TWI772641B - Nonionic photoacid generator and resin composition for photolithography - Google Patents

Abstract

本發明提供一種兼具對於高精細的i-光線用光微影抗蝕劑材料所要求的相容性、高感度、熱穩定性、耐鹼性的所有特性的具有萘二甲醯亞胺結構的非離子系光酸產生劑。本發明為一種非離子系光酸產生劑(A)以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：由通式(1)所表示，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 present invention provides a naphthalimide structure having all the properties of compatibility, high sensitivity, thermal stability, and alkali resistance required for high-definition i-ray photolithography resist materials of non-ionic photoacid generators. The present invention is a nonionic photoacid generator (A) and a resin composition (Q) for photolithography, wherein the nonionic photoacid generator (A) is characterized by being represented by the general formula (1) , the resin composition (Q) for photolithography contains the nonionic photoacid generator (A).

[式(1)中，R1為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2~R6中的一個為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，其餘為氫原子，Rf為氟原子、或至少一個以上的氫被氟取代而成的碳數1~18的烴基] [In formula (1), R1 is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkyl carbonate group, and R2~ One of R6 is a hydrocarbon group with a carbon number of 1 to 12, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and the rest are hydrogen atoms, Rf It is a fluorine atom, or a hydrocarbon group with 1 to 18 carbon atoms in which at least one or more hydrogens are replaced by fluorine]

Description

非離子系光酸產生劑及光微影用樹脂組成物 Nonionic 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。更詳細而言，是有關於適於使紫外線(i-光線)起作用而產生強酸的非離子系光酸產生劑、以及含有其的光微影用樹脂組成物。 The present invention relates to a photoacid generator and a resin composition for photolithography. More specifically, it relates to a nonionic photoacid generator suitable for making ultraviolet rays (i-rays) act to generate a strong acid, and a resin composition for photolithography containing the same.

自先前以來，於半導體的製造所代表的微細加工的領域中，廣泛利用使用波長365nm的i-光線作為光源的光微影步驟。 Conventionally, in the field of microfabrication represented by the manufacture of semiconductors, a photolithography process using i-rays having a wavelength of 365 nm as a light source has been widely used.

作為光微影步驟中所使用的抗蝕劑材料，例如可使用含有具有羧酸的第三丁基酯基或苯酚的第三丁基碳酸酯基的聚合體以及光酸產生劑的樹脂組成物。藉由對該抗蝕劑材料照射光而光酸產生劑進行分解並產生三氟甲磺酸等強酸。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第三丁基碳酸酯基等酸反應性基進行解離而形成羧酸基或酚性羥基，紫外線照射部變得易溶於鹼性顯影液中。為了利用該現象進行圖案形成，需要一種具有高的光分解率並可實現節能化或步驟時間的縮短的i-光線高感度的光酸產生劑。 As the resist material used in the photolithography step, for example, a resin composition containing a polymer having a tertiary butyl ester group of a carboxylic acid or a tertiary butyl carbonate group of a phenol and a photoacid generator can be used . When the resist material is irradiated with light, the photoacid generator is decomposed to generate a strong acid such as trifluoromethanesulfonic acid. Furthermore, by performing post-exposure heating (PEB), acid-reactive groups such as a tertiary butyl ester group or a tertiary butyl carbonate group in the polymer are dissociated by the generated acid to form a carboxylic acid group or a phenolic group. Hydroxyl group, the ultraviolet-irradiated part becomes easily soluble in an alkaline developer. In order to form a pattern by utilizing this phenomenon, a photoacid generator with a high photo-decomposition rate and a high sensitivity to i-rays, which can realize energy saving and shortening of the step time, is required.

為了實現進一步的高精細的光微影步驟，提出一種用以解決由於高精細化而產生的新的問題的方法。例如提出：由於需要限制藉由光酸產生劑的分解而產生的強酸的擴散長度，故作為用以解決所述問題的淬滅劑成分，一般將有機胺類添加至抗蝕劑材料 中。另外，藉由鹼性顯影液而圖案的未曝光部發生膨潤的影響變大，因此需要抑制抗蝕劑材料的膨潤。為了解決所述問題，提出如下方法：藉由使抗蝕劑材料中的聚合體含有脂環式骨架、或含氟骨架等而增大疏水性，抑制抗蝕劑材料的膨潤。 In order to realize further high-definition photolithography steps, a method for solving new problems arising from high-definition is proposed. For example, since it is necessary to limit the diffusion length of the strong acid generated by the decomposition of the photoacid generator, organic amines are generally added to the resist material as a quencher component for solving the above problems. middle. Moreover, since the influence of swelling of the unexposed part of a pattern by an alkaline developing solution becomes large, it is necessary to suppress swelling of a resist material. In order to solve the above-mentioned problems, there has been proposed a method of suppressing swelling of the resist material by increasing the hydrophobicity by including an alicyclic skeleton, a fluorine-containing skeleton, or the like in the polymer in the resist material.

作為該些光微影步驟中所使用的抗蝕劑材料中的產生強酸的光酸產生劑，已知有三芳基鋶鹽(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)、磺醯基重氮甲烷結構(專利文獻4)、鄰苯二甲醯亞胺結構(專利文獻5)、或萘二甲醯亞胺結構(專利文獻6、專利文獻7)等的非離子系光酸產生劑。 As a photoacid generator that generates a strong acid among the resist materials used in these photolithography steps, triaryl perylene salts (Patent Document 1) and benzylmethyl perylene salts having a naphthalene skeleton ( Patent Document 2) Plasma-based photoacid generator, and having an oxime sulfonate structure (Patent Document 3), a sulfonyldiazomethane structure (Patent Document 4), and a phthalimide structure (Patent Document 5) , or a nonionic photoacid generator with a naphthalimide structure (Patent Document 6, Patent Document 7).

但是，三芳基鋶鹽或苯甲醯甲基鋶鹽等離子系光酸產生劑相對於實現高精細的抗蝕劑材料中的具有脂環式骨架、及含氟骨架等的疏水性材料而言相容性低，於抗蝕劑材料中進行相分離，故存在無法發揮充分的抗蝕劑性能，無法形成圖案的問題。 However, ionic photoacid generators such as triaryl perionate salts and benzalkonium methyl perionate salts are relatively incompatible with respect to hydrophobic materials having alicyclic skeletons, fluorine-containing skeletons, etc. in resist materials for realizing high definition. Since the capacitance is low and phase separation occurs in the resist material, there is a problem that sufficient resist performance cannot be exhibited and patterns cannot be formed.

具有肟磺酸鹽結構、及磺醯基重氮甲烷結構的非離子系光酸產生劑具有充分的相容性但缺乏熱穩定性，藉由PEB進行分解而產生酸，未曝光部亦成為鹼可溶性，因此存在容許幅度小的問題。 Non-ionic photoacid generators with oxime sulfonate structure and sulfonyldiazomethane structure have sufficient compatibility but lack thermal stability, and are decomposed by PEB to generate acid, and the unexposed part also becomes alkali Soluble, so there is a problem that the tolerance is small.

具有鄰苯二甲醯亞胺結構、萘二甲醯亞胺結構的非離子系光酸產生劑的相容性、及熱穩定性優異，但缺乏耐鹼性，與抗蝕劑材料中的淬滅劑進行反應，因此存在如下問題：抗蝕劑用樹脂組成物的經時變化大，於調配後隨時間經過而無法獲得所期望 的形狀的圖案。 Nonionic photoacid generators with phthalimide structure and naphthalimide structure are excellent in compatibility and thermal stability, but lack alkali resistance, and are not compatible with quenching in resist materials. Since the exterminator reacts, there is a problem that the resin composition for resists varies greatly with time, and the desired result cannot be obtained with time after the preparation. shape pattern.

[現有技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開昭50-151997號公報 [Patent Document 1] Japanese Patent Laid-Open No. 50-151997

[專利文獻2]日本專利特開平9-118663號公報 [Patent Document 2] Japanese Patent Laid-Open No. 9-118663

[專利文獻3]日本專利特開平6-67433號公報 [Patent Document 3] Japanese Patent Laid-Open No. 6-67433

[專利文獻4]日本專利特開平10-213899號公報 [Patent Document 4] Japanese Patent Laid-Open No. 10-213899

[專利文獻5]日本專利第5126873號公報 [Patent Document 5] Japanese Patent No. 5126873

[專利文獻6]日本專利特開2004-217748號公報 [Patent Document 6] Japanese Patent Laid-Open No. 2004-217748

[專利文獻7]日本專利第5990447號公報 [Patent Document 7] Japanese Patent No. 5990447

即，本發明的目的在於提供一種兼具對於高精細的i-光線用光微影抗蝕劑材料所要求的相容性、高感度、熱穩定性、耐鹼性的所有特性的具有萘二甲醯亞胺結構的非離子系光酸產生劑。 That is, an object of the present invention is to provide a naphthalene-diol having compatibility, high sensitivity, thermal stability, and alkali resistance required for high-definition i-ray photolithography resist materials. A nonionic photoacid generator with a carboximide structure.

本發明者等人為了達成所述目的而進行了研究，結果完成了本發明。 The present inventors have completed the present invention as a result of studies in order to achieve the above-mentioned object.

即，本發明為一種非離子系光酸產生劑(A)以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)所表示，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)。 That is, the present invention is a nonionic photoacid generator (A) and a resin composition (Q) for photolithography, wherein the nonionic photoacid generator (A) is characterized by: As indicated by 1), the resin composition (Q) for photolithography contains the nonionic photoacid generator (A).

[式(1)中，R1為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2~R6中的一個為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，其餘為氫原子，Rf為氟原子、或至少一個以上的氫被氟取代而成的碳數1~18的烴基] [In formula (1), R1 is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkyl carbonate group, and R2~ One of R6 is a hydrocarbon group with a carbon number of 1 to 12, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and the rest are hydrogen atoms, Rf It is a fluorine atom, or a hydrocarbon group with 1 to 18 carbon atoms in which at least one or more hydrogens are replaced by fluorine]

本發明的非離子系光酸產生劑(A)由於導入至與萘二甲醯亞胺結構的醯亞胺羰基鄰接的R1的取代基的立體效果，阻礙與分解有關的鹼對羰基的親核攻擊。進而該R1的立體效果使經過開環的分解的遷移狀態不穩定，因此本非離子系光酸產生劑(A)具有高的耐鹼性。另外，由於在R2~R6中的任一者上具有取代基，故可作用於萘環上的電子狀態，相對於i-光線具有高感度。藉此藉由照射i-光線，非離子系光酸產生劑(A)可容易地分解而產生作為強酸的磺酸。由於一併具有非離子性的萘二甲醯亞胺結 構，故與疏水性抗蝕劑材料的相容性優異，並且熱穩定性優異，可進行曝光後加熱(PEB)。 The nonionic photoacid generator (A) of the present invention inhibits the nucleophilic effect of the base on the carbonyl group involved in decomposition due to the steric effect of the substituent introduced into R1 adjacent to the iminocarbonyl group of the naphthalimide structure. attack. Furthermore, the steric effect of this R1 destabilizes the transition state through ring-opening decomposition, so the present nonionic photoacid generator (A) has high alkali resistance. In addition, since it has a substituent on any one of R2 to R6, it can act on the electronic state of the naphthalene ring and has high sensitivity to i-ray. Thereby, the nonionic photoacid generator (A) can be easily decomposed to generate sulfonic acid as a strong acid by irradiating i-ray. Due to the non-ionic naphthalimide junction Because of its structure, it has excellent compatibility with hydrophobic resist materials, and has excellent thermal stability, and can be subjected to post-exposure heating (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)因相對於i-光線而言為高感度且於抗蝕劑材料中的相容性良好，耐鹼性、熱穩定性良好，故經時變化少，且藉由曝光後加熱(PEB)的容許幅度廣，因此作業性優異。 Therefore, the resin composition (Q) for photolithography containing the nonionic photoacid generator (A) of the present invention has high sensitivity with respect to i-ray rays and has good compatibility with resist materials , Alkali resistance and thermal stability are good, so there is little change over time, and the allowable range by post-exposure heating (PEB) is wide, so it is excellent in workability.

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

[式(1)中，R1為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2~R6中的一個為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，其餘為氫 原子，Rf為氟原子、或至少一個以上的氫被氟取代而成的碳數1~18的烴基] [In formula (1), R1 is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkyl carbonate group, and R2~ One of R6 is a hydrocarbon group with a carbon number of 1 to 12, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and the rest are hydrogen Atom, Rf is a fluorine atom, or a hydrocarbon group with 1 to 18 carbon atoms in which at least one or more hydrogens are replaced by fluorine]

R1為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，較佳為碳數1~12的烴基、烷氧基、烷硫基、烷基羰基、烷氧基羰基或烷基碳酸酯基。 R1 is a hydrocarbon group, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group having 1 to 12 carbon atoms, preferably a group having 1 to 12 carbon atoms. Hydrocarbyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl or alkylcarbonate.

作為碳數1~12的烴基，可列舉：直鏈、分支、或環狀的碳數1~12的烷基、碳數2~12的烯基、碳數2~12的炔基及碳數6~12的芳基。 Examples of the hydrocarbon group having 1 to 12 carbon atoms include linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkynyl groups having 2 to 12 carbon atoms, and alkynyl groups having 2 to 12 carbon atoms. 6~12 aryl groups.

作為碳數1~12的烷基，可列舉直鏈、分支、或環狀的烷基(甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、新戊基、第三戊基、1-甲基丁基、環戊基、環己基、辛基、癸基、十二烷基、十氫萘基、薄荷基、降冰片烷基、金剛烷基、甲氧基甲基、乙氧基甲基、2-甲氧基乙基、1-甲氧基乙基、苄氧基甲基、三甲基矽氧基甲基、三乙基矽氧基甲基、三異丙基矽氧基甲基、第三丁基二甲基矽氧基甲基及第三丁基二苯基矽氧基甲基等)等，就原料的獲取性的觀點而言，較佳為碳數1~6的直鏈、分支、或環狀的烷基，特佳為甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、戊基、己基、環戊基及環己基。 Examples of the alkyl group having 1 to 12 carbon atoms include linear, branched, or cyclic alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, th Tributyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, cyclopentyl, cyclohexyl, octyl, decyl, dodecyl, decalinyl, Menthyl, norbornyl, adamantyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 1-methoxyethyl, benzyloxymethyl, trimethylsilyl Oxymethyl, triethylsiloxymethyl, triisopropylsiloxymethyl, tert-butyldimethylsiloxymethyl and tert-butyldiphenylsiloxymethyl, etc. ) etc., from the viewpoint of availability of raw materials, preferably a straight-chain, branched, or cyclic alkyl group having 1 to 6 carbon atoms, particularly preferably methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopentyl and cyclohexyl.

作為碳數2~12的烯基，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、1-十二烯-1-基及降冰片烯基等)等。 Examples of the alkenyl group having 2 to 12 carbon atoms include linear, branched, or cyclic alkenyl groups (vinyl, 1-propenyl, 2-propenyl, 1-buten-1-yl, 2-butene) -1-base, 2-Methyl-2-propenyl, 1-cyclopenten-1-yl, 1-cyclohexen-1-yl, 1-decen-1-yl, 1-dodecen-1-yl and norm Bornenyl, etc.) etc.

作為碳數2~12的炔基，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、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-癸炔-1-基及1-環辛炔-1-基等)等。 Examples of the alkynyl group having 2 to 12 carbon atoms 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-pentyn-1-yl, 3-pentyn-1-yl, 4 -Pentyn-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-decyn-1-yl and 1-cyclooctyn-1-yl, etc.) and the like.

作為碳數6~12的芳基，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、2,4-二甲苯基、2,6-二甲苯基、3,5-二甲苯基、2,4,6-均三甲苯基、3,5-雙三氟甲基苯基及五氟苯基等。 Examples of the aryl group having 6 to 12 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-azulene, 2-tolyl, 3-tolyl, 4-tolyl, and 2-chlorobenzene base, 3-chlorophenyl, 4-chlorophenyl, 2,4-xylyl, 2,6-xylyl, 3,5-xylyl, 2,4,6-mesitylyl, 3 , 5-bis-trifluoromethylphenyl and pentafluorophenyl, etc.

作為烷氧基，可列舉碳數1~12的烷氧基，為直鏈或分支的烷氧基(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、十二烷氧基、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、第三丁基二甲基矽氧基及第三丁基二苯基矽氧基等)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 include alkoxy groups having 1 to 12 carbon atoms, linear or branched alkoxy groups (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy) Oxy, second butoxy, third butoxy, hexyloxy, phenoxy, tolyloxy, benzyloxy, decyloxy, dodecyloxy, naphthoxy, methoxymethoxy , ethoxymethoxy, 2-methoxyethoxy, 1-methoxyethoxy, benzyloxymethoxy, trimethylsiloxy, triethylsiloxy, triiso propylsiloxy, tert-butyldimethylsilyl, tert-butyldiphenylsiloxy, etc.), etc., from the viewpoint of ease of synthesis, preferably methoxy, ethoxy group, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, benzyloxy and tert-butyldimethylsilyloxy.

作為烷硫基，可列舉碳數1~12的烷硫基，為直鏈或分支的烷硫基(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、甲苯磺醯基硫基、苄硫基、辛硫基、癸硫基及十二烷硫基等)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、辛硫基及十二烷硫基。 Examples of the alkylthio group include alkylthio groups having 1 to 12 carbon atoms, straight-chain or branched alkylthio groups (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutyl) Thio, second-butylthio, third-butylthio, pentylthio, isopentylthio, neopentylthio, third-pentylthio, phenylthio, tosylthio, benzylthio, octylthio, decylthio, dodecylthio, etc.) and the like, from the viewpoint of ease of synthesis, methylthio, ethylthio, propylthio, isopropylthio, butylthio are preferred , benzylthio, octylthio and dodecylthio.

作為烷基羰基，可列舉碳數1~12(包含羰基上的碳在內)的烷基羰基，為直鏈或可分支的烷基羰基(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、癸醯基及十一醯基等)等，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 include alkylcarbonyl groups having 1 to 12 carbon atoms (including the carbon on the carbonyl group), straight-chain or branchable alkylcarbonyl groups (acetyl, propionyl, butyryl, 2-methyl) propylpropionyl, pentamyl, 2-methylbutanoyl, 3-methylbutanoyl, 2,2-dimethylpropanoyl, octanoyl, 2-ethylhexyl, decanoyl and undecanoyl etc.) and the like, from the viewpoint of ease of synthesis, acetyl, propionyl, butyryl, 2-methylbutyryl, and 2,2-dimethylpropionyl are preferred.

作為烷氧基羰基，可列舉碳數2~12(包含羰基上的碳在內)的烷氧基羰基，為直鏈或分支的烷氧基羰基(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、薄荷氧基羰基及十一烷氧基羰基等)等，就合成的容易性的觀點而言，較佳為分支的烷氧基羰基，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、2-乙基己氧基羰基及薄荷氧基羰基。 Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 12 carbon atoms (including carbon on the carbonyl group), and linear or branched alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, propyl) Oxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, third pentoxycarbonyl, octoxycarbonyl, 2-ethyl From the viewpoint of ease of synthesis, branched alkoxycarbonyl groups are preferred, and isopropoxycarbonyl groups are particularly preferred. The second butoxycarbonyl group, the third butoxycarbonyl group, the third pentoxycarbonyl group, the 2-ethylhexyloxycarbonyl group and the menthyloxycarbonyl group.

作為烷基羰氧基，可列舉碳數2~12(包含羰基上的碳 在內)的烷基羰氧基，為直鏈或分支的烷基羰氧基(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、十一烷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 include 2 to 12 carbon atoms (including the carbon on the carbonyl group). The alkylcarbonyloxy in , isobutylcarbonyloxy, 2-butylcarbonyloxy, 3-butylcarbonyloxy, octylcarbonyloxy, 2-ethylhexylcarbonyloxy, undecylcarbonyloxy and benzyl From the viewpoint of availability of raw materials, acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, 2-butylcarbonyloxy, 3-butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy and 2-ethylhexylcarbonyloxy.

作為烷基碳酸酯基，可列舉碳數2~12的烷基碳酸酯基，為甲基碳酸酯基、乙基碳酸酯基、丙基碳酸酯基、2-丙基碳酸酯基、丁基碳酸酯基、2-丁基碳酸酯基、異丁基碳酸酯基、第三丁基碳酸酯基、第三戊基碳酸酯基、苄基碳酸酯基、2-乙基己基碳酸酯基及薄荷基碳酸酯基等，就原料的獲取性的觀點而言，較佳為甲基碳酸酯基、乙基碳酸酯基、丙基碳酸酯基、異丙基碳酸酯基、丁基碳酸酯基、異丁基碳酸酯基、第三丁基碳酸酯基、第三戊基碳酸酯基、2-乙基己基碳酸酯基及薄荷基碳酸酯基。 Examples of the alkyl carbonate group include alkyl carbonate groups having 2 to 12 carbon atoms, such as methyl carbonate group, ethyl carbonate group, propyl carbonate group, 2-propyl carbonate group, butyl group Carbonate, 2-butylcarbonate, isobutylcarbonate, tert-butylcarbonate, tertiary pentylcarbonate, benzylcarbonate, 2-ethylhexylcarbonate and Menthyl carbonate groups and the like are preferably methyl carbonate groups, ethyl carbonate groups, propyl carbonate groups, isopropyl carbonate groups, and butyl carbonate groups from the viewpoint of availability of raw materials , isobutyl carbonate group, tert-butyl carbonate group, tertiary pentyl carbonate group, 2-ethylhexyl carbonate group and menthyl carbonate group.

該些中，就原料的獲取性的觀點而言，R1較佳為碳數1~12的烷基、烷氧基、烷基羰氧基及烷基碳酸酯基，進而佳為碳數1~12的烷基、烷氧基。 Among these, from the viewpoint of availability of raw materials, R1 is preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group, an alkylcarbonyloxy group, and an alkylcarbonate group, and more preferably a carbon number of 1 to 12. 12 alkyl, alkoxy.

R2~R6中的一個為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，其餘為氫原子。 One of R2~R6 is a hydrocarbon group with a carbon number of 1~12, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and the rest are hydrogen atoms .

作為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、 烷氧基羰基、烷基羰氧基或烷基碳酸酯基，與所述列舉者相同。 As a hydrocarbon group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, The alkoxycarbonyl group, the alkylcarbonyloxy group or the alkylcarbonate group are the same as those listed above.

該些中，就作用於萘環上的電子狀態而成為i-光線高感度的觀點而言，較佳為以下(1)~(4)的情況。 Among these, the following cases (1) to (4) are preferred from the viewpoint of the electron state acting on the naphthalene ring to achieve high i-ray sensitivity.

(1)R6為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2~R5為氫原子。 (1) R6 is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R2 to R5 is a hydrogen atom .

R6中較佳為碳數1~12的烴基、烷氧基、烷硫基、烷基羰基、烷氧基羰基或烷基碳酸酯基，特佳為碳數1~12的烷基、烷氧基、烷基碳酸酯基。 R6 is preferably a hydrocarbon group with 1 to 12 carbon atoms, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group or an alkyl carbonate group, particularly preferably an alkyl group with 1 to 12 carbon atoms, an alkoxy group group, alkyl carbonate group.

(2)R5為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2~R4及R6為氫原子。 (2) R5 is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkyl carbonate group, and R2 to R4 and R6 are A hydrogen atom.

R5中較佳為碳數1~12的烴基，特佳為碳數1~12的烷基。 R5 is preferably a hydrocarbon group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 12 carbon atoms.

(3)R2為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R3~R6為氫原子。 (3) R2 is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, and R3 to R6 is a hydrogen atom .

R2中較佳為碳數1~12的烴基，特佳為碳數1~12的烷基。 R2 is preferably a hydrocarbon group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 12 carbon atoms.

(4)R4為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2、R3、R5及R6為氫原子。 (4) R4 is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, R2, R3, R5 and R6 is a hydrogen atom.

R4中較佳為碳數1~12的烴基，特佳為碳數1~12的烷基。 R4 is preferably a hydrocarbon group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 12 carbon atoms.

Rf為氟原子或氫的至少一個以上被取代為氟原子而成 的碳數1~18的烴基，具有控制與抗蝕劑溶液的相容性、光分解性、以及所產生的酸的強度的效果。 Rf is a fluorine atom or at least one of hydrogen is substituted with a fluorine atom. The hydrocarbon group having 1 to 18 carbon atoms has the effect of controlling the compatibility with the resist solution, the photodecomposition property, and the strength of the generated acid.

碳數1~18的烴基可列舉烷基、芳基及雜環式烴基等。 Examples of the hydrocarbon group having 1 to 18 carbon atoms include an alkyl group, an aryl group, and a heterocyclic hydrocarbon group.

作為碳數1~18的至少一個以上的氫被氟取代而成的烴基，可列舉：氫原子被氟原子取代而成的直鏈氟烷基(RF1)、分支氟烷基(RF2)、環狀氟烷基(RF3)以及氟芳基(RF4)等。 Examples of the hydrocarbon group in which at least one or more hydrogen atoms having 1 to 18 carbon atoms are substituted with fluorine include straight-chain fluoroalkyl groups (RF1) in which hydrogen atoms are substituted with fluorine atoms, branched fluoroalkyl groups (RF2), and cyclic fluoroalkyl groups. such as fluoroalkyl (RF3) and fluoroaryl (RF4).

作為氫原子被氟原子取代而成的直鏈氟烷基(RF1)，可列舉：三氟甲基、五氟乙基、七氟丙基、九氟丁基、全氟己基及全氟辛基等。 Examples of straight-chain fluoroalkyl groups (RF1) in which hydrogen atoms are substituted with fluorine atoms include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, perfluorohexyl, and perfluorooctyl Wait.

作為氫原子被氟原子取代而成的分支氟烷基(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) in which a hydrogen atom is substituted with a fluorine atom include hexafluoroisopropyl, nonafluoro-tert-butyl, perfluoro-2-ethylhexyl, and the like.

作為氫原子被氟原子取代而成的環狀氟烷基(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) in which a hydrogen atom is substituted with a fluorine atom include heptafluorocyclobutyl, nonafluorocyclopentyl, perfluorocyclohexyl, perfluoro(1-cyclohexyl)methyl, and the like .

作為氫原子被氟原子取代而成的氟芳基(RF4)，可列舉：五氟苯基、3-三氟甲基四氟苯基及3,5-雙三氟甲基苯基等。 Pentafluorophenyl, 3-trifluoromethyltetrafluorophenyl, 3,5-bis-trifluoromethylphenyl, etc. are mentioned as a fluoroaryl group (RF4) which a hydrogen atom was substituted by a fluorine atom.

於Rf中，就光分解性、光阻劑的脫保護能力、以及原料的獲取的容易度的觀點而言，較佳為氫原子被氟原子取代而成的直鏈氟烷基(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(C₂F₅)、七氟丙基(C₃F₇)、九氟丁基(C₄F₉)及五氟苯基(C₆F₅)。 Among Rf, from the viewpoints of photodecomposability, deprotection ability of the photoresist, and easiness of obtaining raw materials, straight-chain fluoroalkyl groups in which hydrogen atoms are substituted with fluorine atoms (RF1), Branched fluoroalkyl group (RF2) and fluoroaryl group (RF4), further preferably straight-chain fluoroalkyl group (RF1) and fluoroaryl group (RF4), particularly preferably trifluoromethyl (CF ₃ ), pentafluoro Ethyl (C ₂ F ₅ ), heptafluoropropyl (C ₃ F ₇ ), nonafluorobutyl (C ₄ F ₉ ) and pentafluorophenyl (C ₆ F ₅ ).

本發明的非離子系光酸產生劑(A)的合成方法若可合成目標物，則並無特別限定，例如可利用以下敘述的製造方法來製造。 The synthesis method of the nonionic photoacid generator (A) of the present invention is not particularly limited as long as the target object can be synthesized, and for example, it can be produced by the production method described below.

於所述反應式中，R1~R6及Rf與式(1)中的定義相同。 In the above reaction formula, R1 to R6 and Rf have the same definitions as in formula (1).

第一階段的反應是使前驅物(P1)與過氧化物於有機溶劑(乙腈、甲醇、乙醇、異丙醇、氯仿等)中回流6小時~48小時而進行反應。於反應完成後，將反應液投入至水中，對析出的固體進行過濾並利用適當的有機溶媒加以清洗，藉此獲得前驅物(P2)。 The first stage of the reaction is to react the precursor (P1) and the peroxide in an organic solvent (acetonitrile, methanol, ethanol, isopropanol, chloroform, etc.) under reflux for 6 to 48 hours. After completion of the reaction, the reaction solution was put into water, and the precipitated solid was filtered and washed with an appropriate organic solvent to obtain a precursor (P2).

作為過氧化物，若為拜耳-維立格(Bayer-Villiger)氧化 反應中一般利用者，則並無特別限定，可使用公知的有機過氧化物(過乙酸、過苯甲酸、間氯過苯甲酸、三氟過乙酸等)及無機過氧化物(過氧化氫、過氧化單硫酸鉀、過氧化單硫酸鉀/硫酸氫鉀/硫酸鉀三合鹽等)，視需要可併用酸(乙酸、磷酸、鹽酸等)或鹼(氫氧化鈉、碳酸氫鈉、碳酸鉀等)。 As peroxide, if it is Bayer-Villiger oxidation There is no particular limitation on those generally used in the reaction, and known organic peroxides (peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, etc.) and inorganic peroxides (hydrogen peroxide, Potassium peroxymonosulfate, potassium peroxymonosulfate/potassium hydrogensulfate/potassium sulfate triple salt, etc.), if necessary, acid (acetic acid, phosphoric acid, hydrochloric acid, etc.) or base (sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, etc.) can be used in combination Wait).

第二階段的反應是將前驅物(P2)與有機溶劑(乙腈、二噁烷、四氫呋喃(tetrahydrofuran，THF)、N,N-二甲基甲醯胺(N,N-dimethyl formamide，DMF)等)混合並攪拌，使該混合物與羥基胺進行反應。反應時間為10分鐘至48小時，反應溫度為0℃~50℃。於反應完成後，利用稀酸對反應液進行中和。對析出的固體進行過濾，或者利用有機溶劑萃取所分離的油狀物後，將揮發成分餾去，藉此獲得前驅物(P3)。該前驅物(P3)視需要可利用適當的有機溶劑進行清洗，或者利用再結晶法進行純化。 The second-stage reaction is to combine the precursor (P2) with organic solvents (acetonitrile, dioxane, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), etc. ) and stirring to react the mixture with hydroxylamine. The reaction time is 10 minutes to 48 hours, and the reaction temperature is 0°C to 50°C. After the reaction was completed, the reaction solution was neutralized with dilute acid. The precipitated solid is filtered or the separated oily substance is extracted with an organic solvent, and then the volatile component is distilled off to obtain a precursor (P3). The precursor (P3) can be washed with an appropriate organic solvent or purified by a recrystallization method as necessary.

第三階段的反應是將前驅物(P3)、鹼(咪唑、吡啶、二甲基胺基吡啶、三乙胺、甲基嗎啉等)、RfSO₂X所表示的磺酸鹵化物等在有機溶劑(乙腈、氯仿、二氯甲烷、DMF、乙酸乙酯等)中混合。反應溫度為-20℃~30℃，反應時間為1小時~6小時。於反應完成後，利用稀酸進行中和，對析出的固體進行過濾，或者利用有機溶劑萃取所分離的油狀物後，將揮發成分餾去，藉此以固體的形式獲得通式(1)所表示的本發明的非離子系光酸產生劑(A)。所獲得的固體視需要可利用適當的有機溶劑進行清洗，或者利用再結晶進行純化。 The third-stage reaction is to mix the precursor (P3), the base (imidazole, pyridine, dimethylaminopyridine, triethylamine, methylmorpholine, etc.), the sulfonic acid halide represented by RfSO ₂ X, etc. in an organic mixed in a solvent (acetonitrile, chloroform, dichloromethane, DMF, ethyl acetate, etc.). The reaction temperature is -20°C to 30°C, and the reaction time is 1 hour to 6 hours. After the completion of the reaction, neutralize with a dilute acid, filter the precipitated solid, or extract the separated oily substance with an organic solvent, and then distill off the volatile components, thereby obtaining the general formula (1) in the form of a solid. The represented nonionic photoacid generator (A) of this invention. The obtained solid can be washed with an appropriate organic solvent or purified by recrystallization as necessary.

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

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 the solvent include carbonates (propylene carbonate, ethylidene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.), esters (ethyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone, etc.), ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether) Butyl 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 monoethyl ether) Butyl 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, 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(A)可單獨使用一種，或者將兩種以上組合而使用。 Since the resin composition (Q) for photolithography of the present invention contains the nonionic photoacid generator (A) as an essential component, by performing ultraviolet irradiation and post-exposure heating (PEB), the exposed part and the unexposed part are developed. The solubility of the liquid varies. The nonionic photoacid generator (A) may be used alone or in combination of two or more.

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。 Examples of the resin composition (Q) for photolithography include a mixture of a negative-type chemically amplified resin (QN) and a nonionic photoacid generator (A); and a positive-type chemically amplified resin (QP) and a nonionic photoacid generator. Mixtures of acid generators (A).

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)。 The negative-type chemically amplified resin (QN) includes a phenolic hydroxyl group-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 group-containing resin (QN1) is not particularly limited as long as it is a phenolic hydroxyl group-containing resin, and for example, novolak resin, polyhydroxystyrene, copolymer of hydroxystyrene, hydroxystyrene and Copolymers of styrene, hydroxystyrene, copolymers of styrene and (meth)acrylic acid derivatives, phenol-benzenedimethanol condensation resins, cresol-xylenedimethanol condensation resins, polyimide containing phenolic hydroxyl groups , Polyamide acid containing phenolic hydroxyl group, phenol-dicyclopentadiene condensation resin. Among these, preferred are novolak resins, polyhydroxystyrene, copolymers of hydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth)acrylic derivatives , Phenol-benzenedimethanol condensation resin. In addition, these phenolic hydroxyl group containing resin (QN1) may be used individually by 1 type, and may be used in mixture of 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。 The novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

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。 Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Phenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, gallic phenol, 1-naphthol, 2-naphthol.

另外，作為所述醛類，可列舉：甲醛、對甲醛、乙醛、苯甲醛等。 Moreover, as said aldehyde, formaldehyde, p-formaldehyde, 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。 Specific examples of novolak resins include phenol/formaldehyde condensed novolac resins, cresol/formaldehyde condensed novolac resins, and phenol-naphthol/formaldehyde condensed resins. 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。 Moreover, you may contain a phenolic low molecular weight compound as a part of components in the said phenolic hydroxyl group containing resin (QN1).

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。 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-Tetrakis(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.

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 group-containing resin (QN1) is set to 100% by weight, the content ratio of the phenolic low molecular weight compound in the phenolic hydroxyl group-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。 The weight-average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2,000 or more, and more preferably 2,000 to 2,000 to 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。 Moreover, when the whole composition excluding the solvent is taken as 100 wt %, the content ratio of the phenolic hydroxyl group-containing resin (QN1) in the negative chemically amplified resin (QN) is preferably 30 wt % to 30 wt % 90% by weight, more preferably 40% by weight to 80% by weight. The content of the phenolic hydroxyl group-containing resin (QN1) is 30% by weight In the case of ~90% by weight, the film formed using the photosensitive insulating resin composition has sufficient developability due to an alkaline aqueous solution, which is preferable.

作為交聯劑(QN2)，若為可利用自非離子系光酸產生劑(A)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 capable of crosslinking the phenolic hydroxyl group-containing resin (QN1) with 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、含羥甲基的苯并胍胺化合物、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、含烷氧基烷基的苯并胍胺化合物、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、含羧基甲基的苯并胍胺樹脂、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、含羧基甲基的苯并胍胺化合物、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-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolak resin-based epoxy compounds, and resol-based epoxy compounds may be mentioned. Oxygen compound, poly(hydroxystyrene)-based epoxy compound, oxetane compound, methylol-containing melamine compound, methylol-containing benzoguanamine compound, methylol-containing urea compound, hydroxyl group-containing Methyl phenolic compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing phenolic compounds, Carboxymethyl-containing melamine resin, carboxymethyl-containing benzoguanamine resin, carboxymethyl-containing urea resin, carboxymethyl-containing phenol resin, carboxymethyl-containing melamine compound, carboxymethyl-containing benzoguanamine Amine compounds, carboxymethyl-containing urea compounds, and carboxymethyl-containing phenolic 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 these crosslinking agents (QN2), preferred are methylol-containing phenolic compounds, methoxymethyl-containing melamine compounds, methoxymethyl-containing phenolic compounds, and methoxymethyl-containing glycerols. Urea compounds, methoxymethyl-containing urea compounds, and acetoxymethyl-containing phenolic compounds, more preferably methoxymethyl-containing melamine compounds (for example, hexamethoxymethyl melamine), methoxymethyl-containing Methyl glycoluril compounds and methoxymethyl-containing urea compounds, etc. Methoxymethyl-containing melamine compound ismailu (CYMEL) 300, CYMEL 301, CYMEL 303, CYMEL 305 (manufactured by Mitsui Cyanamid) and other trade names are commercially available, containing methoxy The methoxymethyl glycoluril compound is commercially available under the trade names of CYMEL 1174 (manufactured by Mitsui Cyanamid Co., Ltd.), and the methoxymethyl group-containing urea compound is marketed as MX290 (Sanwa Chemical Co., Ltd.) (stock) manufacture) and other trade names are commercially available.

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%。 The content of the crosslinking agent (QN2) is usually 5 mol with respect to all the acidic functional groups in the phenolic hydroxyl group-containing resin (QN1) from the viewpoints of the reduction of the residual film ratio, the warpage or swelling of the pattern, and the developability. %~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)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)。 The positive chemically amplified resin (QP) includes a part or all of the hydrogen atoms of the acidic functional group in the alkali-soluble resin (QP1) containing one or more acidic functional groups such as phenolic hydroxyl group, carboxyl group, or sulfonyl group. A protective group substituted with an acid dissociable group is introduced into the resin (QP2).

再者，酸解離性基為可於自非離子系光酸產生劑(A)產生的強酸的存在下進行解離的基。 In addition, an acid-dissociable group is a group which can be dissociated in the presence of a strong acid generated from a nonionic photoacid generator (A).

保護基導入樹脂(QP2)其自身為鹼不溶性或鹼難溶性。 The protecting group-introducing resin (QP2) itself is alkali-insoluble or alkali-hardly 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。 As alkali-soluble resin (QP1), a phenolic hydroxyl group-containing resin (QP11), a carboxyl group-containing resin (QP12), a sulfonic acid group-containing resin (QP13), etc. are mentioned, for example.

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。 As the phenolic hydroxyl group-containing resin (QP11), the same thing 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(Ba)與視需要的含疏水基的乙烯基單體(Bb)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, the carboxyl group-containing vinyl monomer (Ba) can be mixed with an optional hydrophobic group-containing vinyl monomer (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、丁烯酸及肉桂酸等]、不飽和多元(2價~4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]。 Examples of the carboxyl group-containing vinyl monomer (Ba) include unsaturated monocarboxylic acids [(meth)acrylic acid, crotonic acid, cinnamic acid, etc.], unsaturated polyvalent (divalent to tetravalent) carboxylic acids [ (anhydrous) maleic acid, itaconic acid, fumaric acid and citraconic acid, etc.], unsaturated polycarboxylic acid alkyl (alkyl with 1 to 10 carbons) ester [maleic acid monoalkyl ester, fumaric acid Acid monoalkyl esters, citraconic acid monoalkyl esters, etc.], and their salts [alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), amine salts, and ammonium salts salt, etc.].

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。 Among these, from the viewpoint of polymerizability and easiness of acquisition, 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。 As a hydrophobic group-containing vinyl monomer (Bb), (meth)acrylate (Bb1), an aromatic hydrocarbon monomer (Bb2), etc. are mentioned.

作為(甲基)丙烯酸酯(Bb1)，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)丙烯酸二環戊基酯、(甲基)丙烯酸二環戊烯基酯及(甲基)丙烯酸異冰片酯等]等。 Examples of the (meth)acrylate (Bb1) include alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group [methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate] 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 [(meth)acrylate dicyclopentenyl, (meth)acrylate dicyclopentenyl and (meth)acrylate isobornyl, etc.] and the like.

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[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。 Examples of the aromatic hydrocarbon monomer (Bb2) include hydrocarbon monomers having a styrene skeleton [styrene, α-methylstyrene, vinyltoluene, 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(Ba)/(Bb)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 the input monomers (Ba)/(Bb) in the carboxyl group-containing resin (QP12) is usually 10 to 100/0 to 90, and from the viewpoint of developability, preferably 10 to 80/20 to 90, and 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)進行乙烯基聚合來獲得。 The sulfonic acid group-containing resin (QP13) is not particularly limited as long as it is a polymer having a sulfonic acid group. It can be obtained by vinyl polymerization of the vinyl monomer (Bb) of the base.

作為含疏水基的乙烯基單體(Bb)，可使用與所述相同者。 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 (Bc) include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, 2-( Meth)acryloamide-2-methylpropanesulfonic acid and salts of these. 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(Bc)/(Bb)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 (Bc)/(Bb) in the sulfonic acid group-containing resin (QP13) is usually 10 to 100/0 to 90, preferably 10 to 80/ from the viewpoint of developability. 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。 The HLB value of the alkali-soluble resin (QP1) preferably has a different range depending on the resin skeleton of the alkali-soluble resin (QP1), but is preferably 4 to 19, more preferably 5 to 18, and particularly preferably 6 to 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。 When the HLB value is 4 or more, the developability at the time of image development is more favorable, and when 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。 Furthermore, the HLB value in the present invention is the HLB obtained by the Oda method. value, and the hydrophilicity-hydrophobicity balance value, which can be calculated from the ratio of the organic value to the inorganic value of the organic compound.

<HLB的評價方法> <Evaluation method of HLB>

HLB≒10×無機性/有機性 HLB≒10×inorganic/organic

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」(模書店發行、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 values of inorganic and organic properties are listed on page 501 of the document "Synthesis and Application of Surfactants" (published by Moshudian, written by Oda and Teramura), or "New Introduction to Surfactants" (Takehiko Fujimoto). It is described in detail on page 198 of the book, published by Sanyo Chemical Industry Co., Ltd.

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。 Examples of acid dissociable groups to be introduced into the resin (QP2) as protecting groups include substituted methyl groups, 1-substituted ethyl groups, 1-branched alkyl groups, silyl groups, germyl groups, alkoxycarbonyl groups, Acyl group and cyclic acid dissociable group, etc. These may be used individually by 1 type, and may 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、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。 Examples of the substituted methyl group include methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzylthio Benzylmethyl, benzylmethyl, bromobenzylmethyl, methoxybenzylmethyl, methylthiobenzylmethyl, α-methylbenzylmethyl, cyclopropylmethyl , benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthiobenzyl , piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-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。 Examples of 1-substituted ethyl groups include 1-methoxyethyl, 1-methylthioethyl, 1,1-dimethoxyethyl, 1-ethoxyethyl, and 1-ethylthio 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-n-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-n-butoxycarbonylethyl, 1- The third butoxycarbonylethyl group.

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 the 1-branched alkyl group include isopropyl, 2-butyl, 3-butyl, 1,1-dimethylpropyl, 1-methylbutyl, and 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。 As a silyl group, a trimethylsilyl group, an ethyldimethylsilyl group, a diethylmethylsilyl group, a triethylsilyl group, an isopropyldimethylsilyl group, a diisopropylmethylsilyl group are mentioned, for example. Silyl, triisopropylsilyl, tert-butyldimethylsilyl, di-tert-butylmethylsilyl, tri-tert-butylsilyl, dimethylphenylsilyl, methylbis Tri-carbyl silyl groups such as phenylsilyl, triphenylsilyl, etc.

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 germanyl group, for example, trimethylgermanyl, ethyldimethylgermanyl, methyldiethylgermanyl, triethylgermanyl, isopropyldimethylgermanyl, etc. may be mentioned. Methylgermanyl, methyldiisopropylgermanyl, triisopropylgermanyl, tert-butyldimethylgermyl, di-tert-butylmethylgermanyl, Tri-carbonylgermanyl such as tri-tert-butylgermanyl, dimethylphenylgermanyl, methyldiphenylgermanyl, triphenylgermanyl and the like.

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。 As an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tertiary butoxycarbonyl group are mentioned, for example.

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, propionyl group, butyryl group, heptyl group Acetyl, Hexyl, Pentamyl, Trimethyl Acetyl, Isovaleryl, Lauryl, Myristyl, Palmimyl, Stearyl, Ethylene, Malonyl , succinyl, glutaryl, adipic, heptadiyl, octanedio, azela, sebadio, acryl, propargyl, methacryloyl, Butenyl, oleyl, maleic, fumaric, mesacanoyl, camphordiyl, benzyl, phthalic, isophthalic, terephthalic , naphthyl, tolyl, hydrogen, atro-, atro-, cinnamyl, furan-carbyl, thiophene-carbyl, nicotinyl, isonicotinyl, p-toluenesulfonyl , Methylsulfonyl.

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-methoxytetrahydrothiopyranyl, 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, tert-butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tert-butoxycarbonyl, 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%。 Rate of introduction of acid dissociable groups in protective group-introduced resin (QP2) {Acid dissociable groups relative to the total number of unprotected acidic functional groups and acid dissociable groups in protective group-introduced resin (QP2) The ratio of the number of these groups} cannot be uniformly defined according to the acid dissociable group or the type of the alkali-soluble resin into which the group is introduced, but is preferably 10% to 100%, 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-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the protecting group-introducing resin (QP2) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, 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-introducing resin (QP2) to the number average molecular weight in terms of polystyrene (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC) is usually 1 to 10, preferably 1 to 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(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%。 The content of the nonionic photoacid generator (A) based on the weight of the solid content of the resin composition for photolithography (Q) 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.

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。 When it is 0.001% by weight or more, the sensitivity to ultraviolet rays can be more favorably exhibited, and when it is 20% by weight or less, the physical properties of the portion insoluble in the alkaline developer can be more favorably exhibited.

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 including inorganic fine particles) in a predetermined organic solvent is applied on a substrate, and then the solvent is dried by heating or blowing with hot air.

作為使光微影用樹脂組成物(Q)溶解的有機溶劑，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、丙二醇單甲醚乙 酸酯、丙酮及二甲苯等公知的溶媒。 As the organic solvent for dissolving the resin composition (Q) for photolithography, if it is an organic solvent that can dissolve the resin composition and adjust the physical properties (viscosity, etc.) of the resin solution to be suitable for spin coating, etc. There is no particular limitation. For example, N-methylpyrrolidone, DMF, dimethylsulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl can be used Ether B known solvents such as acid esters, acetone, and xylene.

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。 Among these solvents, those having a boiling point of 200° C. or lower (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, etc.) are preferred from the viewpoint of drying temperature. , propylene glycol monomethyl ether acetate, acetone and xylene), can also be used alone or in combination of two or more.

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%。 In the case of using an organic solvent, the compounding amount of the solvent is not particularly limited, but is usually preferably 30% by weight to 1,000% by weight based on the weight of the solid content of the resin composition for photolithography (Q), 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2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 coating vary depending on the solvent used, but it is preferably carried out in the range of 50° C. to 200° C. for 2 minutes to 30 minutes. The residual solvent amount (% by weight) of (Q) 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 performing post-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)中的非離子系光酸產生劑(A)分解，則並無特別限制。 As a method of performing light irradiation, the method of exposing a resist with actinic rays through a photomask having a wiring pattern is exemplified. The actinic ray used for light irradiation is not particularly limited as long as the nonionic photoacid generator (A) in the resin composition (Q) for photolithography of the present invention can be decomposed.

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、色素雷射、氮雷射、LED、氦鎘雷射 等)等。該些中，較佳為高壓水銀燈及超高壓水銀燈。 Examples of actinic rays include 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, dye lasers, nitrogen lasers) laser, LED, helium-cadmium laser and many more. Among these, a high-pressure mercury-vapor lamp and an ultra-high-pressure mercury-vapor lamp are preferable.

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。 The temperature of post-exposure heating (PEB) 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, and the difference in solubility between the ultraviolet-irradiated part and the ultraviolet-unirradiated part is insufficient, and the pattern cannot be formed. If the temperature is higher than 200°C, the productivity will decrease. The problem.

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 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 when it exceeds 120 minutes, there is a problem that productivity decreases.

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可形成差的條件，則並無特別限制。 As a method of performing alkali development, the method of dissolving and removing in the shape of a wiring pattern using an alkali developing solution is mentioned. The alkaline developer is not particularly limited as long as it is a condition in which the solubility of the UV-irradiated portion and the UV-unirradiated portion of the resin composition for photolithography (Q) is poor.

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。 As an alkaline developing solution, there exist a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, sodium hydrogencarbonate, a tetramethylammonium salt aqueous solution, etc..

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。 Water-soluble organic solvents can also be added to these alkaline developing solutions. Examples of the water-soluble organic solvent include 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。 As a developing method, there exist a dipping method using an alkaline developer, a shower method, and a spray method, but the spray method is preferable.

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。 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.

[實施例] [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。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, % refers to % by weight, and parts refers to parts by weight.

<製造例1> <Production Example 1>

<2,7-二甲基-1,8-萘二甲酸酐[前驅物(P2-1)]的合成> <Synthesis of 2,7-dimethyl-1,8-naphthalenedicarboxylic anhydride [precursor (P2-1)]>

將3,8-二甲基苊醌(東京化成工業股份有限公司製造)1.6份分散於甲醇195份中，一次加入過氧化單硫酸鉀(複鹽)10份、碳酸氫鈉2.5份。將該分散液回流一天後投入至水中而使固體析出。過濾分離固體並進行減壓乾燥，藉此獲得前驅物(P2-1)0.91份。 1.6 parts of 3,8-dimethylacenaphthoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) was dispersed in 195 parts of methanol, and 10 parts of potassium peroxymonosulfate (double salt) and 2.5 parts of sodium bicarbonate were added at one time. This dispersion liquid was poured into water after refluxing for one day, and a solid was precipitated. The solid was separated by filtration and dried under reduced pressure to obtain 0.91 part of a precursor (P2-1).

<製造例2> <Production Example 2>

<N-羥基-2,7-二甲基-1,8-萘二甲醯亞胺[前驅物(P3-1)]的合成> <Synthesis of N-hydroxy-2,7-dimethyl-1,8-naphthalimide [precursor (P3-1)]>

將製造例1中獲得的前驅物(P2-1)1.1份分散於乙腈20份中，加入羥基胺水溶液(東京化成工業股份有限公司製造，50%水溶液)2.0份，於50℃下攪拌一天。將反應液投入至稀鹽酸水溶液中過濾分離析出物並進行水洗、乾燥，藉此獲得前驅物(P3-1)1.1份。 1.1 part of the precursor (P2-1) obtained in Production Example 1 was dispersed in 20 parts of acetonitrile, 2.0 parts of hydroxylamine aqueous solution (manufactured by Tokyo Chemical Industry Co., Ltd., 50% aqueous solution) was added, and the mixture was stirred at 50°C for one day. The reaction liquid was put into a dilute aqueous hydrochloric acid solution, the precipitate was separated by filtration, washed with water, and dried to obtain 1.1 part of the precursor (P3-1).

<製造例3> <Production Example 3>

<2,7-二甲氧基-1,8-萘二甲酸酐[前驅物(P2-2)]的合成> <Synthesis of 2,7-dimethoxy-1,8-naphthalenedicarboxylic acid anhydride [precursor (P2-2)]>

將2,7-二甲氧基萘(東京化成工業股份有限公司製造)作為原料，於氮氣環境下將過氧化單硫酸鉀(複鹽)10份一次加入至 依據文獻(「瑞士化學學報(Helv.Chem.Acta)」，1921,342.)中記載的方法而合成的3,8-二甲氧基苊醌1.8份的甲醇29份分散液中。於強烈攪拌該分散液的同時回流一天。於反應結束後，冷卻至室溫並投入至大量的水中。過濾所獲得的固體並進行減壓乾燥，藉此獲得前驅物(P2-2)1.5份。 Using 2,7-dimethoxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material, 10 parts of potassium peroxymonosulfate (double salt) was added to the mixture at one time under nitrogen atmosphere. In a dispersion liquid of 1.8 parts of 3,8-dimethoxyacenaphthoquinone synthesized according to the method described in the literature ("Helv. Chem. Acta", 1921, 342.) in 29 parts of methanol. The dispersion was refluxed for one day with vigorous stirring. After the reaction was completed, it was cooled to room temperature and poured into a large amount of water. The obtained solid was filtered and dried under reduced pressure to obtain 1.5 parts of a precursor (P2-2).

<製造例4> <Production Example 4>

<N-羥基-2,7-二甲氧基-1,8-萘二甲醯亞胺[前驅物(P3-2)]的合成> <Synthesis of N-hydroxy-2,7-dimethoxy-1,8-naphthalimide [precursor (P3-2)]>

將前驅物(P2-1)1.1份變更為前驅物(P2-2)1.3份，除此以外與製造例2同樣地獲得前驅物(P3-2)1.2份。 Except having changed 1.1 parts of precursor (P2-1) to 1.3 parts of precursor (P2-2), it carried out similarly to manufacture example 2, and obtained 1.2 parts of precursor (P3-2).

<製造例5> <Production Example 5>

<2,7-二甲硫基-1,8-萘二甲酸酐[前驅物(P2-3)]的合成> <Synthesis of 2,7-dimethylthio-1,8-naphthalenedicarboxylic acid anhydride [precursor (P2-3)]>

將2,7-二甲氧基萘變更為2,7-二甲硫基萘(和光純藥製造)，將3,8-二甲氧基苊醌1.8份變更為3,8-二甲硫基苊醌2.0份，除此以外與製造例3同樣地獲得前驅物(P2-3)1.7份。 Changed 2,7-dimethoxynaphthalene to 2,7-dimethylthionaphthalene (manufactured by Wako Pure Chemical Industries, Ltd.), and changed 1.8 parts of 3,8-dimethoxyacenaphthoquinone to 3,8-dimethylthio Except for 2.0 parts of acenaphthenequinone, it carried out similarly to manufacture example 3, and obtained 1.7 parts of precursor (P2-3).

<製造例6> <Production Example 6>

<N-羥基-2,7-二甲硫基-1,8-萘二甲醯亞胺[前驅物(P3-3)]的合成> <Synthesis of N-hydroxy-2,7-dimethylthio-1,8-naphthalimide [precursor (P3-3)]>

將前驅物(P2-1)1.1份變更為前驅物(P2-3)1.5份，除此以外與製造例2同樣地獲得前驅物(P3-3)1.4份。 Except having changed 1.1 parts of precursor (P2-1) to 1.5 parts of precursor (P2-3), it carried out similarly to manufacture example 2, and obtained 1.4 parts of precursor (P3-3).

<製造例7> <Production Example 7>

<2,7-二羥基-1,8-萘二甲酸酐[前驅物(P2-4)]的合成> <Synthesis of 2,7-dihydroxy-1,8-naphthalenedicarboxylic anhydride [precursor (P2-4)]>

將製造例3中合成的前驅物(P2-2)2.6份攪拌分散於二氯甲烷83份中，冷卻至-78℃後，滴加三溴化硼10份並攪拌1小時。除去冷浴而昇溫至室溫為止並攪拌24小時。於反應完成後，投入至大量的飽和碳酸氫鈉水溶液中，過濾分離所獲得的固體。將所獲得的固體分散於稀鹽酸中，攪拌1小時後，再次過濾並充分水洗。將所獲得的黃色固體乾燥而獲得前驅物(P2-4)2.0份。 2.6 parts of the precursor (P2-2) synthesized in Production Example 3 was dispersed in 83 parts of methylene chloride with stirring, and after cooling to -78°C, 10 parts of boron tribromide was added dropwise and stirred for 1 hour. The cooling bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 24 hours. After the reaction was completed, it was put into a large amount of saturated aqueous sodium bicarbonate solution, and the obtained solid was separated by filtration. The obtained solid was dispersed in dilute hydrochloric acid, and after stirring for 1 hour, it was filtered again and washed well with water. The obtained yellow solid was dried to obtain 2.0 parts of precursor (P2-4).

<製造例8> <Production Example 8>

<2,7-二-第三丁氧基羰氧基-1,8-萘二甲酸酐[前驅物(P2-5)]的合成> <Synthesis of 2,7-di-tert-butoxycarbonyloxy-1,8-naphthalenedicarboxylic acid anhydride [precursor (P2-5)]>

將製造例7中合成的前驅物(P2-4)4.4份分散於乙腈75份中，滴加吡啶0.3份，繼而滴加二碳酸二-第三丁酯10份。昇溫至40度為止使反應完成後，加入水使固體析出。將其過濾分離並加以乾燥，藉此獲得前驅物(P2-5)7.8份。 4.4 parts of precursor (P2-4) synthesized in Production Example 7 were dispersed in 75 parts of acetonitrile, 0.3 parts of pyridine was added dropwise, and 10 parts of di-tert-butyl dicarbonate was added dropwise. After the temperature was raised to 40 degrees to complete the reaction, water was added to precipitate a solid. This was separated by filtration and dried to obtain 7.8 parts of precursor (P2-5).

<製造例9> <Production Example 9>

<N-羥基-2,7-二-第三丁氧基羰氧基-1,8-萘二甲醯亞胺[前驅物(P3-4)]的合成> <Synthesis of N-hydroxy-2,7-di-tert-butoxycarbonyloxy-1,8-naphthalimide [precursor (P3-4)]>

將前驅物(P2-1)1.1份變更為前驅物(P2-5)2.2份，除此以外與製造例2同樣地獲得前驅物(P3-4)2.0份。 Except having changed 1.1 parts of precursor (P2-1) to 2.2 parts of precursor (P2-5), it carried out similarly to manufacture example 2, and obtained 2.0 parts of precursor (P3-4).

<製造例10> <Production Example 10>

<2,7-二-第三丁氧基羰基-1,8-萘二甲酸酐[前驅物(P2-6)]的合成> <Synthesis of 2,7-di-tert-butoxycarbonyl-1,8-naphthalenedicarboxylic acid anhydride [precursor (P2-6)]>

將製造例1中合成的前驅物(P2-1)5.9份分散於去離子水 262份中，加入過錳酸鉀21份進行回流的同時攪拌6小時。於反應完成後，加入氫氧化鈉水溶液加以攪拌，並過濾分離固體。將濾液於冰浴中冷卻，加入鹽酸使其成為酸性後攪拌1小時。利用水充分清洗將其過濾而獲得的固體，於燒瓶中進行減壓乾燥。繼而，向該乾燥固體中加入二氯甲烷116份並進行分散，加入DMF 0.1份。利用冰浴來冷卻分散液，緩慢滴加二氯化乙二醯10份。於維持冰浴的狀態下攪拌3小時後，於減壓下將揮發物全部去除。向殘渣物中加入脫水THF 78份，於冰浴下攪拌的同時緩慢滴加第三丁醇鋰的10%THF溶液63份。投入至水中使反應停止後加以過濾，藉此獲得固體。利用管柱層析法進行純化，藉此獲得前驅物(P2-6)3.6份。 Disperse 5.9 parts of the precursor (P2-1) synthesized in Production Example 1 in deionized water To 262 parts, 21 parts of potassium permanganate were added and stirred for 6 hours while refluxing. After the reaction was completed, an aqueous sodium hydroxide solution was added for stirring, and the solid was separated by filtration. The filtrate was cooled in an ice bath, acidified by adding hydrochloric acid, and stirred for 1 hour. The solid obtained by filtration was sufficiently washed with water and dried under reduced pressure in a flask. Next, 116 parts of dichloromethanes were added to this dry solid, and it disperse|distributed, and 0.1 part of DMF was added. The dispersion liquid was cooled with an ice bath, and 10 parts of ethylene glycol dichloride was slowly added dropwise. After stirring for 3 hours while maintaining an ice bath, all volatiles were removed under reduced pressure. To the residue was added 78 parts of dehydrated THF, and 63 parts of a 10% THF solution of lithium tertiary butoxide was slowly added dropwise while stirring in an ice bath. After pouring into water to stop the reaction, it was filtered to obtain a solid. Purified by column chromatography, 3.6 parts of precursor (P2-6) were obtained.

<製造例11> <Production Example 11>

<N-羥基-2,7-二-第三丁氧基羰基-1,8-萘二甲醯亞胺[前驅物(P3-5)]的合成> <Synthesis of N-hydroxy-2,7-di-tert-butoxycarbonyl-1,8-naphthalimide [precursor (P3-5)]>

將前驅物(P2-1)1.1份變更為前驅物(P2-6)2.0份，除此以外與製造例2同樣地獲得前驅物(P3-5)1.7份。 Except having changed 1.1 parts of precursor (P2-1) to 2.0 parts of precursor (P2-6), it carried out similarly to manufacture example 2, and obtained 1.7 parts of precursor (P3-5).

<製造例12> <Production Example 12>

<2,3-二甲基-1,8-萘二甲酸酐[前驅物(P2-7)]的合成> <Synthesis of 2,3-dimethyl-1,8-naphthalenedicarboxylic anhydride [precursor (P2-7)]>

將2,7-二甲氧基萘變更為2,3-二甲基萘(東京化成工業股份有限公司製造)，將3,8-二甲氧基苊醌1.8份變更為3,4-二甲基苊醌1.6份，除此以外與製造例3同樣地獲得前驅物(P2-7)1.3份。 2,7-dimethoxynaphthalene was changed to 2,3-dimethylnaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.8 parts of 3,8-dimethoxyacenaphthylquinone was changed to 3,4-di Except for 1.6 parts of methylacenaphthoquinone, it carried out similarly to manufacture example 3, and obtained 1.3 parts of precursor (P2-7).

<製造例13> <Production Example 13>

<N-羥基-2,3-二甲基-1,8-萘二甲醯亞胺[前驅物(P3-6)]的合成> <Synthesis of N-hydroxy-2,3-dimethyl-1,8-naphthalimide [precursor (P3-6)]>

將前驅物(P2-1)1.1份變更為前驅物(P2-7)1.1份，除此以外與製造例2同樣地獲得前驅物(P3-6)1.2份。 Except having changed 1.1 parts of precursor (P2-1) to 1.1 parts of precursor (P2-7), it carried out similarly to manufacture example 2, and obtained 1.2 parts of precursor (P3-6).

<製造例14> <Production Example 14>

<2,6-二異丙基-1,8-萘二甲酸酐[前驅物(P2-8)]的合成> <Synthesis of 2,6-diisopropyl-1,8-naphthalenedicarboxylic acid anhydride [precursor (P2-8)]>

將2,7-二甲氧基萘變更為2,6-二異丙基萘(東京化成工業股份有限公司製造)，將3,8-二甲氧基苊醌1.8份變更為3,7-二異丙基苊醌2.0份，除此以外與製造例3同樣地獲得前驅物(P2-8)1.7份。 2,7-dimethoxynaphthalene was changed to 2,6-diisopropylnaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.8 parts of 3,8-dimethoxyacenaphthylquinone was changed to 3,7- Except for 2.0 parts of diisopropylacenaphthenequinone, it carried out similarly to manufacture example 3, and obtained 1.7 parts of precursor (P2-8).

<製造例15> <Production Example 15>

<N-羥基-2,6-二異丙基-1,8-萘二甲醯亞胺[前驅物(P3-7)]的合成> <Synthesis of N-hydroxy-2,6-diisopropyl-1,8-naphthalimide [precursor (P3-7)]>

將前驅物(P2-1)1.1份變更為前驅物(P2-8)1.4份，除此以外與製造例2同樣地獲得前驅物(P3-7)1.4份。 Except having changed 1.1 parts of precursor (P2-1) to 1.4 parts of precursor (P2-8), it carried out similarly to manufacture example 2, and obtained 1.4 parts of precursor (P3-7).

<製造例16> <Production Example 16>

<2,5-二甲基-1,8-萘二甲酸酐[前驅物(P2-9)]的合成> <Synthesis of 2,5-dimethyl-1,8-naphthalenedicarboxylic anhydride [precursor (P2-9)]>

將2,7-二甲氧基萘變更為2,5-二甲基萘(東京化成工業股份有限公司製造)，將3,8-二甲氧基苊醌1.8份變更為3,6-二甲基苊醌1.6份，除此以外與製造例3同樣地獲得前驅物(P2-9)1.3份。 2,7-dimethoxynaphthalene was changed to 2,5-dimethylnaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.8 parts of 3,8-dimethoxyacenaphthylquinone was changed to 3,6-di Except for 1.6 parts of methylacenaphthoquinone, it carried out similarly to manufacture example 3, and obtained 1.3 parts of precursor (P2-9).

<製造例17> <Production Example 17>

<N-羥基-2,5-二甲基-1,8-萘二甲醯亞胺[前驅物(P3-8)]的 合成> <N-Hydroxy-2,5-dimethyl-1,8-naphthalimide [precursor (P3-8)] Synthesis>

將前驅物(P2-1)1.1份變更為前驅物(P2-9)1.1份，除此以外與製造例2同樣地獲得前驅物(P3-8)1.2份。 Except having changed 1.1 parts of precursor (P2-1) to 1.1 parts of precursor (P2-9), it carried out similarly to manufacture example 2, and obtained 1.2 parts of precursor (P3-8).

<實施例1> <Example 1>

<2,7-二甲基-1,8-萘二甲醯亞胺三氟甲磺酸鹽[非離子系光酸產生劑(A-1)]的合成> <Synthesis of 2,7-dimethyl-1,8-naphthalimide trifluoromethanesulfonate [nonionic photoacid generator (A-1)]>

將製造例2中合成的前驅物(P3-1)2.5份分散於二氯甲烷70份中，加入吡啶1.0份後於冰浴中冷卻，滴加三氟甲磺酸氯化物(東京化成工業股份有限公司製造)2.0份，並使其反應。於攪拌1小時後，將反應液投入至冰浴冷卻的稀鹽酸中，利用水清洗3次後，將萃取液濃縮而獲得淡褐色的固體。利用異丙醇清洗該固體，並進行乾燥，藉此獲得非離子系光酸產生劑(A-1)3.8份。 Disperse 2.5 parts of the precursor (P3-1) synthesized in Production Example 2 in 70 parts of dichloromethane, add 1.0 part of pyridine, cool in an ice bath, and dropwise add trifluoromethanesulfonic acid chloride (Tokyo Chemical Industry Co., Ltd. Co., Ltd.) 2.0 parts, and reacted. After stirring for 1 hour, the reaction solution was poured into dilute hydrochloric acid cooled in an ice bath, washed three times with water, and the extract was concentrated to obtain a light brown solid. This solid was washed with isopropyl alcohol and dried to obtain 3.8 parts of a nonionic photoacid generator (A-1).

<實施例2> <Example 2>

<2,7-二甲氧基-1,8-萘二甲醯亞胺九氟丁磺酸鹽[非離子系光酸產生劑(A-2)]的合成> <Synthesis of 2,7-dimethoxy-1,8-naphthalimide nonafluorobutanesulfonate [nonionic photoacid generator (A-2)]>

將前驅物(P3-1)變更為前驅物(P3-2)2.9份，將二氯甲烷70份變更為47份，將三氟甲磺酸氯化物2.0份變更為九氟丁磺酸氯化物(奧德里奇(Aldrich)製造)3.7份及將反應時間變更為3小時，除此以外與實施例1同樣地獲得非離子系光酸產生劑(A-2)5.6份。 The precursor (P3-1) was changed to 2.9 parts of the precursor (P3-2), 70 parts of dichloromethane were changed to 47 parts, and 2.0 parts of trifluoromethanesulfonic acid chloride was changed to nonafluorobutanesulfonic acid chloride (manufactured by Aldrich) 3.7 parts, and except having changed the reaction time to 3 hours, it carried out similarly to Example 1, and obtained 5.6 parts of nonionic photoacid generators (A-2).

<實施例3> <Example 3>

<2,7-二甲硫基-1,8-萘二甲醯亞胺三氟甲磺酸鹽[非離子系光 酸產生劑(A-3)]的合成> <2,7-Dimethylthio-1,8-naphthalimide trifluoromethanesulfonate [non-ionic light Synthesis of Acid Generator (A-3)]>

將前驅物(P3-1)變更為前驅物(P3-3)3.2份及將二氯甲烷70份變更為47份，除此以外與實施例1同樣地獲得非離子系光酸產生劑(A-3)4.4份。 A nonionic photoacid generator (A) was obtained in the same manner as in Example 1, except that the precursor (P3-1) was changed to 3.2 parts of the precursor (P3-3) and 70 parts of dichloromethane were changed to 47 parts. -3) 4.4 servings.

<實施例4> <Example 4>

<2,7-二-第三丁氧基羰氧基-1,8-萘二甲醯亞胺五氟苯磺酸鹽[非離子系光酸產生劑(A-4)]的合成> <Synthesis of 2,7-di-tert-butoxycarbonyloxy-1,8-naphthalimide pentafluorobenzenesulfonate [nonionic photoacid generator (A-4)]>

將前驅物(P3-1)變更為前驅物(P3-4)4.7份，將二氯甲烷70份變更為47份，將三氟甲磺酸氯化物2.0份變更為五氟苯磺酸氯化物(奧德里奇(Aldrich)製造)3.1份及將反應時間變更為3小時，除此以外與實施例1同樣地獲得非離子系光酸產生劑(A-4)6.8份。 The precursor (P3-1) was changed to 4.7 parts of the precursor (P3-4), 70 parts of dichloromethane were changed to 47 parts, and 2.0 parts of trifluoromethanesulfonic acid chloride was changed to pentafluorobenzenesulfonic acid chloride (The Aldrich make) 3.1 parts and except having changed the reaction time to 3 hours, it carried out similarly to Example 1, and obtained 6.8 parts of nonionic photoacid generators (A-4).

<實施例5> <Example 5>

<2,7-二-第三丁氧基羰基-1,8-萘二甲醯亞胺三氟甲磺酸鹽[非離子系光酸產生劑(A-5)]的合成> <Synthesis of 2,7-di-tert-butoxycarbonyl-1,8-naphthalimide trifluoromethanesulfonate [nonionic photoacid generator (A-5)]>

將前驅物(P3-1)變更為前驅物(P3-5)4.4份及將二氯甲烷70份變更為47份，除此以外與實施例1同樣地獲得非離子系光酸產生劑(A-5)5.2份。 A nonionic photoacid generator (A) was obtained in the same manner as in Example 1, except that the precursor (P3-1) was changed to 4.4 parts of the precursor (P3-5) and 70 parts of dichloromethane were changed to 47 parts. -5) 5.2 servings.

<實施例6> <Example 6>

<2,7-二乙基羰氧基-1,8-萘二甲醯亞胺三氟甲磺酸鹽[非離子系光酸產生劑(A-6)]的合成> <Synthesis of 2,7-diethylcarbonyloxy-1,8-naphthalimide trifluoromethanesulfonate [nonionic photoacid generator (A-6)]>

於冰浴中冷卻、攪拌非離子系光酸產生劑(A-4)的二氯甲烷 47份溶液，慎重滴加三氟甲磺酸0.5份。隨著反應進行的氣體的產生結束後進而攪拌30分鐘。過濾所析出的固體並利用二氯甲烷加以清洗。繼而，向該固體中加入二氯甲烷47份，向冰浴的分散液中滴加吡啶1.0份。進而加入丙酸氯化物1.1份並攪拌3小時。於反應結束後，利用水對反應液進行3次清洗加以濃縮，並利用異丙醇進行清洗，藉此獲得固體的非離子系光酸產生劑(A-6)4.6份。 Cool and stir dichloromethane of nonionic photoacid generator (A-4) in ice bath 47 parts of the solution, 0.5 part of trifluoromethanesulfonic acid was carefully added dropwise. After the completion of gas generation as the reaction progressed, stirring was continued for 30 minutes. The precipitated solid was filtered and washed with dichloromethane. Next, 47 parts of methylene chloride was added to the solid, and 1.0 part of pyridine was added dropwise to the dispersion liquid in the ice bath. Furthermore, 1.1 parts of propionic acid chloride was added and stirred for 3 hours. After the completion of the reaction, the reaction solution was washed three times with water, concentrated, and washed with isopropanol to obtain 4.6 parts of solid nonionic photoacid generators (A-6).

<實施例7> <Example 7>

<2,3-二甲基-1,8-萘二甲醯亞胺三氟甲磺酸鹽[非離子系光酸產生劑(A-7)]的合成> <Synthesis of 2,3-dimethyl-1,8-naphthalimide trifluoromethanesulfonate [nonionic photoacid generator (A-7)]>

將前驅物(P3-1)變更為前驅物(P3-6)及將二氯甲烷70份變更為47份，除此以外與實施例1同樣地獲得非離子系光酸產生劑(A-7)3.7份。 A nonionic photoacid generator (A-7) was obtained in the same manner as in Example 1, except that the precursor (P3-1) was changed to the precursor (P3-6) and 70 parts of dichloromethane were changed to 47 parts. ) 3.7 servings.

<實施例8> <Example 8>

<2,6-二異丙基-1,8-萘二甲醯亞胺三氟甲磺酸鹽[非離子系光酸產生劑(A-8)]的合成> <Synthesis of 2,6-diisopropyl-1,8-naphthalimide trifluoromethanesulfonate [nonionic photoacid generator (A-8)]>

將前驅物(P3-1)變更為前驅物(P3-7)3.1份及將二氯甲烷70份變更為47份，除此以外與實施例1同樣地獲得非離子系光酸產生劑(A-8)4.1份。 A nonionic photoacid generator (A) was obtained in the same manner as in Example 1, except that the precursor (P3-1) was changed to 3.1 parts of the precursor (P3-7) and 70 parts of dichloromethane were changed to 47 parts. -8) 4.1 servings.

<實施例9> <Example 9>

<2,5-二甲基-1,8-萘二甲醯亞胺三氟甲磺酸鹽[非離子系光酸產生劑(A-9)]的合成> <Synthesis of 2,5-dimethyl-1,8-naphthalimide trifluoromethanesulfonate [nonionic photoacid generator (A-9)]>

將前驅物(P3-1)變更為前驅物(P3-8)及將二氯甲烷70份變更為47份，除此以外與實施例1同樣地獲得非離子系光酸產生劑(A-9)3.7份。 A nonionic photoacid generator (A-9) was obtained in the same manner as in Example 1, except that the precursor (P3-1) was changed to the precursor (P3-8) and 70 parts of dichloromethane were changed to 47 parts. ) 3.7 servings.

以下記載實施例1~實施例9中所獲得的非離子系光酸產生劑(A-1)~非離子系光酸產生劑(A-9)的結構。 The structures of the nonionic photoacid generator (A-1) to the nonionic photoacid generator (A-9) obtained in Examples 1 to 9 are described below.

<比較例1> <Comparative Example 1>

<非離子系光酸產生劑(A'-1)的合成> <Synthesis of nonionic photoacid generator (A'-1)>

直接使用1,8-萘二甲醯亞胺三氟甲磺酸鹽(A'-1)(奧德里奇 (Aldrich)公司製造)。 Direct use of 1,8-naphthalimide triflate (A'-1) (Aldrich (manufactured by Aldrich).

<製造例18> <Production Example 18>

<4-丁硫基-1,8-萘二甲酸酐[前驅物(P2'-1)]的合成> <Synthesis of 4-butylthio-1,8-naphthalenedicarboxylic anhydride [precursor (P2'-1)]>

將4-溴代-1,8-萘二甲酸酐(東京化成工業股份有限公司製造)2.8份分散於二甲基乙醯胺9.5份中，加入1-丁硫醇1.0份。將容器浸泡於水浴中，向該分散液中滴加DBU 1.7份。於滴加完成後，將分散液於70℃下攪拌一天。於冷卻至室溫後，將反應液投入至大量的水中，過濾所析出的固體並充分地進行水洗。將所獲得的固體乾燥而獲得前驅物(P2'-1)2.3份。 2.8 parts of 4-bromo-1,8-naphthalene dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dispersed in 9.5 parts of dimethylacetamide, and 1.0 part of 1-butanethiol was added. The container was immersed in a water bath, and 1.7 parts of DBU was added dropwise to the dispersion. After the dropwise addition was completed, the dispersion was stirred at 70°C for one day. After cooling to room temperature, the reaction liquid was poured into a large amount of water, and the precipitated solid was filtered and sufficiently washed with water. The obtained solid was dried to obtain 2.3 parts of precursor (P2'-1).

<比較例2> <Comparative Example 2>

<非離子系光酸產生劑(A'-2)的合成> <Synthesis of nonionic photoacid generator (A'-2)>

將前驅物(P2-1)2.6份變更為製造例18中所合成的前驅物(P2'-1)3.1份，除此以外與製造例2同樣地獲得前驅物(P3'-1)2.8份。繼而，將前驅物(P3-1)2.9份變更為所合成的前驅物(P3'-1)3.4份，除此以外與實施例1同樣地獲得非離子系光酸產生劑(A'-2)4.3份。 2.8 parts of precursor (P3'-1) were obtained in the same manner as in Production Example 2, except that 2.6 parts of precursor (P2-1) was changed to 3.1 parts of precursor (P2'-1) synthesized in Production Example 18 . Next, the nonionic photoacid generator (A'-2) was obtained in the same manner as in Example 1, except that 2.9 parts of the precursor (P3-1) was changed to 3.4 parts of the synthesized precursor (P3'-1). ) 4.3 servings.

<比較例3> <Comparative Example 3>

<非離子系光酸產生劑(A'-3)的合成> <Synthesis of nonionic photoacid generator (A'-3)>

直接使用1,8-萘二甲醯亞胺對甲苯磺酸鹽(A'-3)(奧德里奇(Aldrich)公司製造)。 1,8-Naphthalimide p-toluenesulfonate (A'-3) (manufactured by Aldrich) was used as it was.

以下記載比較例1~比較例3中所獲得的非離子系光酸產生劑(A'-1)~非離子系光酸產生劑(A'-3)的結構。 The structures of the nonionic photoacid generators (A'-1) to the nonionic photoacid generators (A'-3) obtained in Comparative Examples 1 to 3 are described below.

<實施例1~實施例9、比較例1~比較例3> <Example 1 to Example 9, Comparative Example 1 to Comparative Example 3>

作為光酸產生劑的性能評價，利用以下的方法對實施例1~實施例9中所獲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'-3)的i-光線感度及耐鹼性進行評價，將其結果記載於表1中。 As the performance evaluation of the photoacid generator, the following methods were used to evaluate the nonionic photoacid generator (A-1) to the nonionic photoacid generator (A-9) obtained in Examples 1 to 9. . The i-light sensitivity and alkali resistance of the nonionic photoacid generator (A'-1) ~ nonionic photoacid generator (A'-3) used for comparison were evaluated, and the results were recorded in the table 1 in.

<i-光線感度的評價方法> <i-Evaluation method of light sensitivity>

<曝光部硬化性> <Exposure part curability>

使用旋塗機於200rpm且10秒的條件下，將酚樹脂(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、所合成的光酸產生劑1份、及丙二 醇單甲醚乙酸酯(以下，簡稱為PGMEA)100份的樹脂溶液塗佈於10cm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40μm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，截止未滿340nm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365nm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%以內的最低曝光量設為曝光部硬化性。越以少的曝光量顯示出充分的曝光部硬化性，i-光線感度越良好，因此藉由以下的基準來評價光酸產生劑的i-光線感度。 Using a spin coater at 200 rpm for 10 seconds, 75 parts of phenol resin (manufactured by DIC, "Phenolite TD431"), melamine hardener (Mitsui Cyanamid) Co., Ltd., 25 parts of "Cymel 300"), 1 part of the synthesized photoacid generator, and propylene glycol A resin solution of 100 parts of alcohol monomethyl ether acetate (hereinafter abbreviated as PGMEA) was applied on a 10 cm square glass substrate. Next, after vacuum drying at 25 degreeC for 5 minutes, it dried for 5 minutes on the hotplate of 100 degreeC, and the resist with a film thickness of about 40 micrometers was formed. This resist was exposed to a predetermined amount of light by L-34 (Kenko Optical Co., Ltd., HMW-661F-01) on the entire surface using an ultraviolet irradiation apparatus (ORC MANUFACTURING Co., Ltd. Kougaku) Co., Ltd., a filter that cuts off light less than 340 nm) The filter has a limited wavelength of ultraviolet light. In addition, about the accumulated exposure amount, the wavelength of 365 nm was measured. Then, after performing post-exposure heating (PEB) in a downwind dryer at 150° C. for 10 minutes, it was developed using a 0.5% potassium hydroxide solution and immersed for 60 seconds, and washed with water and dried immediately. The film thickness of the resist was measured using a profile measuring microscope (Ultra-depth profile measuring microscope UK-8550, manufactured by Keyence Co., Ltd.). Here, the minimum exposure amount at which the film thickness change of the resist before and after development is within 10% is defined as the exposure portion curability. The less the exposure amount, the more favorable the i-light sensitivity is, so the i-light sensitivity of the photoacid generator is evaluated according to the following criteria.

○：最低曝光量為500mJ/cm²以下 ○: Minimum exposure is 500mJ/ ^cm2 or less

×：最低曝光量超過500mJ/cm² ×: Minimum exposure exceeds 500mJ/ ^cm2

<耐鹼性的評價方法> <Evaluation method of alkali resistance>

於帶帽的螺旋管中秤量三乙胺2份，加入氘代氯仿200份而進行混合。繼而加入所合成的非離子系光酸產生劑3份，快速攪拌而獲得均勻的光酸產生劑溶液。將該溶液於室溫下靜置24小時 後，利用氟19NMR測定分解率D[%]。分解率D是如以下般求出。 2 parts of triethylamine were weighed in a capped helical tube, and 200 parts of deuterated chloroform was added and mixed. Then, 3 parts of the synthesized nonionic photoacid generators were added, and the solution was rapidly stirred to obtain a uniform photoacid generator solution. The solution was left to stand at room temperature for 24 hours Then, the decomposition rate D [%] was measured by fluorine 19 NMR. The decomposition rate D is obtained as follows.

分解率D[%]：D=分解物的積分比/(光酸產生劑的積分比+分解物的積分比)×100 Decomposition rate D[%]: D=integral ratio of decomposed products/(integral ratio of photoacid generator+integral ratio of decomposed products)×100

此處，根據分解率D[%]如以下般評價光酸產生劑的耐鹼性。 Here, the alkali resistance of the photoacid generator was evaluated from the decomposition rate D [%] as follows.

○：分解率D[%]為20%以下 ○: Decomposition rate D [%] is 20% or less

×：分解率D[%]超過20% ×: Decomposition rate D [%] exceeds 20%

根據表1明確，本發明的實施例1~實施例9的具有萘二甲醯亞胺結構的非離子系光酸產生劑(A)於R1上具有取代基，因此耐鹼性優異，不與淬滅劑發生反應，故抗蝕劑用樹脂組成物的經時變化少，可獲得所期望的形狀的圖案。另外，由於第2個取代基作用於萘環上的電子狀態以及Rf的烴上的一個以上的氫被取代為氟，因此可以i-光線高感度進行分解並產生強酸。進而，由於具有萘二甲醯亞胺結構且熱穩定性優異，故不會藉由PEB發生分解，容許幅度優異。另一方面，於作為具有萘二甲醯亞胺結構且於R1上不具有取代基的非離子系光酸產生劑的比較例1及比 較例2中，由於在醯亞胺羰基附近不含有具有立體阻礙的取代基，故容易與鹼成分發生反應而分解。藉此，與抗蝕劑材料中的淬滅劑發生反應，因此抗蝕劑用樹脂組成物的經時變化大，於調配後隨時間經過而無法獲得所期望的形狀的圖案。另外，可知於作為具有未對Rf進行氟取代的烴基的光酸產生劑的比較例3中，i-光線感度差，因此無法形成圖案。 As is clear from Table 1, the nonionic photoacid generators (A) having a naphthalimide structure of Examples 1 to 9 of the present invention have a substituent on R1, so they are excellent in alkali resistance and are not compatible with Since the quencher reacts, the resin composition for a resist has little change with time, and a pattern of a desired shape can be obtained. In addition, since the second substituent acts on the electronic state of the naphthalene ring and one or more hydrogens on the hydrocarbon of Rf are substituted with fluorine, it can decompose with high i-ray sensitivity and generate a strong acid. Furthermore, since it has a naphthalimide structure and is excellent in thermal stability, it is not decomposed by PEB, and the tolerance is excellent. On the other hand, in Comparative Example 1 and R In Comparative Example 2, since a substituent having a steric hindrance is not contained in the vicinity of the iminocarbonyl group, it is easy to react with an alkali component and decompose. Thereby, since it reacts with the quencher in a resist material, the time-dependent change of the resin composition for resists is large, and the pattern of a desired shape cannot be obtained with time after preparation. In addition, in Comparative Example 3, which is a photoacid generator having a hydrocarbon group in which Rf is not substituted with fluorine, it was found that the i-light sensitivity was poor, so that it was not possible to form a pattern.

[產業上之可利用性] [Industrial Availability]

本發明的非離子系光酸產生劑(A)具有對i-光線的高感度與所需的耐鹼性及熱穩定性，因此作為半導體的製造所代表的微細加工用途的光微影材料而言有用。 Since the nonionic photoacid generator (A) of the present invention has high sensitivity to i-rays and required alkali resistance and thermal stability, it is useful as a photolithography material for microfabrication applications represented by the manufacture of semiconductors. Words are useful.

Claims (7)

一種非離子系光酸產生劑，其特徵在於：由下述通式(1)所表示，

式(1)中，R1為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2~R6中的一個為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，其餘為氫原子，Rf為氟原子、或至少一個以上的氫被氟取代而成的碳數1~18的烴基。 A non-ionic photoacid generator, characterized in that it is represented by the following general formula (1),

In formula (1), R1 is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkyl carbonate group, and R2 to R6 One of them is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group or an alkylcarbonate group, the rest are hydrogen atoms, and Rf is A fluorine atom or a hydrocarbon group having 1 to 18 carbon atoms in which at least one or more hydrogens are 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，其中通式(1)中R6為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2~R5為氫原子。 The non-ionic photoacid generator according to the first item of the scope of application, wherein R6 in the general formula (1) is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkane group Oxycarbonyl, alkylcarbonyloxy or alkylcarbonate, R2~R5 are hydrogen atoms. 如申請專利範圍第1項所述的非離子系光酸產生劑，其中通式(1)中R5為碳數1~12的烴基、羥基、烷氧基、烷硫 基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2~R4及R6為氫原子。 The non-ionic photoacid generator as described in item 1 of the scope of the application, wherein R5 in the general formula (1) is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, or an alkyl sulfide group, alkylcarbonyl group, alkoxycarbonyl group, alkylcarbonyloxy group or alkylcarbonate group, R2~R4 and R6 are hydrogen atoms. 如申請專利範圍第1項所述的非離子系光酸產生劑，其中通式(1)中R2為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R3~R6為氫原子。 The non-ionic photoacid generator according to the first item of the scope of application, wherein R2 in the general formula (1) is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkane group Oxycarbonyl group, alkylcarbonyloxy group or alkylcarbonate group, R3~R6 are hydrogen atoms. 如申請專利範圍第1項所述的非離子系光酸產生劑，其中通式(1)中R4為碳數1~12的烴基、羥基、烷氧基、烷硫基、烷基羰基、烷氧基羰基、烷基羰氧基或烷基碳酸酯基，R2、R3、R5及R6為氫原子。 The non-ionic photoacid generator as described in item 1 of the scope of the application, wherein R4 in the general formula (1) is a hydrocarbon group with 1 to 12 carbon atoms, a hydroxyl group, an alkoxy group, an alkylthio group, an alkylcarbonyl group, an alkane group Oxycarbonyl group, alkylcarbonyloxy group or alkylcarbonate group, R2, R3, R5 and R6 are hydrogen atoms. 如申請專利範圍第1項至第5項中任一項所述的非離子系光酸產生劑，其中於通式(1)中Rf為CF₃、C₂F₅、C₃F₇、C₄F₉、或C₆F₅。 The nonionic photoacid generator according to any one of items 1 to 5 of the scope of application, wherein in the general formula (1), Rf is CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C _4F9 , _{or C6F5 .} 一種光微影用樹脂組成物，其包含如申請專利範圍第1項至第6項中任一項所述的非離子系光酸產生劑。 A resin composition for photolithography, comprising the nonionic photoacid generator described in any one of the first to sixth claims in the scope of application.