TW202030183A

TW202030183A - Photo-acid generator and resin composition for photolithography

Info

Publication number: TW202030183A
Application number: TW108141053A
Authority: TW
Inventors: 柴垣智幸
Original assignee: 日商三亞普羅股份有限公司
Priority date: 2018-11-22
Filing date: 2019-11-12
Publication date: 2020-08-16
Also published as: WO2020105364A1; JP7116669B2; TWI788602B; KR20210092713A; CN112888676A; JP2020086083A

Abstract

The purpose of the present invention is to provide a non-ionic photo-acid generator which exhibits high photosensitivity to i-rays, excellent compatibility with, and solubility in, a resist solution, and excellent thermal stability. The present invention is a non-ionic photo-acid generator that is characterized by being represented by general formula (1). [In formula (1), X denotes an oxygen atom or a sulfur atom, R1 denotes a hydrogen atom or a C1-12 alkyl group that may have a carboxylic acid group, R2 denotes a hydrogen atom or a C1-12 alkyl group, and Rf denotes a C1-12 hydrocarbon group in which some or all of the hydrogen atoms are substituted with fluorine atoms.].

Description

光酸產生劑及光微影用樹脂組成物Photoacid generator and resin composition for photolithography

本發明是有關於一種光酸產生劑及光微影用樹脂組成物。進一步詳細而言，是有關於一種適於作用紫外線（i射線）而產生強酸的非離子系光酸產生劑、及含有其的光微影用樹脂組成物。The invention relates to a photoacid generator and a resin composition for photolithography. More specifically, it relates to a nonionic photoacid generator suitable for generating strong acid by acting on ultraviolet rays (i-rays), and a resin composition for photolithography containing the nonionic photoacid generator.

先前以來，於以半導體的製造為代表的微細加工領域中，廣泛應用利用波長365 nm的i射線作為曝光光的光微影步驟。作為光微影步驟中所使用的抗蝕劑材料，例如一直使用：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物與光酸產生劑的樹脂組成物。作為光酸產生劑，已知：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；以及具有肟磺酸酯結構的酸產生劑（專利文獻3）、具有磺醯基重氮甲烷結構的酸產生劑（專利文獻4）等非離子系酸產生劑。進而藉由進行曝光後加熱（曝光後烘烤，Post-exposure-bake，PEB），聚合物中的第三丁基酯基、或碳酸第三丁酯基因該強酸而解離，形成羧酸或酚性羥基，紫外線照射部變得易溶於鹼性顯影液中。利用該現象而進行圖案形成。In the past, in the field of microfabrication represented by the manufacture of semiconductors, a photolithography step using i-rays with a wavelength of 365 nm as exposure light has been widely used. As the resist material used in the photolithography step, 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 has been used. Things. As photoacid generators, known: triarylsulfonate (Patent Document 1), benzylmethylsulfonate having a naphthalene skeleton (Patent Document 2) plasma-based photoacid generator; and those having an oxime sulfonate structure Nonionic acid generators such as acid generators (Patent Document 3) and acid generators having a sulfodiazomethane structure (Patent Document 4). Furthermore, by performing post-exposure heating (Post-exposure-bake, PEB), the tertiary butyl ester group or tertiary butyl carbonate gene in the polymer is dissociated by the strong acid to form carboxylic acid or phenol Since it is a hydroxyl group, the UV-irradiated part becomes easily soluble in alkaline developer. This phenomenon is utilized for pattern formation.

但是，伴隨著光微影步驟成為更微細的加工，藉由鹼性顯影液而未曝光部的圖案發生膨潤的膨脹的影響變大，從而需要抑制抗蝕劑材料的膨潤。為了解決該些問題而提出有如下方法：使抗蝕劑材料中的聚合物含有脂環式骨架或含氟骨架等而設為疏水性，藉此抑制抗蝕劑材料的膨潤。However, as the photolithography step becomes finer processing, the influence of swelling and swelling of the pattern of the unexposed part due to the alkaline developer becomes greater, and it is necessary to suppress the swelling of the resist material. In order to solve these problems, a method has been proposed in which the polymer in the resist material contains an alicyclic skeleton, a fluorine-containing skeleton, etc., and is made hydrophobic, thereby suppressing swelling of the resist material.

由於離子系光酸產生劑對含有該些脂環式骨架及含氟骨架等的疏水性材料的相溶性不足，故存在因抗蝕劑材料中產生相分離，而無法發揮充分的抗蝕劑性能，從而無法形成圖案的問題。另一方面，雖然非離子系光酸產生劑對疏水性材料的相溶性良好，但存在於鹼性顯影步驟中於曝光部產生浮渣的問題。另外，有對i射線的感度不足的問題；以及因耐熱穩定性不足而於曝光後加熱（PEB）中分解，故而裕度（allowance）窄的問題。 [現有技術文獻] [專利文獻]Since the ionic photoacid generator has insufficient compatibility with hydrophobic materials containing these alicyclic skeletons and fluorine-containing skeletons, there is a phase separation in the resist material, which prevents sufficient resist performance. , Thus unable to form a pattern problem. On the other hand, although the nonionic photoacid generator has good compatibility with the hydrophobic material, there is a problem that scum is generated in the exposed portion during the alkaline development step. In addition, there is a problem of insufficient sensitivity to i-rays; and a problem of a narrow allowance due to decomposition in post-exposure heating (PEB) due to insufficient heat resistance stability. [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]日本專利特開平10-213899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. 10-213899

[發明所欲解決之課題] 因此，目的在於提供一種對i射線具有高感光度、對抗蝕劑溶液的相溶性及溶解性優異、另外耐熱穩定性優異的非離子系光酸產生劑。 [解決課題之手段][The problem to be solved by the invention] Therefore, an object is to provide a nonionic photoacid generator which has high sensitivity to i-rays, is excellent in compatibility and solubility with a resist solution, and is also excellent in heat resistance stability. [Means to solve the problem]

本發明者為了達成所述目的而進行了研究，結果完成了本發明。即，本發明是一種非離子系光酸產生劑（A）及光微影用樹脂組成物（Q），所述非離子系光酸產生劑（A）的特徵在於由下述通式（1）表示；所述光微影用樹脂組成物（Q）包含該非離子系光酸產生劑（A）。The inventors conducted studies to achieve the above-mentioned object, and as a result, completed the present invention. That is, the present invention is a nonionic photoacid generator (A) and a resin composition for photolithography (Q), and the nonionic photoacid generator (A) is characterized by having the following general formula (1) ) Means; the resin composition for photolithography (Q) contains the nonionic photoacid generator (A).

[化1]

[化1]

[式（1）中，X表示氧原子、或硫原子，R1表示氫原子、或可具有羧酸基的碳數1～12的烷基，R2表示氫原子、或碳數1～12的烷基，Rf表示氫的一部分或全部經氟取代的碳數1～12的烴基] [發明的效果][In formula (1), X represents an oxygen atom or a sulfur atom, R1 represents a hydrogen atom or an alkyl group having 1 to 12 carbons which may have a carboxylic acid group, and R2 represents a hydrogen atom or an alkane having 1 to 12 carbons Group, Rf represents a hydrocarbon group with 1 to 12 carbons in which part or all of hydrogen is substituted by fluorine] [Effects of the invention]

本發明的非離子系光酸產生劑（A）於為非離子系的萘二甲醯亞胺骨架上具有醚基、或硫醚基，可對萘環上的電子狀態產生作用，故對i射線具有非常高的吸收，從而成為高感度。藉此，藉由照射i射線，非離子系光酸產生劑（A）容易地分解，而可產生作為強酸的磺酸。另外，由於側鏈上具有酯結構，故對丙二醇單甲醚乙酸酯（propylene glycol monomethyl ether acetate，PGMEA）等具有酯結構的溶劑的溶解性優異。另外，醚基、或硫醚基與C=O基以碳數1的距離接近，故對金屬基板的配向性優異，抗蝕劑圖案形狀的形成性優異。由於一併具有萘二甲醯亞胺骨架，故具有200℃以上的熱分解溫度，熱穩定性優異，可進行曝光後加熱（PEB）。The nonionic photoacid generator (A) of the present invention has an ether group or a thioether group on the nonionic naphthalene dimethymide skeleton, which can have an effect on the electronic state on the naphthalene ring, so it is The rays have very high absorption, which makes them highly sensitive. Thereby, by irradiating i-rays, the nonionic photoacid generator (A) is easily decomposed, and sulfonic acid, which is a strong acid, can be generated. In addition, since the side chain has an ester structure, it has excellent solubility in solvents having an ester structure such as propylene glycol monomethyl ether acetate (PGMEA). In addition, the ether group or the thioether group and the C=O group are close to each other at a distance of 1 carbon atoms, so that the alignment to the metal substrate is excellent, and the resist pattern formability is excellent. Since it has a naphthalenedimethimide skeleton, it has a thermal decomposition temperature of 200°C or higher, and has excellent thermal stability and can be heated after exposure (PEB).

因此，含有本發明的非離子系光酸產生劑（A）的光微影用樹脂組成物（Q）對i射線的感度優異，另外，對抗蝕劑溶液的相溶性、及溶解性良好。另外，曝光後加熱（PEB）中的容許幅度廣，故而作業性優異。Therefore, the resin composition (Q) for photolithography containing the nonionic photoacid generator (A) of the present invention is excellent in sensitivity to i-rays, and has good compatibility and solubility with a resist solution. In addition, the allowable range in post-exposure heating (PEB) is wide, so it has excellent workability.

本發明的非離子系光酸產生劑（A）由下述通式（1）表示。The nonionic photoacid generator (A) of the present invention is represented by the following general formula (1).

[化2]

[化2]

[式（1）中，X表示氧原子、或硫原子，R1表示氫原子、或可具有羧酸基的碳數1～12的烷基，R2表示氫原子、或碳數1～12的烷基，Rf表示氫的一部分或全部經氟取代的碳數1～12的烴基][In formula (1), X represents an oxygen atom or a sulfur atom, R1 represents a hydrogen atom or an alkyl group having 1 to 12 carbons which may have a carboxylic acid group, and R2 represents a hydrogen atom or an alkane having 1 to 12 carbons Group, Rf represents a hydrocarbon group with 1 to 12 carbons in which part or all of hydrogen is substituted by fluorine]

由於X為氧原子、或硫原子，故可對萘環上的電子狀態產生作用，並對i射線具有非常高的吸收。Since X is an oxygen atom or a sulfur atom, it can have an effect on the electronic state on the naphthalene ring and has a very high absorption of i rays.

R1表示氫原子、或可具有羧酸基的碳數1～12的烷基。作為碳數1～12的烷基，可列舉：直鏈的烷基、及分支的烷基、環狀的烷基。R1 represents a hydrogen atom or an alkyl group having 1 to 12 carbons which may have a carboxylic acid group. Examples of the alkyl group having 1 to 12 carbon atoms include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups.

作為直鏈烷基，例如可列舉：甲基、乙基、丙基、丁基、戊基、己基、辛基、癸基、及十二烷基等。作為分支的烷基，例如可列舉：異丙基、異丁基、第三丁基、異戊基、及2-乙基己基等。作為環狀的烷基，可列舉：環戊基、環己基、及3-甲基環己基等。Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl. Examples of branched alkyl groups include isopropyl, isobutyl, tertiary butyl, isopentyl, and 2-ethylhexyl. Examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, 3-methylcyclohexyl, and the like.

作為具有羧酸基的碳數1～12的烷基，例如可列舉：羧甲基、2-羧基乙基、4-羧基丁基、2-羧基丁基、6-羧基己基、3-羧基庚基、4-羧基環己基、4-羧甲基環己基等。Examples of the alkyl group having 1 to 12 carbon atoms having a carboxylic acid group include carboxymethyl, 2-carboxyethyl, 4-carboxybutyl, 2-carboxybutyl, 6-carboxyhexyl, and 3-carboxyheptyl. Group, 4-carboxycyclohexyl, 4-carboxymethylcyclohexyl, etc.

該些R1中，就溶劑溶解性的觀點、以及合成容易度的觀點而言，較佳為氫原子、及碳數1～12的烷基，進而佳為氫原子、碳數1～8的烷基，特佳為氫原子、及直鏈的碳數1～8的烷基。Among these R1, from the viewpoint of solvent solubility and ease of synthesis, a hydrogen atom and an alkyl group having 1 to 12 carbon atoms are preferred, and a hydrogen atom and an alkane having 1 to 8 carbon atoms are more preferred. The group is particularly preferably a hydrogen atom and a linear alkyl group having 1 to 8 carbon atoms.

R2表示氫原子、或碳數1～12的烷基。作為碳數1～12的烷基，可列舉：直鏈的烷基、分支的烷基、及環狀的烷基。作為直鏈的烷基、分支的烷基、及環狀的烷基，可使用與所述相同者。R2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group having 1 to 12 carbon atoms include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups. As the linear alkyl group, the branched alkyl group, and the cyclic alkyl group, the same ones as described above can be used.

該些R2中，就抗蝕劑圖案的形狀的觀點而言，較佳為氫原子、及碳數1～8的烷基，進而佳為氫原子、及碳數1～4的烷基，特佳為氫原子、及第三丁基。Among these R2, from the viewpoint of the shape of the resist pattern, a hydrogen atom and an alkyl group having 1 to 8 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are more preferable. Preferred are a hydrogen atom and a tertiary butyl group.

Rf為氫的一部分或全部經氟取代的碳數1～12的烴基。由於Rf的氫的一部分或全部經氟取代，故具有充分的感光度，並且可產生強酸。Rf is a hydrocarbon group having 1 to 12 carbons in which a part or all of hydrogen is substituted with fluorine. Since part or all of the hydrogen of Rf is replaced by fluorine, it has sufficient sensitivity and can generate strong acid.

作為碳數1～12的烴基的氫的一部分或全部經氟取代的基團，可列舉：由CxFy表示的氫原子經氟原子取代的直鏈烷基（Rf1）、分支鏈烷基（Rf2）、環烷基（Rf3）、及芳基（Rf4）等。Examples of groups in which a part or all of the hydrogen of a hydrocarbon group having 1 to 12 carbon atoms are substituted with fluorine include straight chain alkyl groups (Rf1) and branched chain alkyl groups (Rf2) in which hydrogen atoms represented by CxFy are substituted with fluorine atoms. , Cycloalkyl (Rf3), and aryl (Rf4), etc.

作為氫原子經氟原子取代的直鏈烷基（Rf1），例如可列舉：三氟甲基（x=1，y=3）、五氟乙基（x=2，y=5）、七氟丙基（x=3，y=7）、九氟丁基（x=4，y=9）、全氟己基（x=6，y=13）、及全氟辛基（x=8，y=17）等。Examples of linear alkyl groups (Rf1) in which hydrogen atoms are substituted with fluorine atoms include trifluoromethyl (x=1, y=3), pentafluoroethyl (x=2, y=5), and heptafluoromethyl Propyl (x=3, y=7), nonafluorobutyl (x=4, y=9), perfluorohexyl (x=6, y=13), and perfluorooctyl (x=8, y =17) etc.

作為氫原子經氟原子取代的分支鏈烷基（Rf2），例如可列舉：全氟異丙基（x=3，y=7）、全氟第三丁基（x=4，y=9）、及全氟-2-乙基己基（x=8，y=17）等。Examples of branched chain alkyl groups (Rf2) in which hydrogen atoms are substituted with fluorine atoms include perfluoroisopropyl groups (x=3, y=7) and perfluoro tertiary butyl groups (x=4, y=9) , And perfluoro-2-ethylhexyl (x=8, y=17), etc.

作為氫原子經氟原子取代的環烷基（Rf3），例如可列舉：全氟環丁基（x=4，y=7）、全氟環戊基（x=5，y=9）、全氟環己基（x=6，y=11）、及全氟(1-環己基)甲基（x=7，y=13）等。Examples of cycloalkyl groups (Rf3) in which hydrogen atoms are substituted with fluorine atoms include perfluorocyclobutyl (x=4, y=7), perfluorocyclopentyl (x=5, y=9), all Fluorocyclohexyl (x=6, y=11), and perfluoro(1-cyclohexyl)methyl (x=7, y=13), etc.

作為氫原子經氟原子取代的芳基（Rf4），例如可列舉：五氟苯基（x=6，y=5）、及3-三氟甲基四氟苯基（x=7，y=7）等。As an aryl group (Rf4) in which a hydrogen atom is substituted with a fluorine atom, for example, pentafluorophenyl (x=6, y=5) and 3-trifluoromethyltetrafluorophenyl (x=7, y= 7) Wait.

Rf中，就磺酸酯部分的分解性、光阻劑的脫保護性、及原料的獲取容易度的觀點而言，較佳為氫原子經氟原子取代的直鏈烷基（Rf1）、及芳基（Rf4），進而佳為三氟甲基（x=1，y=3、CF₃ ）、五氟乙基（x=2，y=5、C₂ F₅ ）、七氟丙基（x=3，y=7、C₃ F₇ ）、九氟丁基（x=4，y=9、C₄ F₉ ）及五氟苯基（x=6，y=5、C₆ F₅ ），特佳為三氟甲基（x=1，y=3、CF₃ ）。Among Rf, from the viewpoints of the decomposability of the sulfonate portion, the deprotection of the photoresist, and the ease of obtaining raw materials, a linear alkyl group (Rf1) in which a hydrogen atom is substituted with a fluorine atom is preferred, and Aryl (Rf4), more preferably trifluoromethyl (x=1, y=3, CF ₃ ), pentafluoroethyl (x=2, y=5, C ₂ F ₅ ), heptafluoropropyl ( x=3, y=7, C ₃ F ₇ ), nonafluorobutyl (x=4, y=9, C ₄ F ₉ ) and pentafluorophenyl (x=6, y=5, C ₆ F ₅ ), particularly preferably trifluoromethyl (x=1, y=3, CF ₃ ).

構成本發明的非離子系光酸產生劑（A）的取代基{-X-CH(R1)-COO-R2}的鍵結位置並無特別限制，藉由處於2位，可提升貯存穩定性（耐淬滅劑胺（quencher amine）性），藉由處於3位，可提升量子產率，藉由處於4位，可提升莫耳吸光係數。作為取代基{-X-CH(R1)-COO-R2}鍵結位置，就合成方面、及感度方面而言，較佳為3位、或4位。The bonding position of the substituent {-X-CH(R1)-COO-R2} constituting the nonionic photoacid generator (A) of the present invention is not particularly limited. By being at the 2 position, storage stability can be improved (Quencher amine resistance), by being in the 3 position, the quantum yield can be increased, and by being in the 4 position, the molar absorption coefficient can be increased. The bonding position of the substituent {-X-CH(R1)-COO-R2} is preferably the 3-position or the 4-position in terms of synthesis and sensitivity.

本發明的非離子系光酸產生劑（A）的合成方法若能夠合成目標物，則並無特別限定，例如，使3-羥基-1,8-萘二甲酸酐與下述通式（2）的化合物、或4-溴-羥基-1,8-萘二甲酸酐與下述通式（3）的化合物等反應而獲得前驅物（P1），且使前驅物（P1）與羥基胺反應，繼而，與所對應的磺酸酐或磺醯氯反應，藉此可合成非離子系光酸產生劑（A）。The method for synthesizing the nonionic photoacid generator (A) of the present invention is not particularly limited as long as it can synthesize the target product. For example, 3-hydroxy-1,8-naphthalenedicarboxylic acid anhydride is combined with the following general formula (2 ) Compound or 4-bromo-hydroxy-1,8-naphthalenedicarboxylic acid anhydride reacts with the compound of the following general formula (3) to obtain a precursor (P1), and reacts the precursor (P1) with hydroxylamine , And then react with the corresponding sulfonic anhydride or sulfonyl chloride to synthesize a nonionic photoacid generator (A).

[化3]

[化3]

[式（2）中，R1表示氫原子、或可具有羧酸基的碳數1～12的烷基，R2表示氫原子、或碳數1～12的烷基，Hal表示氯、溴、或碘][In formula (2), R1 represents a hydrogen atom or an alkyl group having 1 to 12 carbons which may have a carboxylic acid group, R2 represents a hydrogen atom or an alkyl group having 1 to 12 carbons, and Hal represents chlorine, bromine, or iodine]

[化4]

[化4]

[式（3）中，R1表示氫原子、或可具有羧酸基的碳數1～12的烷基，R2表示氫原子、或碳數1～12的烷基。SH表示硫醇基][In formula (3), R1 represents a hydrogen atom or an alkyl group having 1 to 12 carbons which may have a carboxylic acid group, and R2 represents a hydrogen atom or an alkyl group having 1 to 12 carbons. SH represents thiol group]

作為3-羥基-1,8-萘二甲酸酐與通式（2）的化合物、或4-溴-羥基-1,8-萘二甲酸酐與通式（3）的化合物等的反應條件，是於溫度-30℃～100℃下進行1小時～50小時，為了快速且產率良好地結束反應，較佳為使用反應溶媒及鹼觸媒。作為反應溶媒，並無特別限定，較佳為乙腈、四氫呋喃、二氯甲烷、氯仿等。作為鹼觸媒，例如較佳為吡啶、甲基嗎啉、二甲基胺基吡啶、2,6-二甲吡啶、三乙胺、咪唑、1,8-二氮雜雙環[5.4.0]十一碳-7-烯（1,8-diazabicyclo[5.4.0]undec-7-ene，DBU）、氫化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉等，通常相對於3-羥基-1,8-萘二甲酸酐而添加1 mol%～100 mol%。 3-羥基-1,8-萘二甲酸酐與通式（2）的化合物、或4-溴-羥基-1,8-萘二甲酸酐與通式（3）的化合物等的莫耳比通常是以1：1～1：4進行。As the reaction conditions of 3-hydroxy-1,8-naphthalenedicarboxylic acid anhydride and the compound of general formula (2), or 4-bromo-hydroxy-1,8-naphthalenedicarboxylic acid anhydride and the compound of general formula (3), etc., It is carried out at a temperature of -30°C to 100°C for 1 hour to 50 hours. In order to complete the reaction quickly and with good yield, it is preferable to use a reaction solvent and an alkali catalyst. The reaction solvent is not particularly limited, but acetonitrile, tetrahydrofuran, dichloromethane, chloroform, etc. are preferred. As the base catalyst, for example, pyridine, methylmorpholine, dimethylaminopyridine, 2,6-lutidine, triethylamine, imidazole, 1,8-diazabicyclo[5.4.0] Undec-7-ene (1,8-diazabicyclo[5.4.0]undec-7-ene, DBU), sodium hydride, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, etc., usually relative to 3- Hydroxy-1,8-naphthalenedicarboxylic acid anhydride is added 1 mol% to 100 mol%. The molar ratio of 3-hydroxy-1,8-naphthalenedicarboxylic acid anhydride and the compound of general formula (2), or 4-bromo-hydroxy-1,8-naphthalic acid anhydride and the compound of general formula (3) is usually It is carried out at 1:1 to 1:4.

關於使前驅物（P1）與羥基胺反應、繼而與所對應的磺酸酐或磺醯氯反應而獲得的本發明的非離子系光酸產生劑（A），視需要可藉由利用適當的有機溶媒進行再結晶而進行精製。Regarding the nonionic photoacid generator (A) of the present invention obtained by reacting the precursor (P1) with hydroxylamine and then reacting with the corresponding sulfonic anhydride or sulfonyl chloride, it can be obtained by using a suitable organic The solvent is recrystallized and refined.

為了使本發明的非離子系光酸產生劑（A）容易地溶解於抗蝕劑材料，亦可預先溶於不阻礙反應的溶劑中。In order to easily dissolve the nonionic photoacid generator (A) of the present invention in the resist material, it may be dissolved in a solvent that does not inhibit the reaction in advance.

作為溶劑，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 include carbonates (propylene carbonate, ethylene carbonate, -1,2-butyl carbonate, dimethyl carbonate, diethyl carbonate, etc.); esters (ethyl acetate, ethyl lactate, etc.) , 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.) and so on.

於使用溶劑的情況下，相對於本發明的光酸產生劑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, 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 relative to 100 parts by weight of the photoacid generator of the present invention.

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（A）作為必須成分，因此藉由進行紫外線照射及曝光後加熱（PEB），而使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（A）可單獨使用一種，或組合兩種以上使用。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（A）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（A）的混合物。The resin composition (Q) for photolithography of the present invention contains a non-ionic photoacid generator (A) as an essential component. Therefore, by performing ultraviolet radiation and post-exposure heating (PEB), the exposed part and the unexposed part There is a difference in the solubility of the developer. The nonionic photoacid generator (A) can be used alone or in combination of two or more. As the resin composition (Q) for photolithography, a mixture of a negative chemically amplified resin (QN) and a nonionic photoacid generator (A); and a positive chemically amplified resin (QP) and a nonionic optical A mixture of acid generators (A).

作為負型化學增幅樹脂（QN），包含：含酚性羥基的樹脂（QN1）與交聯劑（QN2）。As a negative chemically amplified resin (QN), it contains 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等。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。此外，該些含酚性羥基的樹脂（QN1）可單獨使用一種，亦可混合兩種以上使用。The phenolic hydroxyl-containing resin (QN1) is not particularly limited as long as it is a phenolic hydroxyl-containing resin. For example, novolak resin, polyhydroxystyrene, copolymer of hydroxystyrene, hydroxystyrene and benzene can be used Copolymer of ethylene, copolymer of hydroxystyrene, 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, etc. 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 alone or in combination of two or more.

所述酚醛清漆樹脂例如可藉由於觸媒的存在下使酚類與醛類縮合來獲得。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、2,3-二甲苯酚、2,4-二甲苯酚、2,5-二甲苯酚、2,6-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚、2,3,5-三甲苯酚、3,4,5-三甲苯酚、鄰苯二酚、間苯二酚、鄰苯三酚、α-萘酚、β-萘酚等。另外，作為所述醛類，可列舉：甲醛、三聚甲醛（paraformaldehyde）、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, pyrogallol, α-naphthol, β-naphthol, etc. Moreover, as said aldehydes, formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, etc. are mentioned.

作為具體的酚醛清漆樹脂，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等。As specific novolak resins, for example, phenol/formaldehyde condensation novolak resins, cresol/formaldehyde condensation novolak resins, phenol-naphthol/formaldehyde condensation novolak resins, and the like can be cited.

另外，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}雙酚等。該些酚性低分子化合物可單獨使用一種，亦可混合兩種以上使用。In addition, the phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low-molecular compound as a part of the component. As the phenolic low-molecular compound, for example, 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 and the like. These phenolic low-molecular-weight compounds may be used alone or in combination of two or more.

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，更佳為1重量%～30重量%。When the phenolic hydroxyl group-containing resin (QN1) is set to 100% by weight, the content of the phenolic low-molecular compound in the phenolic hydroxyl group-containing resin (QN1) is preferably 40% by weight or less, more preferably It is 1% by weight to 30% by weight.

就所得的絕緣膜的解析性、熱衝擊性、耐熱性、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，更佳為2000～20000左右。另外，於將除去溶劑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%，更佳為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而形成的膜具有基於鹼性水溶液的充分的顯影性，故而較佳。From the viewpoints of the resolution, thermal shock, heat resistance, residual film rate, etc. of the resulting insulating film, the weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2000 or more, more preferably about 2000 to 20000 . In addition, when the entire composition from which the solvent is removed 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 % 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 based on an alkaline aqueous solution, and therefore is relatively good.

作為交聯劑（QN2），若為可藉由自非離子系光酸產生劑（A）產生的強酸而將含酚性羥基的樹脂（QN1）交聯的化合物，則並無特別限定。The crosslinking agent (QN2) is not particularly limited if it is a compound that can crosslink the phenolic hydroxyl group-containing resin (QN1) by a strong acid generated from the nonionic photoacid generator (A).

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（benzoguanamine）化合物、含羥甲基的脲（urea）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、含羧甲基的三聚氰胺樹脂、含羧甲基的苯並胍胺樹脂、含羧甲基的脲樹脂、含羧甲基的酚樹脂、含羧甲基的三聚氰胺化合物、含羧甲基的苯並胍胺化合物、含羧甲基的脲化合物及含羧甲基的酚化合物等。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 resin ring Oxygen compounds, poly(hydroxystyrene) epoxy compounds, oxetane compounds, methylol-containing melamine compounds, methylol-containing benzoguanamine compounds, methylol-containing urea ( urea) compound, methylol-containing phenol compound, alkoxyalkyl-containing melamine compound, alkoxyalkyl-containing benzoguanamine compound, alkoxyalkyl-containing urea compound, alkoxyalkyl-containing Phenolic compounds, carboxymethyl-containing melamine resins, carboxymethyl-containing benzoguanamine resins, carboxymethyl-containing urea resins, carboxymethyl-containing phenol resins, carboxymethyl-containing melamine compounds, carboxymethyl-containing Methyl benzoguanamine compounds, carboxymethyl-containing urea compounds, carboxymethyl-containing phenol compounds, etc.

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等）、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塞梅爾（CYMEL）300、CYMEL301、CYMEL303、CYMEL305（三井氰胺（股）製造）等商品名而市售，含甲氧基甲基的甘脲化合物以CYMEL1174（三井氰胺（股）製造）等商品名而市售，另外，含甲氧基甲基的脲（Urea）化合物以MX290（三和化學（股）製造）等商品名而市售。Among the crosslinking agents (QN2), preferred are methylol-containing phenol compounds, methoxymethyl-containing melamine compounds, methoxymethyl-containing phenol compounds, and methoxymethyl-containing glycolurils Compounds, methoxymethyl-containing urea compounds and acetoxymethyl-containing phenol compounds, more preferably methoxymethyl-containing melamine compounds (such as hexamethoxymethyl melamine, etc.), methoxy-containing Methyl glycoluril compounds and methoxymethyl-containing urea compounds, etc. Methoxymethyl-containing melamine compounds are commercially available under the trade names of Semel (CYMEL) 300, CYMEL301, CYMEL303, CYMEL305 (manufactured by Mitsui Cyanamide Co., Ltd.), and methoxymethyl-containing glycoluril compounds are CYMEL1174 (manufactured by Mitsui Cyanamide Co., Ltd.) is commercially available, and a methoxymethyl-containing urea (Urea) compound is commercially available under brand names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

就殘膜率的降低、圖案的扭曲或膨潤以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 distortion 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%, more preferably 15 mol%～40 mol%.

作為正型化學增幅樹脂（QP），可列舉：將含有酚性羥基、羧基、或磺醯基等一種以上的酸性官能基的鹼可溶性樹脂（QP1）中的酸性官能基的氫原子的一部分或全部以酸解離性基取代而成的保護基導入樹脂（QP2）。此外，酸解離性基是可於強酸的存在下解離的基團，所述強酸由非離子系光酸產生劑（A）產生。關於保護基導入樹脂（QP2），其自身為鹼不溶性或鹼難溶性。Examples of positive chemical amplification resins (QP) include: adding a part of hydrogen atoms of acidic functional groups in alkali-soluble resins (QP1) containing one or more acidic functional groups such as phenolic hydroxyl groups, carboxyl groups, or sulfonyl groups, or All protective groups substituted with acid dissociable groups are introduced into the resin (QP2). In addition, the acid-dissociable group is a group that can be dissociated in the presence of a strong acid generated by the nonionic photoacid generator (A). Regarding the protective group introduction resin (QP2), it itself is alkali-insoluble or poorly alkali-soluble.

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), and sulfonic acid group-containing resins (QP13). As the phenolic hydroxyl group-containing resin (QP11), the same as the 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（Ba）、與視需要的含疏水基的乙烯基單體（Bb）進行乙烯基聚合而獲得。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 (Ba) can be combined with an optional hydrophobic group-containing vinyl monomer. The body (Bb) is obtained by vinyl polymerization.

作為含羧基的乙烯基單體（Ba），例如可列舉：不飽和單羧酸[(甲基)丙烯酸、丁烯酸及桂皮酸等]、不飽和多元（2元～4元）羧酸[(無水)順丁烯二酸、衣康酸、反丁烯二酸及檸康酸等]、不飽和多元羧酸烷基（碳數1～10的烷基）酯[順丁烯二酸單烷基酯、反丁烯二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]。就聚合性及獲取容易度的觀點而言，該些中較佳的是不飽和單羧酸，進而佳的是(甲基)丙烯酸。As the carboxyl group-containing vinyl monomer (Ba), for example, unsaturated monocarboxylic acid [(meth)acrylic acid, crotonic acid, cinnamic acid, etc.], unsaturated polybasic (divalent to tetravalent) carboxylic acid [ (Anhydrous) maleic acid, itaconic acid, fumaric acid, citraconic acid, etc.], unsaturated polycarboxylic acid alkyl (alkyl with 1 to 10 carbons) ester [maleic acid mono Alkyl esters, monoalkyl fumarates and citraconic acid monoalkyl esters, etc.], and their salts [alkali metal salts (sodium and potassium salts, etc.), alkaline earth metal salts (calcium and magnesium Salt, etc.), amine salt and ammonium salt, etc.]. From the viewpoint of polymerizability and ease of availability, among these, unsaturated monocarboxylic acid is preferable, and (meth)acrylic acid is more preferable.

作為含疏水基的乙烯基單體（Bb），可列舉(甲基)丙烯酸酯（Bb1）、及芳香族烴單體（Bb2）等。Examples of the hydrophobic group-containing vinyl monomer (Bb) include (meth)acrylate (Bb1), aromatic hydrocarbon monomer (Bb2), and the like.

作為(甲基)丙烯酸酯（Bb1），例如可列舉：烷基的碳數為1～20的(甲基)丙烯酸烷基酯[例如(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)丙烯酸二環戊基酯、(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 (Bb1) include alkyl (meth)acrylates having an alkyl group of 1 to 20 carbon atoms [for example, methyl (meth)acrylate, ethyl (meth)acrylate) , N-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, etc.] And alicyclic group-containing (meth)acrylates [dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, etc.].

作為芳香族烴單體（Bb2），例如可列舉：具有苯乙烯骨架的烴單體[例如苯乙烯、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]及乙烯基萘等。As the aromatic hydrocarbon monomer (Bb2), for example, hydrocarbon monomers having a styrene skeleton [for example, styrene, α-methylstyrene, vinyl toluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene and benzyl styrene] and vinyl naphthalene.

含羧基的樹脂（QP12）中，（Ba）/（Bb）的添加單體莫耳比通常為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。In the carboxyl group-containing resin (QP12), the molar ratio of (Ba)/(Bb) added monomers 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.

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（Bc）與視需要的含疏水基的乙烯基單體（Bb）進行乙烯基聚合而獲得。作為含疏水基的乙烯基單體（Bb），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 (Bc) can be combined with an optional hydrophobic The base vinyl monomer (Bb) is obtained by vinyl polymerization. As the hydrophobic group-containing vinyl monomer (Bb), the same ones as described above can be used.

作為含磺酸基的乙烯基單體（Bc），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)丙烯醯胺基-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、1級～3級胺鹽、銨鹽及四級銨鹽等。Examples of the sulfonic acid group-containing vinyl monomer (Bc) include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, 2-( Meth)acrylamido-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，（Bc）/（Bb）的添加單體莫耳比通常為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。In the sulfonic acid group-containing resin (QP13), the molar ratio of (Bc)/(Bb) added monomer 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）的親水性-親油性均衡（hydrophile-lipophile balance，HLB）值根據鹼可溶性樹脂（QP1）的樹脂骨架而較佳範圍不同，較佳為4～19，進而佳為5～18，特佳為6～17。 HLB值若為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 hydrophilic-lipophile balance (HLB) value of the alkali-soluble resin (QP1) differs in the preferred range depending on the resin skeleton of the alkali-soluble resin (QP1), and is preferably 4-19, and more preferably 5~ 18. Especially preferred is 6-17. If the HLB value is 4 or more, the developability during development is better; if it is 19 or less, the water resistance of the cured product is better.

此外，本發明中的HLB值是基於小田法的HLB值，是指親水性-疏水性均衡值，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≒10×無機性/有機性另外，無機性的值及有機性的值詳細記載於：文獻「界面活性劑的合成及其應用」（槇書店發行，小田、寺村著）的501頁；或「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。In addition, the HLB value in the present invention is an HLB value based on the Oda method, which means a hydrophilicity-hydrophobicity balance value, and can be calculated from the ratio of the organic value and the inorganic value of an organic compound. HLB≒10×Inorganic/Organic In addition, the values of inorganic and organic properties are described in detail on page 501 of the document "Synthesis and Application of Surfactants" (published by Maki Bookstore, by Oda and Teramura); or "Introduction to New Surfactants" ( By Fujimoto Takehiko, published by Sanyo Chemical Industry Co., Ltd.) page 198.

作為保護基導入樹脂（QP2）中的酸解離性基，例如可列舉：經取代的甲基、1-經取代的乙基、1-分支烷基、矽烷基、鍺烷基（germyl group）、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，亦可組合兩種以上使用。The acid dissociable group introduced into the resin (QP2) as the protective group includes, for example, a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, Alkoxycarbonyl, acyl and cyclic acid dissociable groups, etc. These can be used alone or in combination of two or more.

作為1-經取代的甲基，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、苄氧基甲基、苄硫基甲基、苯甲醯甲基、溴苯甲醯甲基、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（piperonyl）、甲氧基羰基甲基、乙氧基羰基甲基、正丙氧基羰基甲基、異丙氧基羰基甲基、正丁氧基羰基甲基、第三丁氧基羰基甲基等。Examples of 1-substituted methyl groups include methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, and benzyloxymethyl. Benzyl, benzylthiomethyl, benzylmethyl, bromobenzylmethyl, methoxybenzylmethyl, methylthiobenzylmethyl, α-methylbenzylmethyl, cyclo Propylmethyl, benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthio Benzyl, piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tertiary butyl Oxycarbonylmethyl, etc.

作為1-經取代的乙基，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-正丙氧基羰基乙基、1-異丙氧基羰基乙基、1-正丁氧基羰基乙基、1-第三丁氧基羰基乙基等。Examples of 1-substituted ethyl groups include 1-methoxyethyl, 1-methylthioethyl, 1,1-dimethoxyethyl, 1-ethoxyethyl, 1- Ethylthioethyl, 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-n-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1- N-butoxycarbonylethyl, 1-tert-butoxycarbonylethyl, etc.

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、1,1-二甲基丁基等。Examples of 1-branched alkyl groups include isopropyl, second butyl, tertiary butyl, 1,1-dimethylpropyl, 1-methylbutyl, and 1,1-dimethylbutyl Base etc.

作為矽烷基，例如可列舉：三甲基矽烷基、乙基二甲基矽烷基、甲基二乙基矽烷基、三乙基矽烷基、異丙基二甲基矽烷基、甲基二異丙基矽烷基、三異丙基矽烷基、第三丁基二甲基矽烷基、甲基二-第三丁基矽烷基、三-第三丁基矽烷基、苯基二甲基矽烷基、甲基二苯基矽烷基、三苯基矽烷基等三-二價碳基矽烷基。Examples of silyl groups include trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, and methyldiisopropyl Silyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, methyldi-tert-butylsilyl group, tri-tert-butylsilyl group, phenyldimethylsilyl group, methyl Tri-divalent carbosilyl groups such as diphenylsilyl group and triphenylsilyl group.

作為鍺烷基，例如可列舉：三甲基鍺烷基、乙基二甲基鍺烷基、甲基二乙基鍺烷基、三乙基鍺烷基、異丙基二甲基鍺烷基、甲基二異丙基鍺烷基、三異丙基鍺烷基、第三丁基二甲基鍺烷基、甲基二-第三丁基鍺烷基、三-第三丁基鍺烷基、苯基二甲基鍺烷基、甲基二苯基鍺烷基、三苯基鍺烷基等三-二價碳基鍺烷基。Examples of the germanyl group include: trimethylgermanyl, ethyldimethylgermanyl, methyldiethylgermanyl, triethylgermanyl, and isopropyldimethylgermanyl , Methyldiisopropylgermanyl, triisopropylgermanyl, tertiary butyldimethylgermanyl, methyldi-tertiary butylgermanyl, tri-tertiary butylgermane Tri-divalent carbon-germanyl groups such as phenylgermanyl, phenyldimethylgermanyl, methyldiphenylgermanyl, and triphenylgermanyl.

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、第三丁氧基羰基等。Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tertiary 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、特戊醯基、異戊醯基、月桂醯基、肉豆蔻醯基（myristoyl）、軟脂醯基（palmitoyl）、硬脂醯基、乙二醯基、丙二醯基、丁二醯基、戊二醯基、己二醯基、胡椒基（piperoyl）、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、順丁烯二醯基、反丁烯二醯基、中康醯基（mesaconoyl）、莰二醯基、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（hydratropoyl）、阿托醯基（atropoyl）、桂皮醯基、呋喃甲醯基、噻吩甲醯基（thenoyl）、菸醯基（nicotinoyl）、異菸醯基、對甲苯磺醯基、甲磺醯基等。Examples of the acyl group include acetyl group, propyl group, butyryl group, heptyl group, hexyl group, pentamyl group, p-pentylyl group, isopentylyl group, lauryl group, myristoyl group (myristoyl group). ), palmitoyl (palmitoyl), stearyl, oxalanyl, malonyl, diacetyl, glutaryl, hexadiyl, piperoyl, suberyl , Azelayl, sebacyl, acryloyl, propynyl, methacryloyl, butenyl, oleyl, maleyl, fumaryl, medium Conoyl (mesaconoyl), campanyl, benzyl, phthaloyl, m-phthaloyl, terephthaloyl, naphthoyl, toluyl, hydrogen attoran Hydratropoyl, atropoyl, cinnamyl, furanoyl, thenoyl, nicotinyl, isonicotinoyl, p-toluenesulfonyl, methanesulfonate Li Ji et al.

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（tetrahydrothiopyranyl）、四氫硫呋喃基（tetrahydrothiofuranyl）、3-溴四氫吡喃基、4-甲氧基四氫吡喃基、4-甲氧基四氫噻喃基、3-四氫噻吩-1,1-二氧化物基等。Examples of cyclic acid dissociable groups include cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, and tetrahydrothiopyranyl. (Tetrahydrothiopyranyl), tetrahydrothiofuranyl (tetrahydrothiofuranyl), 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl, 3-tetrahydrothiophene- 1,1-dioxide base, etc.

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呋喃基等。Among these acid-dissociable groups, tertiary butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tertiary butoxycarbonyl, third Butoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl and tetrahydrothiofuranyl, etc.

保護基導入樹脂（QP2）中酸解離性基的導入率{酸解離性基的數量相對於保護基導入樹脂（QP2）中未經保護的酸性官能基與酸解離性基的合計數的比例}雖然視酸解離性基或該基所導入的鹼可溶性樹脂的種類而不能籠統地規定，但較佳為10%～100%，進而佳為15%～100%。The introduction rate of acid dissociable groups in the protective group introduction resin (QP2) {the ratio of the number of acid dissociable groups to the total number of unprotected acid functional groups and acid dissociable groups in the protective group introduction resin (QP2)} Although it cannot be specified generally depending on the acid dissociable group or the kind of alkali-soluble resin into which the group is introduced, it is preferably 10% to 100%, and more preferably 15% to 100%.

保護基導入樹脂（QP2）的藉由凝膠滲透層析法（Gel Permeation Chromatography，GPC）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-converted weight average molecular weight (hereinafter referred to as "Mw") measured by Gel Permeation Chromatography (GPC) of the protective group introduction resin (QP2) is preferably 1,000 to 150,000, and more preferably 3,000～100,000.

另外，保護基導入樹脂（QP2）的Mw與藉由凝膠滲透層析法（GPC）測定的聚苯乙烯換算數量平均分子量（以下稱為「Mn」）的比（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-introducing 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.

以攝影術用樹脂組成物（Q）的固體成分的重量為基準，非離子系光酸產生劑（A）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，則可更良好地發揮對紫外線的感度，若為20重量%以下，則可更良好地發揮對鹼性顯影液不溶部分的物性。Based on the weight of the solid content of the resin composition (Q) for photography, the content of the nonionic photoacid generator (A) is preferably 0.001% by weight to 20% by weight, 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.

使用本發明的攝影術用樹脂組成物（Q）的抗蝕劑例如可藉由以下方式形成：使用旋轉塗佈、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）於既定的有機溶劑而成的樹脂溶液塗佈於基板上，然後藉由加熱或熱風吹附而使溶劑乾燥。The resist using the resin composition (Q) for photography 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. , Coating a resin solution made by dissolving (in the case of containing inorganic fine particles, dissolving and dispersing) in a predetermined organic solvent on the substrate, and then drying the solvent by heating or hot air blowing.

作為使攝影術用樹脂組成物（Q）溶解的有機溶劑，若可使樹脂組成物溶解，並能夠將樹脂溶液調整為可應用於旋轉塗佈等的物性（黏度等），則並無特別限定。例如可使用N-甲基吡咯啶酮、N,N-二甲基甲醯胺、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、丙二醇單甲醚乙酸酯、丙酮及二甲苯等公知的溶媒。就乾燥溫度等觀點而言，該些溶劑中，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），亦能夠單獨或組合兩種以上使用。於使用有機溶劑的情況下，溶劑的調配量並無特別限定，以攝影術用樹脂組成物（Q）的固體成分的重量為基準，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%。The organic solvent for dissolving the resin composition (Q) for photography is not particularly limited as long as the resin composition can be dissolved and the resin solution can be adjusted to the physical properties (viscosity, etc.) applicable to spin coating. . For example, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate can be used Well-known solvents such as ester, ethyl lactate, propylene glycol monomethyl ether acetate, acetone and xylene. From the viewpoint of drying temperature, 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) are preferred. , 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 photographic resin composition (Q), 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，較佳為於50℃～2000℃下、在2分鐘～30分鐘的範圍內實施，藉由乾燥後的攝影術用樹脂組成物（Q）的殘留溶劑量（重量%）等來適當決定。The drying conditions of the resin solution after application vary depending on the solvent used, and it is preferably carried out at 50°C to 2000°C in the range of 2 minutes to 30 minutes. The dried resin composition for photography (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。然後，於進行曝光後加熱（PEB）後，進行鹼性顯影，而形成配線圖案。After forming the resist on the substrate, light irradiation in the shape of the wiring pattern is performed. Then, after performing post-exposure heating (PEB), alkaline development is performed to form a wiring pattern.

作為光照射的方法，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。作為光照射所使用的光化射線，若可使本發明的攝影術用樹脂組成物（Q）中的非離子系光酸產生劑（A）分解，則並無特別限制。作為光化射線，有低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙燈、金屬鹵素燈、電子束照射裝置、X射線照射裝置、雷射（氬雷射、色素雷射、氮雷射、發光二極體（light emitting diode，LED）、氦鎘雷射等）等。該些中，較佳為高壓水銀燈及超高壓水銀燈。As a method of 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 they can decompose the nonionic photoacid generator (A) in the resin composition (Q) for photography of the present invention. 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, pigment lasers, nitrogen lasers) , Light emitting diode (light emitting diode, LED), helium cadmium laser, etc.). Among these, high-pressure mercury lamps and ultra-high-pressure mercury lamps 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℃。若未滿40℃，則無法充分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異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，通常若未滿0.5分鐘～120分鐘，則時間與溫度的控制困難；若多於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. If the temperature is less than 40°C, the deprotection reaction or the crosslinking reaction cannot proceed sufficiently, so the difference in solubility between the UV-irradiated part and the UV-unirradiated part is insufficient, and the pattern cannot be formed; if it is higher than 200°C, the productivity may decrease problem. As the heating time, generally, if it is less than 0.5 minutes to 120 minutes, it is difficult to control the time and temperature; if it is longer than 120 minutes, there is a problem of reduced productivity.

作為鹼性顯影的方法，可列舉使用鹼性顯影液而溶解去除為配線圖案形狀的方法。作為鹼性顯影液，若為使攝影術用樹脂組成物（Q）的紫外線照射部與紫外線未照射部的溶解性產生差異的條件，則並無特別限制。作為鹼性顯影液，有氫氧化鈉水溶液、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添加水溶性的有機溶劑。作為水溶性的有機溶劑，有甲醇、乙醇、異丙醇、四氫呋喃、N-甲基吡咯啶酮等。As a method of alkaline development, the method of dissolving and removing into a wiring pattern shape using an alkaline developer is mentioned. The alkaline developer is not particularly limited as long as it is a condition that causes a difference in solubility between the ultraviolet irradiated portion and the ultraviolet non-irradiated portion of the resin composition (Q) for photography. 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 add water-soluble organic solvents. As the water-soluble organic solvent, there are methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone and the like.

作為顯影方法，有使用鹼性顯影液的浸漬方式、沖淋方式、及噴霧方式，較佳為噴霧方式的方法。顯影液的溫度較佳為於25℃～40℃下使用。顯影時間根據抗蝕劑的厚度而適當決定。 [實施例]As the image development method, there are a dipping method, a shower method, and a spray method using an alkaline developer, and a spray method is preferred. The temperature of the developer 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對本發明進一步加以說明，但本發明並不限定於該些例子。以下，只要未作特別說明，則%表示重量%，份表示重量份。Hereinafter, the present invention will be further described with examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, unless otherwise specified,% means weight %, and part means weight part.

＜實施例1＞於三角燒瓶中使3-羥基-1,8-萘二甲酸酐(東京化成工業公司製造)21份、及碳酸鉀27份分散於乙腈400份中之後，投入氯乙酸第三丁酯(東京化成工業公司製造)30份並於75℃下反應6小時。繼而，將碳酸鉀過濾去除後，滴加投入50%羥基胺水溶液（東京化成工業公司製造）18份並於室溫下反應2小時。反應結束後，將反應液投入至離子交換水中，然後投入鹽酸，直至成為pH5為止。攪拌片刻後，將析出物過濾回收，於70℃下進行減壓乾燥，而獲得淡黃色固體的前驅物。使乾燥後的前驅物溶解於二氯甲烷500份、及吡啶20份中之後，冷卻為10℃，滴加投入三氟甲磺酸酐（三菱材料電子化成公司製造，EF-18）42份。滴加投入後，於室溫下反應1小時，然後藉由離子交換水進行水洗。將該水洗後的反應液濃縮，並投入甲醇，藉此使結晶析出。將該結晶過濾回收，並於50℃下減壓乾燥，藉此獲得本發明的非離子系光酸產生劑（A-1）。<Example 1> After dispersing 21 parts of 3-hydroxy-1,8-naphthalenedicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 27 parts of potassium carbonate in 400 parts of acetonitrile in an Erlenmeyer flask, put in tert-butyl chloroacetate (Tokyo Chemical Industry Co., Ltd.) Industrial Co.) 30 parts and reacted at 75°C for 6 hours. Then, after removing potassium carbonate by filtration, 18 parts of 50% hydroxylamine aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped and reacted at room temperature for 2 hours. After the completion of the reaction, the reaction liquid was poured into ion-exchanged water, and then hydrochloric acid was poured into it until the pH reached 5. After stirring for a while, the precipitate was filtered and recovered, and dried under reduced pressure at 70°C to obtain a light yellow solid precursor. After dissolving the dried precursor in 500 parts of dichloromethane and 20 parts of pyridine, it was cooled to 10° C., and 42 parts of trifluoromethanesulfonic anhydride (manufactured by Mitsubishi Materials Electronics Kasei Co., Ltd., EF-18) was dropped. After dropping, the reaction was carried out at room temperature for 1 hour, and then washed with ion-exchanged water. The reaction liquid after washing with water was concentrated, and methanol was added to precipitate crystals. This crystal was filtered and recovered, and dried under reduced pressure at 50°C to obtain the nonionic photoacid generator (A-1) of the present invention.

>實施例2> 將氯乙酸第三丁酯30份變更為2-溴丁酸乙酯（東京化成工業公司製造）40份，除此以外，進行與實施例1相同的操作，獲得本發明的非離子系光酸產生劑（A-2）。>Example 2> Except that 30 parts of tert-butyl chloroacetate was changed to 40 parts of ethyl 2-bromobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was performed except that the non-ionic photoacid of the present invention was obtained Producer (A-2).

＜實施例3＞將氯乙酸第三丁酯30份變更為2-溴己酸甲酯（東京化成工業公司製造）40份，除此以外，進行與實施例1相同的操作，獲得本發明的非離子系光酸產生劑（A-3）。<Example 3> Except that 30 parts of tert-butyl chloroacetate was changed to 40 parts of methyl 2-bromohexanoate (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 1 was performed except that the nonionic photoacid of the present invention was obtained Producer (A-3).

＜實施例4＞將3-羥基-1,8-萘二甲酸酐21份變更為4-溴-1,8-萘二甲酸酐（東京化成工業公司製造）28份、將碳酸鉀27份變更為三乙胺11份、以及將氯乙酸第三丁酯30份變更為硫代乙醇酸丁酯（東京化成工業公司製造）16份，除此以外，進行與實施例1相同的操作，獲得本發明的非離子系光酸產生劑（A-4）。<Example 4> Changed 21 parts of 3-hydroxy-1,8-naphthalenedicarboxylic acid anhydride to 28 parts of 4-bromo-1,8-naphthalenedicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and changed 27 parts of potassium carbonate to triethylamine 11 Parts, and 30 parts of tert-butyl chloroacetate was changed to 16 parts of butyl thioglycolate (manufactured by Tokyo Chemical Industry Co., Ltd.), except that the same operation as in Example 1 was performed to obtain the nonionic system of the present invention Photo acid generator (A-4).

＜實施例5＞將硫代乙醇酸丁酯16份變更為硫代乙醇酸2-乙基己酯（東京化成工業公司製造）22份，除此以外，進行與實施例4相同的操作，獲得本發明的非離子系光酸產生劑（A-5）。<Example 5> Except that 16 parts of butyl thioglycolate was changed to 22 parts of 2-ethylhexyl thioglycolate (manufactured by Tokyo Chemical Industry Co., Ltd.), the same operation as in Example 4 was carried out to obtain the nonionic thioglycolate of the present invention. It is a photoacid generator (A-5).

＜實施例6＞將硫代乙醇酸丁酯16份變更為硫代蘋果酸（東京化成工業公司製造）16份、將三乙胺11份變更為35份，除此以外，進行與實施例4相同的操作，獲得本發明的非離子系光酸產生劑（A-6）。<Example 6> Except that 16 parts of butyl thioglycolate was changed to 16 parts of thiomalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 11 parts of triethylamine was changed to 35 parts, the same operation as in Example 4 was performed to obtain The nonionic photoacid generator (A-6) of the present invention.

＜實施例7＞將硫代乙醇酸丁酯16份變更為硫代乳酸（東京化成工業公司製造）12份、將三乙胺11份變更為22份，除此以外，進行與實施例4相同的操作，獲得本發明的非離子系光酸產生劑（A-7）。<Example 7> Except that 16 parts of butyl thioglycolate was changed to 12 parts of thiolactic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 11 parts of triethylamine was changed to 22 parts, the same operation as in Example 4 was performed to obtain this Invented nonionic photoacid generator (A-7).

＜實施例8＞將實施例1中所得的光酸產生劑（A-1）10份溶解於乙酸乙酯100份、氯化氫-乙酸乙酯溶液（約4 mol/L）（和光純藥公司製造）50份中之後，於75℃下反應6小時而除去酯基。繼而，藉由水洗將酸去除後，將溶劑減壓去除，藉此獲得本發明的非離子系光酸產生劑（A-8）。<Example 8> After dissolving 10 parts of the photoacid generator (A-1) obtained in Example 1 in 100 parts of ethyl acetate and 50 parts of hydrogen chloride-ethyl acetate solution (about 4 mol/L) (manufactured by Wako Pure Chemical Industries, Ltd.) , React at 75°C for 6 hours to remove the ester group. Then, after removing the acid by washing with water, the solvent is removed under reduced pressure, thereby obtaining the non-ionic photoacid generator (A-8) of the present invention.

＜實施例9＞於三角燒瓶中使2-溴丁酸40份、二甲基胺基吡啶4份、及第三丁醇80份溶解於二氯甲烷800份中之後，投入1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺鹽酸鹽50份並於室溫下反應3小時。繼而，利用1%鹽酸水溶液清洗後，將溶劑減壓去除，藉此獲得溴丁酸第三丁酯。繼而，將氯乙酸第三丁酯30份變更為藉由所述而獲得的2-溴丁酸第三丁酯40份，除此以外，進行與實施例1相同的操作，獲得本發明的非離子系光酸產生劑（A-9）。<Example 9> After dissolving 40 parts of 2-bromobutyric acid, 4 parts of dimethylaminopyridine, and 80 parts of tertiary butanol in 800 parts of dichloromethane in an Erlenmeyer flask, 1-(3-dimethylamino 50 parts of propyl)-3-ethylcarbodiimide hydrochloride were reacted at room temperature for 3 hours. Then, after washing with a 1% hydrochloric acid aqueous solution, the solvent was removed under reduced pressure, thereby obtaining tert-butyl bromobutyrate. Then, 30 parts of tert-butyl chloroacetate was changed to 40 parts of tert-butyl 2-bromobutyrate obtained as described above, and except for that, the same operation as in Example 1 was carried out to obtain the non-product of the present invention. Ion-based photo acid generator (A-9).

＜實施例10＞將2-溴丁酸變更為2-溴己酸，除此以外，進行與實施例9相同的操作，獲得本發明的非離子系光酸產生劑（A-10）。<Example 10> Except that 2-bromobutyric acid was changed to 2-bromohexanoic acid, the same operation as in Example 9 was performed to obtain the nonionic photoacid generator (A-10) of the present invention.

＜實施例11＞將光酸產生劑（A-1）變更為實施例9中所得的光酸產生劑（A-9），除此以外，進行與實施例8相同的操作，獲得本發明的非離子系光酸產生劑（A-11）。<Example 11> Except for changing the photoacid generator (A-1) to the photoacid generator (A-9) obtained in Example 9, the same operations as in Example 8 were performed to obtain the nonionic photoacid of the present invention Generator (A-11).

＜實施例12＞將光酸產生劑（A-1）變更為實施例11中所得的光酸產生劑（A-11），除此以外，進行與實施例8相同的操作，獲得本發明的非離子系光酸產生劑（A-12）。<Example 12> Except for changing the photoacid generator (A-1) to the photoacid generator (A-11) obtained in Example 11, the same operations as in Example 8 were performed to obtain the nonionic photoacid of the present invention Producer (A-12).

＜比較例1＞直接使用由下述式（4）表示的1,8-萘二甲醯亞胺三氟甲磺酸酯（奧德里奇（Aldrich）公司製造）。<Comparative example 1> 1,8-Naphthalimide triflate (manufactured by Aldrich) represented by the following formula (4) was used as it was.

[化5]

[化5]

＜比較例2＞依據化學學會會刊（J.Chem.Soc.）(C), 1966, p523記載的方法來合成由下述式（5）表示的3-甲氧基-1,8-萘二甲醯亞胺對甲苯磺酸並加以使用。＜Comparative example 2＞ The 3-methoxy-1,8-naphthalenedimide represented by the following formula (5) was synthesized according to the method described in J. Chem. Soc. (C), 1966, p523 Use p-toluenesulfonic acid.

[化6]

[化6]

＜實施例1～實施例9、比較例1～比較例2＞作為光酸產生劑的性能評價，藉由以下方法對實施例1～實施例9中所得的非離子系光酸產生劑（A-1）～非離子系光酸產生劑（A-9）、用於比較的非離子系光酸產生劑（A'-1）～非離子系光酸產生劑（A'-2）的莫耳吸光係數、光分解率、抗蝕劑感度、溶劑溶解性進行評價，將其結果記載於表1中。<Example 1 to Example 9, Comparative Example 1 to Comparative Example 2> As the performance evaluation of the photoacid generator, the nonionic photoacid generator (A-1) to the nonionic photoacid generator (A-9) obtained in Example 1 to Example 9 were evaluated by the following methods. Comparison of non-ionic photoacid generators (A'-1) to non-ionic photoacid generators (A'-2) in terms of molar absorption coefficient, photodecomposition rate, resist sensitivity, and solvent solubility Evaluation and the results are shown in Table 1.

＜莫耳吸光係數＞藉由乙腈將所合成的光酸產生劑稀釋為0.025 mmol/L，使用紫外可見分光光度計（島津製作所公司製造，UV-2550），於200 nm至500 nm的範圍內測定1 cm的單元長的吸光度。由下述式算出i射線（365 nm）的莫耳吸光係數（ε₃₆₅ ）。 ε₃₆₅ （L･mol^-1 ･cm^-1 ）=A₃₆₅ /（0.00025 mol/L×1 cm） [式中，A₃₆₅ 表示365 nm的吸光度]<Mole Absorption Coefficient> Dilute the synthesized photoacid generator to 0.025 mmol/L with acetonitrile, using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-2550), in the range of 200 nm to 500 nm Measure the absorbance of a cell length of 1 cm. The molar absorption coefficient (ε ₃₆₅ ) of i-rays (365 nm) was calculated from the following formula. ε ₃₆₅ (L･mol ^-1 ･cm ^-1 )=A ₃₆₅ /(0.00025 mol/L×1 cm) [where A ₃₆₅ represents the absorbance at 365 nm]

＜光分解率＞將所述調整的0.025 mmol/L的溶液放入至直徑1 cm的試管內，並照射50 mJ/cm² （365 nm）的光。由該溶液的光照射前後的液相層析（liquid chromatography，LC）的面積比算出光酸產生劑的光分解率。光分解率（%）=（S₀ -S₁ ）/S₀ ×100 S₀ ：光照射前的光酸產生劑的LC峰值面積 S₁ ：光照射後的光酸產生劑的LC峰值面積<Photolysis rate> Put the adjusted 0.025 mmol/L solution into a test tube with a diameter of 1 cm, and irradiate it with 50 mJ/cm ² (365 nm) light. The photodecomposition rate of the photoacid generator was calculated from the area ratio of liquid chromatography (LC) before and after the light irradiation of the solution. Photodegradation rate (%)=(S ₀ -S ₁ )/S ₀ ×100 S ₀ : LC peak area of the photo acid generator before light irradiation S ₁ : LC peak area of the photo acid generator after light irradiation

＜抗蝕劑感度＞將利用非離子系光酸產生劑0.2份、環境穩定的化學放大光阻劑（Environmentally Stable Chemically Amplified Photoresist，ESCAP）系聚合物（羥基苯乙烯與丙烯酸第三丁酯共聚物）100份、及丙二醇單甲醚乙酸酯（PGMEA）900份調整的抗蝕劑溶液旋轉塗佈於矽晶圓上之後，於100℃下乾燥4分鐘，藉此獲得6 μm的膜厚的抗蝕劑膜。使用紫外線照射裝置（奧克（ORC）製作所股份有限公司公司製造，HMW-661F-01），以既定量的藉由L-34（肯高（kenko）光學股份有限公司製造，截止未滿340 nm的光的濾波器）濾波器限定了波長的紫外光對該抗蝕劑膜進行全面曝光。此外，累計曝光量是對365 nm的波長進行測定。繼而，於110℃下進行90秒後烘烤（after-bake），然後利用2.38%氫氧化四甲基銨（tetramethylammonium hydroxide，TMAH）水溶液浸漬處理60秒而進行顯影。由該曝光部分的抗蝕劑膜被完全去除的最小曝光量（Eth），依照以下的基準評價抗蝕劑感度。 ○：最小曝光量為50 mJ/cm² 以下 △：最小曝光量超過50 mJ/cm² 且為100 mJ/cm² 以下 ×：最小曝光量超過100 mJ/cm² <Resist Sensitivity> An environmentally stable chemically amplified photoresist (Environmentally Stable Chemically Amplified Photoresist, ESCAP) polymer (copolymer of hydroxystyrene and tertiary butyl acrylate) using 0.2 parts of a nonionic photoacid generator ) 100 parts and 900 parts of propylene glycol monomethyl ether acetate (PGMEA) adjusted resist solution was spin-coated on the silicon wafer and dried at 100°C for 4 minutes to obtain a 6 μm film thickness Resist film. Use an ultraviolet irradiation device (manufactured by ORC Manufacturing Co., Ltd., HMW-661F-01), with a predetermined amount of L-34 (manufactured by Kenko Optical Co., Ltd., cut-off less than 340 nm) The filter defines the wavelength of ultraviolet light to fully expose the resist film. In addition, the cumulative exposure is measured at a wavelength of 365 nm. Subsequently, after-bake was performed at 110° C. for 90 seconds, and then immersion treatment with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds was used for development. From the minimum exposure amount (Eth) at which the resist film of the exposed portion was completely removed, the resist sensitivity was evaluated according to the following criteria. ○: The minimum exposure amount was 50 mJ / cm ² or less △: The minimum exposure amount exceeds 50 mJ / cm ² and is 100 mJ / cm ² or less ×: The minimum exposure amount exceeds 100 mJ / cm ²

＜溶劑溶解性＞取0.3 g所合成的光酸產生劑至試管中，於25℃的溫度調節下添加丙二醇單甲醚乙酸酯（PGMEA）各0.2 g～0.5 g，添加至光酸產生劑完全溶解為止。將該溶解時的固體成分濃度設為溶劑溶解性。此外，於即便添加30 g仍不完全溶解的情況下，評價為不溶解者。＜Solvent solubility＞ Take 0.3 g of the synthesized photo acid generator into a test tube, add 0.2 g～0.5 g of propylene glycol monomethyl ether acetate (PGMEA) under the temperature adjustment of 25°C, and add until the photo acid generator is completely dissolved. The solid content concentration at the time of this dissolution is defined as solvent solubility. In addition, in the case where it did not completely dissolve even if 30 g was added, it was evaluated as insoluble.

[表1] 光酸產生劑 X R1 R2 Rf 莫耳吸光係數光分解率抗蝕劑感度溶劑溶解性實施例1 A-1 -O- -H -t-Bu -CF₃ 7,000 90% ○ 10% 實施例2 A-2 -O- -Et -Et -CF₃ 7,000 90% ○ 30% 實施例3 A-3 -O- -n-Bu -Me -CF₃ 7,200 90% ○ 30% 實施例4 A-4 -S- -H -n-Bu -CF₃ 10,300 95% ○ 10% 實施例5 A-5 -S- -H -2EH -CF₃ 10,300 95% ○ 30% 實施例6 A-6 -S- -CH₂ COOH -H -CF₃ 12,000 95% ○ 15% 實施例7 A-7 -S- -Me -H -CF₃ 12,000 95% ○ 5% 實施例8 A-8 -O- -H -H -CF₃ 8,600 90% ○ 5% 實施例9 A-9 -O- -Et -t-Bu -CF₃ 7,000 90% ○ 30% 實施例10 A-10 -O- -n-Bu -t-Bu -CF₃ 6,600 90% ○ 50% 實施例11 A-11 -O- -Et -H -CF₃ 7,000 90% ○ 15% 實施例12 A-13 -O- -n-Bu -H -CF₃ 7,000 90% ○ 25% 比較例1 A'-1 - - - -CF₃ 400 30% × 1% 比較例2 A'-2 -OMe - - -PhMe 7,000 10% × 2% [Table 1] Photoacid generator X R1 R2 Rf Mole Absorption Coefficient Light decomposition rate Resist sensitivity Solvent solubility Example 1 A-1 -O- -H -t-Bu -CF ₃ 7,000 90% ○ 10% Example 2 A-2 -O- -Et -Et -CF ₃ 7,000 90% ○ 30% Example 3 A-3 -O- -n-Bu -Me -CF ₃ 7,200 90% ○ 30% Example 4 A-4 -S- -H -n-Bu -CF ₃ 10,300 95% ○ 10% Example 5 A-5 -S- -H -2EH -CF ₃ 10,300 95% ○ 30% Example 6 A-6 -S- -CH ₂ COOH -H -CF ₃ 12,000 95% ○ 15% Example 7 A-7 -S- -Me -H -CF ₃ 12,000 95% ○ 5% Example 8 A-8 -O- -H -H -CF ₃ 8,600 90% ○ 5% Example 9 A-9 -O- -Et -t-Bu -CF ₃ 7,000 90% ○ 30% Example 10 A-10 -O- -n-Bu -t-Bu -CF ₃ 6,600 90% ○ 50% Example 11 A-11 -O- -Et -H -CF ₃ 7,000 90% ○ 15% Example 12 A-13 -O- -n-Bu -H -CF ₃ 7,000 90% ○ 25% Comparative example 1 A'-1 - - - -CF ₃ 400 30% × 1% Comparative example 2 A'-2 -OMe - - -PhMe 7,000 10% × 2%

本發明的非離子系光酸產生劑對i射線（365 nm）的莫耳吸光係數高、另外光分解率優異，故作為薄膜抗蝕劑用途而言有用。另外，可知對溶劑的溶解性亦為5%以上，對於用作光阻劑而言具有充分的性能。另一方面，可知於包含不具有取代基的萘基醯亞胺骨架的比較例1中，對i射線的吸收不充分，且萘基骨架彼此容易發生分子配向而結晶性變高，故對溶劑的溶解性過低。另外，可知於Rf的氫原子未經氟取代的比較例2中，雖然對i射線的吸收充分，但光分解率低。另外，可知取代基為甲氧基，不具有充分的極性及大小，故溶劑溶解性不足。 [產業上之可利用性]The non-ionic photoacid generator of the present invention has a high molar absorption coefficient for i-rays (365 nm) and an excellent photolysis rate, so it is useful as a thin film resist. In addition, it can be seen that the solubility in solvents is also 5% or more, and it has sufficient performance for use as a photoresist. On the other hand, it can be seen that in Comparative Example 1 containing a naphthyl imine skeleton without substituents, the absorption of i-rays is insufficient, and the naphthyl skeletons are likely to be molecularly aligned with each other and the crystallinity becomes high. The solubility is too low. In addition, it can be seen that in Comparative Example 2 in which the hydrogen atom of Rf is not substituted with fluorine, although the absorption of i-rays is sufficient, the photolysis rate is low. In addition, it can be seen that the substituent is a methoxy group, which does not have sufficient polarity and size, so the solvent solubility is insufficient. [Industrial availability]

本發明的非離子系光酸產生劑（A）對i射線具有高感光度、對抗蝕劑溶液的相溶性及溶解性優異、另外耐熱穩定性優異，故作為以半導體的製造為代表的微細加工用的光微影材料而言有用。The nonionic photoacid generator (A) of the present invention has high sensitivity to i-rays, excellent compatibility and solubility with resist solutions, and excellent heat resistance stability, so it is used as a microfabrication typified by the manufacture of semiconductors. The photolithography material used is useful.

Claims

一種非離子系光酸產生劑（A），其特徵在於由下述通式（1）表示；

式（1）中，X表示氧原子、或硫原子，R1表示氫原子、或可具有羧酸基的碳數1～12的烷基，R2表示氫原子、或碳數1～12的烷基，Rf表示氫的一部分或全部經氟取代的碳數1～12的烴基。A non-ionic photoacid generator (A) characterized by being represented by the following general formula (1);

In formula (1), X represents an oxygen atom or a sulfur atom, R1 represents a hydrogen atom or an alkyl group having 1 to 12 carbons which may have a carboxylic acid group, and R2 represents a hydrogen atom or an alkyl group having 1 to 12 carbons , Rf represents a hydrocarbon group of 1 to 12 carbons in which part or all of hydrogen is substituted with fluorine.

如申請專利範圍第1項所述的非離子系光酸產生劑（A），其中於通式（1）中，Rf為CF₃ 、C₂ F₅ 、C₃ F₇ 、C₄ F₉ 、或C₆ F₅ 。The non-ionic photoacid generator (A) described in item 1 of the scope of patent application, wherein in the general formula (1), Rf is CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , Or C ₆ F ₅ .

如申請專利範圍第1項或第2項所述的非離子系光酸產生劑（A），其中於通式（1）中，R2為氫原子、或碳數1～4的烷基。The nonionic photoacid generator (A) described in item 1 or item 2 of the scope of patent application, wherein in the general formula (1), R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

一種光微影用樹脂組成物（Q），包含如申請專利範圍第1項至第3項中任一項所述的非離子系光酸產生劑（A）。A resin composition (Q) for photolithography, comprising the non-ionic photoacid generator (A) described in any one of items 1 to 3 in the scope of patent application.