TW202112742A - Sulfonamide compound, nonionic photoacid generator, and photolithography resin composition - Google Patents
Sulfonamide compound, nonionic photoacid generator, and photolithography resin composition Download PDFInfo
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Abstract
Description
本發明是有關於一種磺醯胺化合物、非離子系光酸產生劑、及光微影用樹脂組成物。更詳細而言，是有關於適於使紫外線（i射線、KrF射線）起作用而可產生超強酸的磺醯胺化合物、含有該磺醯胺化合物的非離子系光酸產生劑、及含有該非離子系光酸產生劑的光微影用樹脂組成物。The present invention relates to a sulfonamide compound, a nonionic photoacid generator, and a resin composition for photolithography. More specifically, it relates to a sulfonamide compound suitable for generating super acid by acting on ultraviolet rays (i-rays, KrF rays), a nonionic photoacid generator containing the sulfonamide compound, and a nonionic photoacid generator containing the non-ionic photoacid generator. A resin composition for photolithography of an ionic photoacid generator.
自先前以來，於半導體的製造所代表的微細加工的領域中，廣泛利用使用各種波長的光而可將理想的圖案轉印至抗蝕劑的光微影步驟。 作為抗蝕劑材料，例如可使用含有具有羧酸的第三丁基酯基、或苯酚的碳酸第三丁酯基的聚合體與光酸產生劑的樹脂組成物。藉由將該抗蝕劑材料溶解於溶媒中而成者塗佈於基板上並照射光，光酸產生劑進行分解並產生三氟甲磺酸等超強酸（顯示出較100%硫酸更高的酸性度的酸）。進而藉由進行曝光後加熱（PEB），由於所產生的酸而聚合體中的第三丁基酯基、或碳酸第三丁酯基等酸反應性基進行解離而形成羧酸基或酚性羥基，光照射部變得易溶於鹼性顯影液中。由於利用該現象進行圖案形成，故為了實現節能化或縮短步驟時間，期望開發出以少的曝光量獲得理想的圖案的高感度的抗蝕劑材料。 因而，作為實現高感度的抗蝕劑材料的光酸產生劑，理想的是光分解率高及產生酸具有更高的酸強度。Since the past, in the field of microfabrication represented by the manufacture of semiconductors, a photolithography step in which a desired pattern can be transferred to a resist using light of various wavelengths has been widely used. As the resist material, for example, a resin composition containing a polymer having a tertiary butyl ester group of carboxylic acid or a tertiary butyl carbonate group of phenol and a photoacid generator can be used. By dissolving the resist material in a solvent and coating it on the substrate and irradiating it with light, the photoacid generator decomposes and generates superacids such as trifluoromethanesulfonic acid (showing higher than 100% sulfuric acid) Acidity of acid). Further, by performing post-exposure heating (PEB), acid-reactive groups such as the tertiary butyl ester group or tertiary butyl carbonate group in the polymer dissociate due to the generated acid to form a carboxylic acid group or a phenolic group. With hydroxyl, the light-irradiated part becomes easily soluble in alkaline developer. Since this phenomenon is used for pattern formation, in order to achieve energy saving or shorten the step time, it is desired to develop a high-sensitivity resist material that obtains an ideal pattern with a small amount of exposure. Therefore, as a photoacid generator that realizes a high-sensitivity resist material, it is desirable that the photodecomposition rate is high and the generated acid has a higher acid strength.
根據以上的理由，作為對光微影步驟而言較佳的光酸產生劑，揭示有三芳基鋶鹽（專利文獻1）、具有萘骨架的苯甲醯甲基鋶鹽（專利文獻2）等離子系光酸產生劑、以及具有肟磺酸鹽結構（專利文獻3）、或萘二甲醯亞胺結構（專利文獻4、專利文獻5）等的非離子系光酸產生劑。 [現有技術文獻] [專利文獻]Based on the above reasons, as photoacid generators suitable for the photolithography step, triarylsulfonate (Patent Document 1), and benzylmethylsulfonate having a naphthalene skeleton (Patent Document 2) are disclosed. A photoacid generator, and a nonionic photoacid generator having an oxime sulfonate structure (Patent Document 3) or a naphthalenedimethimide structure (Patent Document 4, Patent Document 5). [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開昭50-151997號公報 [專利文獻2]日本專利特開平9-118663號公報 [專利文獻3]日本專利特開平6-67433號公報 [專利文獻4]日本專利特開2004-217748號公報 [專利文獻5]日本專利第5990447號公報[Patent Document 1] Japanese Patent Laid-Open No. 50-151997 [Patent Document 2] Japanese Patent Laid-Open No. 9-118663 [Patent Document 3] Japanese Patent Laid-Open No. 6-67433 [Patent Document 4] Japanese Patent Laid-Open No. 2004-217748 [Patent Document 5] Japanese Patent No. 5990447
[發明所欲解決之課題] 作為分解光微影用樹脂組成物中的光酸產生劑的光微影步驟用的光源，就獲取性、穩定性而言，廣泛使用i射線（365 nm）或KrF射線（248 nm）等近紫外線，隨著半導體市場的成長，對該些近紫外線的感度高的光酸產生劑開發的需求不斷提高。另外，於光微影步驟多樣化的現在，為了在高濃度的光微影用樹脂組成物中亦不發生固體的析出或相分離，要求對於光微影用樹脂組成物中含有的抗蝕劑溶媒而言為高溶解性。[The problem to be solved by the invention] As the light source used in the photolithography step of decomposing the photoacid generator in the resin composition for photolithography, in terms of availability and stability, i-rays (365 nm) or KrF rays (248 nm) are widely used. With the growth of the semiconductor market, the demand for the development of photoacid generators with high sensitivity to near-ultraviolet rays is increasing. In addition, in the current diversification of photolithography steps, in order to prevent solid precipitation or phase separation in high-concentration photolithography resin compositions, it is required that the resist contained in the photolithography resin composition The solvent has high solubility.
但是，三芳基鋶鹽或苯甲醯甲基鋶鹽等離子系光酸產生劑對於i射線的光分解率低而為低感度，進而由於為鹽，故存在以下問題：若以高濃度含有於光微影用樹脂組成物中，則會發生相分離或析出。However, the triarylsulfonate or benzylmethylsulfonate ion-based photoacid generator has a low photodecomposition rate for i-rays and is low sensitivity, and because it is a salt, it has the following problem: if it is contained in light at a high concentration In the resin composition for lithography, phase separation or precipitation occurs.
具有肟磺酸鹽結構及萘二甲醯亞胺結構的非離子系光酸產生劑對於i射線的光分解率高，但於實用方面產生酸限於磺酸，存在無法獲得充分的酸性度且為低感度的問題。Nonionic photoacid generators having an oxime sulfonate structure and a naphthalenedimethimide structure have a high photodecomposition rate for i-rays, but in practical terms, the generated acid is limited to sulfonic acid, and sufficient acidity cannot be obtained. The problem of low sensitivity.
即，本發明的目的在於提供一種磺醯胺化合物、含有該磺醯胺化合物的光酸產生劑、及含有該光酸產生劑且對近紫外線的感度高的光微影用樹脂組成物，所述磺醯胺化合物對於i射線、KrF射線等近紫外線的分解率高且產生作為超強酸的雙磺醯胺，且高度溶解於抗蝕劑溶媒。 [解決課題之手段]That is, the object of the present invention is to provide a sulfonamide compound, a photoacid generator containing the sulfonamide compound, and a resin composition for photolithography containing the photoacid generator and having high sensitivity to near-ultraviolet rays. The sulfonamide compound has a high decomposition rate with respect to near ultraviolet rays such as i-rays and KrF rays, produces bissulfonamide as a super acid, and is highly soluble in resist solvents. [Means to solve the problem]
本發明者等人為了達成所述目的而進行了努力研究，結果完成了本發明。 即，本發明為一種磺醯胺化合物（A）、包含該磺醯胺化合物（A）的非離子系光酸產生劑（B）、及包含該非離子系光酸產生劑（B）的光微影用樹脂組成物（Q），所述磺醯胺化合物（A）的特徵在於：由下述通式（1）及通式（2）所表示。The inventors of the present invention conducted diligent studies to achieve the above-mentioned object, and as a result, completed the present invention. That is, the present invention is a sulfonamide compound (A), a nonionic photoacid generator (B) containing the sulfonamide compound (A), and a photomicrograph containing the nonionic photoacid generator (B) The film resin composition (Q), the sulfonamide compound (A) is characterized by being represented by the following general formula (1) and general formula (2).
[化1]
[式中，Rf 分別為氟原子、氟烷基、或氟芳基，R1 分別為氟原子、烷基、氟烷基、芳基、或氟芳基，Rf 與R1 可相互鍵結而形成環，R2 為選自由氧、硫、氮（可具有取代基）所組成的群組中的雜原子，R3 為烷基、烯基、芳基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、或與Ar1 鍵結而形成環的-C(O)-、-C(O)-CH2 -、-C(O)O-、-C(O)-NR5 -、-C(O)S-、-SO2 -，R4 為選自由氟烷基、氟芳基、氰基、硝基芳基所組成的群組中的拉電子性基，Ar1 為芳基、或含雜原子的芳基] [發明的效果][In the formula, R f is a fluorine atom, a fluoroalkyl group, or a fluoroaryl group, and R 1 is a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group, respectively, and R f and R 1 may be bonded to each other Form a ring, R 2 is a heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen (which may have substituents), and R 3 is an alkyl group, an alkenyl group, an aryl group, an alkylcarbonyl group, and an arylcarbonyl group , Alkoxycarbonyl, aryloxycarbonyl, or -C(O)-, -C(O)-CH 2 -, -C(O)O-, -C(O) bonded to Ar 1 to form a ring ) -NR 5 -, -C(O)S-, -SO 2 -, R 4 is an electron withdrawing group selected from the group consisting of fluoroalkyl, fluoroaryl, cyano, and nitroaryl , Ar 1 is an aryl group or an aryl group containing a heteroatom] [Effects of the Invention]
本發明的磺醯胺化合物（A）為對近紫外線的分解率高且產生超強酸的非離子系光酸產生劑（B），對抗蝕劑溶媒的溶解性優異。另外，含有該非離子系光酸產生劑（B）的光微影用樹脂組成物（Q）對於近紫外線為高感度。The sulfonamide compound (A) of the present invention is a nonionic photoacid generator (B) that has a high decomposition rate to near-ultraviolet rays and generates a super acid, and has excellent solubility in a resist solvent. In addition, the resin composition (Q) for photolithography containing the nonionic photoacid generator (B) is highly sensitive to near ultraviolet rays.
本發明的磺醯胺化合物（A）是由下述通式（1）或通式（2）所表示。The sulfonamide compound (A) of the present invention is represented by the following general formula (1) or (2).
[化2]
[式中，Rf 分別為氟原子、氟烷基、或氟芳基，R1 分別為氟原子、烷基、氟烷基、芳基、或氟芳基，Rf 與R1 可相互鍵結而形成環，R2 為選自由氧、硫、氮（可具有取代基）所組成的群組中的雜原子，R3 為烷基、烯基、芳基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、或與Ar1 鍵結而形成環的-C(O)-、-C(O)-CH2 -、-C(O)O-、-C(O)-NR5 -、-C(O)S-、-SO2 -，R4 為選自由氟烷基、氟芳基、氰基、硝基芳基所組成的群組中的拉電子性基，Ar1 為芳基、或含雜原子的芳基][In the formula, R f is a fluorine atom, a fluoroalkyl group, or a fluoroaryl group, and R 1 is a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group, respectively, and R f and R 1 may be bonded to each other Form a ring, R 2 is a heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen (which may have substituents), and R 3 is an alkyl group, an alkenyl group, an aryl group, an alkylcarbonyl group, and an arylcarbonyl group , Alkoxycarbonyl, aryloxycarbonyl, or -C(O)-, -C(O)-CH 2 -, -C(O)O-, -C(O) bonded to Ar 1 to form a ring ) -NR 5 -, -C(O)S-, -SO 2 -, R 4 is an electron withdrawing group selected from the group consisting of fluoroalkyl, fluoroaryl, cyano, and nitroaryl , Ar 1 is an aryl group or an aryl group containing a heteroatom]
通式（1）或通式（2）中，Rf 為氟原子、氟烷基、或氟芳基，亦可具有取代基。Rf 與R1 可鍵結而形成環。In the general formula (1) or (2), R f is a fluorine atom, a fluoroalkyl group, or a fluoroaryl group, and may have a substituent. R f and R 1 may bond to form a ring.
氟烷基為至少一個氫經氟取代的烷基，可列舉碳數1～10（不包含取代基。若無特別記載則以下相同）的氟烷基等，可列舉：直鏈氟烷基（RF1）、分支氟烷基（RF2）、或環狀氟烷基（RF3）等。The fluoroalkyl group is an alkyl group in which at least one hydrogen is substituted with fluorine. Examples include fluoroalkyl groups having 1 to 10 carbon atoms (not including substituents. The same applies to the following unless otherwise specified). Examples include linear fluoroalkyl groups ( RF1), branched fluoroalkyl (RF2), or cyclic fluoroalkyl (RF3), etc.
作為直鏈氟烷基（RF1），可列舉：三氟甲基、五氟乙基、七氟丙基、九氟丁基、全氟己基、全氟辛基、全氟癸基、二氟甲基、1,1,2,2,3,3,4,4,5,5,6,6-十二氟己基、二氟(甲氧基羰基)甲基及2-金剛烷基羰氧基-1,1-二氟乙基等。Examples of linear fluoroalkyl groups (RF1) include: trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, perfluorohexyl, perfluorooctyl, perfluorodecyl, difluoromethyl Group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl, difluoro(methoxycarbonyl)methyl and 2-adamantylcarbonyloxy -1,1-Difluoroethyl and so on.
作為分支氟烷基（RF2），可列舉：六氟異丙基、九氟-第三丁基及全氟-2-乙基己基等。Examples of the branched fluoroalkyl group (RF2) include hexafluoroisopropyl, nonafluoro-tert-butyl, perfluoro-2-ethylhexyl, and the like.
作為環狀氟烷基（RF3），可列舉：七氟環丁基、九氟環戊基、全氟環己基及全氟(1-環己基)甲基等。Examples of the cyclic fluoroalkyl group (RF3) include heptafluorocyclobutyl, nonafluorocyclopentyl, perfluorocyclohexyl, and perfluoro(1-cyclohexyl)methyl.
氟芳基為至少一個氫經氟取代的芳基，可列舉碳數6～10的氟芳基（RF4）等。The fluoroaryl group is an aryl group in which at least one hydrogen is substituted with fluorine, and a fluoroaryl group having 6 to 10 carbon atoms (RF4) can be mentioned.
作為碳數6～10的氟芳基（RF4），可列舉：3,4,5-三氟苯基、五氟苯基、全氟萘基、3-三氟甲基、四氟苯基及3,5-雙三氟甲基苯基等。Examples of the fluoroaryl group (RF4) having 6 to 10 carbon atoms include 3,4,5-trifluorophenyl, pentafluorophenyl, perfluoronaphthyl, 3-trifluoromethyl, tetrafluorophenyl, and 3,5-bistrifluoromethylphenyl, etc.
Rf 中，就光阻劑的脫保護能力、及原料的獲取的容易度的觀點而言，較佳為直鏈氟烷基（RF1）、分支氟烷基（RF2）、及氟芳基（RF4），進而佳為直鏈氟烷基（RF1）、及氟芳基（RF4），特佳為三氟甲基（CF3 ）、五氟乙基（C2 F5 ）、七氟丙基（C3 F7 ）、九氟丁基（C4 F9 ）及五氟苯基（C6 F5 ）。Among R f , from the viewpoints of the deprotection ability of the photoresist and the ease of obtaining raw materials, the linear fluoroalkyl group (RF1), the branched fluoroalkyl group (RF2), and the fluoroaryl group ( RF4), more preferably linear fluoroalkyl (RF1) and fluoroaryl (RF4), particularly preferably trifluoromethyl (CF 3 ), pentafluoroethyl (C 2 F 5 ), heptafluoropropyl (C 3 F 7 ), nonafluorobutyl (C 4 F 9 ) and pentafluorophenyl (C 6 F 5 ).
通式（1）或通式（2）中，R1 為氟原子、烷基、氟烷基、芳基、或氟芳基，亦可具有取代基。In the general formula (1) or (2), R 1 is a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, or a fluoroaryl group, and may have a substituent.
作為烷基，可列舉碳數1～10的烷基等，可列舉：直鏈烷基（RA1）、分支烷基（RA2）及環狀的烷基（RA3）。Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms, and examples thereof include a linear alkyl group (RA1), a branched alkyl group (RA2), and a cyclic alkyl group (RA3).
作為直鏈烷基（RA1），可列舉：甲基、乙基、丙基、丁基、戊基、辛基、癸基、苄基、苄氧基甲基、甲氧基甲基、乙氧基甲基、2-甲氧基乙基、1-甲氧基乙基、三甲基矽氧基甲基、三乙基矽氧基甲基及第三丁基二甲基矽氧基甲基等。Examples of linear alkyl groups (RA1) include methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, benzyl, benzyloxymethyl, methoxymethyl, and ethoxy Methyl, 2-methoxyethyl, 1-methoxyethyl, trimethylsiloxymethyl, triethylsiloxymethyl and tert-butyldimethylsiloxymethyl Wait.
作為分支烷基（RA2），可列舉：異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、第三戊基、1-甲基丁基、2-乙基己基、異癸基等。Examples of branched alkyl groups (RA2) include isopropyl, isobutyl, second butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, 1-methylbutyl, 2 -Ethylhexyl, isodecyl, etc.
作為環狀烷基（RA3），可列舉：環戊基、環己基、降冰片烷基、1-金剛烷基、2-金剛烷基、薄荷基、10-樟腦基及八氫萘基等。Examples of the cyclic alkyl group (RA3) include cyclopentyl, cyclohexyl, norbornyl, 1-adamantyl, 2-adamantyl, menthyl, 10-camphoryl, and octahydronaphthyl.
作為氟烷基，可列舉與所述直鏈氟烷基（RF1）、分支氟烷基（RF2）或環狀氟烷基（RF3）相同者。Examples of the fluoroalkyl group include the same as the linear fluoroalkyl group (RF1), branched fluoroalkyl group (RF2), or cyclic fluoroalkyl group (RF3).
作為芳基，可列舉碳數6～10的芳基（RA4）等，可列舉：苯基、1-萘基、2-萘基、1-薁基、2-甲苯基、3-甲苯基、4-甲苯基、2-氯苯基、3-氯苯基、4-氯苯基、2-硝基苯基、4-硝基苯基、2,4-二甲苯基、2,6-二甲苯基、3,5-二甲苯基、2,4-二硝基苯基及2,4,6-均三甲苯基等。As the aryl group, an aryl group having 6 to 10 carbon atoms (RA4) and the like can be cited, and examples include phenyl, 1-naphthyl, 2-naphthyl, 1-azulenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-nitrophenyl, 4-nitrophenyl, 2,4-xylyl, 2,6-di Tolyl, 3,5-xylyl, 2,4-dinitrophenyl and 2,4,6-mesityl, etc.
作為氟芳基，可列舉與所述氟芳基（RF4）相同者。As the fluoroaryl group, the same as the above-mentioned fluoroaryl group (RF4) can be mentioned.
該些中就原料的獲取性的觀點而言，較佳為碳數1～10的直鏈烷基（RA1）、環狀烷基（RA3）、直鏈氟烷基（RF1）、碳數6～8的芳基及碳數6～8的氟芳基，更佳為甲基、乙基、丙基、丁基、辛基、10-樟腦基、三氟甲基（CF3 ）、五氟乙基（C2 F5 ）、七氟丙基（C3 F7 ）、九氟丁基（C4 F9 ）、苯基、4-甲苯基、2-硝基苯基、4-硝基苯基、2,4-二硝基苯基及五氟苯基（C6 F5 ），特佳為三氟甲基（CF3 ）、五氟乙基（C2 F5 ）、七氟丙基（C3 F7 ）、九氟丁基（C4 F9 ）及五氟苯基（C6 F5 ）。Among these, from the viewpoint of the availability of raw materials, a linear alkyl group having 1 to 10 carbons (RA1), a cyclic alkyl group (RA3), a linear fluoroalkyl group (RF1), and a carbon number of 6 are preferred. ~8 aryl and carbon 6-8 fluoroaryl, more preferably methyl, ethyl, propyl, butyl, octyl, 10-camphoryl, trifluoromethyl (CF 3 ), pentafluoro Ethyl (C 2 F 5 ), heptafluoropropyl (C 3 F 7 ), nonafluorobutyl (C 4 F 9 ), phenyl, 4-tolyl, 2-nitrophenyl, 4-nitro Phenyl, 2,4-dinitrophenyl and pentafluorophenyl (C 6 F 5 ), particularly preferably trifluoromethyl (CF 3 ), pentafluoroethyl (C 2 F 5 ), heptafluoropropyl Group (C 3 F 7 ), nonafluorobutyl (C 4 F 9 ) and pentafluorophenyl (C 6 F 5 ).
通式（1）中，R2 為選自由氧、硫、氮（可具有取代基）所組成的群組中的雜原子。In the general formula (1), R 2 is a heteroatom selected from the group consisting of oxygen, sulfur, and nitrogen (which may have a substituent).
作為氮原子上的取代基，並無特別限定，就合成容易性而言，較佳為烷基、芳基、烷基羰基、碳酸烷基酯基、烷基磺醯基、芳基磺醯基等。The substituent on the nitrogen atom is not particularly limited. In terms of ease of synthesis, an alkyl group, an aryl group, an alkylcarbonyl group, an alkyl carbonate group, an alkylsulfonyl group, and an arylsulfonyl group are preferred. Wait.
R2 中就原料的獲取性的觀點而言，較佳為氧。From the viewpoint of availability of raw materials, R 2 is preferably oxygen.
通式（1）中，R3 為烷基、烯基、芳基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、或與Ar1 鍵結而形成環的-C(O)-、-C(O)-CH2 -、-C(O)O-、-C(O)-NR5 -、-C(O)S-、-SO2 -。Formula (1), R 3 is an alkyl group, an alkenyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or Ar 1 bonded to form a ring, -C ( O)-, -C(O)-CH 2 -, -C(O)O-, -C(O)-NR 5 -, -C(O)S-, -SO 2 -.
作為烷基，可列舉與所述直鏈烷基（RA1）、分支烷基（RA2）及環狀的烷基（RA3）相同者。As an alkyl group, the same thing as the said linear alkyl group (RA1), a branched alkyl group (RA2), and a cyclic alkyl group (RA3) can be mentioned.
作為烯基，可列舉碳數2～10的烯基（RE1）等，可列舉：直鏈、分支、或環狀的烯基（乙烯基、1-丙烯基、2-丙烯基、1-丁烯-1-基、2-丁烯-1-基、2-甲基-2-丙烯基、1-環戊烯-1-基、1-環己烯-1-基、1-癸烯-1-基及降冰片烯基等）等。Examples of alkenyl groups include alkenyl groups having 2 to 10 carbon atoms (RE1) and the like, including linear, branched, or cyclic alkenyl groups (vinyl, 1-propenyl, 2-propenyl, 1-butanyl En-1-yl, 2-buten-1-yl, 2-methyl-2-propenyl, 1-cyclopenten-1-yl, 1-cyclohexen-1-yl, 1-decene- 1-base and norbornenyl, etc.) and so on.
作為芳基，可列舉與所述芳基（RA4）相同者。As an aryl group, the same thing as the said aryl group (RA4) is mentioned.
作為烷基羰基，可列舉碳數1～10（不包含羰基碳）的烷基羰基（RC1）等，可列舉直鏈或分支烷基羰基（乙醯基、丙醯基、丁醯基、2-甲基丙醯基、戊醯基、2-甲基丁醯基、3-甲基丁醯基、2,2-二甲基丙醯基、辛醯基、2-乙基己醯基及癸醯基等）等。Examples of the alkylcarbonyl group include alkylcarbonyl groups (RC1) having 1 to 10 carbon atoms (excluding the carbonyl carbon), etc., and examples include straight-chain or branched alkylcarbonyl groups (acetyl, propyl, butyryl, 2-methyl). Propyl propionyl, pentanoyl, 2-methylbutanoyl, 3-methylbutanoyl, 2,2-dimethyl propanoyl, octanoyl, 2-ethylhexyl and decanoyl, etc.).
作為芳基羰基，可列舉碳數6～10（不包含羰基碳）的芳基羰基（RC2）等，可列舉：苯甲醯基、萘甲醯基、4-甲苯甲醯基等。Examples of the arylcarbonyl group include an arylcarbonyl group (RC2) having 6 to 10 carbon atoms (excluding the carbonyl carbon), and the like, and examples include benzyl, naphthyl, 4-tolyl, and the like.
作為烷氧基羰基，可列舉碳數1～10（不包含羰基上的碳）的烷氧基羰基（RC3）等，可列舉直鏈或分支烷氧基羰基（甲氧基羰基、乙氧基羰基、丙氧基羰基、異丙氧基羰基、丁氧基羰基、異丁氧基羰基、第二丁氧基羰基、第三丁氧基羰基、第三戊氧基羰基、辛氧基羰基、2-乙基己氧基羰基及苄氧基羰基（Cbz）等）等。Examples of the alkoxycarbonyl group include an alkoxycarbonyl group (RC3) having 1 to 10 carbon atoms (excluding the carbon on the carbonyl group) and the like, and examples include linear or branched alkoxycarbonyl groups (methoxycarbonyl, ethoxy Carbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, third pentoxycarbonyl, octoxycarbonyl, 2-ethylhexyloxycarbonyl and benzyloxycarbonyl (Cbz) etc.).
作為芳氧基羰基，可列舉碳數6～10（不包含羰基上的碳）的芳氧基羰基（RC4）等，可列舉：苯氧基羰基、2-甲苯氧基羰基、4-甲苯氧基羰基、4-甲氧基苯氧基羰基、4-氯苯氧基羰基、1-萘氧基羰基、2-萘氧基羰基等。As the aryloxycarbonyl group, an aryloxycarbonyl group (RC4) having 6 to 10 carbon atoms (excluding the carbon on the carbonyl group) and the like can be mentioned. Examples include phenoxycarbonyl, 2-tolyloxycarbonyl, and 4-tolyloxy Carbonyl, 4-methoxyphenoxycarbonyl, 4-chlorophenoxycarbonyl, 1-naphthoxycarbonyl, 2-naphthoxycarbonyl, etc.
R3 與Ar1 鍵結而形成環的-C(O)-NR5 -的R5 並無特別限定，就合成容易性而言，較佳為烷基、芳基及磺醯基等，進而佳為碳數1～4的烷基、苯基、甲磺醯基、苯磺醯基、甲苯磺醯基、硝基苯磺醯基（nosyl）。R 5 of -C(O)-NR 5 -in which R 3 is bonded to Ar 1 to form a ring is not particularly limited. In terms of ease of synthesis, it is preferably an alkyl group, an aryl group, a sulfonyl group, etc. Preferred are alkyl groups having 1 to 4 carbon atoms, phenyl groups, methanesulfonyl groups, benzenesulfonyl groups, toluenesulfonyl groups, and nitrobenzenesulfonyl groups (nosyl).
通式（2）中，R4 為選自由氟烷基、氟芳基、氰基、硝基芳基所組成的群組中的拉電子性基，亦可具有取代基。In the general formula (2), R 4 is an electron withdrawing group selected from the group consisting of a fluoroalkyl group, a fluoroaryl group, a cyano group, and a nitroaryl group, and may have a substituent.
作為氟烷基，可列舉與所述直鏈氟烷基（RF1）、分支氟烷基（RF2）及環狀氟烷基（RF3）相同者。Examples of the fluoroalkyl group include the same ones as the linear fluoroalkyl group (RF1), the branched fluoroalkyl group (RF2), and the cyclic fluoroalkyl group (RF3).
作為氟芳基，可列舉與所述氟芳基（RF4）相同者。As the fluoroaryl group, the same as the above-mentioned fluoroaryl group (RF4) can be mentioned.
作為硝基芳基，可列舉碳數6～10的硝基芳基，可列舉：2-硝基苯基、3-硝基苯基、4-硝基苯基、2,4-二硝基苯基、4-硝基-1-萘基、2,4-二硝基-1-萘基、2,4,6-三硝基苯基等。Examples of the nitroaryl group include nitroaryl groups having 6 to 10 carbon atoms, such as 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, and 2,4-dinitrophenyl. Phenyl, 4-nitro-1-naphthyl, 2,4-dinitro-1-naphthyl, 2,4,6-trinitrophenyl, etc.
通式（1）或通式（2）中，Ar1 為芳基、或含雜原子的芳基，可與R3 鍵結而形成環。另外，亦可具有取代基。In the general formula (1) or (2), Ar 1 is an aryl group or a heteroatom-containing aryl group, which may be bonded to R 3 to form a ring. In addition, it may have a substituent.
作為芳基，可列舉碳數6～14的芳基（RA5）等，可列舉：苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、3-菲基、9-菲基、1-薁基、2-芴基、9',9'-二甲基-2-芴基及9',9'-雙三氟甲基-2-芴基等。As the aryl group, an aryl group having 6 to 14 carbon atoms (RA5) and the like can be cited, and examples include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 3-phenanthryl, 9-phenanthryl, 1-azulenyl, 2-fluorenyl, 9',9'-dimethyl-2-fluorenyl and 9',9'-bistrifluoromethyl-2-fluorene Base and so on.
作為含雜原子的芳基，可列舉碳數4～14的含雜原子的芳基（RA6）等，可列舉：含有選自由氧、氮及硫所組成的群組中的一個以上雜原子的呋喃基、吡咯基、苯硫基（thiophenyl）、苯並呋喃基、異苯並呋喃基、苯並吡喃基、呫噸基、噻噸基、啡噁噻基、二苯並-對碘苯腈基、噻蒽基、氧雜蒽酮基、硫雜蒽酮基、蒽醌基、二苯並呋喃基、芴基及香豆素基等。Examples of the heteroatom-containing aryl group include a C4-14 heteroatom-containing aryl group (RA6), etc. Examples include: those containing one or more heteroatoms selected from the group consisting of oxygen, nitrogen, and sulfur Furanyl, pyrrolyl, thiophenyl, benzofuranyl, isobenzofuranyl, benzopyranyl, xanthyl, thioxanthyl, phenoxathyl, dibenzo-p-iodobenzene Nitrile group, thioxanthone group, xanthone group, thioxanthone group, anthraquinone group, dibenzofuran group, fluoren group and coumarin group, etc.
作為Ar1 的取代基，可列舉與後述的（R6 ）中列舉的基相同者。Examples of the substituent of Ar 1 include the same groups as those exemplified in (R 6) described later.
通式（1）中，Ar1 可於所述芳基（RA5）及含雜原子的芳基（RA6）的芳香族碳上的適當位置與R3 鍵結而形成環狀結構。In the general formula (1), Ar 1 may be bonded to R 3 at an appropriate position on the aromatic carbon of the aryl group (RA5) and the heteroatom-containing aryl group (RA6) to form a cyclic structure.
通式（1）中，所述R2 ～R3 、Ar1 中，就原料的獲取性、合成容易性及穩定性的觀點而言，較佳為可列舉以下的（a）～（c）。In the general formula (1), among the R 2 to R 3 and Ar 1 , from the viewpoints of availability of raw materials, ease of synthesis, and stability, the following (a) to (c) are preferred .
（a）：通式（1）中，R2 為氧原子，R3 為與Ar1 鍵結而形成6員環的-C(O)-、-C(O)-CH2 -、-C(O)O-、-C(O)-NR5 -、或-C(O)S-，R5 為碳數1～4的烷基、苯基、甲磺醯基、苯磺醯基、甲苯磺醯基、或硝基苯磺醯基，Ar1 為碳數6～14的芳基、或碳數4～14的含雜原子的芳基。 較佳為可列舉下述通式（1）-a-1～通式（1）-a-4。進而佳為通式（1）-a-1、通式（1）-a-2、通式（1）-a-4。 式（1）-a-4中，多個R1 相互獨立。(A): In the general formula (1), R 2 is an oxygen atom, and R 3 is -C(O)-, -C(O)-CH 2 -, -C bonded to Ar 1 to form a 6-membered ring (O) O-, -C(O)-NR 5 -, or -C(O)S-, R 5 is an alkyl group with 1 to 4 carbons, phenyl, methanesulfonyl, benzenesulfonyl, Toluenesulfonyl or nitrobenzenesulfonyl, Ar 1 is an aryl group having 6 to 14 carbons, or a heteroatom-containing aryl group having 4 to 14 carbons. Preferably, the following general formula (1)-a-1 to general formula (1)-a-4 can be cited. Furthermore, general formula (1)-a-1, general formula (1)-a-2, and general formula (1)-a-4 are more preferable. In formula (1)-a-4, a plurality of R 1 are independent of each other.
[化3]
（b）：通式（1）中，R2 為氧原子，R3 為與Ar1 鍵結而形成5員環的-C(O)-、-SO2 -，Ar1 為碳數6～14的芳基、或碳數4～14的含雜原子的芳基。 較佳為可列舉下述通式（1）-b-1～通式（1）-b-6。進而佳為通式（1）-b-1、通式（1）-b-2、通式（1）-b-5、及通式（1）-b-6。 式（1）-b-6中，多個R1 相互獨立。(B): In the general formula (1), R 2 is an oxygen atom, R 3 is -C(O)- and -SO 2 -bonded to Ar 1 to form a 5-membered ring, and Ar 1 is carbon number 6 to 14 aryl group or C 4-14 heteroatom-containing aryl group. Preferably, the following general formula (1)-b-1 to general formula (1)-b-6 can be cited. Further preferred are general formula (1)-b-1, general formula (1)-b-2, general formula (1)-b-5, and general formula (1)-b-6. In formula (1)-b-6, a plurality of R 1 are independent of each other.
[化4]
（c）：通式（1）中，R2 為氧原子，R3 為碳數1～10的烷基、碳數6～10的芳基、碳數6～10（不包含羰基碳）的芳氧基、或碳數1～10（不包含羰基碳）的烷氧基羰基，Ar1 為碳數6～14的芳基、或碳數4～14的含雜原子的芳基。 較佳為可列舉下述通式（1）-c-1～通式（1）-c-4。進而佳為通式（1）-c-2。再者，R3 為選自所述基中的基。(C): In the general formula (1), R 2 is an oxygen atom, R 3 is an alkyl group with 1 to 10 carbons, an aryl group with 6 to 10 carbons, and those with 6 to 10 carbons (excluding carbonyl carbon) An aryloxy group or an alkoxycarbonyl group having 1 to 10 carbon atoms (excluding the carbonyl carbon), and Ar 1 is an aryl group having 6 to 14 carbon atoms or a heteroatom-containing aryl group having 4 to 14 carbon atoms. Preferably, the following general formula (1)-c-1 to general formula (1)-c-4 can be cited. Furthermore, the general formula (1)-c-2 is preferable. Furthermore, R 3 is a group selected from the group.
[化5]
通式（2）中，所述R4 、Ar1 中，就原料的獲取性、合成容易性及穩定性的觀點而言，較佳為可列舉以下（d）。In the general formula (2), among the above-mentioned R 4 and Ar 1 , from the viewpoints of availability of raw materials, ease of synthesis, and stability, the following (d) is preferable.
（d）：通式（2）中，R4 為碳數1～8的氟烷基、或氰基，Ar1 為碳數6～14的芳基、或碳數4～14的含雜原子的芳基。 較佳為可列舉下述通式（2）-1～通式（2）-5。再者，R4 為選自所述基中的基。(D): In the general formula (2), R 4 is a fluoroalkyl group with 1 to 8 carbons or a cyano group, and Ar 1 is an aryl group with 6 to 14 carbons, or a heteroatom-containing group with 4 to 14 carbons.的aryl. Preferably, the following general formula (2)-1 to general formula (2)-5 can be cited. Furthermore, R 4 is a group selected from the group.
[化6]
通式（1）-a-3中，G1 為與Ar1 鍵結而形成環的基，可列舉：-CH2 -、-O-、-NR8 -、或-S-等（R8 與所述R5 相同）。In the general formula (1)-a-3, G 1 is a group bonded to Ar 1 to form a ring, and examples thereof include: -CH 2 -, -O-, -NR 8 -, or -S- etc. (R 8 Same as R 5 ).
通式（1）-b-1中，G2 為與Ar1 鍵結而形成環的基，可列舉-C(O)-或-SO2 -等。In the general formula (1)-b-1, G 2 is a group that bonds with Ar 1 to form a ring, and examples thereof include -C(O)- or -SO 2 -.
通式（1）-b-5、通式（1）-c-4、通式（2）-4中，G3 與G4 為構成縮合環的基，將其組合表示為（G3 ,G4 ）時，可列舉：（-O-,-O-）、（-S-,-S-）、（-C(O)-,-O-）、（-C(O)-,-S-）、（-C(O)-,-C(O)-）、（-CH=CH-,單鍵）、（-O-,單鍵）、（-CH2 -,單鍵）或（-C(O)-,單鍵）等。In general formula (1)-b-5, general formula (1)-c-4, and general formula (2)-4, G 3 and G 4 are groups constituting a condensed ring, and their combination is expressed as (G 3 , G 4 ), include: (-O-, -O-), (-S-, -S-), (-C(O)-,-O-), (-C(O)-,- S-), (-C(O)-, -C(O)-), (-CH=CH-, single bond), (-O-, single bond), (-CH 2 -, single bond) or (-C(O)-, single bond) etc.
通式（1）-b-6中，G5 為將兩個芳香環鍵結的基或單鍵，可列舉：-CH2 -、-C(O)-、-O-、-CMe2 -、-C(CF3 )2 -、-SO2 -、或單鍵等，包含於後述的（R6 ）中。In the general formula (1)-b-6, G 5 is a group or a single bond that bonds two aromatic rings, and examples include: -CH 2 -, -C(O)-, -O-, -CMe 2- , -C(CF 3 ) 2 -, -SO 2 -, or a single bond, etc., are included in (R 6 ) described later.
所述通式中，(R6 )n 為Ar1 上的任意位置的相互獨立的n個（n為0～8的整數）取代基，可相互鍵結而形成環，可列舉：烷基、烯基、炔基、芳基、含雜原子的芳基、烷氧基、烷硫基、烷基羰基、芳基羰基、烷氧基羰基、芳氧基羰基、烷基羰氧基、芳基羰氧基、碳酸烷基酯基、碳酸芳基酯基、烷基磺醯基、芳基磺醯基、鹵素原子及下述式所表示的取代基等。In the general formula, (R 6 ) n represents n mutually independent substituents (n is an integer from 0 to 8) at any position on Ar 1 , which may be bonded to each other to form a ring, and examples include: alkyl, Alkenyl, alkynyl, aryl, heteroatom-containing aryl, alkoxy, alkylthio, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylcarbonyloxy, aryl A carbonyloxy group, an alkyl carbonate group, an aryl carbonate group, an alkylsulfonyl group, an arylsulfonyl group, a halogen atom, a substituent represented by the following formula, and the like.
[化7]
[式中，R1 、G5 與所述相同。R7 並無特別限定，為相互獨立的烷基或芳基，可具有取代基亦可相互鍵結而形成環，較佳為碳數1～4的烷基、苯基及相互鍵結的伸丙基、伸丁基][In the formula, R 1 and G 5 are the same as described above. R 7 is not particularly limited. It is an independent alkyl group or an aryl group, which may have a substituent or may be bonded to each other to form a ring, preferably an alkyl group having 1 to 4 carbons, a phenyl group, and a mutually bonded extension. Propyl, butylated]
作為（R6 ）中的烷基，可列舉與所述直鏈烷基（RA1）、分支烷基（RA2）、環狀烷基（RA3）相同者，就原料的獲取性、合成的容易性的觀點而言，較佳為碳數1～8的直鏈、分支、或環狀的烷基，進而佳為甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、戊基、己基、2-乙基己基、環戊基及環己基。Examples of the alkyl group in (R 6 ) include the same as the linear alkyl group (RA1), branched alkyl group (RA2), and cyclic alkyl group (RA3). The availability of raw materials and ease of synthesis From the viewpoint of, it is preferably a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and the first Tributyl, pentyl, hexyl, 2-ethylhexyl, cyclopentyl and cyclohexyl.
作為（R6 ）中的烯基，可列舉與所述烯基（RE1）相同者。Examples of the alkenyl group in (R 6 ) include the same as the alkenyl group (RE1) described above.
作為（R6 ）中的炔基，可列舉碳數2～10的炔基（RY1）等，可列舉直鏈、分支、或環狀的炔基（乙炔基、1-丙炔-1-基、2-丙炔-1-基、1-丁炔-1-基、2-丁炔-1-基、3-丁炔-1-基、1-戊炔-1-基、2-戊炔-1-基、3-戊炔-1-基、4-戊炔-1-基、1-己炔-1-基、3-甲基-1-丁炔-1-基、1-甲基-2-丁炔-1-基、1-甲基-3-丁炔-1-基、1,1-二甲基-2-丙炔-1-基、1-環辛炔-1-基及2-苯基乙炔-1-基等）等，就合成的容易性的觀點而言，較佳為1-丙炔-1-基、1-丁炔-1-基、1-戊炔-1-基、2-苯基乙炔-1-基。Examples of the alkynyl group in (R 6 ) include an alkynyl group having 2 to 10 carbon atoms (RY1), etc., and examples include linear, branched, or cyclic alkynyl groups (ethynyl, 1-propyn-1-yl) , 2-propyn-1-yl, 1-butyn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 2-pentyne -1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-hexyn-1-yl, 3-methyl-1-butyn-1-yl, 1-methyl -2-butyn-1-yl, 1-methyl-3-butyn-1-yl, 1,1-dimethyl-2-propyn-1-yl, 1-cyclooctyn-1-yl And 2-phenylethyn-1-yl etc.). From the viewpoint of ease of synthesis, 1-propyn-1-yl, 1-butyn-1-yl, 1-pentyne- 1-yl, 2-phenylethyn-1-yl.
作為（R6 ）中的芳基，可列舉與所述芳基（RA4）相同者。The aryl group in (R 6 ) may be the same as the aryl group (RA4) described above.
作為（R6 ）中的含雜原子的芳基，可列舉碳數4～10的含雜原子的芳基（RA7）等，可列舉於芳香環上含有選自由氧、氮及硫所組成的群組中的一個以上雜原子的呋喃基、吡咯基、苯硫基、苯並呋喃基、異苯並呋喃基及苯並吡喃基等。Examples of the heteroatom-containing aryl group in (R 6 ) include a C 4-10 heteroatom-containing aryl group (RA7), etc., and examples include those containing oxygen, nitrogen, and sulfur on the aromatic ring. Furanyl, pyrrolyl, thiophenyl, benzofuranyl, isobenzofuranyl, benzopyranyl, etc. of one or more heteroatoms in the group.
作為（R6 ）中的烷氧基，可列舉碳數1～10的烷氧基（RC5）等，為直鏈、分支或環狀烷氧基（甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第二丁氧基、第三丁氧基、己氧基、苯氧基、甲苯氧基、苄氧基、癸氧基、萘氧基、甲氧基甲氧基、乙氧基甲氧基、2-甲氧基乙氧基、1-甲氧基乙氧基、苄氧基甲氧基、三甲基矽氧基、三乙基矽氧基、三異丙基矽氧基及第三丁基二甲基矽氧基等）等，就合成的容易性的觀點而言，較佳為甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第三丁氧基、戊氧基、己氧基、苄氧基及第三丁基二甲基矽氧基。Examples of the alkoxy group in (R 6 ) include alkoxy groups having 1 to 10 carbon atoms (RC5), etc., which are linear, branched or cyclic alkoxy groups (methoxy, ethoxy, propoxy) , Isopropoxy, butoxy, isobutoxy, second butoxy, tertiary butoxy, hexyloxy, phenoxy, tolyloxy, benzyloxy, decyloxy, naphthoxy , Methoxymethoxy, ethoxymethoxy, 2-methoxyethoxy, 1-methoxyethoxy, benzyloxymethoxy, trimethylsiloxy, triethyl Siloxy, triisopropylsiloxy, tert-butyldimethylsiloxy, etc.), etc., from the standpoint of ease of synthesis, preferably methoxy, ethoxy, propoxy , Isopropoxy, butoxy, isobutoxy, tertiary butoxy, pentoxy, hexyloxy, benzyloxy and tertiary butyldimethylsiloxy.
作為（R6 ）中的烷硫基，可列舉碳數1～10的烷硫基（RC6）等，為直鏈、分支或環狀烷硫基（甲硫基、乙硫基、丙硫基、異丙硫基、丁硫基、異丁硫基、第二丁硫基、第三丁硫基、戊硫基、異戊硫基、新戊硫基、第三戊硫基、苯硫基（phenylthio）、甲苯硫基、苄硫基、辛硫基、癸硫基及萘硫基等）等，就合成的容易性的觀點而言，較佳為甲硫基、乙硫基、丙硫基、異丙硫基、丁硫基、苄硫基、辛硫基、苯硫基。Examples of the alkylthio group in (R 6 ) include alkylthio groups having 1 to 10 carbon atoms (RC6), etc., which are linear, branched or cyclic alkylthio groups (methylthio, ethylthio, propylthio) , Isopropylthio, butylthio, isobutylthio, second butylthio, third butylthio, pentylthio, isopentylthio, neopentylthio, third pentylthio, phenylthio (Phenylthio), toluenethio, benzylthio, octylthio, decylthio, naphthylthio, etc.), from the viewpoint of ease of synthesis, methylthio, ethylthio, propylthio Group, isopropylthio, butylthio, benzylthio, octylthio, phenylthio.
作為（R6 ）中的烷基羰基，可列舉與所述烷基羰基（RC1）相同者，就合成的容易性的觀點而言，較佳為乙醯基、丙醯基、丁醯基、2-甲基丁醯基及2,2-二甲基丙醯基。Examples of the alkylcarbonyl group in (R 6 ) include the same as the alkylcarbonyl group (RC1). From the viewpoint of ease of synthesis, acetyl, propionyl, butyryl, 2- Methylbutyryl and 2,2-dimethylpropionyl.
作為（R6 ）中的芳基羰基，可列舉與所述芳基羰基（RC2）相同者。The arylcarbonyl group in (R 6 ) may be the same as the arylcarbonyl group (RC2) described above.
作為（R6 ）中的烷氧基羰基，可列舉與所述烷氧基羰基（RC3）相同者，就合成的容易性的觀點而言，較佳為分支烷氧基羰基，特佳為異丙氧基羰基、第二丁氧基羰基、第三丁氧基羰基、第三戊氧基羰基、及2-乙基己氧基羰基。Examples of the alkoxycarbonyl group in (R 6 ) include the same as the alkoxycarbonyl group (RC3). From the standpoint of ease of synthesis, a branched alkoxycarbonyl group is preferred, and isoforms are particularly preferred. Propoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, third pentoxycarbonyl, and 2-ethylhexyloxycarbonyl.
作為（R6 ）中的芳氧基羰基，可列舉與所述芳氧基羰基（RC4）相同者。Examples of the aryloxycarbonyl group in (R 6 ) include the same as the aryloxycarbonyl group (RC4) described above.
作為（R6 ）中的烷基羰氧基，可列舉碳數1～10（不包含羰基上的碳）的烷基羰氧基（RC7）等，為直鏈或分支烷基羰氧基（乙醯氧基、乙基羰氧基、丙基羰氧基、異丙基羰氧基、丁基羰氧基、異丁基羰氧基、第二丁基羰氧基、第三丁基羰氧基、辛基羰氧基、2-乙基己基羰氧基、癸基羰氧基及苄基羰氧基等）等，就原料的獲取性的觀點而言，較佳為乙醯氧基、乙基羰氧基、丙基羰氧基、異丙基羰氧基、丁基羰氧基、異丁基羰氧基、第二丁基羰氧基、第三丁基羰氧基、戊基羰氧基、己基羰氧基及2-乙基己基羰氧基。Examples of the alkylcarbonyloxy group in (R 6 ) include alkylcarbonyloxy group (RC7) having 1 to 10 carbon atoms (excluding the carbon on the carbonyl group) and the like, which are linear or branched alkylcarbonyloxy groups ( Acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, second butylcarbonyloxy, tertiary butylcarbonyl Oxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, decylcarbonyloxy group, benzylcarbonyloxy group, etc.). From the viewpoint of the availability of raw materials, acetyloxy group is preferred. , Ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, second butylcarbonyloxy, tertiary butylcarbonyloxy, pentyl Carbonyloxy, hexylcarbonyloxy and 2-ethylhexylcarbonyloxy.
作為（R6 ）中的芳基羰氧基，可列舉碳數6～10（不包含羰基上的碳）的芳基羰氧基（RC8）等，可列舉：苯基羰氧基、1-萘基羰氧基、2-萘基羰氧基、1-薁基羰氧基、2-甲苯基羰氧基、3-甲苯基羰氧基、4-甲苯基羰氧基、2-氯苯基羰氧基、3-氯苯基羰氧基、4-氯苯基羰氧基、2,4-二甲苯基羰氧基、2,6-二甲苯基羰氧基、3,5-二甲苯基羰氧基、2,4,6-均三甲苯基羰氧基、3,5-雙三氟甲基苯基羰氧基及五氟苯基羰氧基等。Examples of the arylcarbonyloxy group in (R 6 ) include arylcarbonyloxy (RC8) having 6 to 10 carbon atoms (excluding the carbon on the carbonyl group) and the like. Examples include phenylcarbonyloxy, 1- Naphthylcarbonyloxy, 2-naphthylcarbonyloxy, 1-azulenylcarbonyloxy, 2-tolylcarbonyloxy, 3-tolylcarbonyloxy, 4-tolylcarbonyloxy, 2-chlorobenzene Carbonyloxy, 3-chlorophenylcarbonyloxy, 4-chlorophenylcarbonyloxy, 2,4-xylylcarbonyloxy, 2,6-xylylcarbonyloxy, 3,5-di Tolylcarbonyloxy, 2,4,6-mesitylcarbonyloxy, 3,5-bistrifluoromethylphenylcarbonyloxy and pentafluorophenylcarbonyloxy, etc.
作為（R6 ）中的碳酸烷基酯基，可列舉碳數1～10（不包含羰基上的碳）的碳酸烷基酯基（RC9）等，為碳酸甲酯基、碳酸乙酯基、碳酸丙酯基、碳酸2-丙酯基、碳酸丁酯基、碳酸2-丁酯基、碳酸異丁酯基、碳酸第三丁酯基、碳酸第三戊酯基、碳酸苄酯基、碳酸2-乙基己酯基及碳酸薄荷酯基等，就原料的獲取性的觀點而言，較佳為碳酸甲酯基、碳酸乙酯基、碳酸丙酯基、碳酸異丙酯基、碳酸丁酯基、碳酸異丁酯基、碳酸第三丁酯基、碳酸第三戊酯基、碳酸2-乙基己酯基。Examples of the alkyl carbonate group in (R 6 ) include an alkyl carbonate group (RC9) having 1 to 10 carbon atoms (excluding the carbon on the carbonyl group) and the like, such as methyl carbonate group, ethyl carbonate group, Propyl carbonate, 2-propyl carbonate, butyl carbonate, 2-butyl carbonate, isobutyl carbonate, tertiary butyl carbonate, tertiary amyl carbonate, benzyl carbonate, carbonic acid From the viewpoint of the availability of raw materials, 2-ethylhexyl ester group and menthyl carbonate group are preferably methyl carbonate group, ethyl carbonate group, propyl carbonate group, isopropyl carbonate group, and butyl carbonate group. Ester group, isobutyl carbonate group, tertiary butyl carbonate group, tertiary amyl carbonate group, 2-ethylhexyl carbonate group.
作為（R6 ）中的碳酸芳基酯基，可列舉碳數6～10（不包含羰基上的碳）的碳酸芳基酯基（RC10）等，可列舉：碳酸苯酯基、碳酸1-萘酯基、碳酸2-萘酯基、碳酸1-薁酯基、碳酸2-甲苯酯基、碳酸3-甲苯酯基、碳酸4-甲苯酯基、碳酸2-氯苯酯基、碳酸3-氯苯酯基、碳酸4-氯苯酯基、碳酸2,4-二甲苯酯基、碳酸2,6-二甲苯酯基、碳酸3,5-二甲苯酯基、碳酸2,4,6-均三甲苯酯基、碳酸3,5-雙三氟甲基苯酯基及碳酸五氟苯酯基等。Examples of the aryl carbonate group in (R 6 ) include an aryl carbonate group (RC10) having 6 to 10 carbon atoms (excluding the carbon on the carbonyl group) and the like, and examples include: phenyl carbonate group, 1-carbonic acid 1- Naphthyl carbonate, 2-naphthyl carbonate, 1-azulene carbonate, 2-cresyl carbonate, 3-cresyl carbonate, 4-cresyl carbonate, 2-chlorophenyl carbonate, 3-cresyl carbonate Chlorophenyl ester group, 4-chlorophenyl carbonate group, 2,4-xylenyl carbonate group, 2,6-xylenyl carbonate group, 3,5-xylenyl carbonate group, 2,4,6-carbonic acid group Mesitylene carbonate, 3,5-bistrifluoromethyl phenyl carbonate and pentafluorophenyl carbonate, etc.
作為（R6 ）中的烷基磺醯基，可列舉碳數1～10的烷基磺醯基（RC11）等，可列舉直鏈或分支烷基磺醯基（甲基磺醯基、乙基磺醯基、丙基磺醯基、異丙基磺醯基、丁基磺醯基、異丁基磺醯基、第二丁基磺醯基、第三丁基磺醯基、戊基磺醯基、異戊基磺醯基、新戊基磺醯基、第三戊基磺醯基、辛基磺醯基、癸基磺醯基、三氟甲烷磺醯基、五氟乙烷磺醯基、九氟丁烷磺醯基及全氟辛烷磺醯基等）等，就原料的獲取性的觀點而言，較佳為甲基磺醯基、乙基磺醯基、丁基磺醯基、三氟甲烷磺醯基、九氟丁烷磺醯基及全氟辛烷磺醯基。Examples of the alkylsulfonyl group in (R 6 ) include alkylsulfonyl groups having 1 to 10 carbon atoms (RC11), etc., and linear or branched alkylsulfonyl groups (methylsulfonyl, ethyl Sulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, second butylsulfonyl, tertiary butylsulfonyl, pentylsulfonyl Acetyl, isopentylsulfonyl, neopentylsulfonyl, tertiary pentylsulfonyl, octylsulfonyl, decylsulfonyl, trifluoromethanesulfonyl, pentafluoroethanesulfonyl Sulfonyl, nonafluorobutanesulfonyl, perfluorooctanesulfonyl, etc.). From the viewpoint of the availability of raw materials, methylsulfonyl, ethylsulfonyl, and butylsulfonyl are preferred. Sulfonyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl and perfluorooctanesulfonyl.
作為（R6 ）中的芳基磺醯基，可列舉碳數6～10的芳基磺醯基（RC12）（苯磺醯基、2-甲苯磺醯基、4-甲苯磺醯基、2-硝基苯磺醯基、4-硝基苯磺醯基、2,4-二硝基苯磺醯基、萘基磺醯基、五氟苯磺醯基及3,5-雙三氟甲基苯基等）等，就原料的獲取性的觀點而言，較佳為苯磺醯基、4-甲苯磺醯基、2-硝基苯磺醯基及五氟苯磺醯基。Examples of the arylsulfonyl group in (R 6 ) include arylsulfonyl groups having 6 to 10 carbon atoms (RC12) (benzenesulfonyl, 2-toluenesulfonyl, 4-toluenesulfonyl, 2 -Nitrobenzenesulfonyl, 4-nitrobenzenesulfonyl, 2,4-dinitrobenzenesulfonyl, naphthylsulfonyl, pentafluorobenzenesulfonyl and 3,5-bistrifluoromethane From the viewpoint of availability of raw materials, benzenesulfonyl, 4-toluenesulfonyl, 2-nitrobenzenesulfonyl, and pentafluorobenzenesulfonyl are preferred from the viewpoint of availability of raw materials.
作為（R6 ）中的鹵素原子，可列舉：氟原子、氯原子、溴原子及碘原子等，就原料的獲取性及合成的容易性的觀點而言，較佳為氟原子、氯原子及溴原子。Examples of the halogen atom in (R 6 ) include fluorine atom, chlorine atom, bromine atom and iodine atom. From the viewpoint of availability of raw materials and ease of synthesis, fluorine atom, chlorine atom and Bromine atom.
本發明的磺醯胺化合物（A）的合成方法只要可合成目標物，則並無特別限定，例如通式（1）的化合物可利用以下敘述的製造方法來製造。The method for synthesizing the sulfonamide compound (A) of the present invention is not particularly limited as long as the target product can be synthesized. For example, the compound of the general formula (1) can be produced by the production method described below.
[化8]
所述反應式中，R1 ～R3 、Ar1 及Rf 與通式（1）中的定義相同。 第一階段的反應是於有機溶劑（甲苯、乙酸丁脂、乙腈、二甲基甲醯胺（dimethyl formamide，DMF）、二甲基乙醯胺（dimethyl acetamide，DMAc）、二氯甲烷、氯仿、苯並三氟化物等）或水中、-78℃～回流條件下，使前驅物（P1）、R1 SO2 X所表示的磺酸鹵化物等價體、鹼（碳酸氫鈉、碳酸鉀、氫氧化鈉、氫氧化鉀、吡啶、氯吡啶、二氯吡啶、二甲吡啶、2,6-二第三丁基吡啶、三乙基胺、乙基二異丙基胺、二氮雜雙環十一烯（DBU）、四甲基哌啶（tetramethyl piperidine，TMP）、四甲基胍（tetramethyl guanidine，TMG）、六甲基二矽氮烷（hexamethyl disilazane，HMDS）、第三丁醇鉀、二異丙基醯胺鋰、雙六甲基二矽氮烷鈉等）反應5分鐘～3小時。於反應完成後，過濾析出的固體或利用適當的溶劑進行萃取，藉此獲得前驅物（P2）。（P2）視需要可進行再結晶或利用溶劑進行清洗而加以純化。亦可根據情況於未純化的狀態下繼續進行反應。In the reaction formula, R 1 to R 3 , Ar 1 and R f have the same definitions as in the general formula (1). The first stage of the reaction is in organic solvents (toluene, butyl acetate, acetonitrile, dimethyl formamide (DMF), dimethyl acetamide (DMAc), dichloromethane, chloroform, Benzotrifluoride, etc.) or in water, at -78°C to reflux, make the precursor (P1), the sulfonic acid halide equivalent represented by R 1 SO 2 X, alkali (sodium bicarbonate, potassium carbonate, Sodium hydroxide, potassium hydroxide, pyridine, chloropyridine, dichloropyridine, lutidine, 2,6-di-tertiary butyl pyridine, triethylamine, ethyl diisopropylamine, diazabicyclo ten Monoene (DBU), tetramethyl piperidine (TMP), tetramethyl guanidine (TMG), hexamethyl disilazane (HMDS), potassium tertiary butoxide, two Lithium isopropylamide, sodium bishexamethyldisilazane, etc.) react for 5 minutes to 3 hours. After the reaction is completed, the precipitated solid is filtered or extracted with an appropriate solvent, thereby obtaining the precursor (P2). (P2) Purification can be carried out by recrystallization or washing with solvent as needed. It is also possible to continue the reaction in an unpurified state according to the situation.
第二階段的反應是於有機溶劑（甲苯、乙酸丁脂、乙腈、DMF、DMAc、二氯甲烷、氯仿、苯並三氟化物等）中、-78℃～30℃下，使前驅物（P2）、Rf SO2 X所表示的磺酸鹵化物等價體、鹼（碳酸氫鈉、碳酸鉀、吡啶、氯吡啶、二氯吡啶、2,6-二第三丁基吡啶、三乙基胺、乙基二異丙基胺、TMP、TMG、HMDS、第三丁醇鉀、二異丙基醯胺鋰、雙六甲基二矽氮烷鈉等）反應5分鐘～3小時。於反應完成後，過濾析出的固體或利用適當的溶劑進行萃取，並蒸餾去除揮發成分，藉此獲得作為固體的通式（1）的磺醯胺化合物（A）。所獲得的固體視需要可藉由管柱層析法、利用有機溶劑進行清洗、再結晶等進行純化。The second stage of the reaction is to make the precursor (P2) in an organic solvent (toluene, butyl acetate, acetonitrile, DMF, DMAc, dichloromethane, chloroform, benzotrifluoride, etc.) at -78℃～30℃. ), sulfonic acid halide equivalents represented by R f SO 2 X, alkalis (sodium bicarbonate, potassium carbonate, pyridine, chloropyridine, dichloropyridine, 2,6-di-tert-butylpyridine, triethyl Amine, ethyldiisopropylamine, TMP, TMG, HMDS, potassium tert-butoxide, lithium diisopropylamide, sodium bishexamethyldisilazane, etc.) react for 5 minutes to 3 hours. After the reaction is completed, the precipitated solid is filtered or extracted with an appropriate solvent, and volatile components are distilled off to obtain the sulfonamide compound (A) of the general formula (1) as a solid. If necessary, the obtained solid can be purified by column chromatography, washing with an organic solvent, recrystallization, and the like.
另外，例如通式（2）的化合物可利用以下敘述的製造方法來製造。In addition, for example, the compound of the general formula (2) can be produced by the production method described below.
[化9]
所述反應式中，R1 、R4 、Ar1 及Rf 與通式（2）中的定義相同。 第一階段的反應是於有機溶劑（甲苯、乙酸丁脂、乙腈、乙醇、異丙醇（isopropyl alcohol，IPA）、DMF、DMAc、二氯甲烷、氯仿、苯並三氟化物等）或水中、-78℃～回流條件下，使前驅物（P3）與R1 SO2 NHNH2 所表示的磺醯肼（sulfonyl hydrazide）反應5分鐘～3小時。於反應完成後，過濾析出的固體或利用適當的溶劑進行萃取，藉此獲得前驅物（P4）。前驅物（P4）視需要可進行再結晶或利用溶劑進行清洗而加以純化。In the reaction formula, R 1 , R 4 , Ar 1 and R f have the same definitions as in the general formula (2). The first stage of the reaction is in organic solvents (toluene, butyl acetate, acetonitrile, ethanol, isopropyl alcohol (IPA), DMF, DMAc, dichloromethane, chloroform, benzotrifluoride, etc.) or water, Under -78°C to reflux conditions, react the precursor (P3) with sulfonyl hydrazide represented by R 1 SO 2 NHNH 2 for 5 minutes to 3 hours. After the reaction is completed, the precipitated solid is filtered or extracted with an appropriate solvent to obtain the precursor (P4). The precursor (P4) can be purified by recrystallization or solvent cleaning as needed.
第二階段的反應是於有機溶劑（甲苯、乙酸丁脂、乙腈、DMF、DMAc、二氯甲烷、氯仿、苯並三氟化物等）中、-78℃～30℃下，使前驅物（P4）、Rf SO2 X所表示的磺酸鹵化物等價體、鹼（碳酸氫鈉、碳酸鉀、吡啶、氯吡啶、二氯吡啶、2,6-二第三丁基吡啶、三乙基胺、乙基二異丙基胺、TMP、TMG、HMDS、第三丁醇鉀、二異丙基醯胺鋰、雙六甲基二矽氮烷鈉等）反應5分鐘～3小時。於反應完成後，過濾析出的固體或利用適當的溶劑進行萃取，並蒸餾去除揮發成分，藉此獲得作為固體的通式（2）的磺醯胺化合物（A）。所獲得的固體視需要可藉由管柱層析法、利用有機溶劑進行清洗、再結晶等進行純化。The second stage of the reaction is to make the precursor (P4) in an organic solvent (toluene, butyl acetate, acetonitrile, DMF, DMAc, dichloromethane, chloroform, benzotrifluoride, etc.) at -78℃～30℃. ), sulfonic acid halide equivalents represented by R f SO 2 X, alkalis (sodium bicarbonate, potassium carbonate, pyridine, chloropyridine, dichloropyridine, 2,6-di-tert-butylpyridine, triethyl Amine, ethyldiisopropylamine, TMP, TMG, HMDS, potassium tert-butoxide, lithium diisopropylamide, sodium bishexamethyldisilazane, etc.) react for 5 minutes to 3 hours. After the reaction is completed, the precipitated solid is filtered or extracted with an appropriate solvent, and volatile components are distilled off, thereby obtaining the sulfonamide compound (A) of the general formula (2) as a solid. If necessary, the obtained solid can be purified by column chromatography, washing with an organic solvent, recrystallization, and the like.
本發明的磺醯胺化合物（A）藉由光照射而產生超強酸，故適合作為光微影用樹脂組成物（抗蝕劑）用的非離子系光酸產生劑。The sulfonamide compound (A) of the present invention generates a super acid by light irradiation, and is therefore suitable as a nonionic photoacid generator for a resin composition (resist) for photolithography.
為了容易溶解於抗蝕劑材料中，含有本發明的磺醯胺化合物（A）的非離子系光酸產生劑（B）亦可預先溶解於不阻礙反應的溶劑中。In order to be easily dissolved in the resist material, the nonionic photoacid generator (B) containing the sulfonamide compound (A) of the present invention may be dissolved in a solvent that does not inhibit the reaction in advance.
作為容易溶解於抗蝕劑材料中的溶劑，可列舉：碳酸酯（碳酸伸丙酯、碳酸伸乙酯、碳酸1,2-伸丁酯、碳酸二甲酯及碳酸二乙酯等）、酯（乙酸乙酯、乳酸乙酯、β-丙內酯、β-丁內酯、γ-丁內酯、δ-戊內酯及ε-己內酯等）、醚（乙二醇單甲醚、丙二醇單***、二乙二醇單丁醚、二丙二醇二甲醚、三乙二醇二***、三丙二醇二丁醚等）、及醚酯（乙二醇單甲醚乙酸酯、丙二醇單***乙酸酯及二乙二醇單丁醚乙酸酯等）等。Examples of solvents that are easy to dissolve in the resist material include carbonates (propylene carbonate, ethylene carbonate, 1,2-butyl carbonate, dimethyl carbonate, diethyl carbonate, etc.), esters (Ethyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone, etc.), ether (ethylene glycol monomethyl ether, Propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.), and ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether) Acetate and diethylene glycol monobutyl ether acetate, etc.).
於使用溶劑的情況下，相對於本發明的非離子系光酸產生劑（B）100重量份，溶劑的使用比例較佳為15重量份～1000重量份，進而佳為30重量份～500重量份。In the case of using a solvent, relative to 100 parts by weight of the nonionic photoacid generator (B) of the present invention, the use ratio of the solvent is preferably 15 parts by weight to 1000 parts by weight, and more preferably 30 parts by weight to 500 parts by weight Copies.
本發明的光微影用樹脂組成物（Q）包含非離子系光酸產生劑（B）作為必需成分，因此藉由進行紫外線照射及曝光後加熱（PEB），曝光部與未曝光部對顯影液的溶解性產生差異。非離子系光酸產生劑（B）亦可單獨使用一種，或者將兩種以上組合而使用，亦可與鋶鹽等離子系光酸產生劑併用。 作為光微影用樹脂組成物（Q），可列舉負型化學增幅樹脂（QN）與非離子系光酸產生劑（B）的混合物；以及正型化學增幅樹脂（QP）與非離子系光酸產生劑（B）的混合物。The resin composition (Q) for photolithography of the present invention contains a non-ionic photoacid generator (B) as an essential component. Therefore, by performing ultraviolet radiation and post-exposure heating (PEB), the exposed and unexposed parts are developed The solubility of the liquid is different. The nonionic photoacid generator (B) may be used alone or in combination of two or more, or it may be used in combination with a sulfonate ion-based photoacid generator. As the resin composition (Q) for photolithography, a mixture of a negative chemically amplified resin (QN) and a nonionic photoacid generator (B); and a positive chemically amplified resin (QP) and a nonionic optical A mixture of acid generators (B).
作為負型化學增幅樹脂（QN），包括含酚性羥基的樹脂（QN1）與交聯劑（QN2）。As a negative chemically amplified resin (QN), it includes a phenolic hydroxyl-containing resin (QN1) and a crosslinking agent (QN2).
作為含酚性羥基的樹脂（QN1），若為含有酚性羥基的樹脂，則並無特別限制，例如可使用：酚醛清漆樹脂、聚羥基苯乙烯、羥基苯乙烯的共聚物、羥基苯乙烯與苯乙烯的共聚物、羥基苯乙烯、苯乙烯及(甲基)丙烯酸衍生物的共聚物、苯酚/苯二甲醇縮合樹脂、甲酚/苯二甲醇縮合樹脂、含有酚性羥基的聚醯亞胺、含有酚性羥基的聚醯胺酸、苯酚-二環戊二烯縮合樹脂。該些中，較佳為酚醛清漆樹脂、聚羥基苯乙烯、羥基苯乙烯的共聚物、羥基苯乙烯與苯乙烯的共聚物、羥基苯乙烯、苯乙烯及(甲基)丙烯酸衍生物的共聚物、苯酚/苯二甲醇縮合樹脂。再者，該些含酚性羥基的樹脂（QN1）可單獨使用一種，亦可將兩種以上混合而使用。The phenolic hydroxyl-containing resin (QN1) is not particularly limited as long as it is a phenolic hydroxyl-containing resin. For example, novolac resins, polyhydroxystyrene, copolymers of hydroxystyrene, hydroxystyrene and Copolymers of styrene, hydroxystyrene, copolymers of styrene and (meth)acrylic acid derivatives, phenol/benzenedimethanol condensation resin, cresol/benzenedimethanol condensation resin, polyimide containing phenolic hydroxyl group , Polyamide acid containing phenolic hydroxyl group, phenol-dicyclopentadiene condensation resin. Among these, preferred are novolac resins, polyhydroxystyrene, copolymers of hydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene, and (meth)acrylic acid derivatives. , Phenol/benzenedimethanol condensation resin. In addition, these phenolic hydroxyl group-containing resins (QN1) may be used individually by 1 type, and may mix and use 2 or more types.
所述酚醛清漆樹脂例如可藉由在觸媒的存在下使酚類與醛類進行縮合而獲得。 作為所述酚類，例如可列舉：苯酚、鄰甲酚、間甲酚、對甲酚、鄰乙基苯酚、間乙基苯酚、對乙基苯酚、鄰丁基苯酚、間丁基苯酚、對丁基苯酚、2,3-二甲酚、2,4-二甲酚、2,5-二甲酚、2,6-二甲酚、3,4-二甲酚、3,5-二甲酚、2,3,5-三甲基苯酚、3,4,5-三甲基苯酚、鄰苯二酚、間苯二酚、五倍子酚、1-萘酚、2-萘酚。 另外，作為所述醛類，可列舉：甲醛、對甲醛、乙醛、苯甲醛等。The novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst. As the phenols, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-cresol Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-dimethylphenol Phenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, gallic phenol, 1-naphthol, 2-naphthol. Moreover, as said aldehydes, formaldehyde, p-formaldehyde, acetaldehyde, benzaldehyde, etc. are mentioned.
作為所述酚醛清漆樹脂，例如可列舉：苯酚/甲醛縮合酚醛清漆樹脂、甲酚/甲醛縮合酚醛清漆樹脂、苯酚/萘酚/甲醛縮合酚醛清漆樹脂。Examples of the novolak resin include phenol/formaldehyde condensation novolak resin, cresol/formaldehyde condensation novolak resin, and phenol/naphthol/formaldehyde condensation novolak resin.
另外，於所述含酚性羥基的樹脂（QN1）中亦可含有酚性低分子化合物作為成分的一部分。 作為所述酚性低分子化合物，例如可列舉：4,4'-二羥基二苯基甲烷、4,4'-二羥基二苯基醚、三(4-羥基苯基)甲烷、1,1-雙(4-羥基苯基)-1-苯基乙烷、三(4-羥基苯基)乙烷、1,3-雙[1-(4-羥基苯基)-1-甲基乙基]苯、1,4-雙[1-(4-羥基苯基)-1-甲基乙基]苯、4,6-雙[1-(4-羥基苯基)-1-甲基乙基]-1,3-二羥基苯、1,1-雙(4-羥基苯基)-1-[4-〔1-(4-羥基苯基)-1-甲基乙基〕苯基]乙烷、1,1,2,2-四(4-羥基苯基)乙烷、4,4'-{1-[4-〔1-(4-羥基苯基)-1-甲基乙基〕苯基]亞乙基}雙酚。該些酚性低分子化合物可單獨使用一種，亦可將兩種以上混合而使用。In addition, the phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low-molecular compound as a part of the component. Examples of the phenolic low-molecular compound include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1 -Bis(4-hydroxyphenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl ]Benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl ]-1,3-Dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-〔1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethyl Alkane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, 4,4'-{1-[4-〔1-(4-hydroxyphenyl)-1-methylethyl] Phenyl] ethylene} bisphenol. These phenolic low-molecular-weight compounds may be used alone or in combination of two or more kinds.
於將含酚性羥基的樹脂（QN1）設為100重量%的情況下，該酚性低分子化合物於含酚性羥基的樹脂（QN1）中的含有比例較佳為40重量%以下，進而佳為1重量%～30重量%。When the phenolic hydroxyl-containing resin (QN1) is set to 100% by weight, the content of the phenolic low-molecular compound in the phenolic hydroxyl-containing resin (QN1) is preferably 40% by weight or less, and more preferably It is 1% by weight to 30% by weight.
就所獲得的絕緣膜的解析性、熱衝擊性、熱穩定性、殘膜率等觀點而言，含酚性羥基的樹脂（QN1）的重量平均分子量較佳為2000以上，進而佳為2000～20000。 另外，於將除溶劑以外的組成物的整體設為100重量%的情況下，負型化學增幅樹脂（QN）中的含酚性羥基的樹脂（QN1）的含有比例較佳為30重量%～90重量%，進而佳為40重量%～80重量%。於該含酚性羥基的樹脂（QN1）的含有比例為30重量%～90重量%的情況下，使用感光性絕緣樹脂組成物所形成的膜具有由鹼性水溶液帶來的充分的顯影性，故較佳。From the viewpoints of the resolution, thermal shock, thermal stability, residual film rate, etc. of the obtained insulating film, the weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2000 or more, and more preferably 2000 to 20000. In addition, when the entire composition other than the solvent is 100% by weight, the content of the phenolic hydroxyl group-containing resin (QN1) in the negative chemically amplified resin (QN) is preferably 30% by weight to 90% by weight, more preferably 40% by weight to 80% by weight. When the content of the phenolic hydroxyl group-containing resin (QN1) is 30% by weight to 90% by weight, the film formed using the photosensitive insulating resin composition has sufficient developability by the alkaline aqueous solution, So better.
作為交聯劑（QN2），若為可利用自非離子系光酸產生劑（B）產生的強酸使含酚性羥基的樹脂（QN1）交聯的化合物，則並無特別限定。The crosslinking agent (QN2) is not particularly limited as long as it is a compound that can crosslink the phenolic hydroxyl group-containing resin (QN1) with a strong acid generated from the nonionic photoacid generator (B).
作為交聯劑（QN2），例如可列舉：雙酚A系環氧化合物、雙酚F系環氧化合物、雙酚S系環氧化合物、酚醛清漆樹脂系環氧化合物、可溶酚醛樹脂系環氧化合物、聚(羥基苯乙烯)系環氧化合物、氧雜環丁烷化合物、含羥甲基的三聚氰胺化合物、含羥甲基的苯並胍胺化合物、含羥甲基的脲化合物、含羥甲基的酚化合物、含烷氧基烷基的三聚氰胺化合物、含烷氧基烷基的苯並胍胺化合物、含烷氧基烷基的脲化合物、含烷氧基烷基的酚化合物、含羧基甲基的三聚氰胺樹脂、含羧基甲基的苯並胍胺樹脂、含羧基甲基的脲樹脂、含羧基甲基的酚樹脂、含羧基甲基的三聚氰胺化合物、含羧基甲基的苯並胍胺化合物、含羧基甲基的脲化合物及含羧基甲基的酚化合物。As the crosslinking agent (QN2), for example, bisphenol A epoxy compound, bisphenol F epoxy compound, bisphenol S epoxy compound, novolak resin epoxy compound, resol phenolic ring Oxygen compounds, poly(hydroxystyrene) epoxy compounds, oxetane compounds, methylol-containing melamine compounds, methylol-containing benzoguanamine compounds, methylol-containing urea compounds, hydroxyl radicals Methyl phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound, Carboxymethyl melamine resin, carboxymethyl-containing benzoguanamine resin, carboxymethyl-containing urea resin, carboxymethyl-containing phenol resin, carboxymethyl-containing melamine compound, carboxymethyl-containing benzoguanidine Amine compounds, carboxymethyl-containing urea compounds, and carboxymethyl-containing phenol compounds.
於該些交聯劑（QN2）中，較佳為含羥甲基的酚化合物、含甲氧基甲基的三聚氰胺化合物、含甲氧基甲基的酚化合物、含甲氧基甲基的甘脲化合物、含甲氧基甲基的脲化合物及含乙醯氧基甲基的酚化合物，進而佳為含甲氧基甲基的三聚氰胺化合物（例如六甲氧基甲基三聚氰胺）、含甲氧基甲基的甘脲化合物及含甲氧基甲基的脲化合物等。含甲氧基甲基的三聚氰胺化合物以賽麥盧（CYMEL）300、賽麥盧（CYMEL）301、賽麥盧（CYMEL）303、賽麥盧（CYMEL）305（三井氰胺（Mitsui Cyanamid）（股）製造）等商品名市售，含甲氧基甲基的甘脲化合物以賽麥盧（CYMEL）1174（三井氰胺（Mitsui Cyanamid）（股）製造）等商品名市售，且含甲氧基甲基的脲化合物以MX290（三和化學（股）製造）等商品名市售。Among the crosslinking agents (QN2), preferred are methylol-containing phenol compounds, methoxymethyl-containing melamine compounds, methoxymethyl-containing phenol compounds, and methoxymethyl-containing glycerol compounds. Urea compounds, methoxymethyl-containing urea compounds, and acetoxymethyl-containing phenol compounds, more preferably methoxymethyl-containing melamine compounds (for example, hexamethoxymethylmelamine), and methoxymethyl-containing Methyl glycoluril compounds and methoxymethyl-containing urea compounds, etc. Methoxymethyl-containing melamine compounds are CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 305 (Mitsui Cyanamid) ( Co., Ltd.) and other trade names, and methoxymethyl-containing glycoluril compounds are commercially available under the trade names such as CYMEL 1174 (Mitsui Cyanamid (Stock) Co., Ltd.), etc., and contain The oxymethyl urea compound is commercially available under trade names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).
就殘膜率的下降、圖案的彎曲或膨潤及顯影性的觀點而言，相對於含酚性羥基的樹脂（QN1）中的所有酸性官能基，交聯劑（QN2）的含量通常為5莫耳%～60莫耳%，較佳為10莫耳%～50莫耳%，進而佳為15莫耳%～40莫耳%。From the viewpoints of the reduction of the residual film rate, the bending or swelling of the pattern and the developability, the content of the crosslinking agent (QN2) is usually 5 moles relative to all the acidic functional groups in the phenolic hydroxyl group-containing resin (QN1). Ear%-60 mol%, preferably 10 mol%-50 mol%, and more preferably 15 mol%-40 mol%.
作為正型化學增幅樹脂（QP），可列舉含有酚性羥基、羧基、或磺醯基等中的一種以上的酸性官能基的鹼可溶性樹脂（QP1）、及（QP1）中酸性官能基的氫原子的一部分或全部被酸解離性基取代而成的保護基導入樹脂（QP2）。 保護基導入樹脂（QP2）其自身為鹼不溶性或鹼難溶性。 再者，酸解離性基為可於自磺醯胺化合物（A）產生的超強酸的存在下進行解離的基。Examples of positive chemical amplification resins (QP) include alkali-soluble resins (QP1) containing one or more acidic functional groups among phenolic hydroxyl groups, carboxyl groups, or sulfonyl groups, and hydrogen in the acidic functional groups (QP1). A protective group in which part or all of the atoms are substituted by an acid-dissociable group is introduced into the resin (QP2). The protective group introduction resin (QP2) itself is alkali-insoluble or poorly soluble in alkali. In addition, the acid dissociable group is a group that can be dissociated in the presence of a super acid generated from the sulfonamide compound (A).
作為鹼可溶性樹脂（QP1），例如可列舉：含酚性羥基的樹脂（QP11）、含羧基的樹脂（QP12）、及含磺酸基的樹脂（QP13）等。 作為含酚性羥基的樹脂（QP11），可使用與所述含羥基的樹脂（QN1）相同者。Examples of alkali-soluble resins (QP1) include phenolic hydroxyl group-containing resins (QP11), carboxyl group-containing resins (QP12), sulfonic acid group-containing resins (QP13), and the like. As the phenolic hydroxyl group-containing resin (QP11), the same as the above-mentioned hydroxyl group-containing resin (QN1) can be used.
作為含羧基的樹脂（QP12），若為具有羧基的聚合物，則並無特別限制，例如可藉由使含羧基的乙烯基單體（Va）與視需要的含疏水基的乙烯基單體（Vb）進行乙烯基聚合來獲得。The carboxyl group-containing resin (QP12) is not particularly limited as long as it is a polymer having a carboxyl group. For example, a carboxyl group-containing vinyl monomer (Va) can be combined with an optional hydrophobic group-containing vinyl monomer (Vb) Obtained by vinyl polymerization.
作為含羧基的乙烯基單體（Va），例如可列舉：不飽和單羧酸[(甲基)丙烯酸、丁烯酸及肉桂酸等]、不飽和多元（二價～四價）羧酸[(無水)馬來酸、衣康酸、富馬酸及檸康酸等]、不飽和多元羧酸烷基（碳數1～10的烷基）酯[馬來酸單烷基酯、富馬酸單烷基酯及檸康酸單烷基酯等]、以及該些的鹽[鹼金屬鹽（鈉鹽及鉀鹽等）、鹼土金屬鹽（鈣鹽及鎂鹽等）、胺鹽及銨鹽等]。 該些中，就聚合性、及獲取的容易度的觀點而言，較佳為不飽和單羧酸，進而佳為(甲基)丙烯酸。Examples of the carboxyl group-containing vinyl monomer (Va) include unsaturated monocarboxylic acids [(meth)acrylic acid, crotonic acid, cinnamic acid, etc.], and unsaturated polybasic (divalent to tetravalent) carboxylic acids [ (Anhydrous) maleic acid, itaconic acid, fumaric acid, citraconic acid, etc.], unsaturated polycarboxylic acid alkyl (alkyl with 1 to 10 carbons) ester [maleic acid monoalkyl ester, fumaric acid Acid monoalkyl esters and citraconic acid monoalkyl esters, etc.], and their salts [alkali metal salts (sodium and potassium salts, etc.), alkaline earth metal salts (calcium and magnesium salts, etc.), amine salts and ammonium salts Salt etc.]. Among these, from the viewpoint of polymerizability and ease of availability, unsaturated monocarboxylic acid is preferred, and (meth)acrylic acid is more preferred.
作為含疏水基的乙烯基單體（Vb），可列舉(甲基)丙烯酸酯（Vb1）、及芳香族烴單體（Vb2）等。Examples of the hydrophobic group-containing vinyl monomer (Vb) include (meth)acrylate (Vb1), aromatic hydrocarbon monomer (Vb2), and the like.
作為(甲基)丙烯酸酯（Vb1），可列舉：烷基的碳數1～20的(甲基)丙烯酸烷基酯[(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)丙烯酸正己酯及(甲基)丙烯酸2-乙基己酯等]及含脂環基的(甲基)丙烯酸酯[(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯及(甲基)丙烯酸異冰片酯等]等。Examples of the (meth)acrylate (Vb1) include: alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group [methyl (meth)acrylate, ethyl (meth)acrylate, (former) (Base) n-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, etc.] and alicyclic (Meth)acrylate [dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, etc.] etc.
作為芳香族烴單體（Vb2），例如可列舉：具有苯乙烯骨架的烴單體[苯乙烯、α-甲基苯乙烯、乙烯基甲苯、2,4-二甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、苯基苯乙烯、環己基苯乙烯及苄基苯乙烯等]及乙烯基萘。As the aromatic hydrocarbon monomer (Vb2), for example, a hydrocarbon monomer having a styrene skeleton [styrene, α-methylstyrene, vinyl toluene, 2,4-dimethylstyrene, ethylbenzene Ethylene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene and benzyl styrene, etc.] and vinyl naphthalene.
含羧基的樹脂（QP12）中的（Va）/（Vb）的投入單體莫耳比通常為10～100/0～90，就顯影性的觀點而言，較佳為10～80/20～90，進而佳為25～85/15～75。The molar ratio of (Va)/(Vb) charged monomers in the carboxyl group-containing resin (QP12) is usually from 10 to 100/0 to 90, and from the viewpoint of developability, it is preferably from 10 to 80/20 to 90, more preferably 25-85/15-75.
作為含磺酸基的樹脂（QP13），若為具有磺酸基的聚合物，則並無特別限制，例如可藉由使含磺酸基的乙烯基單體（Vc）與視需要的含疏水基的乙烯基單體（Vb）進行乙烯基聚合來獲得。 作為含疏水基的乙烯基單體（Vb），可使用與所述相同者。As the sulfonic acid group-containing resin (QP13), if it is a sulfonic acid group-containing polymer, it is not particularly limited. For example, a sulfonic acid group-containing vinyl monomer (Vc) can be combined with an optional hydrophobic The base vinyl monomer (Vb) is obtained by vinyl polymerization. As the hydrophobic group-containing vinyl monomer (Vb), the same ones as described above can be used.
作為含磺酸基的乙烯基單體（Vc），例如可列舉：乙烯基磺酸、(甲基)烯丙基磺酸、苯乙烯磺酸、α-甲基苯乙烯磺酸、2-(甲基)丙烯醯基醯胺-2-甲基丙磺酸及該些的鹽。作為鹽，可列舉：鹼金屬（鈉及鉀等）鹽、鹼土金屬（鈣及鎂等）鹽、一級胺鹽～三級胺鹽、銨鹽及四級銨鹽等。Examples of the sulfonic acid group-containing vinyl monomer (Vc) include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, 2-( (Meth)acrylamide-2-methylpropanesulfonic acid and their salts. Examples of the salt include alkali metal (sodium, potassium, etc.) salts, alkaline earth metal (calcium, magnesium, etc.) salts, primary to tertiary amine salts, ammonium salts, and quaternary ammonium salts.
含磺酸基的樹脂（QP13）中的（Vc）/（Vb）的投入單體莫耳比通常為10～100/0～90，就顯影性的觀點而言，較佳為10～80/20～90，進而佳為25～85/15～75。The monomer molar ratio of (Vc)/(Vb) in the sulfonic acid group-containing resin (QP13) is usually 10-100/0-90, and from the viewpoint of developability, it is preferably 10-80/ 20-90, more preferably 25-85/15-75.
鹼可溶性樹脂（QP1）的HLB值根據鹼可溶性樹脂（QP1）的樹脂骨架而較佳的範圍不同，但較佳為4～19，進而佳為5～18，特佳為6～17。 若HLB值為4以上，則於進行顯影時顯影性更良好，若為19以下，則硬化物的耐水性更良好。The preferred range of the HLB value of the alkali-soluble resin (QP1) varies depending on the resin skeleton of the alkali-soluble resin (QP1), but it is preferably 4-19, more preferably 5-18, and particularly preferably 6-17. If the HLB value is 4 or more, the developability during development is more favorable, and if it is 19 or less, the water resistance of the cured product is more favorable.
再者，本發明中的HLB值是利用小田法而得的HLB值，且為親水性-疏水性平衡值，可根據有機化合物的有機性的值與無機性的值的比率來計算。 ＜HLB的評價方法＞ HLB≒10×無機性/有機性 另外，無機性的值及有機性的值於文獻「界面活性劑的合成及其應用」（槙書店發行、小田、寺村著）的501頁，或者「新-界面活性劑入門」（藤本武彥著、三洋化成工業股份有限公司發行）的198頁中有詳細記載。In addition, the HLB value in the present invention is the HLB value obtained by the Oda method, and is a hydrophilicity-hydrophobicity balance value, which can be calculated from the ratio of the organic value and the inorganic value of an organic compound. ＜HLB evaluation method＞ HLB≒10×Inorganic/Organic In addition, the value of inorganicity and the value of organicity can be found on page 501 of the document "Synthesis and Application of Surfactants" (published by Maki Bookstore, by Oda and Teramura), or "Introduction to New Surfactants" (Fujimoto Takehiko The book, issued by Sanyo Chemical Industry Co., Ltd.) has a detailed record on page 198.
作為保護基導入樹脂（QP2）中的酸解離性基，可列舉：取代甲基、1-取代乙基、1-分支烷基、矽烷基、甲鍺烷基（germyl）、烷氧基羰基、醯基及環式酸解離性基等。該些可單獨使用一種，亦可將兩種以上組合而使用。The acid dissociable group introduced into the resin (QP2) as the protective group includes: substituted methyl, 1-substituted ethyl, 1-branched alkyl, silyl, germyl, alkoxycarbonyl, Acetone and cyclic acid dissociable group, etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types.
作為取代甲基，例如可列舉：甲氧基甲基、甲硫基甲基、乙氧基甲基、乙硫基甲基、甲氧基乙氧基甲基、苄基氧基甲基、苄硫基甲基、苯甲醯甲基、溴代苯甲醯甲基、甲氧基苯甲醯甲基、甲硫基苯甲醯甲基、α-甲基苯甲醯甲基、環丙基甲基、苄基、二苯基甲基、三苯基甲基、溴代苄基、硝基苄基、甲氧基苄基、甲硫基苄基、乙氧基苄基、乙硫基苄基、胡椒基、甲氧基羰基甲基、乙氧基羰基甲基、丙氧基羰基甲基、異丙氧基羰基甲基、丁氧基羰基甲基、第三丁氧基羰基甲基。Examples of substituted methyl groups include: methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzyl Thiomethyl, benzyl methyl, bromo benzyl methyl, methoxy benzyl methyl, methylthio benzyl methyl, α-methyl benzyl methyl, cyclopropyl Methyl, benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthiobenzyl Group, piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, tert-butoxycarbonylmethyl.
作為1-取代乙基，例如可列舉：1-甲氧基乙基、1-甲硫基乙基、1,1-二甲氧基乙基、1-乙氧基乙基、1-乙硫基乙基、1,1-二乙氧基乙基、1-乙氧基丙基、1-丙氧基乙基、1-環己氧基乙基、1-苯氧基乙基、1-苯硫基乙基、1,1-二苯氧基乙基、1-苄基氧基乙基、1-苄硫基乙基、1-環丙基乙基、1-苯基乙基、1,1-二苯基乙基、1-甲氧基羰基乙基、1-乙氧基羰基乙基、1-丙氧基羰基乙基、1-異丙氧基羰基乙基、1-丁氧基羰基乙基、1-第三丁氧基羰基乙基。Examples of 1-substituted ethyl include: 1-methoxyethyl, 1-methylthioethyl, 1,1-dimethoxyethyl, 1-ethoxyethyl, 1-ethylsulfide Ethyl, 1,1-diethoxyethyl, 1-ethoxypropyl, 1-propoxyethyl, 1-cyclohexyloxyethyl, 1-phenoxyethyl, 1- Phenylthioethyl, 1,1-diphenoxyethyl, 1-benzyloxyethyl, 1-benzylthioethyl, 1-cyclopropylethyl, 1-phenylethyl, 1 , 1-Diphenylethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxy Carbonylethyl, 1-tertiary butoxycarbonylethyl.
作為1-分支烷基，例如可列舉：異丙基、第二丁基、第三丁基、1,1-二甲基丙基、1-甲基丁基、1,1-二甲基丁基。Examples of 1-branched alkyl groups include isopropyl, second butyl, tertiary butyl, 1,1-dimethylpropyl, 1-methylbutyl, 1,1-dimethylbutyl base.
作為矽烷基，例如可列舉：三甲基矽烷基、乙基二甲基矽烷基、二乙基甲基矽烷基、三乙基矽烷基、異丙基二甲基矽烷基、二異丙基甲基矽烷基、三異丙基矽烷基、第三丁基二甲基矽烷基、二-第三丁基甲基矽烷基、三-第三丁基矽烷基、二甲基苯基矽烷基、甲基二苯基矽烷基、三苯基矽烷基等三碳基（carbyl）矽烷基。Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, diethylmethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, and diisopropylmethylsilyl group. Base silyl group, triisopropyl silyl group, tertiary butyldimethylsilyl group, di-tertiary butyl methylsilyl group, tri-tertiary butyl silyl group, dimethyl phenyl silyl group, methyl two Three-carbon (carbyl) silyl groups such as phenyl silyl group and triphenyl silyl group.
作為甲鍺烷基，例如可列舉：三甲基甲鍺烷基、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、三異丙基甲鍺烷基、第三丁基二甲基甲鍺烷基、二-第三丁基甲基甲鍺烷基、三-第三丁基甲鍺烷基、二甲基苯基甲鍺烷基、甲基二苯基甲鍺烷基、三苯基甲鍺烷基等三碳基甲鍺烷基。As the germyl group, for example, trimethylgermyl, ethyldimethylgermyl, methyldiethylgermyl, triethylgermyl, isopropyl two Methylgermyl, methyldiisopropylgermyl, triisopropylgermyl, tert-butyldimethylgermyl, di-tert-butylmethylgermyl, Three-carbon germyl groups such as tri-tert-butylgermyl, dimethylphenylgermyl, methyldiphenylgermyl, and triphenylgermyl.
作為烷氧基羰基，例如可列舉：甲氧基羰基、乙氧基羰基、異丙氧基羰基、第三丁氧基羰基。Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tert-butoxycarbonyl group.
作為醯基，例如可列舉：乙醯基、丙醯基、丁醯基、庚醯基、己醯基、戊醯基、三甲基乙醯基、異戊醯基、月桂醯基、肉豆蔻醯基、棕櫚醯基、硬脂醯基、乙二醯基、丙二醯基、琥珀醯基、戊二醯基、己二醯基、庚二醯基、辛二醯基、壬二醯基、癸二醯基、丙烯醯基、丙炔醯基、甲基丙烯醯基、丁烯醯基、油醯基、馬來醯基、富馬醯基、中康醯基、樟腦二醯基、苯甲醯基、鄰苯二甲醯基、間苯二甲醯基、對苯二甲醯基、萘甲醯基、甲苯甲醯基、氫阿托醯基、阿托醯基、肉桂醯基、呋喃甲醯基、噻吩甲醯基、菸醯基、異菸醯基、對甲苯磺醯基、甲磺醯基。Examples of the acyl group include: acetyl group, propyl group, butyryl group, heptyl group, hexyl group, pentamyl group, trimethyl acetyl group, isopentyl group, lauryl group, myristyl group , Palmitoyl, stearyl, oxalanyl, malonyl, succinyl, glutaryl, adipyl, pimelic, octanyl, azelayl, decane Diacyl, acrylic, propynyl, methacrylic, butenyl, oleyl, maleic, fumaric, mesoconsinyl, camphor diacyl, benzyl, ortho Phthaloyl, m-phthaloyl, p-phthaloyl, naphthyl, tolyl, hydrogen atoranyl, atoranyl, cinnamyl, furanomyl, Thiophene methionyl, nicotinyl, isonicotinyl, p-toluenesulfonyl, methanesulfonyl.
作為環式酸解離性基，例如可列舉：環丙基、環戊基、環己基、環己烯基、4-甲氧基環己基、四氫吡喃基、四氫呋喃基、四氫噻喃基（thiopyranyl）、四氫硫代呋喃基（thiofuranyl）、3-溴代四氫吡喃基、4-甲氧基四氫吡喃基、4-甲氧基四氫噻喃基、3-四氫噻吩-1,1-二氧化物基。Examples of cyclic acid dissociable groups include cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, and tetrahydrothiopyranyl. (Thiopyranyl), tetrahydrothiofuranyl (thiofuranyl), 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydropyranyl, 3-tetrahydro Thiophene-1,1-dioxide group.
於該些酸解離性基中，較佳為第三丁基、苄基、1-甲氧基乙基、1-乙氧基乙基、三甲基矽烷基、第三丁氧基羰基、第三丁氧基羰基甲基、四氫吡喃基、四氫呋喃基、四氫噻喃基及四氫硫代呋喃基。Among these acid-dissociable groups, tertiary butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tertiary butoxycarbonyl, third Tributoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl and tetrahydrothiofuranyl.
保護基導入樹脂（QP2）中的酸解離性基的導入率{相對於保護基導入樹脂（QP2）中的未經保護的酸性官能基與酸解離性基的合計數而言的酸解離性基的個數的比例}無法根據酸解離性基或導入有該基的鹼可溶性樹脂的種類統一規定，但較佳為10%～100%，進而佳為15%～100%。The introduction rate of acid-dissociable groups in the protective group-introduced resin (QP2) {acid-dissociable groups relative to the total number of unprotected acidic functional groups and acid-dissociable groups in the protective group-introduced resin (QP2) The ratio of the number of} cannot be uniformly defined according to the acid dissociable group or the type of alkali-soluble resin into which the group is introduced, but is preferably 10% to 100%, and more preferably 15% to 100%.
保護基導入樹脂（QP2）的利用凝膠滲透層析法（GPC）而測定的聚苯乙烯換算重量平均分子量（以下，稱為「Mw」）較佳為1,000～150,000，進而佳為3,000～100,000。The polystyrene conversion weight average molecular weight (hereinafter referred to as "Mw") of the protective group introduction resin (QP2) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, and more preferably 3,000 to 100,000 .
另外，保護基導入樹脂（QP2）的Mw與利用凝膠滲透層析法（GPC）而測定的聚苯乙烯換算數量平均分子量（以下，稱為「Mn」）之比（Mw/Mn）通常為1～10，較佳為1～5。In addition, the ratio (Mw/Mn) of the Mw of the protecting group-introduced resin (QP2) to the polystyrene-converted number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC) is usually 1-10, preferably 1-5.
基於光微影用樹脂組成物（Q）的固體成分的重量的非離子系光酸產生劑（B）的含量較佳為0.001重量%～20重量%，進而佳為0.01重量%～15重量%，特佳為0.05重量%～7重量%。 若為0.001重量%以上，則可更良好地發揮相對於紫外線的感度，若為20重量%以下，則可更良好地發揮不溶於鹼性顯影液的部分的物性。The content of the nonionic photoacid generator (B) based on the weight of the solid content of the resin composition (Q) for photolithography is preferably 0.001% by weight to 20% by weight, and more preferably 0.01% by weight to 15% by weight , Particularly preferably 0.05% by weight to 7% by weight. If it is 0.001% by weight or more, the sensitivity to ultraviolet rays can be exhibited more satisfactorily, and if it is 20% by weight or less, the physical properties of the portion insoluble in the alkaline developer can be exhibited more satisfactorily.
出於改善曝光後的圖案的形狀或經時變化等目的，使用本發明的光微影用樹脂組成物（Q）的抗蝕劑可含有淬滅劑（酸擴散控制劑）。作為淬滅劑，只要是具有顯示出較非離子系光酸產生劑（B）產生的酸而言更大的pKa的鹼性位點的化合物，則並無特別限定。例如可列舉：公知的胺類（三戊基胺、三異丙醇胺、二環己基胺、N,N-二環己基甲基胺等）、公知的吡啶類（吡啶、2,6-二甲吡啶、2,6-二-第三丁基吡啶、2,6-二苯基吡啶等）、公知的苯胺類（2,6-二異丙基苯胺等）、公知的咪唑類（2,4,5-三苯基咪唑、4,5-二苯基咪唑、2-苯基咪唑等）、及曝光時分解而產生弱酸的公知的鎓與弱酸根陰離子的鹽類（苯甲酸三苯基鋶、水楊酸三苯基鋶、3,5-雙三氟甲基苯甲酸三苯基鋶、五氟苯甲酸二苯基錪、4-氟苯甲酸-4-異丁基-4'-甲苯基錪等）。淬滅劑的含量依賴於非離子系光酸產生劑（B）的含量，但相對於光微影用樹脂組成物（Q）的總固體成分而為5重量%以下，較佳為3重量%以下。若超過5重量%，則曝光時產生的酸的有效濃度減少，存在於顯影後無法獲得圖案的問題。The resist using the resin composition (Q) for photolithography of the present invention may contain a quencher (acid diffusion control agent) for the purpose of improving the shape of the pattern after exposure or the change with time. The quencher is not particularly limited as long as it is a compound having a basic site showing a larger pKa than the acid generated by the nonionic photoacid generator (B). Examples include: well-known amines (tripentylamine, triisopropanolamine, dicyclohexylamine, N,N-dicyclohexylmethylamine, etc.), well-known pyridines (pyridine, 2,6-di Picoline, 2,6-di-tert-butylpyridine, 2,6-diphenylpyridine, etc.), well-known anilines (2,6-diisopropylaniline, etc.), well-known imidazoles (2, 4,5-triphenylimidazole, 4,5-diphenylimidazole, 2-phenylimidazole, etc.), and salts of known onium and weak acid anion (triphenyl benzoate Alumium, triphenyl alumium salicylate, 3,5-bistrifluoromethyl benzoic acid, triphenyl alumium, pentafluorobenzoic acid diphenyl iodonium, 4-fluorobenzoic acid-4-isobutyl-4'- Tolyl bromide etc.). The content of the quencher depends on the content of the nonionic photoacid generator (B), but it is 5% by weight or less, preferably 3% by weight, relative to the total solid content of the resin composition for photolithography (Q) the following. If it exceeds 5% by weight, the effective concentration of acid generated during exposure is reduced, and there is a problem that a pattern cannot be obtained after development.
使用本發明的光微影用樹脂組成物（Q）的抗蝕劑例如可藉由如下方式來形成：使用旋塗、簾幕式塗佈、輥塗、噴霧塗佈、網版印刷等公知的方法，將溶解（於包含無機微粒子的情況下為溶解與分散）於規定的有機溶劑中的樹脂溶液塗佈於基板上後，利用加熱或熱風吹附來使溶劑乾燥。The resist using the resin composition (Q) for photolithography of the present invention can be formed, for example, by using known methods such as spin coating, curtain coating, roll coating, spray coating, and screen printing. In the method, a resin solution dissolved (dissolved and dispersed in the case of containing inorganic fine particles) in a predetermined organic solvent is applied on a substrate, and then the solvent is dried by heating or hot air blowing.
作為使光微影用樹脂組成物（Q）溶解的有機溶劑（抗蝕劑溶媒），若為可溶解樹脂組成物，並可將樹脂溶液調整為可適用於旋塗等的物性（黏度等）的有機溶劑，則並無特別限定。例如可使用N-甲基吡咯啶酮、DMF、二甲基亞碸、甲苯、乙醇、環己酮、甲醇、甲基乙基酮、乙酸乙酯、乙酸丁酯、乳酸乙酯、γ-丁內酯、丙二醇單甲醚乙酸酯、丙酮及二甲苯等公知的溶媒。 該些溶劑中，就乾燥溫度等觀點而言，較佳為沸點為200℃以下者（甲苯、乙醇、環己酮、甲醇、甲基乙基酮、乙酸乙酯、乙酸丁酯、乳酸乙酯、丙二醇單甲醚乙酸酯、丙酮及二甲苯），亦可單獨或將兩種以上組合而使用。 於使用有機溶劑的情況下，溶劑的調配量並無特別限定，但基於光微影用樹脂組成物（Q）的固體成分的重量，通常較佳為30重量%～1,000重量%，進而佳為40重量%～900重量%，特佳為50重量%～800重量%。As an organic solvent (resist solvent) that dissolves the resin composition (Q) for photolithography, if the resin composition is soluble, the resin solution can be adjusted to have physical properties (viscosity, etc.) suitable for spin coating, etc. The organic solvent is not particularly limited. For example, N-methylpyrrolidone, DMF, dimethyl sulfide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, γ-butyl can be used Known solvents such as lactone, propylene glycol monomethyl ether acetate, acetone, and xylene. Among these solvents, those with a boiling point of 200° C. or less (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, etc.) are preferred in terms of drying temperature and the like. , Propylene glycol monomethyl ether acetate, acetone and xylene), can also be used alone or in combination of two or more. In the case of using an organic solvent, the amount of the solvent is not particularly limited, but based on the weight of the solid content of the resin composition (Q) for photolithography, it is usually preferably 30% by weight to 1,000% by weight, and more preferably 40% by weight to 900% by weight, particularly preferably 50% by weight to 800% by weight.
塗佈後的樹脂溶液的乾燥條件根據所使用的溶劑而不同，但較佳為於50℃～200℃且1分鐘～30分鐘的範圍內實施，藉由乾燥後的光微影用樹脂組成物（Q）的殘留溶劑量（重量%）等適宜決定。The drying conditions of the resin solution after application vary depending on the solvent used, but it is preferably carried out in the range of 50°C to 200°C and 1 minute to 30 minutes, and the dried resin composition for photolithography (Q) The amount of residual solvent (weight%), etc., is appropriately determined.
於基板上形成抗蝕劑後，進行配線圖案形狀的光照射。之後，進行曝光後加熱（PEB）後進行鹼顯影，從而形成配線圖案。After the resist is formed on the substrate, light irradiation in the shape of the wiring pattern is performed. After that, after exposure heating (PEB), alkali development is performed to form a wiring pattern.
作為進行光照射的方法，可列舉介隔具有配線圖案的光罩，利用光化射線進行抗蝕劑的曝光的方法。作為用於光照射的光化射線，若可使本發明的光微影用樹脂組成物（Q）中的磺醯胺化合物（A）分解，則並無特別限制。 作為光化射線，存在低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、金屬鹵素燈、電子束照射裝置、X射線照射裝置、雷射（氬雷射、氬-氟（ArF）準分子雷射、氪-氟（KrF）準分子雷射、色素雷射、氮雷射、LED、氦鎘雷射等）等。該些中，較佳為高壓水銀燈、超高壓水銀燈、LED及氪-氟（KrF）準分子雷射。As a method of performing light irradiation, a method of exposing the resist with actinic rays via a photomask having a wiring pattern is mentioned. The actinic rays used for light irradiation are not particularly limited as long as the sulfonamide compound (A) in the resin composition (Q) for photolithography of the present invention can be decomposed. As actinic rays, there are low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon lasers, argon-fluorine (ArF)) Excimer lasers, krypton-fluorine (KrF) excimer lasers, pigment lasers, nitrogen lasers, LEDs, helium-cadmium lasers, etc.). Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, LEDs, and krypton-fluorine (KrF) excimer lasers are preferred.
作為曝光後加熱（PEB）的溫度，通常為40℃～200℃，較佳為50℃～190℃，進而佳為60℃～180℃。未滿40℃時，無法充分地進行脫保護反應、或交聯反應，因此紫外線照射部與紫外線未照射部的溶解性的差不足而無法形成圖案，若高於200℃，則存在生產性降低的問題。 作為加熱時間，通常為0.5分鐘～120分鐘，未滿0.5分鐘時，難以控制時間與溫度，若大於120分鐘，則存在生產性降低的問題。The post-exposure heating (PEB) temperature is usually 40°C to 200°C, preferably 50°C to 190°C, and more preferably 60°C to 180°C. When the temperature is lower than 40°C, the deprotection reaction or the crosslinking reaction cannot proceed sufficiently. Therefore, the difference in solubility between the UV-irradiated part and the UV-unirradiated part is insufficient and the pattern cannot be formed. If the temperature is higher than 200°C, the productivity is reduced. The problem. The heating time is usually 0.5 minutes to 120 minutes, and when it is less than 0.5 minutes, it is difficult to control the time and temperature, and if it exceeds 120 minutes, there is a problem of reduced productivity.
作為進行鹼顯影的方法，可列舉使用鹼性顯影液以配線圖案形狀進行溶解去除的方法。作為鹼性顯影液，若為光微影用樹脂組成物（Q）的紫外線照射部與紫外線未照射部的溶解性形成差的條件，則並無特別限制。 作為鹼性顯影液，存在氫氧化鈉水溶液、氫氧化鉀水溶液、碳酸氫鈉及四甲基銨鹽水溶液等。 該些鹼性顯影液亦可加入水溶性的有機溶劑。作為水溶性的有機溶劑，存在甲醇、乙醇、異丙醇、THF、N-甲基吡咯啶酮等。As a method of performing alkali development, the method of dissolving and removing in the shape of a wiring pattern using an alkali developer is mentioned. The alkaline developer is not particularly limited as long as the solubility of the UV-irradiated portion and the UV-unirradiated portion of the resin composition (Q) for photolithography is poor. As the alkaline developer, there are sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium bicarbonate, tetramethylammonium salt aqueous solution, and the like. These alkaline developers can also be added with water-soluble organic solvents. As water-soluble organic solvents, there are methanol, ethanol, isopropanol, THF, N-methylpyrrolidone, and the like.
作為顯影方法，存在使用鹼性顯影液的浸漬方式、噴淋方式、及噴霧方式，但較佳為噴霧方式。 關於顯影液的溫度，較佳為於25℃～40℃下使用。顯影時間是根據抗蝕劑的厚度來適宜決定。 [實施例]As the development method, there are a dipping method using an alkaline developer, a shower method, and a spray method, but the spray method is preferred. Regarding the temperature of the developer, it is preferably used at 25°C to 40°C. The development time is appropriately determined according to the thickness of the resist. [Example]
以下，藉由實施例及比較例來對本發明進一步進行說明，但本發明並不限定於該些。以下，只要未特別規定，則%表示重量%，份表示重量份。另外，取代位置是將Ar1 設為母骨架而決定。Hereinafter, the present invention will be further described with examples and comparative examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified,% means weight %, and part means part by weight. In addition, the substitution position is determined by using Ar 1 as the parent skeleton.
＜製造例1＞ ＜N-胺基-1,8-萘二甲醯亞胺[前驅物（P1-1）]的合成＞ 將1,8-萘二甲酸酐作為原料，依照文獻（「高分子化學（Polym. Chem.）」，2015，6，1171.）中記載的方法來獲得前驅物（P1-1）。＜Manufacturing example 1＞ ＜Synthesis of N-amino-1,8-naphthalimide [precursor (P1-1)]＞ Using 1,8-naphthalenedicarboxylic acid anhydride as a raw material, the precursor (P1-1) was obtained according to the method described in the literature ("Polym. Chem.", 2015, 6, 1171.).
＜製造例2＞ ＜N-胺基-2,6-二異丙基-1,8-萘二甲醯亞胺[前驅物（P1-2）]的合成＞ 將2,6-二異丙基-1,8-萘二甲酸酐（依照文獻「有機化學快報（Org. Lett.）」，2010，12，4690.合成）作為原料，依照製造例1中記載的方法來獲得前驅物（P1-2）。＜Manufacturing example 2＞ ＜Synthesis of N-amino-2,6-diisopropyl-1,8-naphthalenedimethimide [precursor (P1-2)]＞ Using 2,6-diisopropyl-1,8-naphthalenedicarboxylic acid anhydride (according to the document "Org. Lett.", 2010, 12, 4690. Synthesis) as a raw material, according to the production example 1 Method to obtain the precursor (P1-2).
＜製造例3＞ ＜N-胺基-3-丁氧基-1,8-萘二甲醯亞胺[前驅物（P1-3）]的合成＞ 將3-丁氧基-1,8-萘二甲酸酐作為原料，依照製造例1中記載的方法來獲得前驅物（P1-3）。＜Manufacturing example 3＞ ＜Synthesis of N-amino-3-butoxy-1,8-naphthalimide [precursor (P1-3)]＞ Using 3-butoxy-1,8-naphthalenedicarboxylic acid anhydride as a raw material, the precursor (P1-3) was obtained in accordance with the method described in Production Example 1.
＜製造例4＞ ＜3-丁氧基-N-甲磺醯基胺基-1,8-萘二甲醯亞胺[前驅物（P2-1）]的合成＞ 於將製造例3中合成的前驅物（P1-3）分散於乙腈中並冷卻至-78℃的漿料中加入甲磺醯氯，並攪拌5分鐘。繼而滴加三乙基胺攪拌1小時後，升溫至0℃為止。放入去離子水停止反應後，對析出的固體進行過濾並減壓乾燥，藉此獲得前驅物（P2-1）。＜Manufacturing example 4＞ ＜Synthesis of 3-butoxy-N-methanesulfonylamino-1,8-naphthalimide [precursor (P2-1)]＞ To the slurry prepared by dispersing the precursor (P1-3) synthesized in Production Example 3 in acetonitrile and cooling to -78°C, methanesulfonyl chloride was added and stirred for 5 minutes. Then, triethylamine was added dropwise and stirred for 1 hour, and then the temperature was raised to 0°C. After putting in deionized water to stop the reaction, the precipitated solid is filtered and dried under reduced pressure, thereby obtaining a precursor (P2-1).
＜製造例5＞ ＜N-胺基-4-苯硫基鄰苯二甲醯亞胺[前驅物（P1-4）]的合成＞ 以4-苯硫基鄰苯二甲醯亞胺（依照文獻「生物有機和藥物化學（Bioorg. Med. Chem.）」，2014，22，5738.合成）為原料，依照文獻（「有機化學期刊（J. Org. Chem.）」，2007，72，9395.）中記載的方法來合成前驅物（P1-4）。＜Manufacturing Example 5＞ ＜Synthesis of N-amino-4-phenylthiophthalimide [precursor (P1-4)]＞ Using 4-phenylthiophthalimide (according to the literature "Bioorg. Med. Chem.", 2014, 22, 5738. Synthesis) as the raw material, according to the literature ("Journal of Organic Chemistry" (J. Org. Chem.)", 2007, 72, 9395.) to synthesize the precursor (P1-4).
＜製造例6＞ ＜N,N'-雙(甲苯磺醯基胺基)均苯四甲酸二醯亞胺[前驅物（P2-2）]的合成＞ 對將均苯四甲酸二醯亞胺分散於乙腈中而得的漿料進行冰浴，加入甲苯磺醯基醯肼。攪拌3小時後，加入去離子水並對析出的固體進行過濾。利用減壓乾燥器將其乾燥，藉此獲得前驅物（P2-2）。＜Manufacturing Example 6＞ ＜Synthesis of N,N'-bis(toluenesulfonylamino)pyromellitic acid diimide [precursor (P2-2)]＞ The slurry obtained by dispersing pyromellitic acid diimide in acetonitrile was subjected to an ice bath, and tosylhydrazine was added. After stirring for 3 hours, deionized water was added and the precipitated solid was filtered. It was dried with a vacuum dryer to obtain a precursor (P2-2).
＜製造例7＞ ＜N'-三氟甲烷磺醯基-N-苄氧基羰基苯並醯肼[前驅物（P4-1）]的合成＞ 將苯甲醯氯的二氯甲烷溶液冰浴，加入2-((三氟甲基)磺醯基)肼-1-羧酸苄酯（依照文獻「有機化學快報（Org. Lett.）」2016，18，3850.合成）。攪拌3小時後，加入去離子水並將有機層水洗三次。將有機層濃縮並利用減壓乾燥器進行乾燥，藉此獲得前驅物（P4-1）。＜Manufacturing Example 7＞ <Synthesis of N'-trifluoromethanesulfonyl-N-benzyloxycarbonyl benzohydrazine [precursor (P4-1)]> The dichloromethane solution of benzyl chloride was ice bathed, and 2-((trifluoromethyl)sulfonyl)hydrazine-1-carboxylic acid benzyl ester was added (according to the document "Org. Lett." 2016 , 18, 3850. Synthesis). After stirring for 3 hours, deionized water was added and the organic layer was washed three times with water. The organic layer was concentrated and dried with a reduced-pressure drier, thereby obtaining a precursor (P4-1).
＜製造例8＞ ＜1-(對甲苯基)-2,2,2-三氟乙酮腙的合成＞ 依照文獻「有機化學快報（Org. Lett.）」2007，9，2625.中記載的方法來合成1-(對甲苯基)-2,2,2-三氟乙酮腙。＜Manufacturing Example 8＞ ＜Synthesis of 1-(p-tolyl)-2,2,2-trifluoroethanone hydrazone＞ The 1-(p-tolyl)-2,2,2-trifluoroethanone hydrazone was synthesized according to the method described in the document "Org. Lett." 2007, 9, 2625.
＜製造例9＞ ＜1-(7-甲氧基-3-香豆素基)-2,2,2-三氟乙酮腙的合成＞ 於乙醇中將1-(7-甲氧基-3-香豆素基)-2,2,2-三氟乙酮（合成法於WO2016/124493中揭示）與肼鹽酸鹽回流24小時後，於大量的水中放入反應液，並對析出的固體進行過濾、乾燥，藉此獲得1-(7-甲氧基-3-香豆素基)-2,2,2-三氟乙酮腙。＜Manufacturing Example 9＞ ＜Synthesis of 1-(7-methoxy-3-coumarinyl)-2,2,2-trifluoroethanone hydrazone＞ Reflux 1-(7-methoxy-3-coumarinyl)-2,2,2-trifluoroethanone (synthesis method disclosed in WO2016/124493) with hydrazine hydrochloride in ethanol for 24 hours , Put the reaction liquid in a large amount of water, and filter and dry the precipitated solid to obtain 1-(7-methoxy-3-coumarinyl)-2,2,2-trifluoroethanone Hydrazone.
＜實施例1＞ ＜化合物（A1）的合成＞ 於將製造例1中合成的前驅物（P1-1）10份分散於二氯甲烷125份中並冷卻至-78℃的漿料中滴加三氟甲磺酸酐39份，並攪拌5分鐘。繼而滴加三乙基胺12份並攪拌30分鐘。將反應液升溫至0℃後，加入去離子水停止反應，利用去離子水對有機層清洗三次。將有機層濃縮後，利用氯仿/IPA對殘渣進行再結晶，藉此獲得乳白色固體的化合物（A1）13份。將各種分析的結果示於表1。<Example 1> <Synthesis of Compound (A1)> To the slurry in which 10 parts of the precursor (P1-1) synthesized in Production Example 1 was dispersed in 125 parts of dichloromethane and cooled to -78°C, 39 parts of trifluoromethanesulfonic anhydride was added dropwise and stirred for 5 minutes. Then, 12 parts of triethylamine was added dropwise and stirred for 30 minutes. After the reaction solution was heated to 0°C, deionized water was added to stop the reaction, and the organic layer was washed three times with deionized water. After concentrating the organic layer, the residue was recrystallized with chloroform/IPA to obtain 13 parts of a milky white solid compound (A1). Table 1 shows the results of various analyses.
[表1]
＜實施例2＞ ＜化合物（A2）的合成＞ 於將製造例2中合成的前驅物（P1-2）10份分散於二氯甲烷90份中並冷卻至-78℃的漿料中滴加三氟甲磺酸酐29份，並攪拌5分鐘。繼而滴加N-乙基二異丙基胺11份並攪拌30分鐘。將反應液升溫至0℃後，加入去離子水停止反應，利用去離子水對有機層清洗三次。將有機層濃縮後，利用IPA對殘渣進行再結晶，藉此獲得乳白色固體的化合物（A2）11份。將各種分析的結果示於表2。<Example 2> <Synthesis of Compound (A2)> To the slurry in which 10 parts of the precursor (P1-2) synthesized in Production Example 2 was dispersed in 90 parts of dichloromethane and cooled to -78°C, 29 parts of trifluoromethanesulfonic anhydride was added dropwise and stirred for 5 minutes. Subsequently, 11 parts of N-ethyldiisopropylamine was added dropwise and stirred for 30 minutes. After the reaction solution was heated to 0°C, deionized water was added to stop the reaction, and the organic layer was washed three times with deionized water. After concentrating the organic layer, the residue was recrystallized with IPA to obtain 11 parts of a milky white solid compound (A2). Table 2 shows the results of various analyses.
[表2]
＜實施例3＞ ＜化合物（A3）的合成＞ 將前驅物（P1-1）設為製造例4中合成的前驅物（P2-1）10份、二氯甲烷設為73份、三氟甲磺酸酐設為12份、三乙基胺設為3.4份，除此以外與實施例1同樣地進行，藉此獲得化合物（A3）9.2份。<Example 3> <Synthesis of Compound (A3)> The precursor (P1-1) was set to 10 parts of the precursor (P2-1) synthesized in Production Example 4, methylene chloride was set to 73 parts, trifluoromethanesulfonic anhydride was set to 12 parts, and triethylamine was set to Except 3.4 parts, it carried out similarly to Example 1, and obtained 9.2 parts of compound (A3).
＜實施例4～實施例9＞ ＜表6中的通式（1）-a的化合物（A4）～化合物（A9）的合成＞ 與實施例1中記載的合成方法同樣地合成化合物（A4）～化合物（A9）。將化合物（A4）的各種分析的結果示於表3。<Example 4 to Example 9> <Synthesis of compound (A4) to compound (A9) of general formula (1)-a in Table 6> Compounds (A4) to (A9) were synthesized in the same manner as the synthesis method described in Example 1. Table 3 shows the results of various analyses of the compound (A4).
[表3]
＜實施例10＞ ＜化合物（A10）的合成＞ 將製造例5中合成的前驅物（P1-4）作為原料，與實施例2同樣地進行，藉此獲得化合物（A10）。<Example 10> <Synthesis of Compound (A10)> Using the precursor (P1-4) synthesized in Production Example 5 as a raw material, the same procedure as in Example 2 was carried out to obtain a compound (A10).
＜實施例11＞ ＜化合物（A11）的合成＞ 將製造例6中合成的前驅物（P2-2）作為原料，與實施例3同樣地進行，藉此獲得下述式的化合物（A11）。<Example 11> <Synthesis of Compound (A11)> Using the precursor (P2-2) synthesized in Production Example 6 as a raw material, the same procedure as in Example 3 was carried out to obtain a compound (A11) of the following formula.
[化10]
＜實施例12～實施例21＞ ＜表7中的通式（1）-b的化合物（A12～A21）的合成＞ 與實施例10或實施例11中記載的合成方法同樣地進行，藉此由對應的原料合成化合物（A12～A21）。<Example 12 to Example 21> <Synthesis of compounds (A12～A21) of general formula (1)-b in Table 7> The synthesis method described in Example 10 or Example 11 was carried out in the same manner, whereby the compounds (A12 to A21) were synthesized from the corresponding raw materials.
＜實施例22＞ ＜化合物（A22）的合成＞ 將製造例7中合成的前驅物（P4-1）作為原料，將三氟甲磺酸酐設為甲苯磺醯氯，除此以外與實施例3同樣地進行，藉此獲得化合物（A22）。<Example 22> <Synthesis of Compound (A22)> The precursor (P4-1) synthesized in Production Example 7 was used as a raw material, and trifluoromethanesulfonic anhydride was used as toluenesulfonyl chloride, and the same procedure as in Example 3 was carried out to obtain a compound (A22).
＜實施例23＞ ＜化合物（A23）的合成＞ 使用由對應的原料依照製造例7中記載的方法合成的前驅物，除此以外與實施例3同樣地進行，藉此合成化合物（A23）。<Example 23> <Synthesis of Compound (A23)> The compound (A23) was synthesized in the same manner as in Example 3 except that the precursor synthesized by the method described in Production Example 7 was used from the corresponding raw material.
＜實施例24～實施例27＞ ＜表8中的通式（1）-c的化合物（A24～A27）的合成＞ 與實施例22或實施例23中記載的合成方法同樣地進行，藉此由對應的原料合成化合物（A24～A27）。<Example 24 to Example 27> <Synthesis of compounds (A24 to A27) of general formula (1)-c in Table 8> By carrying out the same synthesis method as described in Example 22 or Example 23, the compounds (A24 to A27) were synthesized from the corresponding raw materials.
＜實施例28＞ ＜化合物（A28）的合成＞ 將製造例8中合成的1-(對甲苯基)-2,2,2-三氟乙酮腙作為原料，與實施例1同樣地進行，藉此獲得化合物（A28）。<Example 28> <Synthesis of Compound (A28)> Using 1-(p-tolyl)-2,2,2-trifluoroethanone hydrazone synthesized in Production Example 8 as a raw material, the same procedure as in Example 1 was carried out to obtain compound (A28).
＜實施例29～實施例32＞ ＜表9中的通式（2）的化合物（A29～A32）的合成＞ 與實施例28中記載的合成方法同樣地進行，藉此由對應的原料合成化合物（A29～A32）。<Example 29 to Example 32> <Synthesis of compounds (A29 to A32) of the general formula (2) in Table 9> By performing the same method as the synthesis method described in Example 28, the compounds (A29 to A32) were synthesized from the corresponding raw materials.
＜實施例33＞ ＜化合物（A33）的合成＞ 將三氟甲磺酸酐設為市售的全氟丙烷-1,3-二磺醯二氟化物45份，除此以外與實施例1同樣地進行，藉此獲得化合物（A33）12份。<Example 33> <Synthesis of Compound (A33)> Except having used trifluoromethanesulfonic anhydride as 45 parts of commercially available perfluoropropane-1,3-disulfonyl difluoride, the same procedure as in Example 1 was carried out to obtain 12 parts of compound (A33).
＜實施例34＞ ＜化合物（A34）的合成＞ 將前驅物（P1-1）設為3-第三丁氧基羰基-N-胺基-1,8-萘二甲醯亞胺15份，除此以外與實施例1同樣地進行，藉此獲得化合物（A34）22份。<Example 34> <Synthesis of Compound (A34)> The precursor (P1-1) was set to 15 parts of 3-tert-butoxycarbonyl-N-amino-1,8-naphthalenedimethimide, except that it was carried out in the same manner as in Example 1, thereby 22 parts of compound (A34) were obtained.
＜實施例35＞ ＜化合物（A35）的合成＞ 將前驅物（P1-1）設為N-胺基-N-甲基-2-萘甲醯胺（使萘甲醯氯與甲基肼於二氯甲烷溶媒下反應而合成），二氯甲烷設為133份，三氟甲磺酸酐設為56份，三乙基胺設為15份，再結晶溶媒設為乙醇/水，除此以外與實施例1同樣地進行，藉此獲得化合物（A35）9.3份。將各種分析的結果示於表4。<Example 35> <Synthesis of Compound (A35)> The precursor (P1-1) is set to N-amino-N-methyl-2-naphthocarboxamide (synthesized by reacting naphthocarboxyl chloride and methylhydrazine in a dichloromethane solvent), dichloromethane Except that it was set to 133 parts, trifluoromethanesulfonic anhydride was set to 56 parts, triethylamine was set to 15 parts, and the recrystallization solvent was set to ethanol/water, the same procedure as in Example 1 was carried out to obtain the compound (A35 ) 9.3 copies. Table 4 shows the results of various analyses.
[表4]
＜實施例36＞ ＜化合物（A36）的合成＞ 將N-胺基-N-甲基-2-萘甲醯胺設為由對應的萘甲醯氯獲得的3,6-二甲氧基-N-胺基-N-甲基-2-萘甲醯胺13份，除此以外與實施例35同樣地進行，藉此獲得化合物（A36）9.2份。將各種分析的結果示於表5。<Example 36> <Synthesis of Compound (A36)> Set N-amino-N-methyl-2-naphthocarboxamide as 3,6-dimethoxy-N-amino-N-methyl-2-naphthalene obtained from the corresponding naphthocarboxyl chloride Except 13 parts of formamide, it carried out similarly to Example 35, and obtained 9.2 parts of compound (A36) by this. Table 5 shows the results of various analyses.
[表5]
＜實施例37＞ ＜化合物（A37）的合成＞ 以製造例9中合成的1-(7-甲氧基-3-香豆素基)-2,2,2-三氟乙酮腙代替前驅物（P1-2），將二氯甲烷設為93份，三氟甲磺酸酐設為24份，二異丙基乙基胺設為14份，除此以外與實施例2同樣地進行，藉此獲得化合物（A37）5.8份。<Example 37> <Synthesis of Compound (A37)> Replace the precursor (P1-2) with the 1-(7-methoxy-3-coumarinyl)-2,2,2-trifluoroethanone hydrazone synthesized in Production Example 9, and set the dichloromethane as Except 93 parts, trifluoromethanesulfonic anhydride was 24 parts, and diisopropylethylamine was 14 parts, it carried out similarly to Example 2, and obtained 5.8 parts of compound (A37).
[表6]
[表7]
[表8]
[表8中，Ar1 鍵結位置表示於通式（1）-c中與Ar1 -C(O)-N所表示的Ar1 鍵結的碳於Ar1 上的鍵結位置][Table 8, Ar 1 represents a position bonded to the general formula (1) -c with Ar 1 -C (O) -N Ar 1 bonded to the carbon bonded to the indicated position on 1 Ar]
[表9]
[表9中，Ar1 鍵結位置表示於通式（2）中與Ar1 -CR4 =N所表示的Ar1 鍵結的碳於Ar1 上的鍵結位置][Table 9, Ar 1 represents a position bonded to the general formula (2) wherein Ar and Ar 1 -CR 4 = N indicated by a carbon bonded to a bonding position on Ar]
＜比較例1＞ ＜離子系光酸產生劑[化合物（A'1）]的合成＞ 將三苯基溴化鋶10份分散於氯仿109份中，加入雙三氟甲烷磺醯胺鈉9.3份與去離子水109份。遽烈攪拌1小時後靜置並去除分離的水層，進而將有機層水洗兩次。將有機層濃縮並利用減壓乾燥器加以乾燥，藉此獲得比較例的離子系光酸產生劑[化合物（A'1）]13份。＜Comparative example 1＞ <Synthesis of ionic photoacid generator [Compound (A'1)]> Disperse 10 parts of triphenyl bromide in 109 parts of chloroform, add 9.3 parts of bistrifluoromethanesulfonamide sodium and 109 parts of deionized water. After stirring vigorously for 1 hour, it was allowed to stand still and the separated water layer was removed, and then the organic layer was washed twice with water. The organic layer was concentrated and dried with a reduced-pressure drier to obtain 13 parts of the ion-based photoacid generator [compound (A'1)] of the comparative example.
＜比較例2＞ ＜非離子系光酸產生劑[化合物（A'2）]的合成＞ 直接使用1,8-萘二甲酸醯亞胺三氟甲磺酸酯（A'2）（奧德里奇（Aldrich）公司製造）。＜Comparative example 2＞ <Synthesis of Nonionic Photo Acid Generator [Compound (A'2)]> 1,8-Naphthalenedicarboxylic acid imine triflate (A'2) (manufactured by Aldrich) was used directly.
[化11]
＜實施例1～實施例37、比較例1及比較例2＞ 對於實施例1～實施例37中獲得的磺醯胺化合物（非離子系光酸產生劑）（A1）～（A37）、用以比較的離子系光酸產生劑（A'1）及非離子系光酸產生劑（A'2）的i射線感度及抗蝕劑溶媒溶解性，利用以下的方法進行評價，並將其結果記載於表10、表11中。<Example 1 to Example 37, Comparative Example 1, and Comparative Example 2> Regarding the sulfonamide compounds (nonionic photoacid generators) (A1) to (A37) obtained in Examples 1 to 37, the ionic photoacid generators (A'1) and nonionics for comparison The i-ray sensitivity and resist solvent solubility of the photoacid generator (A'2) were evaluated by the following methods, and the results are shown in Table 10 and Table 11.
＜i射線分解率＞ 於重乙腈100份中溶解所合成的實施例及比較例的化合物0.3份、與作為標準物質的全氟苯0.1份，向NMR管中注入0.6 mL，進行19 F-NMR分析。繼而，對於該NMR管而言，使用紫外線照射裝置（奧克製作所（ORC Manufacturing）股份有限公司製造、HMW-661F-01），曝光500 mJ·cm2 的利用L-34（肯高光學（Kenko kougaku）股份有限公司製造、截止未滿340 nm的光的濾波器）濾波器限定了波長的紫外光。再者，對於累計曝光量而言，測定365 nm的波長。再次利用19 F-NMR分析曝光後的NMR管，由曝光前後的化合物的19 F-NMR訊號的積分值（以標準物質為基準）算出i射線分解率。於相同曝光量下分解率高則作為光酸產生劑而言優異，因此如以下般評價i射線分解率，將結果記載於表10、表11中。 i射線分解率=（曝光前的化合物訊號的積分值-曝光後的化合物訊號的積分值）/（曝光前的化合物訊號的積分值）<i-ray decomposition rate> In 100 parts of heavy acetonitrile, 0.3 parts of the compounds of the examples and comparative examples synthesized and 0.1 part of perfluorobenzene as the standard material were dissolved, 0.6 mL was injected into the NMR tube, and 19 F-NMR was performed analysis. Then, for this NMR tube, an ultraviolet irradiation device (manufactured by ORC Manufacturing Co., Ltd., HMW-661F-01) was used to expose 500 mJ·cm 2 using L-34 (Kenko Optics (Kenko Optics) kougaku) Co., Ltd., a filter that cuts off light below 340 nm) The filter limits the wavelength of ultraviolet light. Furthermore, for the cumulative exposure, the wavelength of 365 nm was measured. The 19 F-NMR analysis of the exposed NMR tube was performed again, and the i-ray decomposition rate was calculated from the integrated value of the 19 F-NMR signal of the compound before and after the exposure (based on the standard material). When the decomposition rate is high at the same exposure amount, it is excellent as a photoacid generator. Therefore, the i-ray decomposition rate was evaluated as follows, and the results are shown in Tables 10 and 11. i-ray decomposition rate = (integrated value of compound signal before exposure-integrated value of compound signal after exposure)/(integrated value of compound signal before exposure)
＜溶解性＞ 將實施例及比較例的化合物以成為50%濃度的方式加入至作為通用抗蝕劑溶媒的丙二醇單甲醚乙酸酯中，利用渦輪混合機攪拌一分鐘後，浸泡於25℃的恆溫槽中靜置一小時，藉由目視確認是否均勻溶解。於不均勻的情況下，以濃度逐步減少5%的方式追加丙二醇單甲醚乙酸酯，重覆進行操作。於濃度5%以下時以1%為單位重覆進行。將初次變得均勻的濃度作為該化合物於抗蝕劑溶媒中的溶解性。溶解性高時，製成光微影用樹脂組成物時更不易發生析出或相分離，因此優異。將結果記載於表10、表11中。＜Solubility＞ The compounds of the examples and comparative examples were added to propylene glycol monomethyl ether acetate as a general-purpose resist solvent at a concentration of 50%, stirred with a turbo mixer for one minute, and then immersed in a constant temperature bath at 25°C Let it stand for one hour, and visually confirm whether it is uniformly dissolved. In the case of unevenness, add propylene glycol monomethyl ether acetate in a way that the concentration is gradually reduced by 5%, and repeat the operation. When the concentration is less than 5%, it is repeated in units of 1%. The first uniform concentration was taken as the solubility of the compound in the resist solvent. When the solubility is high, precipitation or phase separation is less likely to occur when the resin composition for photolithography is used, which is excellent. The results are shown in Table 10 and Table 11.
＜正型光微影用樹脂組成物的評價＞ ＜正型光微影用樹脂組成物（QP-1）的製備＞ 將下述式所示的樹脂40份、間甲酚與對甲酚於甲醛及酸觸媒的存在下加成縮合而獲得的酚醛清漆樹脂60份、實施例及比較例的化合物1份溶解於丙二醇單甲醚乙酸酯152份中，通過膜濾器（孔徑0.45 μm、PTFE膜）進行過濾，藉此製備正型光微影用樹脂組成物（QP-1）。＜Evaluation of resin composition for positive photolithography＞ <Preparation of resin composition (QP-1) for positive photolithography> 40 parts of the resin represented by the following formula, 60 parts of novolac resin obtained by addition condensation of m-cresol and p-cresol in the presence of formaldehyde and acid catalyst, and 1 part of the compounds of the examples and comparative examples were dissolved in 152 parts of propylene glycol monomethyl ether acetate were filtered through a membrane filter (pore size 0.45 μm, PTFE membrane) to prepare a resin composition for positive photolithography (QP-1).
[化12]
＜最低曝光量＞ 於矽晶圓基板上旋塗所述製備的正型光微影用樹脂組成物（QP-1）後，進行乾燥而獲得具有約20 μm膜厚的光阻劑層。藉由加熱板於130℃下對該抗蝕劑層預烘烤6分鐘。繼而，使用TME-150RSC（拓普康（Topcon）公司製造）進行圖案曝光（i射線），利用加熱板於75℃下進行5分鐘曝光後加熱（PEB）。之後，利用使用2.38重量%氫氧化四甲基銨水溶液的浸漬法，進行5分鐘顯影處理，並進行流水清洗，利用氮氣加以吹掃，從而獲得10 μm的線與空間（L&S）圖案。進而，測定於其以下無法確認到該圖案的殘渣的最低限度的曝光量、即形成抗蝕劑圖案所需的最低曝光量[mJ/cm2 ]。最低曝光量與i射線感度相對應且少時優異。將其結果記載於表10、表11中。<Minimum Exposure> The resin composition for positive photolithography (QP-1) prepared as described above was spin-coated on a silicon wafer substrate, and then dried to obtain a photoresist layer with a film thickness of about 20 μm. The resist layer was pre-baked at 130°C for 6 minutes on a hot plate. Then, pattern exposure (i-ray) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 75° C. for 5 minutes using a hot plate. After that, a immersion method using a 2.38% by weight tetramethylammonium hydroxide aqueous solution was used for 5 minutes of development treatment, running water cleaning, and purging with nitrogen gas to obtain a 10 μm line and space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount required to form the resist pattern [mJ/cm 2 ] was measured. The minimum exposure corresponds to the i-ray sensitivity and is excellent when it is small. The results are shown in Table 10 and Table 11.
＜負型光微影用樹脂組成物的評價＞ ＜負型光微影用樹脂組成物（QN-1）的製備＞ 溶解於酚樹脂（迪愛生（DIC）公司製造、「酚諾特（Phenolite）TD431」）75份、三聚氰胺硬化劑（三井氰胺（Mitsui Cyanamid）股份有限公司製造、「賽麥盧（Cymel）300」）25份、所合成的實施例及比較例的化合物1份、及丙二醇單甲醚乙酸酯100份，通過膜濾器（孔徑0.45 μm、PTFE膜）進行過濾，藉此製備各自的負型光微影用樹脂組成物（QN-1）。＜Evaluation of resin composition for negative photolithography＞ <Preparation of resin composition (QN-1) for negative photolithography> Dissolved in phenol resin (manufactured by DIC, "Phenolite TD431") 75 parts, melamine hardener (manufactured by Mitsui Cyanamid Co., Ltd., "Cymel 300 ") 25 parts, 1 part of the compounds of the synthesized examples and comparative examples, and 100 parts of propylene glycol monomethyl ether acetate, were filtered through a membrane filter (pore size 0.45 μm, PTFE membrane) to prepare respective negative types Resin composition for photolithography (QN-1).
＜曝光部硬化性＞ 使用旋塗機於200 rpm且10秒的條件下，將所述製備的各個負型光微影用樹脂組成物（QN-1）塗佈於10 cm見方的玻璃基板上。繼而，於25℃下真空乾燥5分鐘後，於100℃的加熱板上乾燥5分鐘，藉此形成膜厚約40 μm的抗蝕劑。對於該抗蝕劑而言，使用紫外線照射裝置（奧克製作所（ORC Manufacturing）股份有限公司製造、HMW-661F-01），對整個面曝光規定量的藉由L-34（肯高光學（Kenko kougaku）股份有限公司製造、340 nm低通濾波器）限定了波長的紫外光。再者，對於累計曝光量而言，測定365 nm的波長。繼而，於150℃的順風乾燥機中進行10分鐘曝光後加熱（PEB）後，使用0.5%氫氧化鉀溶液並浸漬60秒鐘，藉此進行顯影，立即進行水洗、乾燥。使用形狀測定顯微鏡（超深度形狀測定顯微鏡UK-8550、基恩士（Keyence）股份有限公司製造）對該抗蝕劑的膜厚進行測定。此處，將顯影前後的抗蝕劑的膜厚變化處於10%以內的最低曝光量[mJ/cm2 ]設為曝光部硬化性。曝光部硬化性與i射線感度相對應，最低曝光量越少，i射線感度越優異。將其結果記載於表10、表11中。<Curability of exposure area> Using a spin coater at 200 rpm and 10 seconds, each of the resin compositions for negative photolithography (QN-1) prepared as described above were coated on a 10 cm square glass substrate . Then, after vacuum drying at 25°C for 5 minutes, it was dried on a hot plate at 100°C for 5 minutes, thereby forming a resist with a film thickness of about 40 μm. For this resist, an ultraviolet irradiation device (manufactured by ORC Manufacturing Co., Ltd., HMW-661F-01) was used to expose the entire surface to a prescribed amount by L-34 (Kenko Optics (Kenko) kougaku) Co., Ltd., 340 nm low-pass filter) limits the wavelength of ultraviolet light. Furthermore, for the cumulative exposure, the wavelength of 365 nm was measured. Then, after 10 minutes of post-exposure heating (PEB) in a 150°C downwind dryer, 0.5% potassium hydroxide solution was used and immersed for 60 seconds to perform development, and immediately washed and dried. The film thickness of this resist was measured using a shape measuring microscope (Ultra-depth shape measuring microscope UK-8550, manufactured by Keyence Co., Ltd.). Here, the minimum exposure amount [mJ/cm 2 ] at which the film thickness change of the resist before and after development is within 10% is defined as the exposure area curability. The curability of the exposed area corresponds to the i-ray sensitivity. The lower the minimum exposure, the better the i-ray sensitivity. The results are shown in Table 10 and Table 11.
[表10]
[表11]
＜實施例38～實施例52、比較例3～比較例8＞ 對於磺醯胺化合物（非離子系光酸產生劑）及用以比較的離子系光酸產生劑（A'1）及非離子系光酸產生劑（A'2）的正型光微影用樹脂組成物（QP-2）～正型光微影用樹脂組成物（QP-4）的i射線感度及KrF射線感度，利用以下的方法進行評價，將其結果記載於表12～表14中。<Example 38 to Example 52, Comparative Example 3 to Comparative Example 8> For positive photolithography of sulfonamide compounds (nonionic photoacid generators) and comparative ionic photoacid generators (A'1) and nonionic photoacid generators (A'2) The i-ray sensitivity and KrF-ray sensitivity of the resin composition (QP-2) to the positive photolithography resin composition (QP-4) were evaluated by the following methods, and the results are described in Tables 12 to 14 .
＜正型光微影用樹脂組成物的評價＞ ＜正型光微影用樹脂組成物（QP-2）的製備＞ 甲基丙烯酸第三丁酯43份、甲基丙烯酸甲氧基聚乙二醇30份、甲基丙烯酸甲氧基二乙二醇45份、偶氮雙異丁腈0.4份於二噁烷下反應而獲得的具有下述結構單元（m≒9）的樹脂10份、酚醛清漆樹脂20份（利用甲醛使間甲酚與對甲酚縮合而成的共縮合體（間甲酚/對甲酚=40/60（質量比），Mw=7,000））、實施例及比較例的化合物1份、N,N-二環己基甲基胺0.03份與丙二醇單甲醚乙酸酯87份混合並溶解後，通過膜濾器（孔徑0.45 μm、PTFE膜）進行過濾，藉此製備正型光微影用樹脂組成物（QP-2）。＜Evaluation of resin composition for positive photolithography＞ <Preparation of resin composition (QP-2) for positive photolithography> 43 parts of tert-butyl methacrylate, 30 parts of methoxypolyethylene glycol methacrylate, 45 parts of methoxydiethylene glycol methacrylate, 0.4 part of azobisisobutyronitrile react under dioxane And obtained 10 parts of resin with the following structural unit (m≒9) and 20 parts of novolak resin (co-condensate formed by condensation of m-cresol and p-cresol using formaldehyde (m-cresol/p-cresol= 40/60 (mass ratio), Mw=7,000)), 1 part of the compound of the embodiment and the comparative example, 0.03 part of N,N-dicyclohexylmethylamine and 87 parts of propylene glycol monomethyl ether acetate are mixed and dissolved , Filtered through a membrane filter (pore size 0.45 μm, PTFE membrane) to prepare a resin composition for positive photolithography (QP-2).
[化13]
＜最低曝光量＞ 於矽晶圓上蒸鍍有銅的基板上旋塗所述製備的正型光微影用樹脂組成物（QP-2）後，進行乾燥而獲得光阻劑層。藉由加熱板於110℃下對該抗蝕劑層預烘烤3分鐘而獲得膜厚約5 μm的塗膜。繼而，使用TME-150RSC（拓普康（Topcon）公司製造）進行圖案曝光（i射線），利用加熱板於90℃下進行60秒鐘曝光後加熱（PEB）。之後，利用使用2.38重量%氫氧化四甲基銨水溶液的浸漬法，進行5分鐘顯影處理，並進行流水清洗，利用氮氣加以吹掃，從而獲得10 μm的線與空間（L&S）圖案。進而，測定於其以下無法確認到該圖案的殘渣的最低限度的曝光量、即形成抗蝕劑圖案所需的最低曝光量[mJ/cm2 ]。最低曝光量與i射線感度相對應且少時優異。將其結果記載於表12中。<Minimum Exposure> The resin composition for positive photolithography (QP-2) prepared as described above is spin-coated on a substrate on which copper is vapor-deposited on a silicon wafer, and then dried to obtain a photoresist layer. The resist layer was pre-baked at 110° C. for 3 minutes on a hot plate to obtain a coating film with a film thickness of about 5 μm. Then, pattern exposure (i-ray) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 90° C. for 60 seconds using a hot plate. After that, a immersion method using a 2.38% by weight tetramethylammonium hydroxide aqueous solution was used for 5 minutes of development treatment, running water cleaning, and purging with nitrogen gas to obtain a 10 μm line and space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount required to form the resist pattern [mJ/cm 2 ] was measured. The minimum exposure corresponds to the i-ray sensitivity and is excellent when it is small. The results are shown in Table 12.
[表12]
＜正型光微影用樹脂組成物（QP-3）的製備＞ 將具有下述結構單元（結構式中括弧的右下的數字表示樹脂中的結構單元的含有重量%）的樹脂35份、聚羥基苯乙烯樹脂10份（對羥基苯乙烯：苯乙烯：丙烯酸第三丁酯=12：3：5的共聚物，Mw=1.0×104 ）、酚醛清漆樹脂27.5份（利用甲醛使間甲酚與對甲酚縮合而成的共縮合體（間甲酚/對甲酚=40/60（質量比），Mw=5,000））與酚醛清漆樹脂27.5份（利用甲醛使間甲酚與對甲酚縮合而成的共縮合體（間甲酚/對甲酚=40/60（質量比），Mw=7,000））、界面活性劑（BYK310、畢克化學（BYK-Chemie）公司製造）0.05份、實施例及比較例的化合物1份以固體成分濃度為40重量%的方式混合於混合溶劑（乙酸甲氧基丁酯/丙二醇單甲醚乙酸酯=60/40（質量比））中並溶解後，通過膜濾器（孔徑0.45 μm、PTFE膜）進行過濾，藉此製備正型光微影用樹脂組成物（QP-3）。<Preparation of resin composition for positive photolithography (QP-3)> 35 parts of resin having the following structural unit (the lower right number in parenthesis in the structural formula represents the content of the structural unit in the resin in% by weight), 10 parts of polyhydroxystyrene resin (p-hydroxystyrene: styrene: tertiary butyl acrylate=12:3:5 copolymer, Mw=1.0×10 4 ), 27.5 parts of novolac resin (using formaldehyde to make m Co-condensate formed by the condensation of phenol and p-cresol (m-cresol/p-cresol=40/60 (mass ratio), Mw=5,000)) and 27.5 parts of novolak resin (using formaldehyde to make m-cresol and p-cresol Co-condensate formed by condensation of phenol (m-cresol/p-cresol=40/60 (mass ratio), Mw=7,000)), surfactant (BYK310, BYK-Chemie) 0.05 parts , 1 part of the compounds of the Examples and Comparative Examples are mixed in a mixed solvent (methoxybutyl acetate/propylene glycol monomethyl ether acetate = 60/40 (mass ratio)) with a solid content concentration of 40% by weight. After dissolution, it was filtered through a membrane filter (pore size 0.45 μm, PTFE membrane) to prepare a resin composition for positive photolithography (QP-3).
[化14]
＜最低曝光量＞ 於銅基板上旋塗所述製備的正型光微影用樹脂組成物（QP-3）後，進行乾燥而獲得膜厚約11 μm的光阻劑層。藉由加熱板於130℃下對該抗蝕劑層預烘烤5分鐘。繼而，使用TME-150RSC（拓普康（Topcon）公司製造）進行圖案曝光（i射線），利用加熱板於90℃下進行90秒鐘曝光後加熱（PEB）。之後，將2.38重量%氫氧化四甲基銨水溶液滴加至基板上，於23℃下靜置30秒鐘，將所述操作進行兩次後，並進行流水清洗，利用氮氣加以吹掃，從而獲得10 μm的線與空間（L&S）圖案。進而，測定於其以下無法確認到該圖案的殘渣的最低限度的曝光量、即形成抗蝕劑圖案所需的最低曝光量[mJ/cm2 ]。最低曝光量與i射線感度相對應且少時優異。將其結果記載於表13中。<Minimum Exposure> The resin composition for positive photolithography (QP-3) prepared as described above was spin-coated on a copper substrate, and then dried to obtain a photoresist layer with a film thickness of about 11 μm. The resist layer was pre-baked at 130°C for 5 minutes on a hot plate. Then, pattern exposure (i-ray) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 90° C. for 90 seconds using a hot plate. After that, a 2.38% by weight tetramethylammonium hydroxide aqueous solution was dropped onto the substrate, and it was allowed to stand at 23°C for 30 seconds. After the operation was performed twice, it was washed with running water and purged with nitrogen gas. Obtain a 10 μm line and space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount required to form the resist pattern [mJ/cm 2 ] was measured. The minimum exposure corresponds to the i-ray sensitivity and is excellent when it is small. The results are shown in Table 13.
[表13]
＜正型光微影用樹脂組成物（QP-4）的製備＞ 將具有下述結構單元（結構式中括弧的右下的數字表示樹脂中的結構單元的含有重量%）的樹脂100份、實施例及比較例的化合物1份、2-苯基苯並咪唑0.2份、界面活性劑（福傑特（Ftergent）FTX-218，奈奧斯（NEOS）製造）0.1份混合於丙二醇單甲醚乙酸酯230份並溶解後，通過膜濾器（孔徑0.45 μm、PTFE膜）進行過濾，藉此製備正型光微影用樹脂組成物（QP-4）。<Preparation of resin composition (QP-4) for positive photolithography> 100 parts of resin with the following structural units (the lower right number in the brackets in the structural formula represents the weight% of the structural unit in the resin), 1 part of the compounds of the examples and comparative examples, and 2-phenylbenzimidazole 0.2 After mixing 0.1 part of surfactant (Ftergent FTX-218, manufactured by NEOS) in 230 parts of propylene glycol monomethyl ether acetate and dissolving, pass through a membrane filter (pore size 0.45 μm, PTFE Film) was filtered to prepare a resin composition (QP-4) for positive photolithography.
[化15]
＜最低曝光量＞ 於矽晶圓上蒸鍍有銅的基板上旋塗所述製備的正型光微影用樹脂組成物（QP-4）後，進行乾燥而獲得光阻劑層。藉由加熱板於110℃下對該抗蝕劑層預烘烤1分鐘而獲得膜厚6 μm的塗膜。繼而，使用TME-150RSC（拓普康（Topcon）公司製造）進行圖案曝光（i射線），利用加熱板於90℃下進行1分鐘曝光後加熱（PEB）。之後，利用使用2.38重量%氫氧化四甲基銨水溶液的浸漬法，進行80秒鐘顯影處理，並進行流水清洗，利用氮氣加以吹掃，從而獲得10 μm的線與空間（L&S）圖案。進而，測定於其以下無法確認到該圖案的殘渣的最低限度的曝光量、即形成抗蝕劑圖案所需的最低曝光量（i射線）[mJ/cm2 ]。最低曝光量與i射線感度相對應且少時優異。將其結果記載於表14中。<Minimum Exposure> The resin composition for positive photolithography (QP-4) prepared as described above was spin-coated on a substrate on which copper was vapor-deposited on a silicon wafer, and then dried to obtain a photoresist layer. The resist layer was pre-baked at 110° C. for 1 minute on a hot plate to obtain a coating film with a film thickness of 6 μm. Then, pattern exposure (i-ray) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 90° C. for 1 minute using a hot plate. After that, a immersion method using a 2.38% by weight tetramethylammonium hydroxide aqueous solution was used to perform development processing for 80 seconds, followed by running water cleaning, and purging with nitrogen gas to obtain a 10 μm line and space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount (i-ray) required to form the resist pattern [mJ/cm 2 ] was measured. The minimum exposure corresponds to the i-ray sensitivity and is excellent when it is small. The results are shown in Table 14.
＜最低曝光量（KrF射線）＞ 於矽晶圓上蒸鍍有銅的基板上旋塗所述製備的正型光微影用樹脂組成物（QP-4）後，進行乾燥而獲得光阻劑層。藉由加熱板於110℃下對該抗蝕劑層預烘烤1分鐘而獲得膜厚6 μm的塗膜。繼而，使用FPA-5000ES3（佳能（Canon）公司製造）進行圖案曝光（KrF射線），利用加熱板於90℃下進行1分鐘曝光後加熱（PEB）。之後，利用使用2.38重量%氫氧化四甲基銨水溶液的浸漬法，進行80秒鐘顯影處理，並進行流水清洗，利用氮氣加以吹掃，從而獲得10 μm的線與空間（L&S）圖案。進而，測定於其以下無法確認到該圖案的殘渣的最低限度的曝光量、即形成抗蝕劑圖案所需的最低曝光量（KrF射線）[mJ/cm2 ]。最低曝光量與KrF射線感度相對應且少時優異。將其結果記載於表14中。<Minimum exposure (KrF radiation)> The resin composition for positive photolithography (QP-4) prepared as described above was spin-coated on a copper-deposited substrate on a silicon wafer, and then dried to obtain a photoresist Floor. The resist layer was pre-baked at 110° C. for 1 minute on a hot plate to obtain a coating film with a film thickness of 6 μm. Then, pattern exposure (KrF rays) was performed using FPA-5000ES3 (manufactured by Canon), and post-exposure heating (PEB) was performed at 90°C for 1 minute using a hot plate. After that, a immersion method using a 2.38% by weight tetramethylammonium hydroxide aqueous solution was used to perform development processing for 80 seconds, followed by running water cleaning, and purging with nitrogen gas to obtain a 10 μm line and space (L&S) pattern. Furthermore, the minimum exposure amount below which the residue of the pattern cannot be confirmed, that is, the minimum exposure amount (KrF rays) required to form the resist pattern [mJ/cm 2 ] was measured. The minimum exposure amount corresponds to the KrF ray sensitivity and is excellent when it is small. The results are shown in Table 14.
[表14]
由表10～表14明確，可知本發明的實施例1～實施例52的磺醯胺化合物（A）藉由i射線照射而效率良好地分解，且對於光微影用樹脂組成物中通用的丙二醇單甲醚乙酸酯而言發揮高溶解性，因此本發明的磺醯胺化合物（A）為i射線感度及於抗蝕劑溶劑中的溶解性優異的光酸產生劑。另外，由於本發明的化合物藉由i射線照射而效率良好地產生作為超強酸的雙磺醯胺，因此含有其的正型光微影用樹脂組成物的最低曝光量少，負型光微影用樹脂組成物的曝光部硬化性良好，i射線感度優異。 另外，由表14明確，本發明的磺醯胺化合物（A）藉由KrF射線照射而效率良好地分解，產生作為超強酸的雙磺醯胺，因此含有其的正型光微影用樹脂組成物的最低曝光量少，KrF射線感度優異，因此可以說近紫外線感度優異。 另一方面，作為離子系光酸產生劑的比較例（1、3、5、7）中，產生酸為雙磺醯胺，但由於i射線分解率、溶解性差，故含有其的光微影用樹脂組成物的i射線感度及KrF射線感度差。另外可知，作為非離子系光酸產生劑的比較例（2、4、6、8）中i射線分解率相同，但由於產生酸為三氟甲磺酸，故含有其的光微影用樹脂組成物的i射線感度及KrF射線感度低，近紫外線感度差。 [產業上之可利用性]It is clear from Tables 10 to 14 that the sulfonamide compounds (A) of Examples 1 to 52 of the present invention are efficiently decomposed by i-ray irradiation and are commonly used in resin compositions for photolithography. Since propylene glycol monomethyl ether acetate exhibits high solubility, the sulfonamide compound (A) of the present invention is a photoacid generator having excellent i-ray sensitivity and solubility in a resist solvent. In addition, since the compound of the present invention efficiently produces bissulfonamide, which is a super strong acid, by irradiation with i-rays, the resin composition for positive photolithography containing it has a low minimum exposure amount and negative photolithography. The exposed part of the resin composition is excellent in curability and excellent in i-ray sensitivity. In addition, it is clear from Table 14 that the sulfonamide compound (A) of the present invention is efficiently decomposed by irradiation with KrF rays to produce bissulfonamide as a super acid. Therefore, the composition of the positive photolithography resin containing the sulfonamide compound (A) The minimum exposure of the object is small, and the KrF radiation sensitivity is excellent, so it can be said that the near ultraviolet sensitivity is excellent. On the other hand, in the comparative examples (1, 3, 5, 7) which are ionic photoacid generators, the generated acid is bissulfonamide, but due to the poor i-ray decomposition rate and solubility, the photolithography containing it The resin composition has poor i-ray sensitivity and KrF-ray sensitivity. In addition, it can be seen that in the comparative examples (2, 4, 6, 8) which are nonionic photoacid generators, the i-ray decomposition rate is the same, but since the generating acid is trifluoromethanesulfonic acid, the resin for photolithography containing it The composition has low i-ray sensitivity and KrF-ray sensitivity, and poor near-ultraviolet sensitivity. [Industrial availability]
本發明的磺醯胺化合物（A）由於近紫外線（i射線、KrF射線）高感度地分解而產生超強酸，故可有效用作半導體的製造所代表的微細加工用的光微影材料。The sulfonamide compound (A) of the present invention decomposes with high sensitivity in near ultraviolet rays (i-rays, KrF rays) to generate super acid, and therefore can be effectively used as a photolithography material for microfabrication represented by the manufacture of semiconductors.
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