯磺酸鹽、三苯基 鏡苯礦酸鹽、二苯基蔬10 -棒腦礦酸鹽、二苯基鏡正半 烷磺酸鹽、三苯基锍2 -三氟甲基苯磺酸鹽、三苯基鏡4 -三氟甲基苯磺酸鹽、三苯基毓萘磺酸鹽、三苯基毓全氟 苯磺酸鹽、三苯基毓2，4 -二氟甲基苯磺酸鹽、三苯基鏡 1，1，2,2—四氟—2—(四環[4.4.0.12’5.17’1()]十二烷—8—基 )乙烷磺酸鹽、三苯基鏡1，1 一二氟一 2—(雙環[2·2·1]庚 烷一 2 -基）乙烷磺酸鹽等。 作爲式（6-2 )所表示的毓陽離子之鹽，可舉出4-甲 * 基苯基二苯基毓三氟甲烷磺酸鹽、4 一甲基苯基二苯基銃 九氟正丁烷磺酸鹽、4-甲基苯基二苯基毓全氟正辛烷磺 酸鹽、4 一甲基苯基二苯基毓對甲苯磺酸鹽、4一甲基苯基 ~ 二苯基鏡苯磺酸鹽、4 -甲基苯基二苯基鏡1 〇〜樟腦磺酸 . 鹽、4-甲基苯基二苯基毓正辛烷磺酸鹽、4 一甲基苯基二 苯基銃2—三氟甲基苯磺酸鹽、4一甲基苯基二苯基锍4一 三氟甲基苯磺酸鹽、4-甲基苯基二苯基毓萘磺酸鹽、4一 甲基苯基二苯基毓2，4-二氟甲基苯磺酸鹽等。 作爲式（6-6)所表示的鏡陽離子之鹽，可舉出 -31 - 200832068 2,4,6-三甲基苯基二苯基毓三氟甲烷磺酸鹽、2,4,6-三甲基 苯基二苯基毓2,4-二氟苯磺酸鹽、2,4,6-三甲基苯基二苯 基毓對甲苯磺酸鹽、2,4,6-三甲基苯基二苯基毓4-三氟苯 磺酸鹽等。 作爲式（6-8)所表示的毓陽離子鹽，可舉出三（4 一 ' 甲基苯基）毓三氟甲烷磺酸鹽、三（4 一甲基苯基）毓九 氟正丁烷磺酸鹽、三（4 -甲基苯基）鏡全氟正辛烷磺酸 φ 鹽、三（4 一甲基苯基）鏡對甲苯磺酸鹽、三（4 一甲基苯 基）毓苯磺酸鹽、三（4 一甲基苯基）毓1 0 -樟腦磺酸鹽 、三（4 一甲基苯基）锍正辛烷磺酸鹽、三（4 一甲基苯基 )毓2-三氟甲基苯磺酸鹽、三（4 一甲基苯基）鏡4一三 氟甲基苯磺酸鹽、三（4 一甲基苯基）毓萘磺酸鹽、三（4 一甲基苯基）鏑2,4 一二氟甲基苯磺酸鹽等。 作爲式（6-1 2 )所表示的銃陽離子之鹽，可舉出（4 一第三丁基苯基）二苯基毓三氟甲烷磺酸鹽、（4 一第三 # 丁基苯基）二苯基毓九氟正丁烷磺酸鹽、（4 一第三丁基 苯基）二苯基锍全氟正辛烷磺酸鹽、（4 -第三丁基苯基 )二苯基毓正甲苯磺酸鹽、（4 一第三丁基苯基）二苯基 ‘ 锍苯磺酸鹽、（4 一第三丁基苯基）二苯基毓1 0 —樟腦磺 • 酸鹽、（4 一第三丁基苯基）二苯基毓正辛烷磺酸鹽、（4 一第三丁基苯基）二苯基鏡2 —三氟甲基苯磺酸鹽、（4 -第三丁基苯基）二苯基毓4 一三氟甲烷苯磺酸鹽、（4 -第三丁基苯基）二苯基鏑全氟苯磺酸鹽等。 作爲式（6-13)所表示的毓陽離子之鹽，可舉出三（ -32- 200832068 4-第三丁基苯基）銃三氟甲烷磺酸鹽、三（4 一第三丁基 苯基）毓九氟正丁烷磺酸鹽、三（4 -第三丁基苯基）鏡 全氟正辛烷磺酸鹽、三（4-第三丁基苯基）毓對甲苯磺 酸鹽、三（4 一第三丁基苯基）毓苯磺酸鹽、三（4 一第三 丁基苯基）銃1 0 -樟腦磺酸鹽、三（4 一第三丁基苯基） ' 毓正辛烷磺酸鹽、三（4-第三丁基苯基）毓2-三氟甲 基苯磺酸鹽、三（4-第三丁基苯基）鏡4-三氟甲基苯 φ 磺酸鹽、三（4-第三丁基苯基）鏡萘磺酸鹽等。 作爲式（6-18)所表示的毓陽離子之鹽，可舉出（4 -第三丁氧基苯基）二苯基銃三氟甲烷磺酸鹽、（4 一第 三丁氧基苯基）二苯基毓九氟正丁烷磺酸鹽、（4 一第三 丁氧基苯基）二苯基鏡全氟正丁辛烷磺酸鹽、（4 一第三 丁氧基苯基）二苯基锍芘磺酸鹽、（4 一第三丁氧基苯基 )二苯基锍對甲苯磺酸鹽、（4 一第三丁氧基苯基）二苯 基毓苯磺酸鹽、（4 一第三丁氧基苯基）二苯基锍1 0 -樟 • 腦磺酸鹽、（4 一第三丁氧基苯基）二苯基毓正辛烷磺酸 鹽、（4 一第三丁氧基苯基）二苯基毓2 —三氟甲基苯磺 酸鹽、（4 一第三丁氧基苯基）二苯基毓4一三氟甲基苯 ^ 磺酸鹽、（4 一第三丁氧基苯基）二苯基毓全氟苯磺酸鹽 • 等。 作爲式（6-19 )所表示的毓陽離子之鹽，可舉出4 一 第三丁氧羰基甲基氧基苯基二苯基锍三氟甲烷磺酸鹽、4 -第三丁氧羰基甲基氧基苯基二苯基毓九氟正丁烷磺酸鹽 、4-第三丁氧羰基甲基氧基苯基二苯基鏡全氟正辛烷磺 -33- 200832068 酸鹽、4 一第三丁氧羰基甲基氧基苯基二苯基鏑對甲苯磺 酸鹽、4-第三丁氧羰基甲基氧基苯基二苯基毓苯磺酸鹽 、4 -第三丁氧羰基甲基氧基苯基二苯基毓1 0 -樟腦磺酸 鹽、4-第三丁氧羰基甲基氧基苯基二苯基銃正辛烷磺酸 鹽、4-第三丁氧羰基甲基氧基苯基二苯基毓2 -三氟甲 ' 基苯磺酸鹽、4-第三丁氧羰基甲基氧基苯基二苯基毓4 -三氟甲基苯磺酸鹽、4-第三丁氧羰基甲基氧基苯基二 φ 苯基鏑萘磺酸鹽等。 作爲式（6 — 2 7)所表示的毓陽離子之鹽，可舉出三（ 4 -甲氧基苯基）锍三氟甲烷磺酸鹽、三（4 一甲氧基苯基 )毓九氟正丁烷磺酸鹽、三（4 -甲氧基苯基）毓全氟正 辛烷磺酸鹽、三（4-甲氧基苯基）毓正甲苯磺酸鹽、三 (4 一甲氧基苯基）毓苯磺酸鹽、三（4 一甲氧基苯基）毓 10-樟腦磺酸鹽、三（4-甲氧基苯基）毓正辛烷磺酸鹽 、三（4 一甲氧基苯基）毓2—三氟甲基苯磺酸鹽、三（4 0 一甲氧基苯基）毓4一三氟甲基苯磺酸鹽、三（4 一甲氧 基苯基）鏡全氟苯磺酸鹽等。 作爲式（6-28 )所表示的毓陽離子之鹽，可舉出雙（ — 4 一甲氧基苯基）4 一甲苯醯基毓三氟甲烷磺酸鹽、雙（4 ' -甲氧基苯基）4-甲苯醯基磺酸鹽九氟正丁烷磺酸鹽、 雙（4-甲氧基苯基）4-甲苯醯基鏡全氟正辛烷磺酸鹽、 雙（4 一甲氧基苯基）4 一甲苯醯基毓對甲苯磺酸鹽、雙（ 4 一甲氧基苯基）4一甲苯醯基毓苯磺酸鹽、雙（4一甲氧 基苯基）4 一甲苯醯基毓10—樟腦磺酸鹽、雙（4 一甲氧 -34- 200832068 基苯基）4一甲苯醯基毓正辛烷磺酸鹽、雙（4一甲氧基苯 基）4一甲苯醯基毓2—三氟甲基苯磺酸鹽、雙（4 一甲氧 基苯基）4一甲苯醯基锍4一三氟甲基苯磺酸鹽、雙（4一 甲氧基苯基）4-甲苯醯基毓全氟苯磺酸鹽等。 作爲式（6-29 )所表示的毓陽離子之鹽，可舉出（4 ^ 一羥苯基）二苯基毓三氟甲烷磺酸鹽、（4 一羥苯基）二 苯基毓九氟正正丁烷磺酸鹽、（4 -羥苯基）二苯基毓全 φ 氟正辛烷磺酸鹽、（4 -羥苯基）二苯基毓對甲苯磺酸鹽 、（4 一羥苯基）二苯基毓苯磺酸鹽、（4一羥苯基）二苯 基銃1 〇 -樟腦-磺酸鹽、（4 一羥苯基）二苯基毓正辛烷 磺酸鹽、（4 一羥苯基）二苯基毓2 —三氟甲基苯磺酸鹽 、（4 一羥苯基）二苯基毓4 一三氟甲基苯磺酸鹽、（4 一 羥苯基）二苯基鏑全氟苯磺酸鹽等。 作爲式（6-54 )所表示的鏡陽離子之鹽，可舉出4 一 正丁氧基- 1 -萘基四氫噻吩鐵三氟甲烷磺酸鹽、4-正丁 # 氧基- 1 一萘基四氫噻吩鑰九氟-正丁烷磺酸鹽、4 -正丁 氧基- 1 -萘基四氫噻吩鍚全氟正辛烷磺酸鹽、4-正丁氧 基- 1 -萘基四氫噻吩鑰正辛烷磺酸鹽、4 —正丁氧基- 1 ’ -萘基四氫噻吩鎗對甲苯磺酸鹽、4-正丁氧基一 1 一萘基 • 四氫噻吩鑰苯磺酸鹽、4-正丁氧基- 1 一萘基四氫噻吩鐵 1 〇 —樟腦磺酸鹽、4 —正丁氧基一 1 —萘基四氫噻吩鑰2 -三氟甲基苯磺酸鹽、4 -正丁氧基- 1 一萘基四氫噻吩鑰4 -三氟甲基苯磺酸鹽、4 -正丁氧基一 1 一萘基四氫噻吩鑰 全氟苯磺酸鹽等。 -35- 200832068 作爲式（6-62)所表示的銃陽離子之鹽，可舉出三（ 4-氟苯基）銃三氟甲烷磺酸鹽、三（4 一氟苯基）毓九氟 正丁烷磺酸鹽、三（4 -氟苯基）锍1 0 —樟腦磺酸鹽、三 (4 一氟苯基）毓正辛烷磺酸鹽、三（4 一氟苯基）銃對甲 苯磺酸鹽等。 ' 作爲式（6-63 )所表示的鏡陽離子之鹽，可舉出（4 一氟苯基）二苯基毓三氟甲烷磺酸鹽、（4 一氟苯基）二 φ 苯基锍九氟正丁烷磺酸鹽、（4 -氟苯基）二苯基鏡正辛 烷磺酸鹽、（4 一氟苯基）二苯基毓10 -樟腦磺酸鹽、（ 4 一氟苯基）二苯基锍對甲苯磺酸鹽、（4 一氟苯基）二苯 基毓苯磺酸鹽、（4-氟苯基）二苯基鏡2 —三氟甲基苯 磺酸鹽、（4 一氟苯基）二苯基銃4 一三氟甲基苯磺酸鹽 、（4 一氟苯基）二苯基鏡全氟苯磺酸鹽等。 作爲式（7-1 )所表示的碘鑰陽離子之鹽，可舉出二 苯基碘鐵三氟甲烷磺酸鹽、二苯基碘鑰九氟正丁烷磺酸鹽 • 、二苯基碘銷全氟正辛烷磺酸鹽、二苯基碘鑰對甲苯磺酸 鹽、二苯基碘鎩苯磺酸鹽、二苯基碘鑰1 0 —樟腦磺酸鹽 、二苯基碘鏺正辛烷磺酸鹽、二苯基磺鐵2 -三氟甲基苯 ^ 磺酸鹽、二苯基碘鑰4-三氟甲基苯磺酸鹽、二苯基碘鑰 • 全氟苯磺酸鹽等。 作爲式（7-3 )所表示的碘鑰陽離子之鹽，可舉出二 (4 一甲苯醯基）碘鐵三氟甲烷磺酸鹽、二（4 一甲苯醯基 )碘鐡九氟正丁烷磺酸鹽、二（4 -甲苯醯基）碘鑰全氟 正辛烷磺酸鹽、二（4 -甲苯醯基）碘鑰對甲苯磺酸鹽、 -36 - 200832068 二（4 一甲苯醯基）碘鑰苯磺酸鹽、二（4 —甲苯醯基）碘 鑰1 0 -樟腦磺酸鹽、二（4 一甲苯醯基）碘鑰正辛烷磺酸 鹽、二（4 一甲苯醯基）碘鏺2—三氟甲基苯磺酸鹽、二 (4一甲苯醯基）碘鑰4一三氟甲基苯磺酸鹽、二（4 一甲 苯醯基）碘鑰全氟苯磺酸鹽等。 ' 作爲式（7-5 )所表示的碘鑰陽離子之鹽，可舉出雙 (3，4 一二甲基苯基）碘鐵三氟甲烷磺酸鹽、雙（3,4 一二 φ 甲基苯基）碘鐵九氟正丁烷磺酸鹽、雙（3，4 一二甲基苯 基）碘鑰全氟正辛烷磺酸鹽、雙（3,4 一二甲基苯基）碘 鑰對甲苯磺酸鹽、雙（3，4-二甲基苯基）碘鑰苯磺酸鹽 、雙（3,4一二甲基苯基）碘鑰10-樟腦磺酸鹽、雙（3,4 一二甲基苯基）碘鐵正辛烷磺酸鹽、雙（3,4 一二甲基苯 基）碘鑰2-三氟甲基苯磺酸鹽、雙（3,4 一二甲基苯基） .碘鑰4一三氟甲基苯磺酸鹽、雙（3,4一二甲基苯基）碘鐵 全氟苯磺酸鹽等。 # 作爲式（7-11)所表示的碘鑰陽離子之鹽，可舉出雙 (4 -第三丁基苯基）碘鐵三氟甲烷磺酸鹽、雙（4 一第三 丁基苯基）碘鏺九氟正丁烷磺酸鹽、雙（4 一第三丁基苯 ^ 基）碘鑰全氟正辛烷磺酸鹽、雙（4 一第三丁基苯基）碘 ^ 鑰對甲苯磺酸鹽、雙（4 -第三丁基苯基）碘鑰苯磺酸鹽 、雙（4 一第三丁基苯基）碘鑰1 0 -樟腦磺酸鹽、雙（4 -第三丁基苯基）碘鑰正辛烷磺酸鹽、雙（4-第三丁基 苯基）碘鑰2-三氟甲基苯磺酸鹽、雙（4 一第三丁基苯 基）碘鑰4-三氟甲基苯磺酸鹽、雙（4一第三丁基苯基 -37- 200832068 )碘鑰全氟苯磺酸鹽、雙（4 一第三丁基苯基）碘鎩2,4 一 二氟苯磺酸鹽等。 作爲式（7-12)所表示的碘鐵陽離子之鹽，可舉出（ 4 -硝基苯基）苯基碘鑰三氟甲烷磺酸鹽、（4 一硝基苯基 )苯基碘鐵九氟正丁烷磺酸鹽、（4 -硝基苯基）苯基碘 ‘ 鐵全氟正辛烷磺酸鹽、（4 -硝基苯基）苯基碘鑰對甲苯 磺酸鹽、（4 一硝基苯基）苯基碘鏺苯磺酸鹽、（4 一硝基 φ 苯基）苯基碘銷1 〇 —樟腦磺酸鹽、（4 一硝基苯基）苯基 碘鑰正辛烷磺酸鹽、（4 -硝基苯基）苯基碘鑰2 -三氟 甲基苯磺酸鹽、（4 一硝基苯基）苯基碘鑰4 一三氟甲基 苯磺酸鹽、（4 -硝基苯基）苯基碘鑰全氟苯磺酸鹽等。 作爲式（7-15 )所表示的碘鑰陽離子之鹽，可舉出雙 (3 -硝基苯基）碘鑰三氟甲烷磺酸鹽、雙（3 —硝基苯基 )碘鐵九氟正丁烷磺酸鹽、雙（3 -硝基苯基）碘鑰全氟 正辛烷磺酸鹽、雙（3 -硝基苯基）碘鑰對甲苯磺酸鹽、 • 雙（3 -硝基苯基）碘鐵苯磺酸鹽、雙（3 —硝基苯基）碘 鐵1 0 -樟腦磺酸鹽、雙（3 —硝基苯基）碘鐵正辛烷磺酸 鹽、雙（3 -硝基苯基）碘鏺2-三氟甲基苯磺酸鹽、雙 ' (3 -硝基苯基）碘鐵4 一三氟甲基苯磺酸鹽、雙（3 -硝 - 基苯基）碘鐵全氟苯磺酸鹽等。 作爲式（7-16)所表示的碘鐵陽離子之鹽，可舉出（ 4-甲氧基苯基）苯基碘鐵三氟甲烷磺酸鹽、（4 一甲氧基 苯基）苯基碘鐵九氟正丁烷磺酸鹽、（4-甲氧基苯基） 苯基碘鑰全氟正辛烷磺酸鹽、（4-甲氧基苯基）苯基碘 -38- 200832068 鑰對甲苯磺酸鹽、（4 一甲氧基苯基）苯基碘鑰苯磺酸鹽 、（4 一甲氧基苯基）苯基碘銷1 0 —樟腦磺酸鹽、（4 一 甲氧基苯基）苯基碘鐵正辛烷磺酸鹽、（4 -甲氧基苯基 )苯基碘鑰2 —三氟甲基苯磺酸鹽、（4 一甲氧基苯基） 苯基碘鑰4 -三氟甲基苯磺酸鹽、（4 一甲氧基苯基）苯 ' 基碘鐵全氟苯磺酸鹽等。 作爲式（7-19)所表示的碘鑰陽離子之鹽，可舉出雙 φ (4 -氯苯基）碘鑰三氟甲烷磺酸鹽、雙（4 一氯苯基）碘 鎗九氟正丁烷磺酸鹽、雙（4 -氯苯基）碘鑰全氟正辛烷 磺酸鹽、雙（4 一氯苯基）碘鐵對甲苯磺酸鹽、雙（4 一氯 苯基）碘鑰苯磺酸鹽、雙（4 一氯苯基）碘鑰1 0 —樟腦磺 酸鹽、雙（4一氯苯基）碘鐵正辛烷磺酸鹽、雙（4一氯苯 基）碘鑰2 -三氟甲基苯磺酸鹽、雙（4一氯苯基）碘鐺4 -三氟甲基苯磺酸鹽、雙（4-氯苯基）碘鐵全氟苯磺酸 鹽等。 Φ 作爲式（7-25 )所表示的碘鐵陽離子之鹽，可舉出雙 (4-三氟甲基苯基）碘鐵三氟甲烷磺酸鹽、雙（4 一三氟 甲基苯基）碘鐵九氟正丁烷磺酸鹽、雙（4 一三氟甲基苯 ^ 基）碘鐵全氟正辛烷磺酸鹽、雙（4-三氟甲基苯基）碘 - 鑰對甲苯磺酸鹽、雙（4 -三氟甲基苯基）碘鑰苯磺酸鹽 、雙（4 一三氟甲基苯基）碘鑰1 0 -樟腦磺酸鹽、雙（4 -三氟甲基苯基）碘鑰正辛烷磺酸鹽、雙（4 一三氟甲基 苯基）碘鑰2-三氟甲基苯磺酸鹽、雙（4 一三氟甲基苯 基）碘鑰4-三氟甲基苯磺酸鹽、雙（4 一三氟甲基苯基 -39- 200832068 )碘鎩全氟苯磺酸鹽等。 作爲式（7-36 )所表示的碘鑰陽離子之鹽，可舉出二 (1 一萘基）碘鑰三氟甲烷磺酸鹽、二（1 一萘基）碘鐵九 氟正丁烷磺酸鹽、二（1 -萘基）碘鐵全氟正辛烷磺酸鹽 、二（1 一萘基）碘鑰對甲苯磺酸鹽、二（1 一萘基）碘鐵 ' 苯磺酸鹽、二（1 一萘基）碘鐵10 -樟腦磺酸鹽、二（1 一萘基）碘鑰正辛烷磺酸鹽、二（1 一萘基）碘鑰2—三 φ 氟甲基苯磺酸鹽、二（1 -萘基）碘鑰4一三氟甲基苯磺 酸鹽、二（1一萘基）碘鑰全氟苯磺酸鹽等。 作爲式（7-40 )所表示的碘鑰陽離子之鹽，可舉出雙 (4 一氟苯基）碘鐵三氟甲烷磺酸鹽、雙（4 一氟苯基）碘 鐵九氟正丁烷磺酸鹽、雙（4 -氟苯基）碘鑰1 0 —樟腦磺 酸鹽、雙（4 -氟苯基）碘鐵正辛烷磺酸鹽等。 作爲式（7-41 )所表示的碘鐵陽離子之鹽，可舉出（ 4-氟苯基）苯基碘鑰三氟甲烷磺酸鹽、（4 一氟苯基）苯 # 基碘鐺九氟正丁烷磺酸鹽、（4 -氟苯基）苯基碘鏺1 0 -樟腦磺酸鹽、（4 -氟苯基）苯基碘鑰正辛烷磺酸鹽等。 於此等鐵鹽之中，較佳爲雙（4 -第三丁基苯基）碘 鑰三氟甲烷磺酸鹽、雙（4-第三丁基苯基）碘鑰九氟正 - 丁烷磺酸鹽、雙（4 一第三丁基苯基）碘鑰對甲苯磺酸鹽 、雙（4 一第三丁基苯基）碘鑰10-樟腦磺酸鹽、雙（4 一第三丁基苯基）碘鐵2 -三氟甲基苯磺酸鹽、雙（4一 第三丁基苯基）碘鑰4一三氟甲基苯磺酸鹽、雙（4 一第 三丁基苯基）碘鐵2,4-二氟苯磺酸鹽、三苯基锍三氟甲 -40- 200832068 烷磺酸鹽、三苯基毓九氟正丁烷磺酸鹽、三苯基锍對甲苯 磺酸鹽、三苯基鏑1 〇 —樟腦磺酸鹽、三苯基鏡2 -三氟甲 基苯磺酸鹽、三苯基毓4-三氟甲基苯磺酸鹽、三苯基毓 2,4一二氟甲基苯磺酸鹽、三苯基毓1，1，2,2 —四氟一 2—（ 四環[4.4.0.I2’5.17’1G]十二烷一 8 -基）乙烷磺酸鹽、三苯 基鏡1，1 一一氟&lt; 一 2-（雙環[2.2.1]庚院一 2—基）乙院磺 酸鹽、2,4,6-三甲基苯基二苯基毓2,4 一二氟苯磺酸鹽、 φ 2,4,6 —三甲基苯基二苯基毓4 一三氟甲基苯磺酸鹽、4一 甲基苯基二苯基毓三氟甲烷磺酸鹽、4-甲基苯基二苯基 毓全氟正丁烷磺酸鹽、4 一甲基苯基二苯基毓對甲苯磺酸 鹽、4 一甲基苯基二苯基毓1 0 —樟腦磺酸鹽、4 一甲基苯 基二苯基毓2-三氟甲基苯磺酸鹽、4-甲基苯基二苯基 毓4 一三氟甲基苯磺酸鹽、4 一甲基苯基二苯基毓2，4 一二 氟甲基苯磺酸鹽、三（4 一甲基苯基）毓三氟甲烷磺酸鹽 、三（4 一甲基苯基）毓九氟正丁烷磺酸鹽、三（4 一甲基 Φ 苯基）毓對甲苯磺酸鹽、三（4 —甲基苯基）鏡1〇—樟腦 磺酸鹽、三（4一甲基苯基）毓2-三氟甲基苯磺酸鹽、 三（4 一甲基苯基）毓4一三氟甲基苯磺酸鹽、三（4 一甲 ^ 基苯基）毓2,4 一二氟甲基苯磺酸鹽、三（4 一第三丁基苯 ' 基）毓三氟甲烷磺酸鹽三（4 -第三丁基苯基）毓鏡九氟 正丁烷磺酸鹽、三（4-第三丁基苯基）鏡全氟正辛烷磺 酸鹽、三（4 一第三丁基苯基）鏑對甲苯磺酸鹽、三（4 一 第三丁基苯基）銃苯磺酸鹽、三（4-第三丁基苯基）銃 1 0-樟腦磺酸鹽、三（4 一第三丁基苯基）鏡2 _三氟甲 -41 - 200832068 基苯磺酸鹽、三（4 一第三丁基苯基）毓4一三氟甲基苯 磺酸鹽、三（4 一第三丁基苯基）毓萘磺酸鹽、三（4 一甲 氧基苯基）毓三氟甲烷磺酸鹽、三（4-甲氧基苯基）毓 九氟正丁烷磺酸鹽、三（4-甲氧基苯基）毓全氟正辛烷 磺酸鹽、三（4 一甲氧基苯基）毓對甲苯磺酸鹽、三（4 一 ~ 甲氧基苯基）毓苯磺酸鹽、三（4 一甲氧基苯基）毓10- 樟腦磺酸鹽、三（4 -甲氧基苯基）毓2 -三氟甲基苯磺 φ 酸鹽、三（4 一甲氧基苯基）毓4一三氟甲基苯磺酸鹽、 三（4-甲氧基苯基）銃全氟苯磺酸鹽， (4一氟苯基）二苯基毓三氟甲烷磺酸鹽、（4 一氟苯 基）二苯基毓九氟正丁烷磺酸鹽、（4-氟苯基）二苯基 毓全氟正辛烷磺酸鹽、（4 -氟苯基）二苯基毓對甲苯磺 酸鹽、（4 一氟苯基）二苯基毓苯磺酸鹽、（4 一氟苯基） 二苯基毓1 〇 -樟腦磺酸鹽、（4 一氟苯基）二苯基毓2 -三氟甲基苯磺酸鹽、（4一氟苯基）二苯基锍4 一三氟甲 # 基苯磺酸鹽、（4 一氟苯基）二苯基毓全氟苯磺酸鹽， 4 -正丁氧基- 1 -萘基四氫噻吩鑰三氟甲烷磺酸鹽、 4-正丁氧基- 1 -萘基四氫噻吩鐵九氟正丁烷磺酸鹽、4 ' -正丁氧基- 1 -萘基四氫噻吩鐵全氟正辛烷磺酸鹽、4一 - 正丁氧基- 1-萘基四氫噻吩鐵對甲苯磺酸鹽、4一正丁氧 基一 1 一萘基四氫噻吩鎗苯磺酸鹽、4一正丁氧基一 1 一萘 基四氫噻吩鏺10 -樟腦磺酸鹽、4 一正丁氧基一 1—萘基 四氫噻吩鑰2 -三氟甲基苯磺酸鹽、4一正丁氧基一 1 一萘 基四氫噻吩鐵4 -三氟甲基苯磺酸鹽、4 一正丁氧基一 1- -42- 200832068 萘基四氫噻吩鑰全氟苯磺酸鹽， 二苯基碘鑰九氟正丁烷磺酸鹽、二苯基碘鍚三氟甲烷 磺酸鹽、二苯基碘鑰全氟正辛烷磺酸鹽、二苯基碘鎗1〇 -樟腦磺酸鹽、三苯基毓全氟正辛烷磺酸鹽、三（4-氟 苯基）毓九氟正丁烷磺酸鹽、三（4 一氟苯基）鏑1 0 —樟 ^ 腦磺酸鹽、三（4 一氟苯基）毓三氟甲烷磺酸鹽三（4 一氟 苯基）毓對甲苯磺酸鹽、（4-氟苯基）苯基碘鑰三氟甲 φ 烷磺酸鹽、（4 -氟苯基）苯基碘鑰九氟正丁烷磺酸鹽、 (4 一氟苯基）苯基碘鐵10-樟腦磺酸鹽、雙（4一氟苯 基）碘鑰三氟甲烷磺酸鹽、雙（4-氟苯基）碘鍚九氟正 丁烷磺酸鹽、雙（4 一氟苯基）碘鑰1 〇 —樟腦磺酸鹽、（ 4一羥苯基）二苯基毓三氟甲烷磺酸鹽、（4 一羥苯基）二 苯基銃九氟正丁烷磺酸鹽、（4 -羥苯基）二苯基毓10-樟腦磺酸鹽、（4 一羥苯基）二苯基毓2 -三氟甲基苯磺 酸鹽、（4一羥苯基）二苯基鏡4 一三氟甲基苯磺酸鹽。 • 再者，上述鑰鹽可爲單獨1種或組合2種以上使用。 構成本發明所可使用的混合酸產生劑（A )之酸產生 劑（A1 )與酸產生劑（A2 )的使用比例（A1 /A2 )(質量 ， 比），通常爲0.01〜5，較佳爲0.02〜2，而且酸產生劑 . (A1 )與酸產生劑（A2 )的合計使用量，對於每100質 量份的敏輻射線性樹脂組成物中的樹脂成分而言，通常爲 0 · 5〜3 0質量份，較佳爲1〜2 〇質量份。於該情況下，酸 產生劑（A1 )與酸產生劑（A2 )的使用比例（A1/A2 )( 質量比）若低於0 · 01，則作爲光阻的「膜面龜裂」之減低 -43- 200832068 效果有變大的傾向，另一方面若超過5，則作爲光阻的感 度降低，圖型形成會變困難。又，酸產生劑（A1)與酸 產生劑（A2 )的合計使用量若低於0 · 5質量份，則經由曝 光所產生的酸之觸媒作用有難以充分引起化學變化的困難 之虞，另一方面若超過20質量份，於塗佈敏輻射線性樹 ^ 脂組成物時會發生塗佈不均、顯像時有發生浮渣等之虞。 於本發明的正型敏輻射線性樹脂組成物中，視需要可 φ 摻混上述酸產生劑（A )以外的敏輻射線性酸產生劑（以 下亦稱爲「其它酸產生劑」）。作爲其它酸產生劑，例如 可舉出磺醯亞胺化合物、礪化合物、磺酸酯化合物、二磺 醯基重氮甲烷化合物、二磺醯基甲烷化合物、肟磺酸鹽化 合物、胼磺酸鹽化合物等。 作爲磺醯亞胺化合物的具體例子，可舉出N -（三氟 甲基磺醯氧基）琥珀醯亞胺、N—（三氟甲基磺醯氧基） 酞醯亞胺、N-（三氟甲基磺醯氧基）二苯基馬來醯亞胺 ·、N-（三氟甲基磺醯氧基）雙環[2.2.1]庚一5 -烯一 2,3 一二殘醯亞胺、N-（三氟甲基磺醯氧基）一 7-氧雜雙 環[2.2.1]庚一 5 —烯—2,3 -二羧醯亞胺、N— （三氟甲基 磺醯氧基）雙環[2.2.1]庚烷-5,6 —氧基—2,3-二羧醯亞胺 ' 、N —（三氟甲基磺醯氧基）萘基醯亞胺、n —（ 1 0 —樟 腦磺醯氧基）琥珀醯亞胺、N -（ 1 0 -樟腦磺醯氧基）酞 醯亞胺、N — ( 1 0 —樟腦磺醯氧基）二苯基馬來醯亞胺、 N— (10-樟腦磺醯氧基）雙環[2.2.1]庚—5一烯—2,3 一 一竣釀亞胺、N— (10 - |草腦礦釀氧基）—7 —氧雜雙環 -44 - 200832068 [2.2.1]庚一 5 —烯一 2,3 —二羧醯亞胺、N -（ 10 —樟腦磺 醯氧基）雙環[2.2.1]庚烷一 5,6 -氧基一 2,3 —二羧醯亞胺 、N— (10 —樟腦磺醯氧基）萘醯亞胺、N— [(5 —甲基 一 5-羧甲基雙環[2.2.〗]庚烷一 2一基）磺醯氧基；|琥珀醯 亞胺， N-(正辛基磺醯氧基）琥珀醯亞胺、N—(正辛基 磺醯氧基）酞醯亞胺、N-（正辛基磺醯氧基）二苯基馬 # 來酸亞胺、N—(正辛基磺醯氧基）雙環[2 ·2·1]庚—5 —烯 一 2,3 -二羧醯亞胺、ν -（正辛基磺醯氧基）一 7-氧雜 雙環[2.2.1]庚一 5一烯一 2,3 一二羧醯亞胺、Ν—(正辛基 磺醯氧基）雙環[2.2.1]庚烷一 5,6 -氧基一 2,3 -二羧醯亞 胺、Ν—（正辛基磺醯氧基）萘醯亞胺、Ν—（4 一甲基苯 基磺醯氧基）琥珀醯亞胺、Ν—（4-甲基苯基磺醯氧基 )酞醯亞胺、Ν-（4一甲基苯基磺醯氧基）二苯基馬來 醯亞胺、Ν-（4 一甲基苯基磺醯氧基）雙環[2 ·2·1]庚一 5 ® —烯―2,3 -二羧醯亞胺、Ν— (4 —甲基苯基磺醯氧基） 一 7-氧雜雙環[2·2.1]庚—5-烯一 2,3-二羧醯亞胺、Ν — (4 一甲基苯基擴醯氧基）雙環[2.2.1]庚院一 5,6 —氧基一 — 2,3 -二羧醯亞胺、Ν-（4 一甲基苯基磺醯氧基）萘醯亞 ， 胺， Ν -（ 2 -三氟甲基苯基磺醯氧基）琥珀醯亞胺、ν -(2-三氟甲基苯基磺醯氧基）酞醯亞胺、Ν— (2—三氟 甲基苯基磺醯氧基）二苯基馬來醯亞胺、Ν-（2—三氟 甲基苯基磺醯氧基）雙環[2.2.1]庚一 5-烯一 2,3 —二羧醯 -45- 200832068 亞胺、N—（2— Ξ氟甲基苯基磺醯氧基）一 7一氧雜雙環 [2·2·1]庚一 5 —烯〜2,3〜二羧醯亞胺、N— (2 一三氟甲基 苯基磺醯氧基）雙環[2·21]庚烷一 5,6 一氧基_2,3一二羧 . 釀亞胺、Ν— (2〜三氟甲基苯基磺醯氧基）萘醯亞胺、ν 一（4 一二氯甲基苯基磺醯氧基）琥珀醯亞胺、Ν—（4一 二氯甲基苯基礦驢氧基）酞醯亞胺、Ν—（4 一三氟甲基 苯基磺醯氧基）二苯基馬來醯亞胺、Ν— (4 一三氟甲基 # 苯基磺醯氧基）雙環[2.2.1]庚—5 —烯—2,3 -二羧醯亞胺 、Ν— (4 - 一氟甲基苯基磺醯氧基）一 7_氧雜雙環 [2·2·1]庚一5-烯—2,3〜二羧醯亞胺、Ν— (4 一三氟甲基 苯基磺醯氧基）雙環[2.2.1]庚烷一 5，6 —氧基一 2,3 —二羧 醯亞胺、Ν-（4〜三氟甲基苯基磺醯氧基）萘醯亞胺， Ν-（全氟苯基磺醯氧基）琥珀醯亞胺、ν-（全氟 苯基磺醯氧基）酞醯亞胺、Ν-（全氟苯基磺醯氧基）二 苯基馬來醯亞胺、Ν-（全氟苯基磺醯氧基）雙環[2.2.1] Φ 庚一 5 —烯一 2,3 -二羧醯亞胺、Ν—(全氟苯基磺醯氧基 )—7—氧雜雙環[2·2·1]庚—5—烯一 2,3 —二羧醯亞胺、Ν 一（全氟苯基磺醯氧基）雙環[2·2·1]庚烷一 5,6 —氧基一 ‘ 2,3 -二羧醯亞胺、Ν-（全氟苯基磺醯氧基）萘醯亞胺、 - Ν -（1 一萘基磺醯氧基）琥珀醯亞胺、Ν- （1 一萘基磺 醯氧基）酞醯亞胺、Ν-（1 一萘基磺醯氧基）二苯基馬 來醯亞胺、Ν-（ 1 一萘基磺醯氧基）雙環[2.2.1]庚一 5 -烯—2,3—二羧醯亞胺、ν-（1 一萘基磺醯氧基）—7-氧 雜雙環[2.2.1]庚一 5 一烯一 2,3 一二羧醯亞胺、Ν— ( 1 一萘 -46- 200832068 基磺醯氧基）雙環[2.2·1]庚烷一 5，6 一氧基一 2，3 一二羧醯 亞胺、N—（1 一萘基磺醯氧基）萘醯亞胺’ N-（九氟正丁基磺醯氧基）琥珀醯亞胺、N—（九 氟正丁基磺醯氧基）酞醯亞胺、N—(九氟正丁基磺醯氧 基）二苯基馬來醯亞胺、N-（九氟正丁基磺醯氧基）雙 — 環[2.2.1]庚—5 —烯一 2,3 —二羧醯亞胺、N—（九氟正丁 基磺醯氧基）一 7 —氧雜雙環[2.2·1]庚—5 -烯一 2,3 —二 φ 羧醯亞胺、Ν-（九氟正丁基磺醯氧基）雙環[2.2.1]庚烷 一 5,6-氧基一 2,3 -二羧醯亞胺、Ν—（九氟正丁基磺醯 氧基）萘醯亞胺、Ν-（全氟正辛基磺醯氧基）琥珀醯亞 胺、Ν-（全氟正辛基磺醯氧基）酞醯亞胺、Ν—（全氟 正辛基磺醯氧基）二苯基馬來醯亞胺、Ν-（全氟正辛基 磺醯氧基）雙環[2.2.1]庚〜5 -烯—2，3 -二竣醯亞胺、Ν 一（全氟辛基磺醯氧基）—7-氧雜雙環[2.2·1]庚一 5—儲 一 2，3 -二羧醯亞胺、Ν-（全氟正辛基磺醯氧基）雙環 • [2·2·1]庚院一 5,6 —氧基—2,3 —二竣醯亞胺、Ν-（全氟 正辛基磺醯氧基）萘醯亞胺， Ν -（苯基磺醯氧基）號拍醯亞胺、Ν -（苯基擴醯 ' 氧基）酞醯亞胺、Ν-（苯基磺醯氧基）二苯基馬來醯亞 - 胺、Ν—(苯基磺醯氧基）雙環[2.2.1]庚一 5-烯一 2，3 -二羧醯亞胺、Ν—（苯基磺醯氧基）一 7一氧雜雙環[2.2.1] 庚一 5-烯一 2,3 -二羧醯亞胺、ν-（苯基磺醯氧基）雙 環[2.2.1]庚烷一5,6—氧基一2,3—二羧醯亞胺、1^—(苯 基磺醯氧基）萘醯亞胺等。 -47- 200832068 於此等磺醯亞胺化合物之中，較佳爲N -（三氟甲基 磺醯氧基）雙環[2.2.1]庚—5 -烯一 2,3 -二羧醯亞胺、N 一（10—樟腦磺醯氧基）琥珀醯亞胺、N— （4一甲基苯 基磺醯氧基）琥珀醯亞胺、N-（九氟正丁基磺醯氧基） 雙環[2 ·2·1]庚一 5-烯一 2,3 -二羧醯亞胺、N—（苯基磺 醯氧基）雙ί哀[2.2.1]庚一 5 —燒一 2,3 —二竣醯亞胺、Ν—[ (5 -甲基一 5—羧甲基雙環[2,2·1]庚烷一 2-基）磺醯氧 # 基]琥珀醯亞胺。再者，磺醯亞胺化合物可爲單獨1或組 合2種以上來使用。 作爲上述颯化合物，例如可舉出 β 一酮基楓、β 一磺 醯基颯、此等α -重氮化合物等。又，作爲上述颯化合物 的更具體例子，可舉出苯甲醯甲基苯基礪、茱基苯甲醯甲 基礪、雙（苯基磺醯基）甲烷、4-三苯甲醯甲基礪等。 作爲上述磺酸酯化合物，例如可舉出烷基磺酸酯、鹵 烷基磺酸酯、芳基磺酸酯、亞胺基磺酸酯等。又，作爲上 ® 述磺酸酯化合物的更具體例子，可舉出苯偶姻甲苯磺酸酯 、焦掊酚三（三氟甲烷磺酸鹽）、焦掊酚三（九氟正丁基 磺酸鹽）、焦掊酚三（甲基磺酸鹽）、硝基苄基—9，1 0 — 二乙氧基蒽一 2-磺酸鹽、α —經甲基苯偶姻甲苯磺酸酯 • 、^ 一羥甲基苯偶姻三氟甲烷磺酸鹽、α -羥甲基苯偶姻 正辛烷磺酸鹽、α -羥甲基苯偶姻正十二烷磺酸鹽等。 作爲上述二磺醯基重氮甲烷化合物，例如可舉出下述 式（20)所表示的化合物。 -48- 200832068 [化 26]Specific examples of the acid generator (A 1 ) represented by the above formula (1) include triphenylsulfonium salicylate, 4-hydroxyphenyldiphenylphosphonium salicylate, and tris(4). Fluorophenyl) Mirror Salicylate, 4-Methylphenyl Diphenyl Mirror 1 - Adamantane Carboxylate, 2,4,6 Trimethylphenyl Diphenylhydrazine Salicylate, Double (4 Monofluorophenyl)iodosalicylate, tris(4-fluorophenyl) mirror 1 adamantane carboxylate, (4 fluorophenyl) iodine salicylate, bis(4-fluorophenyl) Iodine 1 - adamantane carboxylate, 2,4,6-trimethylphenyldiphenylphosphonium 1 adamantane carboxylate, 4-tert-butoxycarbonylmethyloxyphenyl diphenyl Salicylic acid and so on. Further, the acid generator (A1) represented by the above formula (1) may be used alone or in combination of two or more. Further, the acid generator (A2)' represented by the formula (2-30-200832068) which generates an acid other than a carboxylic acid by irradiation with radiation is, for example, a key salt compound. Examples of the key salt compound include a phosphonium salt and an iron iodide salt. Specific examples of the key salt compound represented by the formula (2) include the following examples. * As the salt of the phosphonium cation represented by the formula (6-1), triphenyl* fluorene trifluoromethanesulfonate, triphenyl mirror nonafluorobutane sulfonate, triphenylsulfonium perfluoride may be mentioned. N-octane sulfonate, triphenylsulfonium p-toluenesulfonate, triphenyl mirror benzoate, diphenyl vegetable 10 - rod brain mineral acid, diphenyl mirror n-halosulfonate, three Phenylindole-2-trifluoromethylbenzenesulfonate, triphenyl mirror 4-trifluoromethylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, three Phenylhydrazine 2,4-difluoromethylbenzenesulfonate, triphenyl mirror 1,1,2,2-tetrafluoro-2-(tetracycline [4.4.0.12'5.17'1()]dodecane 8-octyl)ethanesulfonate, triphenyl mirror 1,1-difluoro-2-(bicyclo[2·2·1]heptane-2-yl)ethanesulfonate, and the like. The salt of the phosphonium cation represented by the formula (6-2) includes 4-methylphenyl phenyl diphenyl sulfonium trifluoromethanesulfonate and 4-methylphenyl diphenyl sulfonium hexafluoro-n-butyl hydride. Alkane sulfonate, 4-methylphenyldiphenylphosphonium perfluorooctane sulfonate, 4-methylphenyldiphenylphosphonium p-toluenesulfonate, 4-methylphenyl~diphenyl Benzene sulfonate, 4-methylphenyl diphenyl mirror 1 〇~ camphorsulfonic acid. Salt, 4-methylphenyldiphenylphosphonium n-octane sulfonate, 4-methylphenyl diphenyl 2-铳trifluoromethylbenzenesulfonate, 4-methylphenyldiphenylphosphonium 4-trifluoromethylbenzenesulfonate, 4-methylphenyldiphenylsulfonium naphthalenesulfonate, 4 Monomethylphenyldiphenylphosphonium 2,4-difluoromethylbenzenesulfonate and the like. The salt of the mirror cation represented by the formula (6-6) includes -31 - 200832068 2,4,6-trimethylphenyldiphenylphosphonium trifluoromethanesulfonate, 2,4,6- Trimethylphenyldiphenylphosphonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylphosphonium p-toluenesulfonate, 2,4,6-trimethyl Phenyldiphenylphosphonium 4-trifluorobenzenesulfonate and the like. The phosphonium cation salt represented by the formula (6-8) includes tris(4-monomethylphenyl)phosphonium trifluoromethanesulfonate and tris(4-methylphenyl)phosphonium hexafluoro-n-butane. Sulfonic acid salt, tris(4-methylphenyl) mirror perfluoro-n-octane sulfonate φ salt, tris(4-methylphenyl) mirror p-toluenesulfonate, tris(4-methylphenyl)anthracene Benzene sulfonate, tris(4-methylphenyl)phosphonium 10-camphorsulfonate, tris(4-methylphenyl)phosphonium n-octane sulfonate, tris(4-methylphenyl)phosphonium 2-trifluoromethylbenzenesulfonate, tris(4-methylphenyl) mirror 4-trifluoromethylbenzenesulfonate, tris(4-methylphenyl)phosphonium naphthalate, tris(4) Monomethylphenyl)phosphonium 2,4-difluoromethylbenzenesulfonate. Examples of the salt of the phosphonium cation represented by the formula (6-1 2 ) include (4-tetrabutylphenyl)diphenylphosphonium trifluoromethanesulfonate, and (4-third #butylphenyl). Diphenyl sulfonium hexafluoro n-butane sulfonate, (4 - tert-butylphenyl) diphenyl fluorene perfluoro-n-octane sulfonate, (4 - tert-butylphenyl) diphenyl毓-toluenesulfonate, (4-tetrabutylphenyl)diphenyl' benzenesulfonate, (4-tetrabutylphenyl)diphenylphosphonium 10-camphorsulfonate, (4 - tert-butylphenyl) diphenylphosphonium n-octane sulfonate, (4 - tert-butylphenyl) diphenyl mirror 2 - trifluoromethylbenzene sulfonate, (4 - Tributylphenyl)diphenylphosphonium 4-trifluoromethanebenzenesulfonate, (4-tributylphenyl)diphenylphosphonium perfluorobenzenesulfonate, and the like. Examples of the salt of the phosphonium cation represented by the formula (6-13) include tris(-32-200832068 4-t-butylphenyl)phosphonium trifluoromethanesulfonate and tris(4-tert-butylbenzene). Nine) nonafluoro-n-butane sulfonate, tris(4-t-butylphenyl) mirror perfluoro-n-octane sulfonate, tris(4-t-butylphenyl)phosphonium p-toluenesulfonate , tris(4-butylphenyl)toluenesulfonate, tris(4-monobutylphenyl)phosphonium 10-camphorsulfonate, tris(4-tert-butylphenyl)毓-octane sulfonate, tris(4-t-butylphenyl)fluorene 2-trifluoromethylbenzenesulfonate, tris(4-t-butylphenyl) mirror 4-trifluoromethylbenzene φ sulfonate, tris(4-t-butylphenyl) mirror naphthalene sulfonate, and the like. Examples of the salt of the phosphonium cation represented by the formula (6-18) include (4-t-butoxyphenyl)diphenylphosphonium trifluoromethanesulfonate and (4-t-butoxyphenyl). Diphenylphosphonium n-butane sulfonate, (4 - 3 -butoxyphenyl) diphenyl mirror perfluoro-n-octyl sulfonate, (4 - 3 -butoxyphenyl) Diphenylphosphonium sulfonate, (4-t-butoxyphenyl)diphenylphosphonium p-toluenesulfonate, (4-tert-butoxyphenyl)diphenylsulfonium benzenesulfonate, (4-t-butoxyphenyl)diphenylphosphonium 1 0-indole • ceramide, (4-t-butoxyphenyl) diphenylphosphonium n-octane sulfonate, (4 Third butoxyphenyl)diphenylphosphonium 2-trifluoromethylbenzenesulfonate, (4-tritoxyphenyl)diphenylphosphonium 4trifluoromethylbenzenesulfonate, (4 - 3 -butoxyphenyl) diphenyl sulfonium perfluorobenzene sulfonate • Etc. The salt of the phosphonium cation represented by the formula (6-19) includes 4-tert-butyloxycarbonylmethyloxyphenyldiphenylphosphonium trifluoromethanesulfonate and 4-tert-butoxycarbonylmethyl. Benzyloxydiphenylphosphonium nonafluorobutane sulfonate, 4-tert-butoxycarbonylmethyloxyphenyldiphenyl mirror perfluoro-n-octane sulfonate-33- 200832068 acid salt, 4 Third butoxycarbonylmethyloxyphenyldiphenylphosphonium p-toluenesulfonate, 4-tert-butoxycarbonylmethyloxyphenyldiphenylsulfonate, 4-tert-butoxycarbonyl Methyloxyphenyldiphenylphosphonium 10 - camphorsulfonate, 4-tert-butoxycarbonylmethyloxyphenyldiphenylphosphonium n-octanesulfonate, 4-tert-butoxycarbonyl Benzyloxydiphenylphosphonium 2-trifluoromethyl'benzenesulfonate, 4-tert-butoxycarbonylmethyloxyphenyldiphenylphosphonium 4-trifluoromethylbenzenesulfonate, 4 - a third butoxycarbonylmethyloxyphenyl bis phenyl phenyl phthalene naphthalene sulfonate or the like. Examples of the salt of the phosphonium cation represented by the formula (6-27) include tris(4-methoxyphenyl)phosphonium trifluoromethanesulfonate and tris(4-methoxyphenyl)phosphonium hexafluoride. N-butane sulfonate, tris(4-methoxyphenyl)phosphonium perfluorooctane sulfonate, tris(4-methoxyphenyl)phosphonium tosylate, tris(4-methoxy) Phenyl phenyl) anthracenene sulfonate, tris(4-methoxyphenyl)indole 10-camphorsulfonate, tris(4-methoxyphenyl)phosphonium n-octane sulfonate, three (4 Methoxyphenyl)phosphonium 2-trifluoromethylbenzenesulfonate, tris(40-methoxyphenyl)phosphonium 4-trifluoromethylbenzenesulfonate, tris(4-methoxyphenyl) ) Mirror perfluorobenzenesulfonate and the like. The salt of the phosphonium cation represented by the formula (6-28) includes bis(-4-methoxyphenyl)4-tolylhydrazinium trifluoromethanesulfonate and bis(4'-methoxy group). Phenyl) 4-toluenesulfonate nonafluoro-n-butane sulfonate, bis(4-methoxyphenyl) 4-toluene-based mirror perfluoro-n-octane sulfonate, double (4 A Oxyphenyl)4-tolylhydrazinyl p-toluenesulfonate, bis(4-methoxyphenyl)-4-methylphenylsulfonate, bis(4-methoxyphenyl)4 Tolylhydrazinium 10 - camphorsulfonate, bis(4-methoxy-34-200832068-phenyl) 4-methylphosphonium n-octane sulfonate, bis(4-methoxyphenyl) 4 Tolylhydrazinium 2-trifluoromethylbenzenesulfonate, bis(4-methoxyphenyl)-4-methylphenylphosphonium 4-trifluoromethylbenzenesulfonate, bis(4-methoxybenzene) Base) 4-toluene fluorenyl perfluorobenzenesulfonate and the like. Examples of the salt of the phosphonium cation represented by the formula (6-29) include (4^-hydroxyphenyl)diphenylphosphonium trifluoromethanesulfonate and (4-hydroxyphenyl)diphenylphosphonium hexafluoride. Ortho-butane sulfonate, (4-hydroxyphenyl) diphenyl sulfonium φ fluoro-n-octane sulfonate, (4-hydroxyphenyl) diphenyl hydrazine p-toluene sulfonate, (4 hydroxy Phenyl)diphenylsulfonium benzenesulfonate, (4-hydroxyphenyl)diphenylphosphonium 1 〇-camphor-sulfonate, (4-hydroxyphenyl)diphenylphosphonium n-octane sulfonate, (4-hydroxyphenyl)diphenylfluorene-2-trifluoromethylbenzenesulfonate, (4-hydroxyphenyl)diphenylphosphonium 4-trifluoromethylbenzenesulfonate, (4-hydroxyphenyl) Diphenylphosphonium perfluorobenzenesulfonate and the like. The salt of the mirror cation represented by the formula (6-54) includes 4-n-butoxy- 1 -naphthyltetrahydrothiophene iron trifluoromethanesulfonate and 4-n-butyl #oxy-1 1 Naphthyltetrahydrothiophene hexafluoro-n-butane sulfonate, 4-n-butoxy- 1 -naphthyltetrahydrothiophene fluorinated perfluorooctane sulfonate, 4-n-butoxy- 1 -naphthalene Tetrahydrothiophene key n-octane sulfonate, 4-n-butoxy-1'-naphthyltetrahydrothiophene p-toluenesulfonate, 4-n-butoxy-l-naphthyl•tetrahydrothiophene Benzene sulfonate, 4-n-butoxy- 1 -naphthyltetrahydrothiophene iron 1 〇-camphor sulfonate, 4-n-butoxy- 1 -naphthyltetrahydrothiophene 2 -trifluoromethylbenzene Sulfonate, 4-n-butoxy-1 1-naphthyltetrahydrothienyl 4-trifluoromethylbenzenesulfonate, 4-n-butoxy-1,4-naphthyltetrahydrothiophene-perfluorobenzenesulfonic acid Salt and so on. -35-200832068 The salt of the phosphonium cation represented by the formula (6-62) includes tris(4-fluorophenyl)phosphonium trifluoromethanesulfonate and tris(4-fluorophenyl)phosphonium hexafluoride. Butane sulfonate, tris(4-fluorophenyl)锍10-camphorsulfonate, tris(4-fluorophenyl)phosphonium octane sulfonate, tris(4-fluorophenyl)fluorene toluene Sulfonate and the like. 'As a salt of the mirror cation represented by the formula (6-63), (4-fluorophenyl)diphenylphosphonium trifluoromethanesulfonate, (4-fluorophenyl)di-phenylphenylphosphonium Fluorine butane sulfonate, (4-fluorophenyl) diphenyl mirror n-octane sulfonate, (4 fluorophenyl) diphenyl fluorene 10-camphorsulfonate, (4 fluorophenyl) Diphenylphosphonium p-toluenesulfonate, (4-fluorophenyl)diphenylsulfonium benzenesulfonate, (4-fluorophenyl)diphenyl mirror 2-trifluoromethylbenzenesulfonate, 4-fluorophenyl)diphenylphosphonium 4-trifluoromethylbenzenesulfonate, (4-fluorophenyl)diphenyl mirror perfluorobenzenesulfonate, and the like. Examples of the salt of the iodine cation represented by the formula (7-1) include diphenyl iodonium trifluoromethanesulfonate, diphenyl iodine hexafluoro n-butane sulfonate, and diphenyl iodine. P-perfluorooctane sulfonate, diphenyl iodine p-toluene sulfonate, diphenyl iodonium benzene sulfonate, diphenyl iodine 10 - camphor sulfonate, diphenyl iodonium Octane sulfonate, diphenyl sulfonate 2-trifluoromethylbenzene sulfonate, diphenyl iodine 4-trifluoromethylbenzene sulfonate, diphenyl iodine • perfluorobenzene sulfonic acid Salt and so on. The salt of the iodine cation represented by the formula (7-3) includes bis(4-methylphenyl) iodine trifluoromethanesulfonate and bis(4-methylphenyl) iodonium nonafluoro-n-butyl Alkane sulfonate, bis(4-tolylthio)iodo-perfluoro- n-octane sulfonate, bis(4-tolylthio)iodo-p-toluenesulfonate, -36 - 200832068 bis(4-toluene oxime) Iodine benzene sulfonate, bis(4-toluene) iodine 10 - camphorsulfonate, bis(4-methylphenyl) iodine octane sulfonate, bis(4-toluene) Iodine 2-difluoromethylbenzenesulfonate, bis(4-methylphenyl)iodo- 4-trifluoromethylbenzenesulfonate, bis(4-methylphenyl)iodo-perfluorobenzenesulfonate Acid salt, etc. 'As a salt of the iodine cation represented by the formula (7-5), bis(3,4-dimethylphenyl) iodine trifluoromethanesulfonate, bis(3,4 1-2 φ A) Phenyl phenyl) iodized iron nonafluoro n-butane sulfonate, bis(3,4-dimethylphenyl) iodine perfluoro-n-octane sulfonate, bis(3,4-dimethylphenyl) Iodine p-toluenesulfonate, bis(3,4-dimethylphenyl)iodobenzenesulfonate, bis(3,4-dimethylphenyl)iodonium 10-camphorsulfonate, double 3,4 dimethyl phenyl) iron iodide n-octane sulfonate, bis(3,4-dimethylphenyl) iodine 2-trifluoromethylbenzene sulfonate, double (3, 4 Dimethylphenyl). Iodine 4 monotrifluoromethylbenzenesulfonate, bis(3,4-dimethylphenyl)iron iodide perfluorobenzenesulfonate, and the like. # As a salt of the iodine cation represented by the formula (7-11), bis(4-butylbutylphenyl) iodine trifluoromethanesulfonate and bis(4-butylphenyl) are mentioned. Iodine nonafluoro-n-butane sulfonate, bis(4-butylbutyl) iodine perfluoro-n-octane sulfonate, bis(4-butylphenyl) iodine Tosylate, bis(4-butylbutyl)iodobenzenesulfonate, bis(4-butylphenyl) iodine 10 - camphorsulfonate, double (4 - third Butylphenyl) iodine-n-octane sulfonate, bis(4-t-butylphenyl) iodine 2-trifluoromethylbenzenesulfonate, bis(4-butylphenyl) iodine Key 4-trifluoromethylbenzenesulfonate, bis(4-tert-butylphenyl-37-200832068) iodine-perfluorobenzenesulfonate, bis(4-butylphenyl)iodonium 2 , 4 difluorobenzene sulfonate and the like. Examples of the salt of the iron iodide cation represented by the formula (7-12) include (4-nitrophenyl)phenyl iodide trifluoromethanesulfonate and (4-nitrophenyl)phenyliron iodide. Nonafluoro-n-butane sulfonate, (4-nitrophenyl)phenyliodo' iron perfluoro-n-octane sulfonate, (4-nitrophenyl)phenyl iodide p-toluenesulfonate, 4 mononitrophenyl)phenyliodonium benzene sulfonate, (4 nitro φ phenyl) phenyl iodine pin 1 〇 - camphor sulfonate, (4 nitrophenyl) phenyl iodine Octanesulfonate, (4-nitrophenyl)phenyl iodide 2-trifluoromethylbenzenesulfonate, (4-nitrophenyl)phenyl iodide 4 trifluoromethylbenzenesulfonic acid Salt, (4-nitrophenyl)phenyl iodide perfluorobenzenesulfonate, and the like. Examples of the salt of the iodine cation represented by the formula (7-15) include bis(3-nitrophenyl)iodotrifluoromethanesulfonate and bis(3-nitrophenyl)iodolyl nonafluorocarbon. N-butane sulfonate, bis(3-nitrophenyl)iodonium perfluoro-n-octane sulfonate, bis(3-nitrophenyl)iodyl p-toluenesulfonate, • double (3-nitrate) Phenyl phenyl) iron iodide benzene sulfonate, bis(3-nitrophenyl) iodine iron 10 - camphor sulfonate, bis(3-nitrophenyl) iodine iron n-octane sulfonate, double ( 3-nitrophenyl)iodonium 2-trifluoromethylbenzenesulfonate, bis-(3-nitrophenyl)iodoferrate 4-trifluoromethylbenzenesulfonate, bis(3-nitro-phenyl) Phenyl) iron iodide perfluorobenzenesulfonate and the like. The salt of the iron iodide cation represented by the formula (7-16) includes (4-methoxyphenyl)phenyl iodide iron trifluoromethanesulfonate and (4-methoxyphenyl)phenyl group. Iodine iron nonafluoro-n-butane sulfonate, (4-methoxyphenyl) phenyl iodide perfluoro-n-octane sulfonate, (4-methoxyphenyl) phenyl iodide-38- 200832068 p-Toluenesulfonate, (4-methoxyphenyl)phenyl iodide benzenesulfonate, (4-methoxyphenyl)phenyl iodide pin 10-camphorsulfonate, (4-methoxy Phenyl phenyl) iodide iron n-octane sulfonate, (4-methoxyphenyl) phenyl iodide 2-trifluoromethylbenzene sulfonate, (4-methoxyphenyl) phenyl Iodine 4-tetrafluoromethylbenzenesulfonate, (4-methoxyphenyl)benzene' iodide iron perfluorobenzenesulfonate, and the like. The salt of the iodine cation represented by the formula (7-19) includes bis (4-chlorophenyl) iodine trifluoromethanesulfonate and bis(4-chlorophenyl) iodine gun nonafluorocarbon. Butane sulfonate, bis(4-chlorophenyl)iodonium perfluorooctane sulfonate, bis(4-chlorophenyl)iodoferric p-toluenesulfonate, bis(4-chlorophenyl)iodine Phthamatesulfonate, bis(4-chlorophenyl)iodonium 10 - camphorsulfonate, bis(4-chlorophenyl)iron iodide octanesulfonate, bis(4-chlorophenyl)iodine Key 2-trifluoromethylbenzenesulfonate, bis(4-chlorophenyl)iodonium 4-trifluoromethylbenzenesulfonate, bis(4-chlorophenyl)iodoferrofluorobenzenesulfonate, etc. . Φ is a salt of an iron iodide cation represented by the formula (7-25), and examples thereof include bis(4-trifluoromethylphenyl)iodotrifluoromethanesulfonate and bis(4-trifluoromethylphenyl). Iodine iron nonafluoro-n-butane sulfonate, bis(4-trifluoromethylphenyl)iron iodide perfluoro-n-octane sulfonate, bis(4-trifluoromethylphenyl)iodine-key pair Tosylate, bis(4-trifluoromethylphenyl)iodobenzenesulfonate, bis(4-trifluoromethylphenyl)iodonium 10 -camphorsulfonate, bis(4-trifluoro) Methylphenyl) iodine-n-octane sulfonate, bis(4-trifluoromethylphenyl)iodine 2-trifluoromethylbenzenesulfonate, bis(4-trifluoromethylphenyl)iodine Key 4-trifluoromethylbenzenesulfonate, bis(4-trifluoromethylphenyl-39-200832068) iodonium perfluorobenzenesulfonate, and the like. Examples of the salt of the iodine cation represented by the formula (7-36) include bis(1-naphthyl)iodotrifluoromethanesulfonate and bis(1-naphthyl)iodronium hexafluoro-n-butane sulfonate. Acid salt, bis(1-naphthyl)iron iodide perfluoro-n-octane sulfonate, bis(1-naphthyl)iodyl p-toluenesulfonate, bis(1-naphthyl)iodronium benzenesulfonate , bis(1-naphthyl)iodoferrin 10 - camphorsulfonate, bis(1-naphthyl)iodyl n-octane sulfonate, bis(1-naphthyl)iodonium 2-tris-fluoromethylbenzene A sulfonate, a bis(1-naphthyl)iodonyl 4-trifluoromethylbenzenesulfonate, a di(l-naphthyl)iodo-perfluorobenzenesulfonate or the like. The salt of the iodine cation represented by the formula (7-40) may, for example, be bis(4-fluorophenyl)iodotrifluoromethanesulfonate or bis(4-fluorophenyl)iodoferric hexafluoro-n-butyl An alkane sulfonate, bis(4-fluorophenyl)iodonium 10 - camphorsulfonate, bis(4-fluorophenyl)iron iodide octanesulfonate, and the like. Examples of the salt of the iron iodide cation represented by the formula (7-41) include (4-fluorophenyl)phenyl iodide trifluoromethanesulfonate and (4-fluorophenyl)benzene #yl iodide. Fluorine n-butanesulfonate, (4-fluorophenyl)phenyliodonium 10 - camphorsulfonate, (4-fluorophenyl)phenyl iodide n-octanesulfonate, and the like. Among these iron salts, preferred are bis(4-butylbutylphenyl)iodotrifluoromethanesulfonate and bis(4-t-butylphenyl)iodonium nonafluoro-n-butane. Sulfonic acid salt, bis(4-butylphenyl) iodine p-toluenesulfonate, bis(4-butylphenyl) iodine 10-camphorsulfonate, double (4-third) Phenyl phenyl) iron iodide 2-trifluoromethylbenzene sulfonate, bis(4-butylphenyl) iodine 4 monotrifluoromethylbenzene sulfonate, bis(4-t-butylbenzene) Iodine iron 2,4-difluorobenzenesulfonate, triphenylsulfonium trifluoromethyl-40-200832068 alkanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium toluene Sulfonate, triphenylsulfonium 1 〇-camphorsulfonate, triphenyl mirror 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium 2,4-difluoromethylbenzenesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-2-(tetracycline [4.4.0.I2'5.17'1G]dodecane-8- Ethane sulfonate, triphenyl mirror 1,1 fluoro &lt; One 2-(bicyclo[2.2.1] Gengyuan-2-yl) phenylsulfonate, 2,4,6-trimethylphenyldiphenylphosphonium 2,4 difluorobenzenesulfonate , φ 2,4,6 —trimethylphenyldiphenylphosphonium 4 -trifluoromethylbenzenesulfonate, 4-methylphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methylbenzene Diphenylphosphonium perfluoro-n-butane sulfonate, 4-methylphenyldiphenylphosphonium p-toluenesulfonate, 4-methylphenyldiphenylphosphonium 10-camphorsulfonate, 4 Methylphenyldiphenylfluorene 2-trifluoromethylbenzenesulfonate, 4-methylphenyldiphenylphosphonium 4-trifluoromethylbenzenesulfonate, 4-methylphenyldiphenylphosphonium 2,4-difluoromethylbenzenesulfonate, tris(4-methylphenyl)phosphonium trifluoromethanesulfonate, tris(4-methylphenyl)phosphonium nonafluorobutane sulfonate, three (4 monomethyl phenyl phenyl) fluorene p-toluene sulfonate, tris(4-methylphenyl) mirror 1 〇 - camphor sulfonate, tris(4-methylphenyl) fluorene 2-trifluoromethyl Toluenesulfonate, tris(4-methylphenyl)phosphonium 4-trifluoromethylbenzenesulfonate, tris(4-methylphenyl)phosphonium 2,4-difluoromethylbenzenesulfonate, (4-tert-butylphenyl 'yl) fluorene trifluoromethanesulfonate tris(4-tributylphenyl) fluorene mirror nonafluoro-n-butane sulfonate, tris(4-tert-butylphenyl) Mirror perfluoro-n-octane sulfonate, tris(4-butylphenyl)phosphonium p-toluenesulfonate, tris(4-butylphenyl)toluenesulfonate, tris(4- Tert-butylphenyl) 铳1 0-camphorsulfonate, tris(4-butylphenyl) mirror 2 _trifluoromethyl-41 - 200832068 base benzene sulfonate, three (4 a third Phenyl)phosphonium 4-trifluoromethylbenzenesulfonate, tris(4-butylphenyl)phosphonium naphthalate, tris(4-methoxyphenyl)phosphonium trifluoromethanesulfonate , tris(4-methoxyphenyl)fluorene nonafluoro-n-butane sulfonate, tris(4-methoxyphenyl)phosphonium perfluoro-n-octane sulfonate, tris(4-methoxyphenyl) ) p-toluenesulfonate, tris(4-methoxyphenyl)toluenesulfonate, tris(4-methoxyphenyl)phosphonium 10-decamphorsulfonate, tris(4-methoxyl) Phenyl)phosphonium 2-trifluoromethylbenzenesulfonate, tris(4-methoxyphenyl)phosphonium 4-trifluoromethylbenzenesulfonate, (4-methoxyphenyl)phosphonium perfluorobenzenesulfonate, (4-fluorophenyl)diphenylsulfonium trifluoromethanesulfonate, (4-fluorophenyl)diphenylphosphonium hexafluoro-n-butyl Alkane sulfonate, (4-fluorophenyl)diphenylphosphonium perfluorooctane sulfonate, (4-fluorophenyl)diphenylphosphonium p-toluenesulfonate, (4 fluorophenyl) Phenyl benzene sulfonate, (4 fluorophenyl) diphenyl hydrazide 1 〇-camphor sulfonate, (4 fluorophenyl) diphenyl fluorene 2-trifluoromethyl benzene sulfonate, 4-fluorophenyl)diphenylphosphonium 4-trifluoromethyl #benzenesulfonate, (4-fluorophenyl)diphenylsulfonium perfluorobenzenesulfonate, 4-n-butoxy-1 -naphthalene Tetrahydrothiophene trifluoromethanesulfonate, 4-n-butoxy- 1 -naphthyltetrahydrothiophene iron nonafluoro-n-butane sulfonate, 4 '-n-butoxy- 1 -naphthyltetrahydrol Thiophene iron perfluoro-n-octane sulfonate, 4-mono-n-butoxy-1-naphthyltetrahydrothiophene iron p-toluenesulfonate, 4-n-butoxy-l-naphthyltetrahydrothiophene Acid salt, 4-n-butoxy-l-naphthyltetrahydrothiophene 10 - camphorsulfonate, 4-n-butoxy-l-naphthyltetrahydrothiazide Key 2-trifluoromethylbenzenesulfonate, 4-n-butoxy-1,4-naphthyltetrahydrothiophene iron 4-trifluoromethylbenzenesulfonate, 4-n-butoxy- 1--42- 200832068 Naphthyltetrahydrothiophene perfluorobenzenesulfonate, diphenyliodide nonafluoro-n-butanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodopyl perfluoro-n-octane Sulfonate, diphenyl iodine gun 1〇-camphorsulfonate, triphenylsulfonium perfluoro-n-octane sulfonate, tris(4-fluorophenyl)phosphonium hexafluoro-n-butane sulfonate, three ( 4-fluorophenyl)镝1 0 —樟^ cerebral sulfonate, tris(4-fluorophenyl)phosphonium trifluoromethanesulfonate tris(4-fluorophenyl)indole p-toluenesulfonate, (4- Fluorophenyl)phenyl iodide trifluoromethanesulfonate, (4-fluorophenyl)phenyl iodide nonafluorobutane sulfonate, (4-fluorophenyl)phenyliodoferrate 10- Camphorsulfonate, bis(4-fluorophenyl)iodotrifluoromethanesulfonate, bis(4-fluorophenyl)iodonium nonafluoro-n-butanesulfonate, bis(4-fluorophenyl)iodine Key 1 〇 - camphor sulfonate, ( 4 - hydroxyphenyl) diphenyl sulfonium trifluoromethane sulfonate, (4 hydroxyphenyl) Diphenylphosphonium n-butane sulfonate, (4-hydroxyphenyl)diphenylphosphonium 10-camphorsulfonate, (4-hydroxyphenyl)diphenylphosphonium-2-trifluoromethylbenzenesulfonate Acid salt, (4-hydroxyphenyl) diphenyl mirror 4 monotrifluoromethylbenzenesulfonate. In addition, the above-mentioned key salts may be used alone or in combination of two or more. The ratio (A1 / A2) (mass, ratio) of the acid generator (A1) and the acid generator (A2) constituting the mixed acid generator (A) which can be used in the present invention is usually 0.01 to 5, preferably It is 0.02 to 2, and the total amount of the acid generator (A1) and the acid generator (A2) is usually 0. 5~ for every 100 parts by mass of the resin component in the radiation sensitive linear resin composition. 30 parts by mass, preferably 1 to 2 parts by mass. In this case, when the ratio (A1/A2) (mass ratio) of the acid generator (A1) to the acid generator (A2) is less than 0.01, the "film crack" of the photoresist is reduced. -43- 200832068 The effect tends to be large. On the other hand, if it exceeds 5, the sensitivity as a photoresist is lowered, and pattern formation becomes difficult. When the total amount of the acid generator (A1) and the acid generator (A2) is less than 0.5 parts by mass, the catalyst action of the acid generated by the exposure may be difficult to sufficiently cause chemical changes. On the other hand, when it exceeds 20 parts by mass, coating unevenness may occur when the radiation sensitive linear resin composition is applied, and scum may occur when developing. In the positive-type radiation-sensitive linear resin composition of the present invention, a sensitive radiation linear acid generator other than the above acid generator (A) (hereinafter also referred to as "other acid generator") may be blended as needed. Examples of the other acid generator include a sulfonimide compound, an anthraquinone compound, a sulfonate compound, a disulfonyldiazomethane compound, a disulfonylmethane compound, an anthracene sulfonate compound, and an anthracene sulfonate. Compounds, etc. Specific examples of the sulfonium imine compound include N-(trifluoromethylsulfonyloxy) succinimide, N-(trifluoromethylsulfonyloxy) quinone imine, and N-( Trifluoromethylsulfonyloxy)diphenylmaleimine·, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]gly-5-ene-2,3 Imine, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(trifluoromethylsulfonate醯oxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyindoleimine', N-(trifluoromethylsulfonyloxy)naphthylimine, n —( 1 0 — camphorsulfonyloxy) amber imine, N —( 10 — camphorsulfonyloxy) quinone imine, N — ( 1 0 — camphorsulfonyloxy) diphenyl mala Yttrium, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3 -1,1,1,1,7,7,7,7,7 —7 —Oxobicyclo-44 - 200832068 [2.2.1] Glycine-5-ene-2,3-dicarboxyindoleimine, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]heptane a 5,6-oxy group 2,3-dicarboxylic quinone imine, N-(10-camphorsulfonyloxy)naphthyl imine, N-[(5-methyl-5-carboxymethylbicyclo[2.2.]]heptane-2 a sulfonyloxy group;|succinimide, N-(n-octylsulfonyloxy) succinimide, N-(n-octylsulfonyloxy) quinone imine, N-(positive Octylsulfonyloxy)diphenyl horse# acid imine, N-(n-octylsulfonyloxy)bicyclo[2 ·2·1]hept-5-ene-2,3-dicarboxyfluorene Amine, ν-(n-octylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyxanimide, anthracene-(n-octylsulfonyloxy) Bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyarsenine, anthracene-(n-octylsulfonyloxy)naphthylimine, Ν-(4-methyl Phenylsulfonyloxy) succinimide, Ν-(4-methylphenylsulfonyloxy) quinone imine, Ν-(4-methylphenylsulfonyloxy) diphenyl malay Yttrium, Ν-(4-methylphenylsulfonyloxy)bicyclo[2 ·2·1]gly-5®-ene-2,3-dicarboxyarmine, hydrazine-(4-methyl Phenylsulfonyloxy)-7-oxabicyclo[2·2.1]g 5-ene-2,3-dicarboxylimine imine, fluorene-(4-methylphenyl fluorenyloxy)bicyclo[2.2.1]geptane-5,6-oxy--2,3-di Carboxylimine, Ν-(4-methylphenylsulfonyloxy)naphthoquinone, amine, Ν-(2-trifluoromethylphenylsulfonyloxy) amber quinone imine, ν-(2 -trifluoromethylphenylsulfonyloxy)imine, fluorene-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, fluorene-(2-trifluoromethyl) Phenyl sulfonyloxy)bicyclo[2.2.1]heptane-5-ene-2,3-dicarboxyindole-45- 200832068 imine, N-(2-fluoromethylphenylsulfonyloxy) 77-oxabicyclo[2·2·1]gly-5-ene~2,3~dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2·21 Heptane-5,6-oxy-2,3-dicarboxylate. Brewed imine, hydrazine-(2~trifluoromethylphenylsulfonyloxy)naphthyl imine, ν-(4-dichloro Methylphenylsulfonyloxy) succinimide, Ν-(4-dichloromethylphenyl decyloxy) quinone imine, Ν-(4-trifluoromethylphenylsulfonyloxy ) diphenylmaleimide, hydrazine - (4 one three Fluoromethyl # phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, Ν-(4-fluoromethylphenylsulfonyloxy) 7_oxabicyclo[2·2·1]hept-5-ene-2,3~dicarboxylimineimine, anthracene-(4-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1] Heptane-5,6-oxy-2,3-dicarboxyarsenine, fluorene-(4~trifluoromethylphenylsulfonyloxy)naphthylimine, fluorene-(perfluorophenylsulfonate) Oxy) succinimide, ν-(perfluorophenylsulfonyloxy) quinone imine, Ν-(perfluorophenylsulfonyloxy)diphenylmaleimide, Ν-(all Fluorophenylsulfonyloxy)bicyclo[2.2.1] Φ hept-5-ene-2,3-dicarboxyarsenine, fluorene-(perfluorophenylsulfonyloxy)-7-oxabicyclo[ 2·2·1]hept-5-ene-2,3-dicarboxyarmine, fluorene mono(perfluorophenylsulfonyloxy)bicyclo[2·2·1]heptane-5,6-oxygen一-' 2,3 -dicarboxylimine imine, fluorene-(perfluorophenylsulfonyloxy)naphthylimine, - Ν-(1-naphthylsulfonyloxy) amber quinone imine, hydrazine - (1-naphthylsulfonyloxy) quinone imine, Ν-(1 -naphthyl醯oxy)diphenylmaleimide, Ν-(1-naphthylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, ν-( 1-naphthylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxycarbonitrile, hydrazine-(1-naphthalene-46-200832068 Bis[bi]cyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxycarboximine, N-(1-naphthylsulfonyloxy)naphthylimine 'N-(nonafluoro n-Butyl sulfonyloxy) amber imine, N-(nonafluoro-n-butylsulfonyloxy) quinone imine, N-(nonafluoro-n-butylsulfonyloxy) diphenyl mala Imine, N-(nonafluoro-n-butylsulfonyloxy) bis-cyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenine, N-(nonafluoro-n-butylsulfonate) Oxy))-7-oxabicyclo[2.2.1]hept-5-ene-2,3-di-ruthenium carbarylimine, fluorene-(nonafluoro-n-butylsulfonyloxy)bicyclo[2.2.1] Heptane-5,6-oxy-2,3-dicarboxyarmine, fluorene-(nonafluoro-n-butylsulfonyloxy)naphthylimine, fluorene-(perfluoro-n-octylsulfonyloxy) Amber imine, Ν-(perfluoro-n-octane Sulfomethoxy) quinone imine, fluorene-(perfluoro-n-octylsulfonyloxy)diphenylmaleimide, fluorene-(perfluoro-n-octylsulfonyloxy)bicyclo[2.2.1 Geng~5-ene-2,3-diimine, fluorene (perfluorooctylsulfonyloxy)-7-oxabicyclo[2.2.1]g- 5 -storage 2,3 - Dicarboxylated imine, Ν-(perfluoro-n-octylsulfonyloxy)bicyclophene • [2·2·1] Gengyuan-5,6-oxy-2,3-diimine, Ν- (perfluoro-n-octylsulfonyloxy)naphthoquinone imine, Ν-(phenylsulfonyloxy) oxime imine, Ν-(phenyl 醯'oxy) quinone imine, Ν- (phenylsulfonyloxy)diphenylmaleimide-amine, anthracene-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximine, Ν-(phenylsulfonyloxy)-7-oxabicyclo[2.2.1] hept-5-ene-2,3-dicarboxyarsenine, ν-(phenylsulfonyloxy)bicyclo[2.2 .1] heptane-5,6-oxy-2,3-dicarboxyarsenine, 1^-(phenylsulfonyloxy)naphthylimine, and the like. -47- 200832068 Among these sulfonimide compounds, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene is preferred. Amine, N-(10-camphorsulfonyloxy) succinimide, N-(4-methylphenylsulfonyloxy) succinimide, N-(nonafluoro-n-butylsulfonyloxy) Bicyclo[2 ·2·1]gly-5-ene-2,3-dicarboxyarsenine, N-(phenylsulfonyloxy) double sorrow [2.2.1] Geng-5 - burn one 2, 3 - Diimine, hydrazine - [(5-methyl-5-carboxymethylbicyclo[2,2·1]heptan-2-yl)sulfonyloxy #yl] amber quinone. Further, the sulfonimide compound may be used alone or in combination of two or more. Examples of the ruthenium compound include β-keto-based maple, β-sulfonylfluorene, and the like α-diazonium compounds. Further, as a more specific example of the above ruthenium compound, benzamidine methylphenyl fluorene, decylbenzhydrylmethyl hydrazine, bis(phenylsulfonyl)methane, 4-trityl fluorene methyl group Hey. The sulfonate compound may, for example, be an alkylsulfonate, a haloalkylsulfonate, an arylsulfonate or an imidosulfonate. Further, as a more specific example of the above-mentioned sulfonate compound, benzoin tosylate, pyrogallol tris(trifluoromethanesulfonate), and pyrogallol tris(nonafluoro-n-butylsulfonate) Acid salt), pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyindole-2-sulfonate, α-methylbenzoin tosylate • 一 hydroxymethyl benzoin trifluoromethanesulfonate, α-hydroxymethyl benzoin n-octane sulfonate, α-hydroxymethyl benzoin n-dodecane sulfonate, and the like. The disulfonyldiazomethane compound may, for example, be a compound represented by the following formula (20). -48- 200832068 [Chem. 26]

上述式（20 )中’各R25係互相獨立地爲1價有機基 。作爲1價有機基’可舉出院基、芳基、鹵素取代烷基、 鹵素取代芳基等。 作爲式（20)所表示的二磺醯基重氮甲烷化合物之具 體例子，可舉出雙（三氟甲烷磺醯基）重氮甲烷、雙（環 己基磺醯基）重氮甲院、雙（苯基磺醯基）重氮甲烷、雙 (4 一甲基苯基磺醯基）重氮甲烷、雙（2,4 一二甲基苯磺 醯基）重氮甲烷、雙（4 一第三丁基苯基磺醯基）重氮甲 烷、雙（4 一氯苯基磺醯基）重氮甲烷、（甲基磺醯基）4 -甲基苯基磺醯基重氮甲院、（環己基磺醯基）4-甲基 苯基磺酿基重氮甲院、（環己基磺醯基）1，1 一二甲基乙 基磺醯基重氮甲烷、雙（i，1—二甲基乙基磺醯基）重氮 甲烷、雙（1 一甲基乙基擴醯基）重氮甲烷、雙（3,3—二 甲基一 1，5 一二氧雜螺[5·5]十二烷一 8一磺醯基）重氮甲烷 、雙（1，4一二氧雜螺[4·5]癸垸一 7—磺醯基）重氮甲院、 雙（4 一第三丁基磺醯基）重氮甲烷等。 於此等二磺醯基重氮甲烷化合物之中，較佳爲雙（環 己基磺醯基）重氮甲烷、雙（1，1 一二甲基乙基磺醯基） 重氮甲烷、雙（3,3—二甲基一 1，5—二氧雜螺[5.5]十二烷 一 8—磺醯基）重氮甲烷、雙（1，4 一二氧雜螺[4· 5]十一烷 -49- 200832068 一 7-磺醯基）重氮甲烷、雙（4 一第三丁磺醯基）重氮甲 烷。再者，二磺醯基重氮甲烷化合物係可爲單獨1種或組 合2種以上來使用。 作爲上述二磺醯基甲烷化合物，例如可舉出下述式（ 2 1 )所表示的化合物。 [化 27]In the above formula (20), each R25 is independently a monovalent organic group. The monovalent organic group 'is a hospital group, an aryl group, a halogen-substituted alkyl group, a halogen-substituted aryl group or the like. Specific examples of the disulfonyldiazomethane compound represented by the formula (20) include bis(trifluoromethanesulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazide, and double (phenylsulfonyl) diazomethane, bis(4-methylphenylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, double (4-first Tributylphenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, (methylsulfonyl) 4-methylphenylsulfonyldiazepine, ( Cyclohexylsulfonyl) 4-methylphenylsulfonic acid diazotamine, (cyclohexylsulfonyl) 1,1 dimethyl sulfonyldiazomethane, double (i, 1-2) Methyl ethyl sulfonyl) diazomethane, bis(1-methylethyl fluorenyl) diazomethane, bis(3,3-dimethyl-1,5-dioxaspiro[5·5 ]Dodecane-8-sulfonyl)diazomethane, bis(1,4-dioxospiro[4·5]癸垸7-sulfonyl) diazo A, double (4 to third Butylsulfonyl) diazomethane and the like. Among these disulfonyldiazomethane compounds, preferred are bis(cyclohexylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, and bis ( 3,3-Dimethyl-1,5-dioxaspiro[5.5]dodecane-8-sulfonyl)diazomethane, bis(1,4-dioxaspiro[4·5]11 Alkane-49- 200832068 a 7-sulfonyl)diazomethane, bis(4-galsulphonyl)diazomethane. Further, the disulfonyldiazomethane compound may be used alone or in combination of two or more. The disulfonylmethane compound is, for example, a compound represented by the following formula (2 1 ). [化27]

(21 R26I OHHHSnnoVIcIwI onHsuno 上述式（2 1 )中，各R26互相獨立地係直鏈狀或支鏈 狀的1價脂肪族烴基、環烷基、芳基、芳烷基、或具有雜 原子的其它1價有機基。又，V及W互相獨立地係芳基 、氫原子、直鏈狀或支鏈狀的1價脂肪族烴基、或具有雜 原子的其它1價有機基。再者，上述式（21)中的V及 W係滿足以下所示的（1 )〜（3 )中任一條件。 (1 ) : V及W中至少一者爲芳基。 (2 ) : V及W互相連結以形成具有至少1個不飽和 鍵的碳單環構造或碳多環構造。 (3 ) : V及W互相連結以形成下述所表示的基。 [化 28] V， w， -50- 200832068 上述式中，V’及W’互相獨立地（但是，^及w，各以 複數存在時，複數的V’及W’可各自相同或不同）、氮原 子、鹵素原子、直鏈狀或支鏈狀的烷基、環烷基、芳基、 或芳烷基，Γ係2〜10的整數。再者，鍵結於相同或不同 的碳原子之V’及W’，係可互相連結以形成碳單環構造。 又，二磺醯基甲烷化合物可爲單獨1種或組合2種以上來 使用。 作爲上述肟磺酸鹽化合物，例如可舉出下述式（2 2 -1 )或式（22-2 )所表示的化合物。 [化 29] Ο R27 (22-1) NC —C=N—Ο—S — R28(21 R26I OHHHSnnoVIcIwI onHsuno In the above formula (2 1 ), each R26 is independently a linear or branched monovalent aliphatic hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group, or the like having a hetero atom. Further, V and W are each independently an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, or another monovalent organic group having a hetero atom. The V and W in (21) satisfy any of the conditions (1) to (3) shown below. (1) : At least one of V and W is an aryl group. (2) : V and W are connected to each other. To form a carbon monocyclic structure or a carbon polycyclic structure having at least one unsaturated bond. (3): V and W are bonded to each other to form a group represented below. [Chem. 28] V, w, -50- 200832068 In the above formula, V' and W' are independent of each other (however, ^ and w, each in the plural, the plural V' and W' may be the same or different), a nitrogen atom, a halogen atom, a linear chain or a branch a chain alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, an integer of from 2 to 10. Further, V' and W' bonded to the same or different carbon atoms may be In addition, the disulfonyl methane compound may be used alone or in combination of two or more. The oxime sulfonate compound may, for example, be represented by the following formula (2 2 -1). Or a compound represented by the formula (22-2). [Chem. 29] Ο R27 (22-1) NC — C=N—Ο—S — R28

II 〇 R25- OII -S-II 〇 R27 R27 ΟII -S-II 〇 R28 (22-2)II 〇 R25- OII -S-II 〇 R27 R27 ΟII -S-II 〇 R28 (22-2)

上述式（22 -1 )及（22-2 )中，各R27及R28互相獨 立地爲1價有機基。再者，於上述式（22-1)及（22-2) 中，作爲R27的合適例子，可舉出甲基、乙基、正丙基、 苯基、甲苯磺醯基、三氟甲基、五氟乙基等。又，作爲 R28的合適例子’可舉出苯基、甲苯磺醯基、1 一萘基等。 作爲上述肼磺酸鹽化合物的具體例子，可舉出雙（苯 基磺醯基）肼、雙（4 一甲基苯基磺醯基）肼、雙（三氟 甲基磺醯基）肼 '雙（五氟乙基磺醯基）肼、雙（正丙基 -51 - 200832068 磺醯基）肼、苯基磺醯基肼、4-甲基苯基磺醯基肼、三 氟甲基磺醯基肼、五氟乙基磺醯基肼、正丙基磺醯基胼、 (三氟甲基磺醯基）4 一甲基苯基磺醯基肼等。再者，肼 磺酸鹽化合物可爲單獨1種或組合2種以上來使用。 上述其它酸產生劑的使用比例，對於1 〇〇質量份的混 合酸產生劑成分而言，通常爲50質量份以下，較佳爲30 質量份以下。其它酸產生劑的使用比例，對於10 0質量份 • 的混合酸產生劑成分而言，若超過3 0質量份，則有損害 本發明的正型敏輻射線性樹脂組成物的效果之傾向。 &lt;樹脂（B ) &gt; 構成本發明的正型感放射優性樹脂組成物之樹脂，係 藉由樹脂中所含有的酸解離性基之解離而成爲鹼可溶性之 鹼不溶性或難溶性的樹脂（B )。 此處，本說明書中所言的「鹼不溶性或難溶性」，係 ® 意味由使用含有該樹脂（B )的正型敏輻射線性樹脂組成 物所形成的光阻被膜來形成光阻圖型時，在所採用的鹼顯 像條件下，代替該光阻被膜，僅將使用樹脂（B )的被膜 作顯像時，該被膜的初期膜厚之50 %以上在顯像後殘留 ' 的性質。該樹脂（B )含有重複單位（i )、重複單位（ii )及重複單位（iii)。 重複單位（i )係下述式（3 )所示的重複單位。 -52- 200832068 [化 30] R1In the above formulae (22-1) and (22-2), each of R27 and R28 is independently a monovalent organic group. Further, in the above formulas (22-1) and (22-2), examples of R27 include a methyl group, an ethyl group, a n-propyl group, a phenyl group, a toluenesulfonyl group, and a trifluoromethyl group. , pentafluoroethyl and the like. Further, as a suitable example of R28, a phenyl group, a tolsulfonyl group, a 1-naphthyl group or the like can be given. Specific examples of the above hydrazine sulfonate compound include bis(phenylsulfonyl)fluorene, bis(4-methylphenylsulfonyl)fluorene, and bis(trifluoromethylsulfonyl)fluorene. Bis(pentafluoroethylsulfonyl)anthracene, bis(n-propyl-51 - 200832068 sulfonyl) fluorene, phenylsulfonyl hydrazine, 4-methylphenylsulfonyl hydrazine, trifluoromethyl sulfonate Mercaptopurine, pentafluoroethylsulfonylhydrazine, n-propylsulfonylhydrazine, (trifluoromethylsulfonyl) 4-methylphenylsulfonylhydrazine, and the like. Further, the sulfonium sulfonate compound may be used alone or in combination of two or more. The use ratio of the above-mentioned other acid generator is usually 50 parts by mass or less, preferably 30 parts by mass or less, per 1 part by mass of the mixed acid generator component. When the ratio of use of the other acid generator is more than 30 parts by mass based on 100 parts by mass of the mixed acid generator component, there is a tendency to impair the effect of the positive-sensitive radiation linear resin composition of the present invention. &lt;Resin (B) &gt; The resin constituting the positive-type radiation-sensitive resin composition of the present invention is an alkali-soluble alkali-insoluble or poorly soluble resin by dissociation of the acid-dissociable group contained in the resin ( B). Here, the term "alkali-insoluble or poorly soluble" as used in the present specification means that when a photoresist pattern is formed by using a photoresist film formed of a positive-type radiation-sensitive linear resin composition containing the resin (B). In the case of the alkali development condition to be used, in place of the photoresist film, only when the film of the resin (B) is used for development, 50% or more of the initial film thickness of the film remains as a property after development. The resin (B) contains a repeating unit (i), a repeating unit (ii), and a repeating unit (iii). The repeating unit (i) is a repeating unit represented by the following formula (3). -52- 200832068 [Chem. 30] R1

⑶ 式（3 )中，R1係氫原子或甲基，R2係！價有機基， φ 於r2以複數存在時，該複數的R2可互相相同或不同，p 係0〜3的整數，q係1〜3的整數。 作爲R2所表示的1價有機基，例如可舉出碳數！〜 12的直鏈狀、支鏈狀、或環狀的烷基、碳數6〜20的1 價芳香族烴基、1價含氧原子的有機基、1價含氮原子的 有機基等。 作爲上述烷基，例如可舉出甲基、乙基、正丙基、異 丙基、正丁基、2 —甲基丙基、1 一甲基丙基、第三丁基、 • 環戊基、環己基等。 作爲上述1價芳香族烴基，例如可舉出苯基、鄰甲苯 基、間甲苯基、對甲苯基、2，4一二甲苯基、2，6 —二甲苯 ' 基、3,5 一二甲苯基、釆基、鄰異丙苯基、間異丙苯基、 - W異丙本基、本甲基、苯乙基'1 一萘基、2—蔡基等。 作爲上述1價含氧原子的有機基，例如可舉出羧基； 羥甲基、1一羥乙基、2—羥乙基、1一羥丙基、2—羥丙基 、3-羥丙基、1—羥丁基、2一羥丁基、3 一羥丁基、4 — 羥丁基、3—羥環戊基、4 一羥基環己基等的碳數1〜8的 -53- 200832068 直鏈狀、支鏈狀、或環狀的羥烷基；甲氧基、乙氧基、正 丙氧基、異丙氧基、正丁氧基、2 一甲基丙氧基、丨一甲基 丙氧基、第三丁氧基、環戊氧基、環己氧基等的碳數！〜 8的直鏈狀、支鏈狀、或環狀的烷氧基；甲氧基羰氧基、 乙氧基羰氧基、正丙氧基羰氧基、正丁氧基羰氧基等的碳 數2〜9的直鏈狀烷氧基羰氧基；（1 一甲氧基乙氧基）甲 基、（1 一乙氧基乙氧基）甲基、（1 一正丙氧基乙氧基） φ 甲基、（1—正丁氧基乙氧基）甲基、（1 一環戊氧基乙氧 基）甲基、（1—環己氧基乙氧基）甲基、（〗一甲氧基丙 氧基）甲基、（1 一乙氧基丙氧基）甲基、乙氧基乙基等 的碳數3〜11的直鏈狀、支鏈狀、或環狀的（1 一烷氧基 烷氧基）烷基；甲氧基羰氧基甲基、乙氧基羰氧基甲基、 正丙氧基羰氧基甲基、共丙氧基羰氧基甲基、正丁氧基羰 氧基甲基、第三丁氧基羰氧基甲基、環戊氧基羰氧基甲基 、環己氧基羰氧基甲基等的碳數3〜10的直鏈狀、支鏈狀 • 、或環狀的烷氧基羰氧基烷基等。 作爲上述1價含氮原子的有機基，例如可舉出氰基； 氰甲基、1—氰乙基、2-氰乙基、1 一氰丙基、2 —氰丙基 • 、3-氰丙基、1 一氰丁基、2-氰丁基、3—氰丁基、4一 氰丁基、3 -氰環戊基、4 一氰環己基等的碳數2〜9的直 鏈狀、支鏈狀、或環狀的氰烷基等。 作爲合適的重複單位（i )之具體例子，可舉出2 -羥 基苯乙烯、3 -羥基苯乙烯、4一羥基苯乙烯、2—羥基一 α —甲基苯乙烯、3—羥基一 α —甲基苯乙烯、4一羥基— -54- 200832068 α —甲基苯乙烯、2—甲基一 3 —經基苯乙燒、4 —甲基一 3 —羥基苯乙烯、5 —甲基一 3 —羥基苯乙烯、2 —甲基一 4 — 羥基苯乙烯、3 -甲基一 4一羥基苯乙烯、3，4 一二羥基苯 乙烯、2,4,6 -三羥基苯乙烯等的聚合性不飽和鍵裂解的 重複單位。再者，於樹脂（Β )中，亦可以含有2種以上 的重複單位（i )。(3) In the formula (3), R1 is a hydrogen atom or a methyl group, and R2 is a compound! The valence organic group, when φ is present in plural in r2, the plural R2 may be the same or different from each other, p is an integer of 0 to 3, and q is an integer of 1 to 3. The monovalent organic group represented by R2 may, for example, be a carbon number! A linear, branched or cyclic alkyl group of ～12, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, an organic group having a monovalent oxygen atom, and an organic group having a monovalent nitrogen atom. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a tert-butyl group, and a cyclopentyl group. , cyclohexyl and the like. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-dimethylphenyl group, a 2,6-xylene group, and a 3,5-xylene group. Base, fluorenyl, o-isopropylphenyl, m-isopropylphenyl, -W-isopropylidene, methyl, phenethyl '1-naphthyl, 2-cyano, and the like. Examples of the organic group of the above-mentioned monovalent oxygen atom include a carboxyl group; a methylol group, a monohydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and a 3-hydroxypropyl group; , 1-hydroxy-butyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 3-hydroxycyclopentyl, 4-hydroxycyclohexyl, etc., carbon number 1 to 8 -53- 200832068 a chain, branched, or cyclic hydroxyalkyl group; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, fluorenylmethyl Carbon number of propoxy, tert-butoxy, cyclopentyloxy, cyclohexyloxy, etc.! a linear, branched, or cyclic alkoxy group of -8; a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group, a n-butoxycarbonyloxy group, or the like a linear alkoxycarbonyloxy group having 2 to 9 carbon atoms; (1-methoxyethoxy)methyl, (1-ethoxyethoxy)methyl, (1-n-propoxy B) Oxy) φ methyl, (1-n-butoxyethoxy)methyl, (1-cyclopentyloxyethoxy)methyl, (1-cyclohexyloxyethoxy)methyl, (〗 a linear, branched, or cyclic carbon number of 3 to 11 such as monomethoxypropoxy)methyl, (1-ethoxypropoxy)methyl, ethoxyethyl or the like ( 1-alkoxyalkoxy)alkyl; methoxycarbonyloxymethyl, ethoxycarbonyloxymethyl, n-propoxycarbonyloxymethyl, copropoxycarbonyloxymethyl, a linear chain having a carbon number of 3 to 10 such as n-butoxycarbonyloxymethyl, tert-butoxycarbonyloxymethyl, cyclopentyloxycarbonyloxymethyl or cyclohexyloxycarbonyloxymethyl a branched or branched chain, or a cyclic alkoxycarbonyloxyalkyl group. Examples of the organic group of the above-mentioned monovalent nitrogen atom include a cyano group; a cyanomethyl group, a 1-cyanoethyl group, a 2-cyanoethyl group, a 1-cyanopropyl group, a 2-cyanopropyl group, and a 3-cyanide group. a linear chain of 2 to 9 carbons such as propyl, 1-cyanobutyl, 2-cyanobutyl, 3-cyanobutyl, 4-cyanobutyl, 3-cyanocyclopentyl or 4-cyanocyclohexyl A branched or cyclic cyanoalkyl group. Specific examples of suitable repeating units (i) include 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, and 3-hydroxy-α- Methylstyrene, 4-hydroxy--54- 200832068 α-methylstyrene, 2-methyl-3-pyridylbenzene, 4-methyl-3-hydroxystyrene, 5-methyl-3 Polymerization of hydroxystyrene, 2-methyl-4-hydroxydol, 3-methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene Repeat unit for cleavage of unsaturated bonds. Further, in the resin (Β), two or more types of repeating units (i) may be contained.

重複單位（ii )係下述式（4 )所示的重複單位。 [化 31] R3The repeating unit (ii) is a repeating unit represented by the following formula (4). [化31] R3

⑷ 式（4 )中，R3係氫原子或甲基，R4係1價有機基（ 但是，相當於-OR5的基係除外），R5係從1-支鏈烷基、 • 三有機矽烷基、及三有機甲鍺烷基所組成族群所選出的1 價酸解離性基，於R4及R5各以複數存在時，該複數的 R4及R5各可互相相同或不同，r係〇〜3的整數、s係1 〜3的整數。 &quot; r4所表示的1價有機基，係將下述相當於-OR5的基 除外’爲與上述式（3 )的R2所表示的丨價有機基相同。 R5所表示的1-支鏈烷基，例如可舉出異丙基、第二 丁基、第三丁基、1，1 一二甲基丙基、〗一甲基丁基、Ii -55- 200832068 作爲R5所表示的三有機矽烷基，例如可舉出三甲基 矽烷基、乙基二甲基矽烷基、甲基二乙基矽烷基、三乙基 矽烷基、異丙基二甲基矽烷基、甲基二異丙基矽烷基、三 異丙基矽烷基、第三丁基二甲基矽烷基、甲基第三丁基矽 烷基、三第三丁基矽烷基、苯基二甲基矽烷基、甲基二苯 ' 基矽烷基、三苯基矽烷基等。 作爲R5所表示的三有機甲鍺烷基，例如可舉出三甲 φ 基甲鍺烷基、乙基二甲基甲鍺烷基、甲基二乙基甲鍺烷基 、三乙基甲鍺烷基、異丙基二甲基甲鍺烷基、甲基二異丙 基甲鍺烷基、三異丙基甲鍺院基、第三丁基二甲基甲鍺院 基、甲基二第三丁基甲鍺烷基、三第三丁基甲鍺烷基、苯 基二甲基甲鍺烷基、甲基二苯基甲鍺烷基、三苯基甲鍺烷 基等。 作爲合適的重複單位（ii)之具體例子，可舉出4 -第 二丁氧基苯乙烯、4-第三丁氧基- α 一甲基苯乙燒等的 • 聚合性不飽和鍵裂解的重複單位。再者，於樹脂（Β )中 ，亦可含有2種以上的重複單位（ii )。 重複單位（iii)係由下述式（5-1 )〜式（5-4 )所組 ^ 成族群所選出的至少1個重複單位。 -56- 200832068 [化 32] r R8 ,I R11 -^c-ch2-&gt;- ， \ % 十一 CH} \ y c=o / 0 / o \ u (R7)t R9 0 O-CH-R12 Ϊ \ €=0 〇 1 ch2 / -fC-CHf)- R10 (5-1) (5-2) (5-3) 个14 -fC-CH2·)- c=o ο R15 (5—4) 式（5-1)〜式（5·4)中，R6、R8、R10、R11 及 R14 各自獨立地係氫原子或甲基，R7係1價有機基（但是， 相當於式（4)的-OR5之基係除外），於R7以複數存在 時，該複數的R7可互相相同或不同，t係0〜3的整數， R9係2價的酸解離性之有機基，R12係碳數1〜4的烷基 ，R13係氫原子、甲基、或乙基，R15係3級烷基。 作爲式（5 - 1 )中的R7所表示的1價有機基，例如可 舉出甲基、乙基、第三丁基、異丙基、甲氧基等。 式（5 -2 )中的R9係2價的酸解離性之有機基。作爲 該有機基，例如可舉出2,3 —二甲基一 2,3— 丁二基、2,3 一二乙基—2,3— 丁 二基、2,3 — 二正丙基一2,3—丁 二基、 2,3— __* 苯基—2,3 — 丁 __^基、2,4 — —* 甲基一 2,4 —戊 __^基 、2,4—二乙基—2,4—戊二基、2,4一二正丙基一2,4—戊 —* 基、2,4 — 一^苯基—2,4 —戊一基、2,5 — ^甲基一2,5-己二基、2,5 -二乙基一2,5 —己二基、2,5 —二正丙基— -57-(4) In the formula (4), R3 is a hydrogen atom or a methyl group, R4 is a monovalent organic group (except for a group corresponding to -OR5), and R5 is a 1-branched alkyl group, a triorganoalkylene group, And a monovalent acid dissociable group selected from the group consisting of triorganomynyl groups. When R4 and R5 are each present in plural, the plurality of R4 and R5 may be the same or different from each other, and the integer of r is 〇~3. , s is an integer from 1 to 3. &quot; The monovalent organic group represented by r4 is the same as the valence organic group represented by R2 of the above formula (3) except that the following group corresponding to -OR5 is excluded. Examples of the 1-branched alkyl group represented by R5 include an isopropyl group, a second butyl group, a tert-butyl group, a 1,1-dimethyl group, a monomethyl butyl group, and an Ii-55- group. 200832068 As the triorganoalkylene group represented by R5, for example, trimethyldecylalkyl group, ethyldimethyldimethylalkyl group, methyldiethyldecyl group, triethyldecyl group, isopropyldimethylpentane may be mentioned. , methyl diisopropyl decyl, triisopropyl decyl, tert-butyl dimethyl decyl, methyl tert- butyl decyl, tri-tert-butyl fluorenyl, phenyl dimethyl A decyl group, a methyl diphenyl ' decyl group, a triphenyl decyl group, and the like. Examples of the triorganomylalkyl group represented by R5 include trimethyl φ methoxymethyl decyl group, ethyl dimethyl methoxy decyl group, methyl diethyl methoxy decyl group, and triethyl dimethyl decane. Base, isopropyl dimethylformamidinyl, methyldiisopropylformamidinyl, triisopropylcarbendendyl, tert-butyldimethylformyl, methyldi-third Butylmethyl decyl, tri-tert-butyl carboxymethyl, phenyl dimethyl methoxyalkyl, methyl diphenyl methoxyalkyl, triphenyl methoxyalkyl, and the like. Specific examples of the suitable repeating unit (ii) include a polymerizable unsaturated bond cracked by 4-butoxybutyrene, 4-tert-butoxy-α-methylacetophenone or the like. Repeat the unit. Further, in the resin (Β), two or more kinds of repeating units (ii) may be contained. The repeating unit (iii) is at least one repeating unit selected from the group consisting of the following formulas (5-1) to (5-4). -56- 200832068 r R8 , I R11 -^c-ch2-&gt;- , \ % eleven CH} \ yc=o / 0 / o \ u (R7)t R9 0 O-CH-R12 Ϊ \ €=0 〇1 ch2 / -fC-CHf)- R10 (5-1) (5-2) (5-3) 14 -fC-CH2·)- c=o ο R15 (5-4) In the formulae (5-1) to (5·4), R6, R8, R10, R11 and R14 each independently represent a hydrogen atom or a methyl group, and R7 is a monovalent organic group (however, equivalent to the formula (4) Except for the base of -OR5, when R7 is present in plural, the plural R7 may be the same or different from each other, t is an integer of 0 to 3, R9 is a divalent acid dissociable organic group, and R12 is a carbon number of 1 An alkyl group of 〜4, R13 is a hydrogen atom, a methyl group or an ethyl group, and R15 is a tertiary alkyl group. The monovalent organic group represented by R7 in the formula (5-1) may, for example, be a methyl group, an ethyl group, a tert-butyl group, an isopropyl group or a methoxy group. R9 in the formula (5-2) is a divalent acid-dissociable organic group. Examples of the organic group include 2,3-dimethyl- 2,3-butanediyl, 2,3-diethyl- 2,3-butadienyl, and 2,3-di-n-propyl- 2,3-butanediyl, 2,3- __* phenyl-2,3-butyl __^, 2,4 —**methyl-2,4-pentyl __^, 2,4— Diethyl- 2,4-pentanediyl, 2,4-di-n-propyl- 2,4-pentyl-*yl, 2,4-diphenyl- 2,4-pentyl-based, 2,5 —^Methyl-2,5-hexanediyl, 2,5-diethyl- 2,5-hexanediyl, 2,5-di-n-propyl--57-

200832068 2，5 —己 _.基、2，5 — _&gt; 苯基—2，5 —己 _.基、2，6 — _. —2,6 —庚—^基、2,6 — —•乙基一 2,6 —庚 _^基、2,6- 丙基一 2,6-庚二基、2,6 —二苯基一 2,6-庚二基、： 二甲基一 3 — （2-羥丙基一 2，4一戊二基、2，4 一二乙 3— (2 —羥丙基）—2,4 一戊二基、2,5 —二甲基—3- —羥丙基）一2,5 —己二基、2,5 —二乙基一 3— （2 — 基）一 2,5 — 己二基、2,4一 二甲基—3,3 — 二（2 —羥 )一 2,4 一戊二基、2,4 —二乙基一 3,3 —二（2 —羥丙 一2,4 —戊 一^基、2,5 - 一^甲基一3,4一 一^ (2 —經丙基 2,5 —己 _•基、2,5 - 一乙基 3,4 — 一（2 —經丙基）一： 己二基、及2,7 —二甲基—2,7—辛二基及下述式（ )〜（5-2-3 )所示的官能基。 W 匕 33] 甲基 二正 :，4一 基一 -(2 羥丙 丙基 基） )-:，4 一 ;-2 -1200832068 2,5 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — Ethyl-2,6-heptyl, 2,6-propyl-2,6-heptyldiyl, 2,6-diphenyl-2,6-heptyldiyl, dimethyl- 3 - (2-Hydroxypropyl-2,4-pentyldiyl, 2,4-diethylene-3-(2-hydroxypropyl)-2,4-pentyldiyl, 2,5-dimethyl-3-- Hydroxypropyl)-2,5-hexanediyl, 2,5-diethyl-3-(2-yl)- 2,5-hexanediyl, 2,4-dimethyl--3,3- (2-hydroxyl)-2,4-pentyldiyl, 2,4-diethyl-3,3-bis(2-hydroxypropanyl 2,4-penta-yl, 2,5-methyl) a 3,4 -1 ^ (2 - propyl 2,5 -hexyl), 2,5 - ethyl 3,4 - one (2 - propyl) one: hexamethylene, and 2, 7-dimethyl- 2,7-octyldiyl group and a functional group represented by the following formula ( ) to (5-2-3 ): W 匕 33] methyl di-positive: 4-yl---2 Hydroxypropylpropyl) )-:,4 a;-2 -1

作爲式（5-4)中的R15所表示的3級烷基，例 舉出第三丁基、1 一甲基環戊基、1—乙基環戊基、2 基—2 —金剛烷基、2 —乙基一 2 —金剛烷基、8 —甲i —三環癸基、8-乙基—8 —三環癸基、3 —甲基—3 — -58- 如可 一甲 c - 8 四環 200832068 十二烯基、3 —乙基一 3—四環十二烯基等。 作爲合適的重複單位（iii)之具體例子，可舉出苯乙 烯、α—甲基苯乙烯、2—甲基苯乙烯、3 —甲基苯乙烯、4 —甲基苯乙烯、2 —甲氧基苯乙烯、3 —甲氧基苯乙烯'4 —甲氧基苯乙烯、4 一乙氧基甲氧基苯乙烯、ρ— 1 一甲氧 • 基乙氧基苯乙烯、：ρ—1 —乙氧基乙氧基苯乙烯、p—l —甲 氧基丙氧基苯乙烯、ρ— 1 -乙氧基丙氧基苯乙烯等的乙烯 φ 基芳香族化合物；（甲基）丙烯酸第三丁酯、（甲基）丙 烯酸1一甲基環戊酯、（甲基）丙烯酸1一乙基環戊酯、 (甲基）丙烯酸2 —甲基一 2—金剛院酯、（甲基）丙烯 酸2 -乙基一 2-金剛烷酯、（甲基）丙烯酸8—甲基一 8 一三環癸酯、（甲基）丙烯酸8 —乙基一 8—三環癸酯、 (甲基）丙細酸 3—甲基一 3 —四環十二燃醋、（甲基） 丙烯酸3 —乙基一 3 -四環十二烯酯、2，5 —二甲基己烷一 2,5-二（甲基）丙烯酸酯、2,6 -二甲基庚烷—2,6 —二丙 • 烯酸酯、2，7 -二甲基辛烷一 2,7 —二丙烯酸酯等的（甲基 )丙烯酸酯類；之聚合性不飽和鍵裂解的重複單位。再者 ’於樹脂（Β )中，亦可含有2種以上的重複單位（iii ) 〇 • 於樹脂（B )中，亦可含有上述重複單位（i )〜（iii )以外的重複單位。例如，4-（2 -第三丁氧羰基甲基氧 基）苯乙烯等的乙烯基芳香族化合物；（甲基）丙烯酸甲 酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲 基）丙烯酸異丙酯、（甲基）丙烯酸正丁酯、（甲基）丙 -59- 200832068 烯酸2—甲基丙酯、（甲基）丙烯酸1 一甲基丙酯、（甲 基）丙烯酸正戊酯、（甲基）丙烯酸新戊酯、（甲基）丙 烯酸正己酯、（甲基）丙烯酸2—乙基己酯、（甲基）丙 烯酸2-羥基乙酯、（甲基）丙烯酸2—羥基正丙酯、（ 甲基）丙烯酸3-羥基正丙酯、（甲基）丙烯酸苯酯、（ 甲基）丙烯酸苄酯、（甲基）丙烯酸、巴豆酸、馬來酸、 馬來酸酐、富馬酸、肉桂酸等的不飽和羧酸（酐）類；（ 甲基）丙烯酸2—羧基乙酯、（甲基）丙烯酸2—羧基正 丙酯、（甲基）丙烯酸3-羧基正丙酯等的不飽和羧酸之 羧基烷基酯類；（甲基）丙烯腈、α -氯丙烯腈、巴豆腈 、馬來腈、富馬腈等的不飽和腈化合物；（甲基）丙烯醯 胺、Ν，Ν —二甲基（甲基）丙烯醯胺、巴豆醯胺、馬來醯 胺、富馬醯胺等的不飽和醯胺化合物；馬來醯亞胺、Ν -苯基馬來醯亞胺、Ν-環己基馬來醯亞胺等的不飽和醯亞 胺化合物；Ν -乙烯基一 ε -己內醯胺、Ν —乙烯基吡咯啶 酮、2 -乙烯基吡啶、3—乙烯基吡啶、4一乙烯基吡啶、2 -乙烯基咪唑、4-乙烯基咪唑等的含氮乙烯基化合物等 的不飽和鍵裂解的重複單位。 本發明的正型敏輻射線性樹脂組成物所含有的樹脂（ Β)成分，較佳爲含有4 -羥基苯乙烯與4一第三丁氧基苯 乙烯當作必要成分的樹脂（Β )。 若例示較佳的具體例子，可舉出4-羥基苯乙烯/苯乙 烯/4 -第三丁氧基苯乙烯共聚物、4一羥基苯乙烯/4 一第 三丁氧基苯乙烯/丙烯酸1 -甲基環戊基共聚物、4一羥基 -60- 200832068 苯乙烯/4-第三丁氧基苯乙烯/丙烯酸1 一乙基環戊基共聚 物、4 一羥基苯乙烯/4 一第三丁氧基苯乙烯/苯乙烯共聚物 、4-羥基苯乙烯/丙烯酸第三丁基/4 一第三丁氧基苯乙烯 共聚物、4一羥基苯乙烯/4 一第三丁氧基苯乙烯/2,5—二甲 基己烷—2,5 —二丙烯酸酯共聚物、4 一羥基苯乙烯/4 一第 ^ 三丁氧基苯乙烯/2,5 —二甲基己烷一 2,5 —二丙烯酸酯/苯 乙烯共聚物、4 一羥基苯乙烯/4 -第三丁氧基苯乙烯/丙烯 φ 酸2-甲基—2—金剛烷基共聚物、4一羥基苯乙烯/4 一第 三丁氧基苯乙烯/丙烯酸2 -乙基一 2 -金剛烷基共聚物、4 -羥基苯乙烯/4-第三丁氧基苯乙烯/1 一乙氧基乙氧基苯 乙烯共聚物、4-羥基苯乙烯/4-第三丁氧基苯乙烯/1 一 乙氧基乙氧基苯乙烯/苯乙烯共聚物等。 酸解離性基對樹脂（B )的導入率（對於樹脂（B ) 中未保護酸性官能基與酸解離性基的合計數而言，酸解離 性基的數之比例）的合適範圍，由於被酸解離性基或導入 # 該酸解離性基的鹼可溶性樹脂之種類等所左右，故不能一 槪言之，但較佳爲10〜100%，更佳爲15〜100%。 樹脂（B )中所含有的重複單位（i )之比例，以全部 ‘ 重複單位的合計爲1〇〇莫耳％時，較佳爲45〜90莫耳％ • ，更佳爲6 5〜7 5莫耳％。若低於4 5莫耳％，則光阻圖型 對基板的密接性有降低的傾向。另一方面，若超過9 0莫 耳％，則顯像後的對比有降低的傾向。 樹脂（B )中所含有的重複單位（ii )之比例，以全 部重複單位的合計爲1 0 0莫耳％時，較佳爲5〜5 0莫耳％ -61 -The tertiary alkyl group represented by R15 in the formula (5-4) is exemplified by a third butyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 2-based-2-adamantyl group. , 2-ethyl 2- 2 - adamantyl, 8-methyl-tricyclodecyl, 8-ethyl-8-tricyclodecyl, 3-methyl- 3 - -58- 8 four rings 200832068 dodecenyl, 3-ethyl 3-cyclotetradecenyl and the like. Specific examples of suitable repeating units (iii) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, and 2-methoxyl. Styrene, 3-methoxystyrene '4-methoxystyrene, 4-ethoxymethoxystyrene, ρ-1 1-methoxyethoxy styrene, ρ-1 Ethylene φ-based aromatic compound such as ethoxyethoxystyrene, p-l-methoxypropoxystyrene, ρ-1 -ethoxypropoxystyrene; (meth)acrylic acid third Butyl ester, 1-methylcyclopentyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 2-methyl-2-cycloartanyl (meth)acrylate, (meth)acrylic acid 2-ethyl-2-adamantyl ester, 8-methyl-8-tricyclodecyl (meth)acrylate, 8-ethyl-8-tricyclodecyl (meth)acrylate, (methyl) propyl Fine acid 3-methyl-3-tetracyclododecan vinegar, (meth)acrylic acid 3-ethyl-1,3-tetracyclododecyl ester, 2,5-dimethylhexane-2,5-di (Methacrylate (meth) acrylates such as 2,6-dimethylheptane-2,6-dipropenate and 2,7-dimethyloctane-2,7-diacrylate; Repeating unit for the cleavage of polymerizable unsaturated bonds. Further, in the resin (Β), two or more kinds of repeating units (iii) may be contained. In the resin (B), a repeating unit other than the above repeating units (i) to (iii) may be contained. For example, a vinyl aromatic compound such as 4-(2-tritoxycarbonylmethyloxy)styrene; methyl (meth)acrylate, ethyl (meth)acrylate, or n-propyl (meth)acrylate Ester, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (methyl) propyl-59- 200832068 2-methyl propyl acrylate, 1-methyl propyl (meth) acrylate, N-amyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ( 2-hydroxy-n-propyl methacrylate, 3-hydroxy-n-propyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate, crotonic acid, Malay Unsaturated carboxylic acids (anhydrides) such as acid, maleic anhydride, fumaric acid, cinnamic acid, etc.; 2-carboxyethyl (meth)acrylate, 2-carboxy-n-propyl (meth)acrylate, (methyl) a carboxyalkyl ester of an unsaturated carboxylic acid such as 3-carboxy-n-propyl acrylate; (meth)acrylonitrile, α- Unsaturated nitrile compound of acrylonitrile, crotononitrile, maleonitrile, fumaronitrile, etc.; (meth) acrylamide, hydrazine, hydrazine-dimethyl(meth) acrylamide, crotonamide, malayan An unsaturated guanamine compound such as an amine or fumazamide; an unsaturated quinone imine compound such as maleimide, fluorene-phenylmaleimide or fluorene-cyclohexylmaleimide; Of vinyl-ε-caprolactam, anthracene-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 4-vinylimidazole, etc. A repeating unit of cleavage of an unsaturated bond such as a nitrogen-vinyl compound. The resin (Β) component contained in the positive-sensitive radiation linear resin composition of the present invention is preferably a resin (Β) containing 4-hydroxystyrene and 4-tert-butoxystyrene as essential components. Preferred examples of the exemplified are 4-hydroxystyrene/styrene/4-t-butoxystyrene copolymer, 4-hydroxystyrene/4-t-butoxystyrene/acrylic acid 1 -Methylcyclopentyl copolymer, 4-hydroxy-60-200832068 Styrene/4-tert-butoxystyrene/acrylic acid 1-ethylcyclopentyl copolymer, 4-hydroxystyrene/4, third Butoxy styrene/styrene copolymer, 4-hydroxystyrene/butyl butyl acrylate/4-t-butoxy styrene copolymer, 4-hydroxy styrene/4-t-butoxy styrene /2,5-dimethylhexane-2,5-diacrylate copolymer, 4-hydroxystyrene/4-tris-butoxystyrene/2,5-dimethylhexane-2 5-diacrylate/styrene copolymer, 4-hydroxystyrene/4-tert-butoxystyrene/propylene φ acid 2-methyl-2-adamantyl copolymer, 4-hydroxy styrene/4 a tert-butoxystyrene/2-ethyl-2-anomantyl copolymer, 4-hydroxystyrene/4-tert-butoxystyrene/1-ethoxyethoxystyrene copolymer 4-hydroxyphenyl Alkene/4-tert-butoxystyrene/1-ethoxyethoxystyrene/styrene copolymer, and the like. The appropriate range of the introduction rate of the acid-dissociable group to the resin (B) (the ratio of the number of the acid-dissociable groups in the total number of unprotected acidic functional groups and acid-dissociable groups in the resin (B)) is The acid-dissociable group or the type of the alkali-soluble resin of the acid-dissociable group is not so much, but it is preferably 10 to 100%, more preferably 15 to 100%. The ratio of the repeating unit (i) contained in the resin (B) is preferably from 45 to 90 mol%, more preferably from 6 5 to 7 when the total of all repeating units is 1 mol%. 5 moles %. If it is less than 45 mol%, the adhesion of the photoresist pattern to the substrate tends to be lowered. On the other hand, if it exceeds 90% by mole, the contrast after development tends to decrease. The ratio of the repeating unit (ii) contained in the resin (B) is, when the total of the repeating units is 100% by mole, preferably 5 to 50% by mole - 61 -

200832068 ，更佳爲1 5〜40莫耳％。若低於5莫耳％，則庵 降低的傾向。另一方面，若超過5 0莫耳％，則为 對基板的密接性有降低的傾向。 樹脂（B )中所含有的重複單位（iii )之比倒 部重複單位的合計爲100莫耳％時，就上述通式 所表示的重複單位而言，較佳爲1〜30莫耳％，1 〜25莫耳％。若低於1莫耳％，則解像度有降侣 。另一方面，若超過30莫耳％，則乾触刻耐性窄 分的傾向。又，就上述通式（5-2 )〜（5-4 )所_ 複單位而言，各自較佳爲3〜3 0莫耳％，更佳爲3 耳％。若低於3莫耳％，則解像度有降低的傾向。 面，若超過3 0莫耳％，則乾蝕刻耐性有變不充另 樹脂（B )的凝膠滲透層析術（GPC )所測劳 乙烯換算質量平均分子量（以下亦稱爲「Mw」） 爲 1，000 〜150,000，更佳爲 3,000 〜100,000, 5,000〜30,000。又，（B)成分的Mw與凝膠滲| (GPC)所測定的聚苯乙烯換算數量平均分子量&lt; 稱爲「Μη」）的比（Mw/Mn )，通常爲1〜1 0，華 〜5。再者，樹脂（B )可爲單獨1種或組合2種 用。 &lt;其它成分&gt; 於本實施形態的正型敏輻射線性樹脂組成物 像度有 阻圖型 ，以全 (5 -1 ) 〔佳爲5 的傾向 變不充 示的重 〜25莫 另一方 的傾向 的聚苯 ，較佳 特佳爲 層析術 以下亦 ί佳爲1 上來使 ，視需 -62- 200832068 要可含有鹼溶解性控制劑、酸擴散控制劑、界面活性劑、 增感劑、溶劑等的成分。以下，說明此等成分的詳細。 鹼溶解控制劑： 作爲鹼溶解控制劑，例如可舉出酚性羥基、羧基等的 ^ 酸性官能基的氫原子經酸解離性基或第三丁氧羰基甲基所 取代的化合物等。 φ 作爲上述酸解離性基，例如可舉出將取代甲基、1 -取 代乙基、1-取代正丙基、1-支鏈烷基、矽烷基、甲鍺烷基 、烷氧羰基、醯基、環式酸解離性基等。作爲鹼溶解控制 劑的合適例子，膽酸、脫氧膽酸、石膽酸等的類固醇類（ 膽汁酸類）中，或金剛烷羧酸、金剛烷二羧酸等的脂環族 環或具芳香族環的羧酸化合物中的羧基之氫原子，以上述 酸解離性基或第三丁氧羰基甲基所取代的化合物等。 鹼溶解控制劑的使用比例，對於1 〇〇質量份的樹脂（ • B)而言，較佳爲0.5〜50質量份，更佳爲1〜30質量份 ，特佳爲2〜20質量份。再者，鹼溶解控制劑可爲單獨1 種或組合2種以上來使用。 - 酸擴散控制劑： 於本實施形態的正型敏輻射線性樹脂組成物中，視需 要摻混酸擴散控制劑。藉由摻混該酸擴散控制劑，經EB 、X射線、或EUV照射而由酸產生劑所產生的酸係可控 制光阻被膜中的擴散現象，可抑制非照射區域的不宜化學 -63- 200832068 反應。再者，藉由摻混酸擴散控制劑，可提高所得到的正 型敏輻射線性樹脂組成物之儲存安定性，同時提高作爲光 阻的解像度，可抑制從照射起到照射後的加熱處理之擱置 時間（PED )的變動所致的光阻圖型之線寬變化。因此， 製程安定性爲極優異者。 = 作爲酸擴散控制劑的合適例子，可舉出即使經由光阻 圖型的形成步驟中之輻射線照射或加熱處理，鹼性也難以 φ 變化的含氮有機化合物。作爲如此的含氮有機化合物，例 如可舉出下述式（23)所表示的化合物（以下稱爲「含氮 化合物（α )」）、同一分子內具有2個氮原子的二胺基 化合物（以下稱爲「含氮化合物（A )」）、同一分子內 具有3個以上的氮原子之二胺基聚合物（以下稱爲「含氮 化合物（7 )」）、含醯胺基的化合物、脲化合物、含氮 雜環化合物等。 [化 34]200832068, better for 1 5~40 mol%. If it is less than 5 mol%, the tendency of 庵 is lowered. On the other hand, when it exceeds 50% by mole, the adhesion to the substrate tends to be lowered. When the total of the repeating units (iii) contained in the resin (B) is 100 mol%, the repeating unit represented by the above formula is preferably 1 to 30 mol%. 1 to 25 mol%. If it is less than 1 mol%, the resolution is reduced. On the other hand, if it exceeds 30 mol%, the dry contact tends to be narrow. Further, in the above formula (5-2) to (5-4), each unit is preferably from 3 to 30 mol%, more preferably 3 mol%. If it is less than 3 mol%, the resolution tends to decrease. When the surface exceeds 30% by mole, the dry etching resistance is changed by the gel permeation chromatography (GPC) of the resin (B), and the mass average molecular weight (hereinafter also referred to as "Mw") It is 1,000 to 150,000, more preferably 3,000 to 100,000, and 5,000 to 30,000. Further, the ratio (Mw/Mn) of Mw of the component (B) and the number average molecular weight (referred to as "Μη") measured by gel permeation (GPC) is usually 1 to 1 0, and ~5. Further, the resin (B) may be used alone or in combination of two or more. &lt;Other components&gt; The positive-type radiation-sensitive linear resin composition of the present embodiment has an image-resistance pattern, and has a total of (5 -1 ) [good as a tendency of 5, and does not show the weight of the other side. The tendency of polyphenylene, preferably better than tomography, is also better than 1 to be used, as needed -62- 200832068 to contain alkali solubility control agent, acid diffusion control agent, surfactant, sensitizer , components such as solvents. The details of these components will be described below. Alkali-solubilization controlling agent: Examples of the alkali-solubilizing controlling agent include a compound in which a hydrogen atom of an acidic functional group such as a phenolic hydroxyl group or a carboxyl group is substituted with an acid-dissociable group or a third butoxycarbonylmethyl group. φ As the acid-dissociable group, for example, a substituted methyl group, a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a decyl group, a decyl group, an alkoxycarbonyl group or an anthracene group is exemplified. Base, cyclic acid dissociable groups, and the like. A suitable example of the alkali dissolution controlling agent is a steroid (bile acid) such as cholic acid, deoxycholic acid or lithocholic acid, or an alicyclic ring such as adamantanecarboxylic acid or adamantane dicarboxylic acid or aromatic. A hydrogen atom of a carboxyl group in the carboxylic acid compound of the ring, a compound substituted with the above acid-cleavable group or a third butoxycarbonylmethyl group, or the like. The use ratio of the alkali dissolution controlling agent is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, particularly preferably 2 to 20 parts by mass, per 1 part by mass of the resin (•B). Further, the alkali dissolution controlling agent may be used alone or in combination of two or more. - Acid Diffusion Control Agent: In the positive-type radiation-sensitive linear resin composition of the present embodiment, an acid diffusion controlling agent is blended as needed. By blending the acid diffusion control agent, the acid generated by the acid generator by EB, X-ray, or EUV irradiation can control the diffusion phenomenon in the photoresist film, and can suppress the unsuitable chemical in the non-irradiation region-63- 200832068 Reaction. Further, by blending the acid diffusion controlling agent, the storage stability of the obtained positive-sensitive radiation linear resin composition can be improved, and the resolution as a photoresist can be improved, and the heat treatment from irradiation to irradiation can be suppressed. The line width variation of the photoresist pattern due to the change in time (PED). Therefore, the process stability is extremely excellent. = A suitable example of the acid diffusion controlling agent is a nitrogen-containing organic compound which is hard to change in basicity even by radiation irradiation or heat treatment in the formation step of the resist pattern. Examples of such a nitrogen-containing organic compound include a compound represented by the following formula (23) (hereinafter referred to as "nitrogen-containing compound (α)"), and a diamine compound having two nitrogen atoms in the same molecule ( Hereinafter, it is referred to as "nitrogen-containing compound (A)"), a diamine-based polymer having three or more nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen-containing compound (7)"), a guanamine-containing compound, A urea compound, a nitrogen-containing heterocyclic compound, or the like. [34]

R29_N_ R29 (23) 上述式（23 )中，各R29互相獨立地爲氫原子、烷基 、芳基、或芳烷基。再者，此等基例如亦可經羥基等的官 能基所取代。 作爲含氮化合物（α )，例如正己胺、正庚胺、正辛 胺、正壬胺、正癸胺、環己胺等的直鏈狀、支鏈狀或環狀 的單烷基胺類；二正丁胺、二正戊胺、二正己胺、二正庚 -64- 200832068 胺、二正辛胺、二正壬胺、二正癸胺、甲基•環己基胺、 二環己胺等的直鏈狀、支鏈狀或環狀的二烷基胺類；三乙 基胺、三正丙基胺、三正丁胺、三正戊胺、三正己胺、三 正庚胺、三正辛基胺、三正壬胺、三正癸胺、環己基二甲 基胺、甲基二環己基胺、三環己胺等的直鏈狀、支鏈狀或 環狀的三烷基胺類；乙醇胺、二乙醇胺、三乙醇胺等的直 鏈狀、支鏈狀或環狀的烷醇胺類；苯胺、N -甲基苯胺、 φ N，N —二甲基苯胺、2 -甲基苯胺、3 —甲基苯胺、4 —甲 基苯胺、4 -硝基苯胺、二苯基胺、三苯基胺、1 一萘基胺 等的芳香族胺類等。 作爲含氮化合物（/3 )，例如可舉出伸乙二胺、 N，N，N’，N，—四甲基伸乙二胺、N，N，N’，N，一四（2 —羥丙 基）伸乙二胺、四亞甲二胺、六亞甲二胺、4，4 ’ —二胺基 二苯基甲烷、4,4’ 一二胺基二苯基醚、4，4’ 一二胺基二苯 甲酮、4,4’一二胺基二苯基胺、2,2’ 一雙（4 一胺基苯基） # 丙烷、2-（3-胺基苯基）-2— (4-胺基苯基）丙烷、 2— (4 —胺基苯基）一 2— (3 —羥苯基）丙烷、2 -（4 一 胺基苯基）一 2— (4-經苯基）丙院、1，4 一雙[1 一（4 一 胺基苯基）一 1 —甲基乙基]苯、1，3 —雙[1 一 （ 4 一胺基苯 - 基）一 1一甲基乙基〕苯等。 作爲含氮化合物（γ )，例如可舉出聚伸乙亞胺、聚 丙細釀fl女、一甲基胺基乙基丙嫌釀胺的聚合物等。 作爲上述含醯胺基的化合物，例如可舉出甲醯胺、N —甲基甲醯胺、N，N —二甲基甲醯胺、乙醯胺、n—甲基 -65 - 200832068 乙醯胺、N，N —二甲基乙醯胺、丙醯胺、苯甲醯胺、吡咯 啶酮、N —甲基卩比略淀_等^ 作爲上述脲化合物，例如可舉出尿素、甲基脲、1，1 —二甲基脲、i，3 —二甲基脲、1，1，3,3—四甲基脲、1，3 — 二苯基脲、三丁基硫脲等。 作爲上述曰勸雑^化合物’例如可舉出味嗤、4 -甲 基咪唑、4一甲基一 2 —苯基咪唑、苯并咪唑、2—苯基苯 φ 并咪唑等的咪唑類；吡啶、2 —甲基吡啶、4 一甲基吡啶、 2 -乙基吡啶、4 一乙基吡啶、2 —苯基吡啶、4 一苯基吡啶 、N—甲基一 4 —本基卩比D疋、薛鹼、蔽驗酸、薛驗酸醯胺 、喹啉、8 -羥基喹啉、吖啶等的吡啶類，以及吡畊、吡 唑、嗒畊、喹噁啉、嘌呤、吡咯啶、哌啶、嗎啉、4 —甲 基嗎啉、哌D并、1,4 —二甲基哌畊、1，4 一二氮雜雙環 [2 · 2 · 2 ]羊院、非繞琳％。 又，作爲含氮有機化合物，亦可使用具有酸解離性基 ® 的含氮化合物。作爲存在有該酸解離性基的含氮化合物， 例如可舉出N-（第三丁氧羥基）哌啶、N-（第三丁氧 羯基）咪唑'N-（第三丁氧羰基）苯并咪唑、N一（第 三丁氧羰基）2-苯基苯并咪唑、N—（第三丁氧羰基） ‘ 二辛基胺、N—（第三丁氧羰基）二乙醇胺、N— （第三 丁氧鑛基）二環己基胺、N—（第三丁氧羥基）二苯基胺 等。 於此等含氮有機化合物之中，特佳爲含氮化合物（α )、含氮化合物（Θ )、含氮雜環化合物、具酸解離性基 -66 - 200832068 的含氮化合物等。酸擴散控制劑可爲單獨1種或組合2種 以上來使用。 酸擴散控制劑的配合量，對於每1 0 0質量的含酸解離 性基的樹脂（B )而言，通常爲1 5質量份以下，較佳爲 0 · 0 0 1〜1 0質量份，更佳爲〇 . 〇 〇 5〜5質量份。於此情況下 ' ，酸擴散控制劑的配合量若多於指定値，則作爲光阻的感 度或曝光部的顯像性有降低的傾向。再者，酸擴散控制劑 φ 的配合量若低於0.001質量份，取決於製程條件，作爲光 阻的圖型形狀或尺寸忠實度有降低之虞。 界面活性劑： 於本實施形態的正型敏輻射線性樹脂組成物中，視需 要亦可摻混界面活性劑。藉由摻混該界面活性劑，可改良 塗佈性、條紋、作爲光阻的顯像性等。 作爲界面活性劑的合適例子，可舉出聚氧化乙烯月桂 • 基醚、聚氧化乙烯硬脂基醚、聚氧化乙烯油基醚、聚氧化 乙烯正辛基苯酚醚、聚氧化乙烯正壬基酚醚、聚乙二醇二 月桂酸酯、聚乙二醇二硬脂酸酯等。又，作爲市售品，例 ” 如可舉出 Eftop EF301、同 EF3 03、同 EF3 52 (以上爲 . TOHKEM PRODUCTS 公司製）、Megafacs F171、同 F173 (以上爲大日本油墨工業公製）、Florad FC430、同 FC431 (以上爲住友 3M 公司製）、Asahiguard AG710、 Suflon S-3 82、同 SC101、同 SC102、同 SC103、同 SC104、同SC105、同 SC106(以上爲旭硝子公司製）、 -67- 200832068 KP341 (信越化學工業社製）、Polyfron No.75、同Νο·95 (以上爲共榮社化學公司製）等。 界面活性劑可爲單獨1種或組合2種以上來使用。界 面活性劑的配合量，對於1 00質量份的樹脂（B )而言， 較佳爲2質量份以下。 增感劑： 作爲增感劑，例如可舉出咔唑類、二苯甲酮類、玫瑰 氧化鐵紅類、蒽類等。此等增感劑可爲單獨1種或組合2 種以上來使用。增感劑的配合量，對於1 00質量份的樹脂 (B )而言，較佳爲50質量份以下。 溶劑： 本發明的正型敏輻射線性樹脂組成物，於使用時，對 於全部固體成分的濃度而言，通常以成爲〇·1〜50質量％ ，較佳1〜30質量％的方式，使均勻溶解在溶劑中後，例 如藉由孔徑0 · 2 // m左右的過濾器來過濾，以調製成組成 物溶液。作爲該組成物溶液之調製時所用的溶劑，例如胃 舉出乙二醇單甲基醚醋酸酯、乙二醇單乙基醚醋酸酯、乙 二醇單正丙基醚醋酸酯、乙二醇單正丁基醚醋酸酯等的乙 二醇單烷基醚醋酸酯類；丙二醇單甲基醚、丙二醇單乙基 醚、丙二醇單正丙基醚、丙二醇單正丁基醚等的丙二醇單 烷基醚類；丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二 正丙基醚、丙二醇二正丁基醚等的丙二醇二烷基醚類；丙 -68- 200832068 二醇單甲基醚醋酸酯、丙二醇單乙基醚醋酸酯、丙二醇單 正丙基醚醋酸酯、丙二醇單正丁基醚醋酸酯等的丙二醇單 烷基醚醋酸酯類；乳酸甲酯、乳酸乙酯'乳酸正丙酯、乳 酸異丙酯等的乳酸酯類；甲酸正戊酯、甲酸異戊酯、醋酸 乙酯、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁 — 酯、醋酸正戊酯、醋酸異戊酯、丙酸異丙酯、丙酸正丁酯 、丙酸異丁酯等的脂肪族羧酸酯類；羥基醋酸乙酯、2一 φ 羥基一 2 —甲基丙酸乙酯、2-羥基—3 —甲基丁酸甲酯、 甲氧基醋酸乙酯、乙氧基醋酸乙酯、3 —甲氧基丙酸甲酯 、3 -甲氧基丙酸乙酯、3 —乙氧基丙酸甲酯、3 —乙氧基 丙酸乙酯、3 —甲氧基丁基醋酸酯、3 —甲基一 3 —甲氧基 丁基醋酸酯、3 —甲基一 3 -甲氧基丁基丙酸酯、3 —甲基 一 3 -甲氧基丁基丁酸酯、乙醯基醋酸甲酯、乙醯基醋酸 乙酯、丙酮酸甲基、丙酮酸乙基等的其它酯類；甲苯、二 甲苯等的芳香族烴類；甲基乙基酮、甲基丙基酮、甲基丁 # 基酮、2 —庚酮、3 —庚酮、4 —庚酮、環己酮等的酮類； N —甲基甲醯胺、N，N —二甲基甲醯胺、N —甲基乙醯胺、 N，N —二甲基乙醯胺、N—甲基吡咯啶酮等的醯胺類；r &quot; - 丁丙酯等的丙酯類等。此等溶劑可爲單獨1種或組合2 • 種以上來使用。 &lt;光阻圖型的形成&gt; 爲了使用本發明的正型敏輻射線性樹脂組成物來形成 光阻圖型，將如前述所調製的組成物溶液，經由回轉塗佈 -69- 200832068 、流延塗佈、輥塗佈等的適宜塗佈手段，例如塗佈在矽 圓、經鋁所被覆的晶圓等之基板上。接著，按照需要， 先在70°C〜16(TC左右的溫度進行加熱處理（以下亦稱 ^ PB」）），以形成光阻被膜後，藉由照射輻射線、 來描繪。該描繪條件係按照正型敏輻射線性樹脂組成物 配合組成、各種添加劑的種類等來適宜選定。 爲了安定地形成高精度的微細圖型，照射後，通常 • 50〜200 °C、較佳在70〜160 °C的溫度，進行30砂以上 加熱處理（以下亦稱爲「PEB」）。再者，PEB的溫度 低於50°C，則隨著基板的種類，感度的變動有變寬的傾 。然後，藉由鹼顯像液，通常在10〜50 °C、10〜200秒 較佳在15〜30°C、15〜100秒的條件下進行顯像，可形 指定的光阻圖型。 作爲上述鹼顯像液，例如使用將鹼金屬氫氧化物、 水、單-、二-、或三-院基胺類、單-、二-、或三-焼醇 • 類、雜環式胺類、氫氧化四烷基銨類、膽鹼、1，8 —二 雜雙環一 [5·4·0] - 7-十一烯、1，5 —二氮雜雙環一 [4.3 一 5 -壬烯等的鹼性化合物，通常以成爲1〜1 0質量％ ^ 濃度，較佳成爲1〜5質量％的濃度，更佳成爲1〜3質 • %的濃度之方式，溶解成的鹼性水溶液。又，於由如此 鹼性水溶液所成的顯像液中，例如亦可適宜添加甲醇、 醇等的水溶性有機溶劑或界面活性劑。於光阻圖型的形 時，爲了防環境氣氛中所含有的鹼性雜質等之影響或被 中的帶電，可以在光阻被膜上設置保護膜或抗靜電劑。 晶 預 爲 ΕΒ 的 在 的 若 向 成 氨 胺 氮 • 0] 的 量 的 乙 成 膜 -70- 200832068 實施例 以下，以實施例爲基礎來具體說明本發明’惟本發明 不受此等實施例所限定。再者，實施例、比較例中的「份 」及「％」只要沒有特別預先指明，則以質量爲基準。又 ^ ，以下顯示各種物性値的測定方法、及諸特性的評價方法 。溶劑係使用在鈉金屬的存在下，回流6小時後，在氮氣 Φ 氛下蒸餾者。又，單體係使用以乾燥氮氣進行1小時的冒 泡後，蒸餾者。 [質量平均分子量（Mw)、數量平均分子量（Μη)] :東曹公司製的GPC管柱（商品名「G2000HXL」2支， 商品名「G3 000HXL」1支，商品名「G4000HXL」1支） ，在流量：1.0ml/分鐘，洗提溶劑：四氫呋喃，管柱溫度 :40 °C的分析條件下，以單分散聚苯乙烯當作標準，藉由 凝膠滲透層析術（GPC )來測定。 合成例1 :樹脂（B-1) 使104克4一乙醯氧基苯乙烯、5克苯乙烯、52克4 一第三丁氧基苯乙烯、6.5克偶氮雙異丁腈（AIBN)、及 - 1克t一十二烷硫醇溶解於160克丙二醇單甲基醚後，在 氮氣氛下，將反應溫度保持在7 0 °C，使聚合1 6小時。聚 合後將反應溶液滴到2000克正己烷中，將所生成的樹脂 凝固精製。.接著，於經凝固精製的樹脂中，再度添加i 5 〇 克丙二醇單甲基醚後，更添加300克甲醇、80克三乙胺 -71 - 200832068 、及15克水，邊在沸點使回流，邊進行8小時的水解反 應。水解反應後，減壓蒸餾去除溶劑及三乙胺而得到樹脂 。將所得到的樹脂，以固體成分濃度成爲2 0 %的方式， 再溶解於丙酮中後，滴到2000克的水中使凝固。藉由過 濾所生成的白色粉末，在減壓下於5 0 °C經一夜的乾燥，得 ^ 到最終生成物之樹脂。所得到的樹脂之M w爲1 5 0 0 0，R29_N_ R29 (23) In the above formula (23), each R29 is independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Further, these groups may be substituted, for example, by a functional group such as a hydroxyl group. a nitrogen-containing compound (α) such as a linear, branched or cyclic monoalkylamine such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine or cyclohexylamine; Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-g-64-200832068 Amine, di-n-octylamine, di-n-decylamine, di-n-decylamine, methyl • cyclohexylamine, dicyclohexylamine, etc. Linear, branched or cyclic dialkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, three-positive a linear, branched or cyclic trialkylamine such as octylamine, tri-n-decylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine or tricyclohexylamine a linear, branched or cyclic alkanolamine such as ethanolamine, diethanolamine or triethanolamine; aniline, N-methylaniline, φ N,N-dimethylaniline, 2-methylaniline, An aromatic amine such as 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine or 1-naphthylamine. Examples of the nitrogen-containing compound (/3) include ethylenediamine, N, N, N', N, -tetramethylethylenediamine, N, N, N', N, and a four (2 - Hydroxypropyl) ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4 'monodiaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2'-double (4-aminophenyl) #propane, 2-(3-aminophenyl) 2-(4-Aminophenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl)-2—(4 -Phenyl)propyl, 1,4, bis[1 -(4-aminophenyl)-1-methylethyl]benzene, 1,3 -bis[1 -(4-aminophenyl-yl) ) 1-methylethyl benzene and the like. The nitrogen-containing compound (γ) may, for example, be a polymer of a polyethylenimine, a polypropylene, or a monomethylaminoethyl amide. Examples of the above-mentioned guanamine-containing compound include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, n-methyl-65-200832068 acetamidine. Amine, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N-methyl hydrazine, etc. As the above urea compound, for example, urea, methyl Urea, 1,1-dimethylurea, i,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea, and the like. Examples of the above-mentioned compound include 'imidazoles such as miso, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzene φ-imidazole; and pyridine. , 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-benzol ratio D疋, sulphuric acid, sulphate acid, sulphonic acid amide, quinoline, 8-hydroxyquinoline, acridine, etc., and pyridinium, pyrazole, argon, quinoxaline, hydrazine, pyrrolidine, piperazine Acridine, morpholine, 4-methylmorpholine, piperidine, 1,4-dimethylpiped, 1,4-diazabicyclo[2 · 2 · 2 ] sheep, non-circular. Further, as the nitrogen-containing organic compound, a nitrogen-containing compound having an acid dissociable group ® can also be used. Examples of the nitrogen-containing compound in which the acid-dissociable group is present include N-(t-butoxyl) piperidine and N-(t-butoxycarbonyl)imidazole 'N-(t-butoxycarbonyl). Benzimidazole, N-(t-butoxycarbonyl) 2-phenylbenzimidazole, N-(t-butoxycarbonyl) 'dioctylamine, N-(t-butoxycarbonyl)diethanolamine, N- (Third butoxide base) dicyclohexylamine, N-(t-butoxyhydroxy)diphenylamine, and the like. Among these nitrogen-containing organic compounds, a nitrogen-containing compound (α), a nitrogen-containing compound (Θ), a nitrogen-containing heterocyclic compound, a nitrogen-containing compound having an acid-dissociable group of -66 to 200832068, and the like are particularly preferable. The acid diffusion controlling agent may be used alone or in combination of two or more. The amount of the acid-diffusion controlling agent is usually 15 parts by mass or less, preferably 0. 0 0 1 to 10 parts by mass, per 100 parts by mass of the acid-dissociable group-containing resin (B). More preferably 〇. 〇〇 5 to 5 parts by mass. In this case, when the amount of the acid diffusion controlling agent is more than the specified amount, the sensitivity of the resist or the developability of the exposed portion tends to decrease. Further, if the amount of the acid diffusion controlling agent φ is less than 0.001 part by mass, depending on the process conditions, the pattern shape or dimensional fidelity of the photoresist is lowered. Surfactant: In the positive-type radiation-radiating linear resin composition of the present embodiment, a surfactant may be blended as needed. By blending the surfactant, coating properties, streaks, development as a photoresist, and the like can be improved. Suitable examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, and polyoxyethylene n-nonylphenol. Ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and the like. In addition, as an example of a commercial item, Eftop EF301, EF3 03, EF3 52 (above. TOHKEM PRODUCTS), Megafacs F171, F173 (above, Dainippon Ink Industrial Co., Ltd.), Florad FC430, with FC431 (above is Sumitomo 3M), Asahiguard AG710, Suflon S-3 82, same as SC101, same as SC102, same as SC103, with SC104, with SC105, with SC106 (above is Asahi Glass Co., Ltd.), -67- 200832068 KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyfron No. 75, the same as Ν95 (the above is manufactured by Kyoeisha Chemical Co., Ltd.), etc. The surfactants may be used alone or in combination of two or more. The amount of the compound (B) is preferably 2 parts by mass or less based on 100 parts by mass of the resin (B). Sensitizer: Examples of the sensitizer include oxazoles, benzophenones, and rose oxidation. The sensitizer may be used alone or in combination of two or more. The amount of the sensitizer is preferably 50 for 100 parts by mass of the resin (B). Parts by mass or less. Solvent: Positive sensitizing radiation linearity of the present invention When the resin composition is used, the concentration of all the solid components is usually 1 to 50% by mass, preferably 1 to 30% by mass, so that the resin composition is uniformly dissolved in the solvent, for example, by the pore diameter. A filter of about 0 · 2 // m is filtered to prepare a composition solution. As a solvent used for the preparation of the composition solution, for example, ethylene glycol monomethyl ether acetate or ethylene glycol is used as a stomach. Ethylene glycol monoalkyl ether acetate such as ethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol di-n-butyl ether, etc. Propylene glycol dialkyl ethers; propylene-68- 200832068 diol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, etc. Monoalkyl ether acetates; methyl lactate, Acid esters such as n-propyl lactate and isopropyl lactate; n-amyl formate, isoamyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid An aliphatic carboxylic acid ester such as butyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate or isobutyl propionate; ethyl hydroxyacetate, 2 φ hydroxy group 2 —ethyl methacrylate, methyl 2-hydroxy-3-methylbutanoate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxy Ethyl propyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, ethyl acetoxyacetate, ethyl acetoxyacetate, acetone Other esters such as base, pyruvic acid ethyl; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-g Ketone, 4-heptanone, ring Ketones such as ketones; N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidine A phthalamide such as a ketone; a propyl ester such as r &quot; -butyl propyl ester; These solvents may be used alone or in combination of two or more. &lt;Formation of Photoresist Pattern&gt; In order to form a photoresist pattern using the positive-type radiation-sensitive linear resin composition of the present invention, the composition solution prepared as described above is subjected to rotary coating-69-200832068, flow A suitable coating means such as a coating method or a roll coating is applied to a substrate such as a wafer or a wafer coated with aluminum. Then, if necessary, heat treatment (hereinafter also referred to as "PB") at a temperature of about 70 ° C to 16 (hereinafter referred to as TC) is performed to form a photoresist film, and then irradiated with radiation. The drawing conditions are appropriately selected in accordance with the composition of the positive-type sensitive radiation linear resin composition, the type of various additives, and the like. In order to form a high-precision fine pattern in a stable manner, after irradiation, a heat treatment of 30 or more sands (hereinafter also referred to as "PEB") is usually carried out at a temperature of 50 to 200 ° C, preferably 70 to 160 ° C. Further, when the temperature of the PEB is lower than 50 °C, the variation in sensitivity varies depending on the type of the substrate. Then, the image is developed by an alkali developing solution, usually at 10 to 50 ° C for 10 to 200 seconds, preferably at 15 to 30 ° C for 15 to 100 seconds, and the shape of the resist pattern can be specified. As the above-mentioned alkali developing solution, for example, an alkali metal hydroxide, water, a mono-, di-, or tri-homoamine, a mono-, di-, or tri-nonanol, a heterocyclic amine can be used. Classes, tetraalkylammonium hydroxides, choline, 1,8-diheterobicyclo-[5·4·0]-7-undecene, 1,5-diazabicyclo-[4.3-5-壬The basic compound such as a olefin is usually dissolved in an aqueous solution having a concentration of 1 to 10% by mass, preferably 1 to 5% by mass, more preferably 1 to 3% by mass. . Further, in the developing solution prepared from such an alkaline aqueous solution, for example, a water-soluble organic solvent such as methanol or alcohol or a surfactant may be added as appropriate. In the case of the pattern of the photoresist pattern, a protective film or an antistatic agent may be provided on the photoresist film in order to prevent the influence of the alkaline impurities or the like contained in the ambient atmosphere or to be charged. The invention is based on the following examples, and the present invention is not limited to these examples. The invention is based on the following examples. Limited. In addition, "parts" and "%" in the examples and comparative examples are based on mass unless otherwise specified. Further, the following describes the measurement methods of various physical properties and the evaluation methods of the properties. The solvent was used in the presence of sodium metal, and after refluxing for 6 hours, it was distilled under a nitrogen atmosphere. Further, the single system was subjected to bubbling with dry nitrogen for 1 hour, and then distilled. [Mass average molecular weight (Mw), number average molecular weight (Μη)]: GPC pipe made by Tosoh Corporation (2 product names "G2000HXL", 1 product name "G3 000HXL", 1 product name "G4000HXL") In the flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C analysis conditions, using monodisperse polystyrene as a standard, by gel permeation chromatography (GPC) . Synthesis Example 1: Resin (B-1) 104 g of 4-ethoxylated styrene, 5 g of styrene, 52 g of 4 -t-butoxystyrene, 6.5 g of azobisisobutyronitrile (AIBN) And - 1 g of t-dodecyl mercaptan was dissolved in 160 g of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 ° C under a nitrogen atmosphere to cause polymerization for 16 hours. After the polymerization, the reaction solution was dropped into 2000 g of n-hexane, and the resulting resin was solidified and purified. Then, after adding i 5 gram of propylene glycol monomethyl ether to the solidified resin, 300 g of methanol, 80 g of triethylamine-71 - 200832068, and 15 g of water are added, and the reflux is made at the boiling point. , an 8-hour hydrolysis reaction was carried out. After the hydrolysis reaction, the solvent and triethylamine were distilled off under reduced pressure to give a resin. The obtained resin was dissolved in acetone so that the solid content concentration became 20%, and then dropped into 2000 g of water to be solidified. The white powder formed by filtration was dried overnight at 50 ° C under reduced pressure to obtain a resin of the final product. The M w of the obtained resin is 1 500.

Mw/Mn爲1 ·7。又，13C-NMR分析的結果爲：4 —羥基苯 φ 乙烯（1)與苯乙烯（2)和4 一第三丁氧基苯乙烯（3) 的共聚合莫耳比係（1 ) : ( 2 ) : ( 3 ) = 6 5 : 5 : 3 0。將 此樹脂當作「樹脂（B1 )」。 合成例2 :樹脂（B_2) 使100克4-乙醯氧基苯乙烯、25克丙烯酸第三丁酯 、1 8克苯乙烯、6克AIBN、及1克t —十二烷硫醇溶解 於230克丙二醇單甲基醚後，在氮氣氛下，將反應溫度保 # 持在70°C，使聚合16小時。聚合後將反應溶液滴到2000 克正己烷中，將所生成的樹脂凝固精製。 接著，於經凝固精製的樹脂中，再度添加1 50克丙二 ^ 醇單甲基醚後，更添加300克甲醇、80克三乙胺、及15 ' 克水’邊在沸點使回流，邊進行8小時的水解反應。水解 反應後，減壓蒸餾去除溶劑及三乙胺而得到樹脂。將所得 到的樹脂，以固體成分濃度成爲20 %的方式，再溶解於 丙酮中後，滴到2000克的水中使凝固。藉由過濾所生成 的白色粉.末，在減壓下於5 0 °C經一夜的乾燥，得到最終生 -72- 200832068 成物之樹脂。所得到的樹脂之Mw爲1 1 500，Mw/Mn爲 1.6。又’ 13C-NMR分析的結果爲：4一羥基苯乙烯（1) 與丙烯酸第三丁酯（2 )和苯乙烯（3 )的共聚合莫耳比係 (1 ) : ( 2 ) : ( 3 ) =6 1 : 1 9 : 20。將此樹脂當作「樹脂 (B-2 )」。 合成例3 :樹脂（B-3 ) 使37.6克4 一乙氧基乙氧基苯乙烯、11.0克4 一第三 丁氧基苯乙烯、及1.4克苯乙烯溶解於200克環己烷後， 置入經乾燥的耐壓玻璃瓶內，以附Neoprene (商品名（ 杜邦公司））製墊圈的有孔瓶蓋來密栓。將此耐壓玻璃瓶 冷卻到-20°C後，依順序添加2.96ml的正丁鋰（1.83m〇l/l 的環己烷溶液）、0·98克N，N，N’，N’ —四甲基伸乙二胺， 邊將溫度保持在-20 °C，邊使反應1小時。然後，將1.〇克 甲醇注入，使反應停止。確認溶液的顏色從紅色變成無色 。以200克的3%草酸水來洗淨後，添加200克丙二醇單 甲基醚及1.5克對甲苯磺酸，於室溫（23〜25 °C )攪拌3 小時使水解，而得到共聚物用液。將所得到的共聚物溶液 滴到2000克的水中而使凝固。過濾所生成的白色粉末， 於減壓下在50 °C經一夜的乾燥，得到最終生成物之共聚物 。所得到的共聚物之Mw爲16000，Mw/Mn爲1.3。又， 13C-NMR分析的結果爲：4一羥基苯乙烯（1)與苯乙烯（ 2)及4 一第三丁氧基苯乙烯（3)的共聚合莫耳比係（1 ):(2) : ( 3 ) =72: 5: 23。將此共聚物當作「樹脂（ -73- 200832068 B-3)」。 合成例4 ··樹脂（b _ 4 ) 使173克4 —乙醯氧基苯乙烯、56克4 一第三丁氧基 氳 苯乙烯、11克2，5 —二甲基己烷一 2,5—二丙烯酸酯、14 克AIBN、及11克t_十二烷硫醇溶解於24〇克丙二醇單 甲基醚後，在氮氣氛下，將反應溫度保持在70 t，使聚合 鲁 1 6小時。聚合後將反應溶液滴到2 0 0 〇克己院中，將所生 成的樹脂凝固精製。將經凝固精製的共聚物，在減壓下， 於5 0 °C乾燥3小時。於經乾燥的〗9 〇克共聚物中，再度添 加150克的丙二醇單甲基醚後，更添加3〇〇克甲醇、1〇〇 克三乙胺、及1 5克水，邊在沸點使回流，邊進行8小時 的水解反應。水解反應後，減壓蒸餾去除溶劑及三乙胺以 得共聚物。得將所得到的共聚物，以固體成分濃度成爲 2 0 %的方式，溶解於丙酮後，滴到2 〇 〇 〇克水中使凝固。 Φ 藉由過濾所生成的白色粉末，在減壓下於5 0 °C經一夜的乾 燥，得到最終生成物之共聚物。所得到的共聚物之M w爲 27000，Mw/Mn 爲 2.6。又，i3C-NMR 分析的結果爲：4一 • 羥基苯乙烯（1 )與4 一第三丁氧基苯乙烯（2 )和2，5 — « 二甲基己烷一 2,5-二丙烯酸酯（3)的共聚合莫耳比係（ 1 ) : ( 2 ) ·· ( 3 ) = 7 5 : 2 2 : 3。將此共聚物當作「樹脂 (B-4)」。 合成例5 :樹脂（B-5 ) -74- 200832068 使25克4 -羥基苯乙烯與4 -第三丁氧基苯乙烯共聚 合物（商品名「VPT1503S」，日本曹達公司製，4 —經基 苯乙儲與4-第三丁氧基苯乙儲的莫耳比= 90: 1〇)溶解 在100克醋酸正丁酯中，以氮氣進行30分鐘的冒泡。然 後’添加3 · 3克乙基乙矯基魅’添加1克對甲苯礦酸卩比jj定 鑰鹽當作觸媒，在室溫使反應1 2小時。接著，將反應溶 液滴到1 %氨水溶液中，使樹脂沈澱，過濾後，在5 〇。〇的 φ 真空乾燥器內經一夜乾燥，而得到最終生成物的樹脂。所 得到的樹脂之Mw爲13000、Mw/Mn爲1.〇1。又，對所得 到的樹脂進行13C-NMR分析，結果該樹脂係一種共聚物 ，其中聚（4 一羥基苯乙烯）爲67莫耳％，聚（4 —羥基 苯乙烯）中的酚性羥基之氫原子被乙氧基乙基所取代的構 成單位爲23旲耳％，從4-第三丁氧基苯乙儲而來的構 成單位爲10莫耳％。將該共聚物稱爲「樹脂（B-5 )」。 • 合成例6 :樹脂（B-6) 使104克4 —乙醯氧基苯乙烯、5克苯乙烯、52克4 一第三丁氧基苯乙烯、5·8克二第三丁基過氧化物、及1 ' 克t -十二烷硫醇溶解於1 6 0克丙二醇單甲基醚後，在氮 、 氣氛下，將反應溫度保持在7 0 °C，使聚合1 6小時。聚合 後將反應溶液滴到2 0 0 0克正己烷中，將所生成的樹脂凝 固精製。接著，於經凝固精製的樹脂中，再度添加1 5 0克 丙二醇單甲基醚後，更添加300克甲醇、80克三乙胺、 及1 5克水，邊在沸點使回流，邊進行8小時的水解反應 -75- 200832068 。水解反應後，減壓蒸餾去除溶劑及三乙胺而得到樹脂。 將所得到的樹脂，以固體成分濃度成爲2 0 %的方式，再 溶解於丙酮中後，滴到2000克的水中使凝固。藉由過濾 所生成的白色粉末，在減壓下於50 °C經一夜的乾燥，得到 最終生成物之樹脂。所得到的樹脂之Mw爲1 5 000， _ Mw/Mn爲1.7。又，13C-NMR分析的結果爲：4—羥基苯 乙烯（1)與苯乙烯（2)和4 —第三丁氧基苯乙烯（3) φ 的共聚合莫耳比係（1) : (2) : (3) =64 : 5 : 3 1。將 此樹脂當作「樹脂（B - 6 )」。 實施例1〜1 5、比較例1〜4 將表1所示各成分以表1所示量作混合而成爲均勻溶 液後’以孔徑20〇nm的薄膜過濾器來過濾，調製組成物 溶液。接著，東京電子公司製的商品名「Cleantruck ACT-8」內，在矽晶圓上旋塗各組成物溶液後，於表2所 φ 示的條件下進行PB，而形成膜厚l〇〇nm的光阻被膜。接 著，使用簡易型的電子線描繪裝置（型式「HL800D」， 日立製作所公司製，輸出：50KeV，電流密度：5.0安培 * /cm2)，將電子線照射在所形成的光阻被膜，於表2所示 - 的條件下進行PEB。然後，使用2.3 8%氫氧化四甲錢水溶 液，在2 3 °C歷1分鐘，藉由槳式（p a d d 1 e )法作顯像後， 以純水來水洗，進行乾燥而形成光阻圖型。表2中顯示所 形成的各光阻圖型之評價結果。又，以下顯示各實施例及 比較例所用的樹脂（B-1 )〜樹脂（B-6 )以外之材料。 -76- 200832068 混合酸產生劑（A ) A 1 -1 ··三苯基鏟水楊酸鹽 A 1-2 : 4_羥苯基二苯基銃水楊酸鹽 A 1-3 :三（4·氟苯基）锍水楊酸鹽 &gt; A1-4 : 4-甲基苯基二苯基毓1-金剛烷羧基羧酸鹽 A 1-5 : 2，4,6-三甲基苯基二苯基鏡水楊酸鹽 φ A1-6 :雙（4-氟苯基）碘鑰水楊酸鹽 A2-1 :三苯基毓三氟甲烷磺酸鹽 A2-2 : ( 4-羥苯基）二苯基毓三氟甲烷磺酸鹽 A2-3 :三（4-氟苯基）毓三氟甲烷磺酸鹽 A2_4 : 4-甲基苯基二苯基锍三氟甲烷磺酸鹽 A2-5: 2,4,6-三甲基苯基二苯基毓4-三氟甲基苯磺酸 鹽 A2-6:雙（4-氟苯基）碘鐵三氟甲烷磺酸鹽 # A2-7 :三苯基毓 1，1，2,2-四氟-2-(四環 [4·4·0·12’5·Γ’1()]十二烷-8-基）乙烷磺酸鹽 Α2-8 :三苯基毓1，1-二氟-2-(雙環[2· 2.1]庚烷-2-基 ' )乙烷磺酸鹽 其它酸產生劑（C ) C-1 : Ν-(三氟甲基磺醯氧基）雙環[2·2·1]庚-5-烯-2，3 _二羧醯亞胺 -77- 200832068 溶劑（D ) D-l :乳酸乙酯 D-2 : 3-乙氧基丙酸乙酯 D-3 :丙二醇單甲基醚醋酸酯 ' 酸擴散控制劑（E ) E-1 :三正辛胺 φ Ε-2:Ν·(第三丁氧羰基）2-苯基苯并咪唑 再者，各種評價方法係如以下（1 )〜（5 )中所示。 (1 )感度（L/S): 對矽晶圓上所形成的光阻被膜進行曝光後，立刻進行 ΡΕΒ，然後作鹼顯像，進行水洗、乾燥，而形成光阻圖型 。此時，以在1對1的線寬形成線寬1 50nm的線與間隙 圖型（1L1S)之曝光量當作最合適的曝光量，由該最合適 φ 的曝光量來評價感度。 (2)解像度（L/S): | 關於線與間隙圖型（1 L 1 S )，以最合適的曝光量所解 - 像的線圖型之最小線寬（nm )當作解像度。 (3 )感度（1L/5S、孤立的線圖型）： 對矽晶圓上所形成的光阻被膜進行曝光後，立刻進行 PEB，然後作鹼顯像，進行水洗、乾燥，而形成光阻圖型 -78- 200832068 。此時，以在1對5的線寬形成線寬15 Onm的線與間隙 圖型（1L5S)之曝光量當作最合適的曝光量，由該最纟適 的曝光量來評價感度。 (4)解像度（1L/5S ): - 關於線與間隙圖型（1 L 5 S )’以最合適的曝光量所解 像的線圖型之最小線寬（nm )當作解像度。 (5 )奈米邊緣粗糙度： 以半導體用掃描電子顯微鏡（高解析能力FEB測長 裝置，商品名「S-9220」，日立製作所公司製）來觀察設 計線寬1 5 〇nm的線與間隙圖型（1 L 1 S )之線圖型。第1 圖係顯示線圖型的模式圖（但，凹凸係比實際還誇大）。 再者，第1圖中，（a)顯示平面圖，（b)顯示矽晶圓1 上所形成的線圖型2之截面圖。關於各實施例中所觀察的 Φ 形狀，在沿著線圖型的橫側面2a所發生的凹凸之最顯著 的地方，測定線寬與設計線寬150nm的差「ACD」而評 價。 -79- 200832068 [表l]Mw/Mn is 1 · 7. Further, as a result of 13C-NMR analysis, a copolymerized molar ratio of 4-hydroxybenzene φ ethylene (1) to styrene (2) and 4-t-butoxy styrene (3) (1) : ( 2) : ( 3 ) = 6 5 : 5 : 3 0. This resin was referred to as "resin (B1)". Synthesis Example 2: Resin (B_2) 100 g of 4-acetoxystyrene, 25 g of tert-butyl acrylate, 18 g of styrene, 6 g of AIBN, and 1 g of t-dodecanethiol were dissolved. After 230 g of propylene glycol monomethyl ether, the reaction temperature was maintained at 70 ° C under a nitrogen atmosphere to allow polymerization for 16 hours. After the polymerization, the reaction solution was dropped into 2000 g of n-hexane, and the resulting resin was solidified and purified. Next, after adding 150 g of propylene glycol monomethyl ether to the solidified resin, 300 g of methanol, 80 g of triethylamine, and 15' g of water were added to reflux at the boiling point. An 8 hour hydrolysis reaction was carried out. After the hydrolysis reaction, the solvent and triethylamine were distilled off under reduced pressure to give a resin. The obtained resin was redissolved in acetone so that the solid content concentration became 20%, and then dropped into 2000 g of water to be solidified. The resulting white powder was filtered through a night-time drying at 50 ° C under reduced pressure to obtain a resin of the final product -72-200832068. The obtained resin had a Mw of 11,500 and an Mw/Mn of 1.6. Further, the results of '13C-NMR analysis were: copolymerization of 4-hydroxystyrene (1) with tributyl acrylate (2) and styrene (3) (1) : ( 2 ) : ( 3 ) =6 1 : 1 9 : 20. This resin was referred to as "resin (B-2)". Synthesis Example 3: Resin (B-3) After dissolving 37.6 g of 4-ethoxyethoxystyrene, 11.0 g of 4-tert-butoxystyrene, and 1.4 g of styrene in 200 g of cyclohexane, Place it in a dry, pressure-resistant glass bottle and attach it to a perforated cap with a washer made of Neoprene (trade name (DuPont)). After cooling the pressure-resistant glass bottle to -20 ° C, 2.96 ml of n-butyl lithium (1.83 m〇l / l of cyclohexane solution), 0. 98 g of N, N, N', N' were added in order. —Tetramethylethylenediamine, the reaction was allowed to stand for 1 hour while maintaining the temperature at -20 °C. Then, 1. gram of methanol was injected to stop the reaction. Make sure the color of the solution changes from red to colorless. After washing with 200 g of 3% oxalic acid water, 200 g of propylene glycol monomethyl ether and 1.5 g of p-toluenesulfonic acid were added, and the mixture was stirred at room temperature (23 to 25 ° C) for 3 hours to be hydrolyzed to obtain a copolymer. liquid. The obtained copolymer solution was dropped into 2000 g of water to solidify. The resulting white powder was filtered and dried overnight at 50 ° C under reduced pressure to give a copolymer of the final product. The obtained copolymer had Mw of 16,000 and Mw/Mn of 1.3. Further, as a result of 13C-NMR analysis, a copolymerized molar ratio (4) of 4-hydroxystyrene (1) with styrene (2) and 4-t-butoxystyrene (3): (2) ) : ( 3 ) =72: 5: 23. This copolymer was referred to as "resin (-73-200832068 B-3)". Synthesis Example 4··Resin (b _ 4 ) 173 g of 4-ethoxylated styrene, 56 g of 4 -tributoxystilbene styrene, and 11 g of 2,5-dimethylhexane-2. 5-diacrylate, 14 g AIBN, and 11 g t-dodecyl mercaptan were dissolved in 24 g of propylene glycol monomethyl ether, and the reaction temperature was maintained at 70 t under a nitrogen atmosphere to make the polymer 1 6 hour. After the polymerization, the reaction solution was dropped into a 2,000 gram hospital, and the resulting resin was solidified and refined. The coagulated and purified copolymer was dried at 50 ° C for 3 hours under reduced pressure. After adding 150 g of propylene glycol monomethyl ether to the dried 9 gram copolymer, add 3 gram of methanol, 1 gram of triethylamine, and 15 gram of water, at the boiling point. The reflux reaction was carried out for 8 hours while refluxing. After the hydrolysis reaction, the solvent and triethylamine were distilled off under reduced pressure to give a copolymer. The obtained copolymer was dissolved in acetone so that the solid content concentration became 20%, and then it was dripped into 2 〇 〇 gram of water to solidify. Φ By filtering the resulting white powder, it was dried overnight at 50 ° C under reduced pressure to obtain a copolymer of the final product. The obtained copolymer had a Mw of 27,000 and a Mw/Mn of 2.6. Further, the results of i3C-NMR analysis were: 4-hydroxysilane (1) and 4-tert-butoxystyrene (2) and 2,5 - «dimethylhexane-2,5-diacrylic acid The copolymerized molar ratio of the ester (3) (1): (2) · (3) = 7 5 : 2 2 : 3. This copolymer was referred to as "resin (B-4)". Synthesis Example 5: Resin (B-5) -74- 200832068 25 g of 4-hydroxystyrene and 4 -t-butoxystyrene copolymer (trade name "VPT1503S", manufactured by Nippon Soda Co., Ltd., 4 - The molar ratio of the storage of the phenylene bromide to the 4-t-butoxyphenethyl group = 90: 1 〇) was dissolved in 100 g of n-butyl acetate and bubbled with nitrogen for 30 minutes. Then, '3·3 g of ethyl bromide' was added to add 1 g of p-toluene orthophosphate as a catalyst, and the reaction was allowed to proceed for 12 hours at room temperature. Next, the reaction solution was dropped into a 1% aqueous ammonia solution to precipitate a resin, and after filtration, it was 5 Torr. The φ vacuum dryer was dried overnight to obtain a resin of the final product. The obtained resin had a Mw of 13,000 and an Mw/Mn of 1.〇1. Further, 13C-NMR analysis of the obtained resin revealed that the resin was a copolymer in which poly(4-hydroxystyrene) was 67 mol%, and phenolic hydroxyl group in poly(4-hydroxystyrene) The constituent unit in which the hydrogen atom was replaced by the ethoxyethyl group was 23 旲%, and the constituent unit derived from 4-t-butoxyphenyl benzene was 10 mol%. This copolymer is referred to as "resin (B-5)". • Synthesis Example 6: Resin (B-6) 104 g of 4-ethoxylated styrene, 5 g of styrene, 52 g of 4 -t-butoxystyrene, 5 · 8 g of di-tert-butyl After the oxide and 1' gram of t-dodecyl mercaptan were dissolved in 1600 g of propylene glycol monomethyl ether, the reaction temperature was maintained at 70 ° C under nitrogen and atmosphere, and polymerization was carried out for 16 hours. After the polymerization, the reaction solution was dropped into 200 g of n-hexane, and the resulting resin was solidified. Next, after adding 150 kg of propylene glycol monomethyl ether to the resin which was solidified and refined, 300 g of methanol, 80 g of triethylamine, and 15 g of water were further added, and while refluxing was carried out at the boiling point, 8 was carried out. Hour hydrolysis reaction -75- 200832068. After the hydrolysis reaction, the solvent and triethylamine were distilled off under reduced pressure to give a resin. The obtained resin was dissolved in acetone so that the solid content concentration became 20%, and then dropped into 2000 g of water to be solidified. The resulting white powder was filtered and dried under reduced pressure at 50 ° C overnight to obtain a resin of the final product. The obtained resin had a Mw of 15,000 and _Mw/Mn of 1.7. Further, as a result of 13C-NMR analysis, a copolymerized molar ratio of 4-hydroxystyrene (1) to styrene (2) and 4-t-butoxystyrene (3) φ (1) : ( 2) : (3) =64 : 5 : 3 1. This resin was referred to as "resin (B-6)". Examples 1 to 5, and Comparative Examples 1 to 4 The components shown in Table 1 were mixed in an amount shown in Table 1 to obtain a homogeneous solution, and then filtered by a membrane filter having a pore diameter of 20 〇 nm to prepare a composition solution. Then, in the product name "Cleantruck ACT-8" manufactured by Tokyo Electronics Co., Ltd., after each composition solution was spin-coated on a tantalum wafer, PB was performed under the conditions shown in Table 2 to form a film thickness of l〇〇nm. The photoresist film. Next, using a simple electronic wire drawing device (type "HL800D", manufactured by Hitachi, Ltd., output: 50KeV, current density: 5.0 amps * / cm2), the electron beam is irradiated on the formed photoresist film, in Table 2 PEB is carried out under the conditions shown. Then, using 2.3 8% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 1 minute, after paddle (padd 1 e ) method for development, washed with pure water, dried to form a photoresist pattern. type. The evaluation results of the respective photoresist patterns formed are shown in Table 2. Further, materials other than the resins (B-1) to (B-6) used in the respective examples and comparative examples are shown below. -76- 200832068 Mixed acid generator (A) A 1 -1 ··Triphenyl shovel salicylate A 1-2 : 4_hydroxyphenyldiphenylhydrazine salicylate A 1-3 : three ( 4·fluorophenyl)hydrazine salicylate&gt; A1-4 : 4-methylphenyldiphenylphosphonium 1-adamantanecarboxycarboxylate A 1-5 : 2,4,6-trimethylbenzene Diphenyl mirror salicylate φ A1-6 : bis(4-fluorophenyl)iodonium salicylate A2-1 : triphenylsulfonium trifluoromethanesulfonate A2-2 : ( 4-hydroxyl Phenyl)diphenylphosphonium trifluoromethanesulfonate A2-3: tris(4-fluorophenyl)phosphonium trifluoromethanesulfonate A2_4 : 4-methylphenyldiphenylphosphonium trifluoromethanesulfonate A2-5: 2,4,6-trimethylphenyldiphenylphosphonium 4-trifluoromethylbenzenesulfonate A2-6: bis(4-fluorophenyl)iodotrifluoromethanesulfonate# A2-7: Triphenylsulfonium 1,1,2,2-tetrafluoro-2-(tetracyclo[4·4·0·12'5·Γ'1()]dodecane-8-yl)B Alkanesulfonate Α2-8: Triphenylsulfonium 1,1-difluoro-2-(bicyclo[2·2.1]heptan-2-yl')ethanesulfonate Other acid generator (C) C- 1 : Ν-(trifluoromethylsulfonyloxy)bicyclo[2·2·1]hept-5-ene-2,3 _dicarboxy quinone imine-77- 200832068 Solvent (D) Dl: Lactic acid Ester D-2 : Ethyl 3-ethoxypropionate D-3 : Propylene glycol monomethyl ether acetate 'acid diffusion control agent (E ) E-1 : tri-n-octylamine φ Ε-2: Ν·( Further, tributyloxycarbonyl) 2-phenylbenzimidazole, various evaluation methods are shown in the following (1) to (5). (1) Sensitivity (L/S): After exposing the photoresist formed on the wafer to the film, it is immediately etched, then subjected to alkali development, washed with water, and dried to form a photoresist pattern. At this time, the exposure amount of the line and the gap pattern (1L1S) having a line width of 1 50 nm in a line width of 1 to 1 was taken as the optimum exposure amount, and the sensitivity was evaluated from the exposure amount of the optimum φ. (2) Resolution (L/S): | Regarding the line and gap pattern (1 L 1 S ), the solution is solved with the most appropriate exposure amount - the minimum line width (nm) of the line pattern of the image is taken as the resolution. (3) Sensitivity (1L/5S, isolated line pattern): After exposure of the photoresist formed on the wafer, PEB is immediately performed, and then alkali image is developed, washed and dried to form a photoresist. Graphic type -78- 200832068. At this time, the exposure amount of the line and the gap pattern (1L5S) having a line width of 15 Onm at a line width of 1 to 5 was taken as the optimum exposure amount, and the sensitivity was evaluated from the optimum exposure amount. (4) Resolution (1L/5S): - Regarding the line and gap pattern (1 L 5 S )', the minimum line width (nm) of the line pattern solved by the most appropriate exposure amount is taken as the resolution. (5) Nano-edge roughness: The line and gap of the design line width of 15 〇nm are observed by a scanning electron microscope for semiconductors (high-resolution FEB length measuring device, trade name "S-9220", manufactured by Hitachi, Ltd.). Line pattern of the pattern (1 L 1 S ). Figure 1 shows a pattern diagram of the line pattern (however, the bump is more exaggerated than it actually is). In addition, in Fig. 1, (a) shows a plan view, and (b) shows a cross-sectional view of the line pattern 2 formed on the wafer 1 . With respect to the Φ shape observed in each of the examples, the difference "ACD" between the line width and the design line width of 150 nm was evaluated and evaluated in the most prominent portion along the lateral side surface 2a of the line pattern. -79- 200832068 [Table l]

棚旨⑻ 酸產生劑 (A1) 酸產生劑 (A2) 其它酸產生齊ί (C) 溶劑(D) 酸擴散控制劑 (E) 種類 份 種類 份 種類 份 種類 份 種類 份 種類 份 實施例1 B-1 100 A1-1 2.5 A2-1 9 - - D-l 1500 - - D-3 700 實施例2 B-1 100 A1-2 2.8 A2-2 10 - - D-l 1500 - - D-3 700 實施例3 B-1 100 A1-3 2.5 A2-3 10 - - D-l 1500 - - D-3 700 實施例4 B-1 100 A1-4 2.5 A2-4 9 - - D-l 1500 - - D-3 700 實施例5 B-3 100 A1-2 2.8 A2-2 10 - - D-l 1500 - - D-2 700 實施例6 B-4 100 A1-1 2.5 A2-1 9 - - D-l 1500 - - D-3 700 實施例7 B-5 100 A1-1 2.5 A2-1 9 - - D-l 1500 - - D-3 700 實施例8 B-1 100 A1-1 2.5 A2-1 9 - - D-l 1500 E-l 0.2 D-3 700 實施例9 B-1 100 A1-5 2.7 A2-5 10 - - D-l 1500 - 畢 D-3 700 實施例10 B-1 100 A1-4 2.5 Α2·4 9 C-l 2 D-l 1500 - - D-3 700 實施例11 B-1 100 A1-6 2.8 Α2-6 10 - - D-l 1500 - - D-2 700 實施例12 B-1 100 AM 2.5 Α2-1 9 - - D-l 1500 - _ Α2-7 1 D-3 700 實施例13 B-1 100 AM 2.5 Α2-1 9 - - D-l 1500 - - Α2-8 1 D-2 700 實施例14 B-6 100 AM 2.5 Α2-1 9 - - D-l 1500 • - D-3 700 實施例15 B-6 100 Al-1 2.5 Α2-1 9 - - D-l 1500 - - Α2-8 1 D-3 700 實施例16 B-6 100 Al-1 2.5 Α2-1 9 - - D-l 1500 - - Α2-8 1 D-3 700 比較例1 B-1 100 Α1·3 2.5 Α2-1 9 - - D-l 1500 - - D-3 700 比較例2 B-1 100 Al-1 2.5 - - C-l 9 D-l 1500 - - D-3 700 比較倒3 B-2 100 Al-1 2.5 Α2·1 9 - 讎 D-l 1500 - - D-3 700 比較例4 B-1 100 - - - • C-l 9 D-l 1500 E-2 2.5 D-3 700 -80- 200832068 [表2]BOX (8) Acid generator (A1) Acid generator (A2) Other acid generators (C) Solvent (D) Acid diffusion control agent (E) Types, parts, parts, parts, parts, parts, parts, parts, Examples, Examples B -1 100 A1-1 2.5 A2-1 9 - - Dl 1500 - - D-3 700 Example 2 B-1 100 A1-2 2.8 A2-2 10 - - Dl 1500 - - D-3 700 Example 3 B -1 100 A1-3 2.5 A2-3 10 - - Dl 1500 - - D-3 700 Example 4 B-1 100 A1-4 2.5 A2-4 9 - - Dl 1500 - - D-3 700 Example 5 B -3 100 A1-2 2.8 A2-2 10 - - Dl 1500 - - D-2 700 Example 6 B-4 100 A1-1 2.5 A2-1 9 - - Dl 1500 - - D-3 700 Example 7 B -5 100 A1-1 2.5 A2-1 9 - - Dl 1500 - - D-3 700 Example 8 B-1 100 A1-1 2.5 A2-1 9 - - Dl 1500 El 0.2 D-3 700 Example 9 B -1 100 A1-5 2.7 A2-5 10 - - Dl 1500 - Bi D-3 700 Example 10 B-1 100 A1-4 2.5 Α2·4 9 Cl 2 Dl 1500 - - D-3 700 Example 11 B -1 100 A1-6 2.8 Α2-6 10 - - Dl 1500 - - D-2 700 Example 12 B-1 100 AM 2.5 Α2-1 9 - - Dl 1500 - _ Α 2-7 1 D-3 700 Example 13 B-1 100 AM 2.5 Α2-1 9 - - Dl 1500 - - Α2-8 1 D-2 700 Example 14 B-6 100 AM 2.5 Α2-1 9 - - Dl 1500 • - D-3 700 Example 15 B-6 100 Al-1 2.5 Α2-1 9 - - Dl 1500 - - Α2 -8 1 D-3 700 Example 16 B-6 100 Al-1 2.5 Α2-1 9 - - Dl 1500 - - Α2-8 1 D-3 700 Comparative Example 1 B-1 100 Α1·3 2.5 Α2-1 9 - - Dl 1500 - - D-3 700 Comparative Example 2 B-1 100 Al-1 2.5 - - Cl 9 Dl 1500 - - D-3 700 Comparison 3 B-2 100 Al-1 2.5 Α2·1 9 -雠Dl 1500 - - D-3 700 Comparative Example 4 B-1 100 - - - • Cl 9 Dl 1500 E-2 2.5 D-3 700 -80- 200832068 [Table 2]

PB條件 PEB條件 解像度 L/S感度 解像度 1L/5S感度 奈米邊緣粗 (V) (秒） (°c) (秒) L/S(nm) (pC/cm2) lL/5S(nm) (pC/cm2) 糖度(nm) 實施例1 130 60 130 60 80 31.0 80 26.0 9 實施例2 130 60 130 60 90 32.5 80 28.5 10 實施例3 130 60 130 60 80 32.0 80 28,0 10 實施例4 120 60 130 60 90 32.0 80 28.5 12 實施例5 130 60 130 60 90 32.5 80 28.5 11 實施例6 130 60 130 60 80 32.0 70 27.0 9 實施例7 110 60 110 60 90 33.0 90 33.0 13 實施例8 130 60 130 60 90 33.0 80 28.0 10 實施例9 130 60 130 60 90 32.0 80 29.0 10 實施例10 130 60 130 60 90 33.0 80 29.0 12 實施例11 130 60 130 60 90 32.0 80 29.0 11 實施例12 130 60 130 60 90 33.0 90 30.0 11 實施例13 130 60 130 60 90 32.0 90 31.0 10 實施例14 130 60 130 60 80 31.0 80 25.0 9 實施例15 130 60 130 60 90 32.0 80 31.0 9 實施例16 140 60 90 60 90 30.0 80 25.0 8 比較例1 130 60 130 60 110 35.0 100 35.0 15 比較例2 130 60 130 60 120 31.0 110 31.0 18 比較例3 130 60 130 60 100 34.0 100 34.0 15 比較例4 130 60 130 60 120 40.0 120 40.0 16 -81 - 200832068 產業上的利用可能性 本發明的正型敏輻射線性樹脂組成物，由於在圖型形 成時不僅線與間隙圖型的解像度優異，而且1L5S圖型的 解像度亦優異，且奈米邊緣粗糙度優異，故適用於EB、 EUV、X射線的微細圖型形成。因此，本發明的正型敏幅 ^ 射線性樹脂組成物，係極適用於在今後預料M ^ ,細彳匕_ @ 的半導體裝置製造用之化學增幅型光阻。 【圖式簡單說明】 第1圖係顯示線圖型的模式圖。 【主要元件符號說明】 1 :矽晶圓 2 :線圖型 2a :線圖型的橫側面 -82-PB condition PEB condition resolution L/S sensitivity resolution 1L/5S sensitivity nano edge thick (V) (seconds) (°c) (seconds) L/S(nm) (pC/cm2) lL/5S(nm) (pC /cm2) Brix (nm) Example 1 130 60 130 60 80 31.0 80 26.0 9 Example 2 130 60 130 60 90 32.5 80 28.5 10 Example 3 130 60 130 60 80 32.0 80 28,0 10 Example 4 120 60 130 60 90 32.0 80 28.5 12 Example 5 130 60 130 60 90 32.5 80 28.5 11 Example 6 130 60 130 60 80 32.0 70 27.0 9 Example 7 110 60 110 60 90 33.0 90 33.0 13 Example 8 130 60 130 60 90 33.0 80 28.0 10 Example 9 130 60 130 60 90 32.0 80 29.0 10 Example 10 130 60 130 60 90 33.0 80 29.0 12 Example 11 130 60 130 60 90 32.0 80 29.0 11 Example 12 130 60 130 60 90 33.0 90 30.0 11 Example 13 130 60 130 60 90 32.0 90 31.0 10 Example 14 130 60 130 60 80 31.0 80 25.0 9 Example 15 130 60 130 60 90 32.0 80 31.0 9 Example 16 140 60 90 60 90 30.0 80 25.0 8 Comparative Example 1 130 60 130 60 110 35.0 100 35.0 15 Comparative Example 2 130 60 130 60 120 31.0 110 31.0 18 Comparative Example 3 130 60 130 60 100 34.0 100 34.0 15 Comparative Example 4 130 60 130 60 120 40.0 120 40.0 16 -81 - 200832068 Industrial Applicability The positive-sensitive radiation linear resin composition of the present invention is not only a line and a gap pattern when formed in a pattern The resolution is excellent, and the resolution of the 1L5S pattern is excellent, and the nano-edge roughness is excellent, so it is suitable for the formation of fine patterns of EB, EUV, and X-ray. Therefore, the positive-type sensitive radiation resin composition of the present invention is extremely suitable for chemically amplified photoresists for semiconductor devices in which M ^ and fine 彳匕 @ are expected to be produced in the future. [Simple description of the drawing] Fig. 1 shows a pattern diagram of the line pattern. [Main component symbol description] 1 : 矽 wafer 2 : line pattern 2a : horizontal side of line pattern -82-

Claims (1)

200832068 十、申請專利範園 1. 一種正型敏輻射線性樹脂組成物，其含有敏輻射 線性酸產生劑（A )、及藉由樹脂中所含有的酸解離性基 之解離而成爲鹼可溶性之鹼不溶性或難溶性的樹脂（B ) ，其特徵爲： &quot; 該敏輻射線性酸產生劑（A )係含有酸產生劑（A 1 ) 及酸產生劑（A2 )的混合酸產生劑，該酸產生劑（A 1 ) φ 與該酸產生劑（A2)具有相同的陽離子，該酸產生劑（ A1 )係經由輻射線照射而產生常壓之沸點爲150°C以上的 羧酸，且由下述式（1 )所表示，該酸產生劑（A2 )係經 由輻射線照射而產生該羧酸以外的酸，且由下述式（2 ) 所表示， 該樹脂（B)係含有下述重複單位（i)、下述重複單 位（Π)及下述重複單位（iii)的樹脂； 酸產生劑（A 1 ): •[化 1] M + RCOCT (1) 酸產生劑（A2): [化2] M + X· (2) (式（1 )及式（2 )中，1^! +係下述式（6)或下述式（7) 所表示的1價鎗陽離子 -83- 200832068 [化3] R16 R19 \ | R17 —矿 1 r 1 | R18 1 R20 (6) (7) (式（6)及式（7)中，R16、R17、R18、R19 及 R20 獨立地係取代或未取代的碳數1〜10的直鏈狀或支鏈 烷基、或碳數6〜18的芳基，R16、R17及R18中的二 • 上可互相鍵結而與式中的硫原子一起形成環’ R19與 可互相鍵結而與式中的碘原子一起形成環）， 式（1 )的R表示碳數5〜20的直鏈狀、支鏈狀 狀的烷基、碳數5〜20的直鏈狀、支鏈狀或環狀的烯 碳數5〜20的直鏈狀、支鏈狀或環狀的炔基、碳數f 的直鏈狀、支鏈狀或環狀的烷氧基、上述烷基的氫原 至少一部分經鹵素原子及/或羥基取代的基、上述烯 氫原子之至少一部分經鹵素原子及/或羥基取代的基 鲁碳數6〜2 0的取代或未取代的芳基， 式（2 )的X表示取代或未取代的碳數1〜2〇的 _ 狀、支鏈狀或環狀的烷基、或取代或未取代的碳數6 的具有方基的磺酸陰離子，上述烷基的氫原子之至少 为經鹵素原子及/或羥基取代的基、或碳數6〜〗8的 或未取代的芳基）， 重複單位（Ο :下述式（3)所示的重複單位 互相 狀的 個以 R20 或環 基、 〜20 子之 基的 、或 直鏈 〜18 一部 取代 * 84 - 200832068 [化4]200832068 X. Patent application garden 1. A positive-type radiation-radiating linear resin composition containing a sensitive radiation linear acid generator (A) and dissociation by an acid dissociable group contained in the resin to become alkali-soluble An alkali-insoluble or poorly soluble resin (B) characterized by: &quot; the radiation-sensitive linear acid generator (A) is a mixed acid generator containing an acid generator (A1) and an acid generator (A2), The acid generator (A 1 ) φ has the same cation as the acid generator (A2), and the acid generator (A1) is irradiated with radiation to generate a carboxylic acid having a boiling point of 150 ° C or higher at normal pressure, and In the following formula (1), the acid generator (A2) is produced by irradiation with radiation to generate an acid other than the carboxylic acid, and is represented by the following formula (2), and the resin (B) contains the following Repeating unit (i), repeating unit (Π) and resin of the following repeating unit (iii); acid generator (A 1 ): • [Chemical 1] M + RCOCT (1) Acid generator (A2): [Chem. 2] M + X· (2) (In the formula (1) and the formula (2), 1^! + is expressed by the following formula (6) or the following formula (7) 1 price gun cation -83- 200832068 [Chemical 3] R16 R19 \ | R17 - mine 1 r 1 | R18 1 R20 (6) (7) (in equations (6) and (7), R16, R17, R18 R19 and R20 are independently substituted or unsubstituted linear or branched alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 18 carbon atoms; and two of R16, R17 and R18 may be bonded to each other. And forming a ring 'R19 together with a sulfur atom in the formula to form a ring together with an iodine atom in the formula), and R of the formula (1) represents a linear or branched chain having a carbon number of 5 to 20. a linear alkyl group, a linear, branched or cyclic olefin having 5 to 20 carbon atoms, a linear, branched or cyclic alkynyl group having 5 to 20 carbon atoms, and a linear chain having a carbon number f a branched or cyclic alkoxy group, a hydrogen atom of at least a part of the above alkyl group, a group substituted with a halogen atom and/or a hydroxyl group, and at least a part of the above-mentioned olefin hydrogen atom substituted with a halogen atom and/or a hydroxyl group. a substituted or unsubstituted aryl group of 6 to 20, wherein X of the formula (2) represents a substituted or unsubstituted 1-4 ring, a branched or cyclic alkyl group having 1 to 2 carbon atoms, or a substituted or unsubstituted Substituted carbon number 6 has a sulfonic acid anion of a aryl group, wherein at least a hydrogen atom of the above alkyl group is substituted with a halogen atom and/or a hydroxyl group, or a carbon number of 6 to 8 or an unsubstituted aryl group, a repeating unit (Ο: The repeating units represented by the formula (3) are substituted with R20 or a ring group, a group of -20 or a straight chain of -18; * 84 - 200832068 [Chem. 4] (R2)P (OH), ⑶ • (式（3 )中，R1係氫原子或甲基，R2係1價有機基，於 R2以複數存在時，該複數的R2可互相相同或不同’ P係0 〜3的整數，q係1〜3的整數）’ 重複單位（ii):下述式（4)所示的重複單位 [化5] R3(R2)P (OH), (3) • (In the formula (3), R1 is a hydrogen atom or a methyl group, and R2 is a monovalent organic group. When R2 is present in plural, the plural R2 may be the same or different from each other' P An integer of 0 to 3, q is an integer of 1 to 3) ' Repeating unit (ii): a repeating unit represented by the following formula (4) [Chemical 5] R3 (R4)r (OR5)s ⑷ (式（4 )中，R3係氫原子或甲基，R4係1價有機基（但 ® 是，相當於-OR5的基係除外），R5係從1-支鏈烷基、三 有機矽烷基、及三有機甲鍺烷基所組成族群所選出的1價 酸解離性基，於R4及R5各以複數存在時，該複數的R4 及R5各可互相相同或不同，r係0〜3的整數、s係1〜3 ' 的整數）， 重複單位（iii):從下述式（5-1)〜式（5_4)所組 成族群所選出的至少1個重複單位 -85- 200832068 R8 c=o(R4)r (OR5)s (4) (In the formula (4), R3 is a hydrogen atom or a methyl group, and R4 is a monovalent organic group (except that the product is equivalent to the -OR5 group), and the R5 is from 1 to a monovalent acid dissociable group selected from the group consisting of a branched alkyl group, a triorganoalkylene group, and a triorganomylalkyl group. When R4 and R5 are each present in plural, the plural R4 and R5 may be the same as each other. Or different, r is an integer of 0 to 3, s is an integer of 1 to 3 ', and repeating unit (iii): at least one selected from the group consisting of the following formulas (5-1) to (5_4) Repeat unit -85- 200832068 R8 c=o R14 c=o / o \ Ris (5-3) [化6] R6R14 c=o / o \ Ris (5-3) [6] R6 J? O \ c=o 十一 Ο!〆 R10 (5-1) (5-2) (5—4)J? O \ c=o 十一 Ο!〆 R10 (5-1) (5-2) (5-4) (式（5-1)〜式（5-4)中，116、118、111()、1111及 R14 各 自獨立地係氫原子或甲基，R7係1價有機基（但是，相當 於式（4 )的-OR5之基係除外），於R7以複數存在時，該 複數的R7可互相相同或不同，t係0〜3的整數，119係2 價的酸解離性之有機基，R12係碳數1〜4的烷基，R13係 氫原子、甲基、或乙基，R15係3級烷基）。 2.如申請專利範圍第1項之正型敏輻射線性樹脂組 φ 成物，其中該酸產生劑（A1 )係從三苯基銃水楊酸鹽、4 -羥苯基，二苯基毓水楊酸鹽、三（4 -氟苯基）毓水楊酸 鹽、4一甲基苯基二苯基毓1 一金剛烷羧酸鹽、2,4,6-三 _ 甲基苯基二苯基毓水楊酸鹽、雙（4-氟苯基）碘鍚水楊 、 酸鹽、三（4 一氟苯基）鏑1 一金剛烷羧酸鹽、（4 一氟苯 基）碘鑰水楊酸鹽、雙（4-氟苯基）碘鐵1 一金剛烷羧酸 鹽、2,4,6 -三甲基苯基二苯基锍1 一金剛烷羧酸鹽、4一 第三丁氧羰基甲基氧基苯基二苯基鏡水楊酸鹽中所選出的 至少1種， -86- 200832068 該酸產生劑（A2 )係從鏡鹽及碘鑰鹽中所選出的至少 一種鑰鹽化合物。 3 ·如申請專利範圍第2項之正型敏輻射線性樹脂組 成物，其中該酸產生劑（A 1 )係從三苯基銃水楊酸鹽、4 -經苯基二苯基Μ水楊酸鹽、三（4-氟苯基）鏡水楊酸 * 鹽、4一甲基苯基二苯基鏡1 一金剛烷羧酸鹽、2,4,6-三 甲基苯基二苯基毓水楊酸鹽、及雙（4 -氟苯基）碘鐵水 φ 楊酸鹽中所選出的至少1種， 該酸產生劑（Α2 )係從三苯基毓三氟甲烷磺酸鹽、（ 4一羥苯基）二苯基锍三氟甲烷磺酸鹽、三（4 一氟苯基） 鏟三氟甲院磺酸鹽、4 一甲基苯基二苯基锍三氟甲院磺酸 鹽、2,4,6—二甲基苯基一^苯基鏡4 一二氯甲基苯礦酸鹽、 雙（4 一氟苯基）碘鑰三氟甲烷磺酸鹽、三苯基鏡1，1，2,2 —四氟一2—(四環[4.4.0.12,5.17，1()]十二院一8—基）乙垸 磺酸鹽、及三苯基鏡1，1一二氟一 2-（雙環[2.2.1]庚烷一 φ 2 —基）乙烷磺酸鹽中所選出的至少1種。 4 ·如申請專利範圍第1項之正型敏輻射線性樹脂組 成物，其中該敏輻射線性酸產生劑（A )之酸產生劑（A i • )與酸,產生劑（A2)的比例（A1/A2)以質量比計係0.01 . 〜5 〇 5 .如申請專利範圍第1項之正型敏輻射線性樹脂組 成物，其中該重複單位（i )係從2 -羥基苯乙烯、3 一羥 基苯乙烯、4一羥基苯乙烯、2—羥基一 α —甲基苯乙烯、 3 —羥基一 α —甲基苯乙烯、4一羥基一 α —甲基苯乙烯、 -87- 200832068 2 —甲基—3 —羥基苯乙烯、4一甲基一 3 —羥基苯乙烯、5 一甲基一 3 —經基苯乙嫌'2 —甲基一 4 —經基本乙細、3 — 甲基一 4一羥基苯乙烯、3,4 一二羥基苯乙烯、及2,4,6—三 羥基苯乙烯中所選出的至少1種單體之聚合性不飽和鍵裂 解的重複單位。 ' 6 ·如申請專利範圍第1項之正型敏輻射線性樹脂組 成物，其中該重複單位（ii )係從4 -第三丁氧基苯乙烯 φ 及4-第三丁氧基—α 一甲基苯乙烯中所選出的至少1種單 體之聚合性不飽和鍵裂解的重複單位。 7·如申請專利範圍第1項之正型敏輻射線性樹脂組 成物’其中該重複單位（iii )係從該重複單位（i )及（ii )以外的乙烯基芳香族化合物、及（甲基）丙烯酸酯中所 選出的至少1種單體之聚合性不飽和鍵裂解的重複單位。 8 ·如申請專利範圍第1項之正型敏輻射線性樹脂組 成物’其中該樹脂（B)含有作爲該重複單位（i)的4一 • 羥基苯乙烯之聚合性不飽和鍵裂解的重複單位、作爲上述 重複單位（ii )的4 -第三丁氧基苯乙烯之聚合性不飽和 鍵裂解的重複單位當作必要成分。 • 9 ·如申請專利範圍第8項之正型敏輻射線性樹脂組 • 成物，其中對於該樹脂（B )中未被保護的酸性官能基與 酸解離性基之合計數而言，該樹脂（B )的酸解離性基之 數的比例係1 0〜1 〇 〇 %。 10·如申請專利範圍第1項之正型敏輻射線性樹脂組 成物’其中以全部重複單位的合計爲〗〇〇莫耳％時，該樹 -88- 200832068 脂（B )之該重複單位（i ) 重複單位（Π)的比例係5 )的比例係1〜3 0莫耳％。 的比例係45〜9〇莫耳％，該 一 5〇吳耳％，該重複單位（iii 1 1 ·如申請專利範圍第1項，γρ并 ^ 國弟負之正型敏輻射線性樹脂組 成物’其中該輪射線係電子線或極 丁电丁織4 @糸外線，由樹脂組成物 所得到的被膜係被該電子線或極紫外線所圖型化。(In the formulae (5-1) to (5-4), 116, 118, 111 (), 1111 and R14 are each independently a hydrogen atom or a methyl group, and R7 is a monovalent organic group (however, equivalent to the formula ( 4) Except for the base of -OR5), when R7 is present in plural, the plural R7 may be the same or different from each other, t is an integer of 0 to 3, 119 is a divalent acid dissociable organic group, and R12 is An alkyl group having 1 to 4 carbon atoms, R13 is a hydrogen atom, a methyl group or an ethyl group, and R15 is a tertiary alkyl group). 2. The positive-type radiation-sensitive linear resin group φ according to claim 1, wherein the acid generator (A1) is derived from triphenylsulfonium salicylate, 4-hydroxyphenyl group, diphenylanthracene Salicylate, tris(4-fluorophenyl)hydrazine salicylate, 4-methylphenyldiphenylphosphonium-1 adamantane carboxylate, 2,4,6-tri-methylphenyl Phenylhydrazine salicylate, bis(4-fluorophenyl)iodonium salicylate, acid salt, tris(4-fluorophenyl)indole-1 adamantane carboxylate, (4 fluorophenyl) iodine Salicylate, bis(4-fluorophenyl)iodoferrate 1 adamantane carboxylate, 2,4,6-trimethylphenyldiphenylphosphonium 1 adamantane carboxylate, 4 to 3 At least one selected from butoxycarbonylmethyloxyphenyldiphenyl mirror salicylate, -86-200832068 The acid generator (A2) is at least one selected from the group consisting of a mirror salt and an iodine salt Key salt compound. 3. The positive-type radiation-sensitive linear resin composition of claim 2, wherein the acid generator (A 1 ) is derived from triphenylsulfonium salicylate, 4-phenylphenyldiphenylhydrazine Acid salt, tris(4-fluorophenyl) mirror salicylic acid* salt, 4-methylphenyl diphenyl mirror 1 adamantane carboxylate, 2,4,6-trimethylphenyl diphenyl At least one selected from the group consisting of salicylic acid sulphate and bis(4-fluorophenyl) iodine water φ salicylate, the acid generator (Α2) is derived from triphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)diphenylphosphonium trifluoromethanesulfonate, tris(4-fluorophenyl) shovel trifluoromethanesulfonate, 4-methylphenyldiphenylphosphonium trifluoromethane Acid salt, 2,4,6-dimethylphenyl-phenylene mirror 4-dichloromethylbenzene mineralate, bis(4-fluorophenyl)iodotrifluoromethanesulfonate, triphenyl Mirror 1,1,2,2-tetrafluoro-2-(tetracycline [4.4.0.12, 5.17,1()] 12-in-one 8-yl) acetophenone sulfonate, and triphenyl mirror 1,1 At least one selected from the group consisting of difluoro-2-(bicyclo[2.2.1]heptane-φ 2 -yl)ethanesulfonate. 4. The positive-type radiation-sensitive linear resin composition of claim 1, wherein the ratio of the acid generator (A i • ) of the sensitive radiation linear acid generator (A) to the acid, the generator (A2) ( A1/A2) is a positive-type sensitive radiation linear resin composition according to the first aspect of the patent application, wherein the repeating unit (i) is derived from 2-hydroxystyrene, 3 Hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, -87- 200832068 2 — A Benzyl 3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-isomer-based benzene, '2-methyl-4, via basic propyl, 3-methyl- 4 A repeating unit of polymerizable unsaturated bond cleavage of at least one monomer selected from monohydroxystyrene, 3,4-dihydroxystyrene, and 2,4,6-trihydroxystyrene. [6] The positive-type radiation-sensitive linear resin composition of claim 1, wherein the repeating unit (ii) is from 4-tert-butoxystyrene φ and 4-tert-butoxy-α A repeating unit of polymerizable unsaturated bond cleavage of at least one monomer selected from methyl styrene. 7. The positive-type radiation-sensitive linear resin composition of claim 1, wherein the repeating unit (iii) is a vinyl aromatic compound other than the repeating units (i) and (ii), and (methyl) a repeating unit of polymerizable unsaturated bond cleavage of at least one monomer selected from the acrylate. 8. The positive-type radiation-sensitive linear resin composition of claim 1 wherein the resin (B) contains a repeating unit of polymerizable unsaturated bond cleavage of 4-hydroxy styrene as the repeating unit (i) The repeating unit of the polymerizable unsaturated bond cleavage of the 4-tetrabutoxystyrene as the above repeating unit (ii) is regarded as an essential component. • 9 • The positive-type radiation-sensitive linear resin group according to item 8 of the patent application, wherein the resin is the total number of unprotected acidic functional groups and acid-dissociable groups in the resin (B) The ratio of the number of acid dissociable groups of (B) is 10 to 1%. 10. The positive-type radiation-sensitive linear resin composition of the first application of the patent scope, wherein the total repeating unit is 〇〇mol%, the repeating unit of the tree-88-200832068 lipid (B) i) The ratio of the repeating unit (Π) to the ratio of 5) is 1 to 3 0 mol%. The ratio is 45~9〇mol%, the one 5〇吴耳%, the repeat unit (iii 1 1 · as claimed in the first item, γρ and ^ Guodi negative positive-sensitive radiation linear resin composition 'Where the ray-based electron beam or the butyl wire 4 糸 outer line, the film obtained from the resin composition is patterned by the electron beam or the extreme ultraviolet ray. 1 2 . —種圖型之形成方法，其係以曝光光束對使用敏 輻射線性樹脂組成物所形成的光阻被膜作曝光而形成圖型 的圖型形成方法，其特徵爲該敏輻射線性樹脂組成物係如 申請專利範圍第1項之正型敏輻射線性樹脂組成物，該曝 光係藉由電子線或極紫外線來曝光。1 2 . A method for forming a pattern, which is a pattern forming method for forming a pattern by exposing a resist beam to a photoresist film formed by using a linear radiation-sensitive resin composition, characterized in that the sensitive radiation linear resin The composition is a positive-type radiation-sensitive linear resin composition as claimed in claim 1, and the exposure is exposed by electron rays or extreme ultraviolet rays. -89--89-