TW201843526A - Photosensitive resin composition and method for forming resist pattern - Google Patents

Photosensitive resin composition and method for forming resist pattern Download PDF

Info

Publication number
TW201843526A
TW201843526A TW107114324A TW107114324A TW201843526A TW 201843526 A TW201843526 A TW 201843526A TW 107114324 A TW107114324 A TW 107114324A TW 107114324 A TW107114324 A TW 107114324A TW 201843526 A TW201843526 A TW 201843526A
Authority
TW
Taiwan
Prior art keywords
group
protecting group
resin composition
added
compound
Prior art date
Application number
TW107114324A
Other languages
Chinese (zh)
Inventor
岩下建一
横澤勉
Original Assignee
日商日立化成股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商日立化成股份有限公司 filed Critical 日商日立化成股份有限公司
Publication of TW201843526A publication Critical patent/TW201843526A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polyamides (AREA)
  • Materials For Photolithography (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

The present invention is, in one aspect, a photosensitive resin composition containing: a resin having a structural unit represented by formula (1); and a photoacid generator. In the formula, each of R1 and R2 independently represents a monovalent protecting group deprotected under acidic conditions, and each of X1 and Z1 independently represents a divalent organic group.

Description

感光性樹脂組成物及抗蝕劑圖案的形成方法Photosensitive resin composition and method for forming resist pattern

本發明是有關於一種感光性樹脂組成物及抗蝕劑圖案（resist pattern）的形成方法。The present invention relates to a method of forming a photosensitive resin composition and a resist pattern.

聚醯胺樹脂具有高耐熱性、高強度、高耐溶劑性等多個優異的特性，因此作為各種基材塗佈劑而廣泛使用。例如，作為聚醯胺樹脂的用途，可列舉電子構件的絕緣保護膜（外塗膜（overcoat film））、液晶單元配向膜等（參照專利文獻1及專利文獻2）。另外，聚醯胺樹脂亦作為對環氧樹脂等的特性進行改質的添加劑、硬化劑等而被開發，且包含其作為一成分的環氧組成物通常為耐熱性、機械特性、耐化學品性等優異的硬化物，可於接著劑、塗料、積層板、成形材料、澆鑄材料等寬廣領域中利用（參照專利文獻3）。 [現有技術文獻] [專利文獻]Polyamine resin is widely used as various substrate coating agents because it has many excellent properties such as high heat resistance, high strength, and high solvent resistance. For example, examples of the use of the polyamide resin include an insulating protective film (overcoat film) of an electronic component, a liquid crystal cell alignment film, and the like (see Patent Document 1 and Patent Document 2). In addition, polyamine resin has been developed as an additive or a curing agent for modifying characteristics of an epoxy resin or the like, and an epoxy composition containing the same as a component is generally heat resistance, mechanical properties, and chemical resistance. The cured product excellent in properties and the like can be used in a wide range of fields such as an adhesive, a paint, a laminate, a molding material, and a casting material (see Patent Document 3). [Prior Art Document] [Patent Literature]

[專利文獻1]日本專利特開平05-150452號公報 [專利文獻2]日本專利特開平10-195193號公報 [專利文獻3]國際公開第2007/052523號[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei No. Hei 10-195193 (Patent Document 3) International Publication No. 2007/052523

[發明所欲解決之課題] 且說，於在所述般的用途中使用聚醯胺樹脂的情況下，多使其暫且溶解於有機溶劑中而使用，但現有的聚醯胺樹脂不可謂具有於有機溶劑中的充分的溶解性，會產生無法添加獲得所期望的特性所需的量的問題。[Problems to be Solved by the Invention] In the case where a polyamide resin is used in the above-mentioned applications, it is often used by dissolving it in an organic solvent, but the conventional polyamide resin cannot be said to have The sufficient solubility in the organic solvent causes a problem that the amount required to obtain the desired characteristics cannot be added.

因此，本發明的目的在於為了解決所述問題而提供一種含有在有機溶劑中的溶解性優異的樹脂且可將該樹脂轉換為聚醯胺樹脂的感光性樹脂組成物、及使用該感光性樹脂組成物的抗蝕劑圖案的形成方法。 [解決課題之手段]Therefore, an object of the present invention is to provide a photosensitive resin composition containing a resin excellent in solubility in an organic solvent and capable of converting the resin into a polyamide resin, and using the photosensitive resin in order to solve the above problems. A method of forming a resist pattern of a composition. [Means for solving the problem]

本發明者等人為了解決所述問題而進行了努力研究，結果發現，藉由利用規定的保護基保護構成聚醯胺結構的氮原子可獲得於有機溶劑中的溶解性優異的樹脂、及藉由將該樹脂與光酸產生劑組合可將該樹脂轉換為聚醯胺樹脂。即，本發明於一態樣中為一種感光性樹脂組成物，其含有具有下述式（1）所表示的結構單元的樹脂、以及光酸產生劑。 [化1]（式中，R1 及R2 分別獨立地表示於酸性條件下脫保護的一價保護基，X1 及Z1 分別獨立地表示二價有機基）In order to solve the problem, the present inventors have made an effort to solve the problem, and have found that a resin having a solubility in an organic solvent can be obtained by protecting a nitrogen atom constituting a polyamine structure by a predetermined protecting group. The resin can be converted into a polyamide resin by combining the resin with a photoacid generator. In other words, the present invention is a photosensitive resin composition containing a resin having a structural unit represented by the following formula (1) and a photoacid generator. [Chemical 1] (wherein R 1 and R 2 each independently represent a monovalent protecting group deprotected under acidic conditions, and X 1 and Z 1 each independently represent a divalent organic group)

保護基較佳為於pKa為0以下的酸性條件下脫保護的保護基。The protecting group is preferably a protecting group which is deprotected under acidic conditions having a pKa of 0 or less.

相對於樹脂100質量份，光酸產生劑的含量較佳為1質量份～100質量份。The content of the photoacid generator is preferably from 1 part by mass to 100 parts by mass based on 100 parts by mass of the resin.

本發明於另一態樣中為一種抗蝕劑圖案的形成方法，其包括：於基材上配置所述感光性樹脂組成物而形成感光層的步驟；以及對感光層利用規定的圖案進行曝光後，進行加熱的步驟。In another aspect, the present invention provides a method for forming a resist pattern, comprising: a step of disposing the photosensitive resin composition on a substrate to form a photosensitive layer; and exposing the photosensitive layer to a predetermined pattern After that, the step of heating is performed.

本發明者等人如以下般考慮所述樹脂於有機溶劑中的溶解性優異的理由。現有的聚醯胺樹脂具有構成醯胺鍵的NH鍵，NH鍵形成氫鍵，藉此具有強的分子間相互作用。因此，有機溶劑的分子難以浸透至樹脂間，結果聚醯胺樹脂於有機溶劑中的溶解性變低。另一方面，本發明的樹脂代替NH鍵的H原子而導入保護基，藉此並不具有氫鍵，與聚醯胺樹脂相比，可減低分子間相互作用。因此，本發明者等人推斷該樹脂於有機溶劑中的溶解性優異。 [發明的效果]The inventors of the present invention considered the reason why the solubility of the resin in an organic solvent is excellent as follows. The existing polyamine resin has an NH bond constituting a guanamine bond, and the NH bond forms a hydrogen bond, thereby having strong intermolecular interaction. Therefore, it is difficult for the molecules of the organic solvent to permeate into the resin, and as a result, the solubility of the polyamide resin in the organic solvent is lowered. On the other hand, the resin of the present invention introduces a protective group instead of the H atom of the NH bond, thereby not having a hydrogen bond, and the intermolecular interaction can be reduced as compared with the polyamine resin. Therefore, the inventors of the present invention have estimated that the resin is excellent in solubility in an organic solvent. [Effects of the Invention]

根據本發明，可提供一種含有在有機溶劑中的溶解性優異的樹脂且可將該樹脂轉換為聚醯胺樹脂的感光性樹脂組成物、及使用該感光性樹脂組成物的抗蝕劑圖案的形成方法。According to the present invention, it is possible to provide a photosensitive resin composition containing a resin excellent in solubility in an organic solvent and capable of converting the resin into a polyamide resin, and a resist pattern using the photosensitive resin composition. Forming method.

以下，對本發明的實施形態進行具體說明，但本發明並不限定於此。Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited thereto.

＜感光性樹脂組成物＞ 一實施形態的感光性樹脂組成物含有具有下述式（1）所表示的結構單元的樹脂、以及光酸產生劑。 [化2]（式中，R1 及R2 分別獨立地表示於酸性條件下脫保護的一價保護基，X1 及Z1 分別獨立地表示二價有機基）<Photosensitive Resin Composition> The photosensitive resin composition of the embodiment contains a resin having a structural unit represented by the following formula (1) and a photoacid generator. [Chemical 2] (wherein R 1 and R 2 each independently represent a monovalent protecting group deprotected under acidic conditions, and X 1 and Z 1 each independently represent a divalent organic group)

[N-保護基聚醯胺樹脂] 具有式（1）所表示的結構單元的樹脂為代替構成聚醯胺樹脂的醯胺鍵的NH鍵的H原子而導入有保護基的樹脂（以下亦稱為「N-保護基聚醯胺樹脂」）。[N-Protective Polyamine Resin] The resin having the structural unit represented by the formula (1) is a resin in which a protective group is introduced instead of the H atom constituting the NH bond of the guanamine bond of the polyamide resin (hereinafter also referred to as It is "N-protected polyamine resin").

R1 或R2 所表示的保護基較佳為於pKa（=-logKa（Ka為酸解離常數））為0以下的酸性條件下脫保護的保護基。保護基例如可為下述式（2）所表示的對烷氧基苄基、苄基氧基羰基、第三丁氧基羰基等。 [化3]式中，R3 表示烷基，*表示結合鍵。烷基較佳為直鏈烷基。烷基的碳數例如可為1～10。The protecting group represented by R 1 or R 2 is preferably a protecting group which is deprotected under acidic conditions in which pKa (=-logKa (Ka is an acid dissociation constant)) is 0 or less. The protective group may be, for example, a p-alkoxybenzyl group, a benzyloxycarbonyl group, a third butoxycarbonyl group or the like represented by the following formula (2). [Chemical 3] In the formula, R 3 represents an alkyl group, and * represents a bond. The alkyl group is preferably a linear alkyl group. The alkyl group may have a carbon number of, for example, 1 to 10.

作為式（2）所表示的對烷氧基苄基，具體可列舉：對甲氧基苄基、對乙氧基苄基、對丙基氧基苄基、對丁氧基苄基、對戊基氧基苄基、對己基氧基苄基、對庚基氧基苄基、對辛基氧基苄基、對壬基氧基苄基、對癸烷基氧基苄基等。Specific examples of the p- alkoxybenzyl group represented by the formula (2) include p-methoxybenzyl group, p-ethoxybenzyl group, p-propyloxybenzyl group, p-butoxybenzyl group, and p-pentyl group. Alkoxybenzyl, p-hexyloxybenzyl, p-heptyloxybenzyl, p-octyloxybenzyl, p-nonyloxybenzyl, p-decyloxybenzyl, and the like.

X1 所表示的二價有機基例如為具有至少一個芳香環的有機基。N-保護基聚醯胺樹脂亦可具有下述式（1-1）或式（1-2）所表示的結構單元作為式（1）所表示的結構單元。 [化4][化5] The divalent organic group represented by X 1 is, for example, an organic group having at least one aromatic ring. The N-protecting polyamine resin may have a structural unit represented by the following formula (1-1) or formula (1-2) as a structural unit represented by the formula (1). [Chemical 4] [Chemical 5]

式中，R4 ～R7 分別獨立地與式（1）中的R1 、R2 為相同含義，Z2 及Z3 分別獨立地與式（1）中的Z1 為相同含義。X2 表示二價基，例如可為氧原子、硫原子、伸烷基或磺醯基，較佳為氧原子。X2 所表示的伸烷基的碳數例如可為1～10。In the formula, R 4 to R 7 each independently have the same meaning as R 1 and R 2 in the formula (1), and Z 2 and Z 3 each independently have the same meaning as Z 1 in the formula (1). X 2 represents a divalent group, and may be, for example, an oxygen atom, a sulfur atom, an alkylene group or a sulfonyl group, preferably an oxygen atom. The carbon number of the alkylene group represented by X 2 may be, for example, 1 to 10.

Z1 、Z2 或Z3 所表示的二價有機基例如為氧原子、硫原子或可經鹵素原子取代的二價烴基。該烴基可為脂肪族烴基或芳香族烴基。烴基的碳數例如可為1～20。The divalent organic group represented by Z 1 , Z 2 or Z 3 is, for example, an oxygen atom, a sulfur atom or a divalent hydrocarbon group which may be substituted by a halogen atom. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may have a carbon number of, for example, 1 to 20.

脂肪族烴基可為鏈狀亦可為環狀，例如可為直鏈或分支的伸烷基、直鏈或分支的伸烯基、伸環烷基、伸環烯基等，較佳為直鏈或分支的伸烷基、或直鏈或分支的伸烯基。該些脂肪族烴基可經氟原子取代，作為經氟原子取代的脂肪族烴基，例如可列舉-C(CF3 )2 -等。The aliphatic hydrocarbon group may be a chain or a ring, and may be, for example, a linear or branched alkyl group, a linear or branched alkenyl group, a cycloalkyl group, a cycloalkenyl group or the like, preferably a linear chain. Or branched alkyl, or linear or branched alkenyl. These aliphatic hydrocarbon groups may be substituted by a fluorine atom, and examples of the aliphatic hydrocarbon group substituted by a fluorine atom include -C(CF 3 ) 2 -.

伸烷基較佳為直鏈伸烷基。伸烷基的碳數例如可為1～10或3～10。伸烯基例如可為包含下述式（3-1）所表示的結構單元及下述式（3-2）所表示的結構單元的一者或兩者的基。 [化6] The alkylene group is preferably a linear alkylene group. The carbon number of the alkylene group may be, for example, 1 to 10 or 3 to 10. The alkenyl group may be, for example, one or both of a structural unit represented by the following formula (3-1) and a structural unit represented by the following formula (3-2). [Chemical 6]

伸烯基於一實施形態中可為包含式（3-1）所表示的結構單元及式（3-2）所表示的結構單元的一者或兩者的基。該情況下，伸烯基中的聚合度（式（3-1）所表示的結構單元及式（3-2）所表示的結構單元的合計數）例如可為5～200。In one embodiment, the alkenyl group may be a group comprising one or both of the structural unit represented by the formula (3-1) and the structural unit represented by the formula (3-2). In this case, the degree of polymerization in the alkenyl group (the total number of the structural units represented by the formula (3-1) and the structural unit represented by the formula (3-2)) may be, for example, 5 to 200.

伸烯基於另一實施形態中可為包含式（3-1）所表示的結構單元及式（3-2）所表示的結構單元的一者或兩者、與下述式（4）所表示的結構單元的基。 [化7]該情況下，伸烯基中，式（3-1）所表示的結構單元及式（3-2）所表示的結構單元的合計數（聚合度）n1、與式（4）所表示的結構單元的數量（聚合度）n2滿足0＜n2/（n1+n2）≦0.13且10≦n1+n2≦200。In another embodiment, the alkenyl group may be one or both of the structural unit represented by the formula (3-1) and the structural unit represented by the formula (3-2), and represented by the following formula (4). The basis of the structural unit. [Chemistry 7] In this case, in the alkenyl group, the total number of the structural units represented by the formula (3-1) and the structural unit represented by the formula (3-2) (polymerization degree) n1 and the structure represented by the formula (4) The number of cells (degree of polymerization) n2 satisfies 0<n2/(n1+n2)≦0.13 and 10≦n1+n2≦200.

芳香族烴基具有至少一個芳香環。具體而言，例如N-保護基聚醯胺樹脂亦可具有下述式（1-3）或式（1-4）所表示的結構單元作為式（1）所表示的結構單元。芳香族烴基例如可為茀基等。 [化8][化9] The aromatic hydrocarbon group has at least one aromatic ring. Specifically, for example, the N-protecting polyamine resin may have a structural unit represented by the following formula (1-3) or formula (1-4) as a structural unit represented by the formula (1). The aromatic hydrocarbon group may be, for example, a fluorenyl group or the like. [化8] [Chemistry 9]

式中，R8 ～R11 分別獨立地與式（1）中的R1 、R2 為相同含義，X3 及X4 分別獨立地與式（1）中的X1 為相同含義。Z4 表示單鍵或二價基，該二價基例如可為氧原子、硫原子、伸烷基或磺醯基，較佳為氧原子。Z4 所表示的伸烷基的碳數例如為1～10。In the formula, R 8 to R 11 each independently have the same meaning as R 1 and R 2 in the formula (1), and X 3 and X 4 each independently have the same meaning as X 1 in the formula (1). Z 4 represents a single bond or a divalent group, and the divalent group may be, for example, an oxygen atom, a sulfur atom, an alkylene group or a sulfonyl group, preferably an oxygen atom. The carbon number of the alkylene group represented by Z 4 is, for example, 1 to 10.

N-保護基聚醯胺樹脂於一實施形態中亦可具有下述式（1-5）、式（1-6）、式（1-7）或式（1-8）所表示的結構單元作為式（1）所表示的結構單元。 [化10][化11][化12][化13] The N-protecting polyamine resin may have a structural unit represented by the following formula (1-5), formula (1-6), formula (1-7) or formula (1-8) in one embodiment. The structural unit represented by the formula (1). [化10] [11] [化12] [Chemistry 13]

式中，R12 ～R19 分別獨立地與式（1）中的R1 、R2 為相同含義，X5 及X6 分別獨立地與式（1-2）中的X2 為相同含義，Z5 及Z6 分別獨立地與式（1-4）中的Z4 為相同含義。In the formula, R 12 to R 19 each independently have the same meaning as R 1 and R 2 in the formula (1), and X 5 and X 6 each independently have the same meaning as X 2 in the formula (1-2). Z 5 and Z 6 each independently have the same meaning as Z 4 in the formula (1-4).

N-保護基聚醯胺樹脂可為均聚物亦可為共聚物。均聚物可為僅包含所述式（1）所表示的結構單元的均聚物、或僅包含所述式（1-1）～式（1-8）的任一者所表示的結構單元的均聚物。共聚物可為僅包含所述式（1）所表示的結構單元或所述式（1-1）～式（1-8）的任一者所表示的結構單元的共聚物、或除了所述式（1）所表示的結構單元及/或所述式（1-1）～式（1-8）的任一者所表示的結構單元以外亦具有其他結構單元的共聚物。The N-protecting polyamine resin may be a homopolymer or a copolymer. The homopolymer may be a homopolymer including only the structural unit represented by the formula (1), or a structural unit represented by only one of the formula (1-1) to the formula (1-8). Homopolymer. The copolymer may be a copolymer comprising only the structural unit represented by the formula (1) or the structural unit represented by any one of the formulae (1-1) to (1-8), or in addition to the A copolymer having another structural unit other than the structural unit represented by the formula (1) and/or the structural unit represented by any one of the formulae (1-1) to (1-8).

N-保護基聚醯胺樹脂的重量平均分子量較佳為3,000～200,000，更佳為5,000～100,000。重量分子量是指藉由凝膠滲透層析法（Gel Permeation Chromatography）進行測定並基於標準聚苯乙烯標準曲線進行換算而得的值。The weight average molecular weight of the N-protecting polyamine resin is preferably from 3,000 to 200,000, more preferably from 5,000 to 100,000. The weight molecular weight refers to a value measured by gel permeation chromatography (Gel Permeation Chromatography) and converted based on a standard polystyrene standard curve.

N-保護基聚醯胺樹脂例如可藉由如下方式獲得：使代替構成二胺化合物的NH鍵的H原子而導入有保護基的化合物（以下亦稱為「N-保護基二胺化合物」）、與二羧酸於觸媒的存在下縮合。The N-protecting polyamine resin can be obtained, for example, by introducing a compound having a protective group (hereinafter also referred to as "N-protected diamine compound") instead of the H atom constituting the NH bond of the diamine compound. Condensation with a dicarboxylic acid in the presence of a catalyst.

作為二胺化合物，例如可列舉：4,4'-（或3,4'-、3,3'-、2,4'-、2,2'-）二胺基二苯基醚、4,4'-（或3,4'-、3,3'-、2,4'-、2,2'-）二胺基二苯基甲烷、4,4'-（或3,4'-、3,3'-、2,4'-、2,2'-）二胺基二苯基碸、4,4'-（或3,4'-、3,3'-、2,4'-、2,2'-）二胺基二苯基硫醚、對苯二胺、間苯二胺、對苯二甲胺、間苯二甲胺、鄰聯甲苯胺、鄰聯甲苯胺碸、2,2'-二甲基-4,4'-二胺基聯苯、4,4'-亞甲基-雙(2,6-二乙基苯胺)、4,4'-亞甲基-雙(2,6-二異丙基苯胺)、2,4-二胺基均三甲苯、1,5-二胺基萘、4,4'-二苯甲酮二胺、雙-{4-(4'-胺基苯氧基)苯基}碸、2,2-雙{4-(4'-胺基苯氧基)苯基}丙烷、3,3'-二甲基-4,4'-二胺基二苯基甲烷、3,3',5,5'-四甲基-4,4'-二胺基二苯基甲烷、雙{4-(3'-胺基苯氧基)苯基}碸、2,2-雙(4-胺基苯基)丙烷等。該些二胺化合物單獨使用一種或將兩種以上組合使用。Examples of the diamine compound include 4,4′-(or 3,4′-, 3,3′-, 2,4′-, 2,2′-)diaminodiphenyl ether, 4, 4'-(or 3,4'-, 3,3'-, 2,4'-, 2,2'-)diaminodiphenylmethane, 4,4'- (or 3,4'-, 3,3'-, 2,4'-, 2,2'-)diaminodiphenylphosphonium, 4,4'- (or 3,4'-, 3,3'-, 2,4'- , 2,2'-)diaminodiphenyl sulfide, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, o-toluidine, o-toluidine oxime, 2 , 2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylene-bis(2,6-diethylaniline), 4,4'-methylene-double (2,6-diisopropylaniline), 2,4-diamino mesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenone diamine, bis-{4-( 4'-Aminophenoxy)phenyl}anthracene, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4' -diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy) Phenyl}anthracene, 2,2-bis(4-aminophenyl)propane, and the like. These diamine compounds may be used alone or in combination of two or more.

N-保護基二胺化合物為對所述示出的二胺化合物導入有於酸性條件下可脫保護的保護基（具體而言，與所述R1 、R2 所表示的基相同的基）的二級二胺化合物。The N-protecting diamine compound is a protecting group which is deprotectable under acidic conditions introduced to the diamine compound shown (specifically, the same group as the group represented by R 1 and R 2 ) A secondary diamine compound.

N-保護基二胺化合物的合成方法並無特別限制。於保護基為第三丁氧基羰基的情況下，例如可為如下方法：使不會產生難以去除的副產物的二碳酸二-第三丁酯（二-第三丁基二碳酸酯）對所述二胺化合物於吡啶、三乙胺等鹼存在下發揮作用，藉此合成N-保護基二胺化合物的方法。The method for synthesizing the N-protecting diamine compound is not particularly limited. In the case where the protecting group is a third butoxycarbonyl group, for example, it may be a method of making a di-tert-butyl dicarbonate (di-tert-butyldicarbonate) pair which does not produce a by-product which is difficult to remove. The method in which the diamine compound functions in the presence of a base such as pyridine or triethylamine to synthesize an N-protected diamine compound.

於保護基為苄基氧基羰基的情況下，該合成方法例如可為如下方法：使氯甲酸苄基酯對所述二胺化合物於吡啶、三乙胺等鹼存在下發揮作用，藉此進行合成的方法。In the case where the protecting group is a benzyloxycarbonyl group, the synthesis method may be, for example, a method in which benzyl chloroformate is allowed to act on the diamine compound in the presence of a base such as pyridine or triethylamine. The method of synthesis.

於保護基為對烷氧基苄基的情況下，該合成方法例如可為如下方法：使對烷氧基苄基氯化物對所述二胺化合物於吡啶、三乙胺等鹼存在下發揮作用，合成醯胺體並進行分離，利用硼烷-四氫呋喃錯合物使該醯胺體還原而獲得的方法；另外，亦可為如下方法：使對烷氧基苄基醛對所述二胺化合物發揮作用而合成亞胺體並進行分離，對該亞胺體利用硼氫化鈉進行還原而獲得的方法。該些方法中，較佳為經由亞胺體而進行合成的方法。In the case where the protecting group is a p-alkoxybenzyl group, the synthesis method may be, for example, a method in which p-alkoxybenzyl chloride is allowed to act on the diamine compound in the presence of a base such as pyridine or triethylamine. a method of synthesizing a guanamine and separating it, and reducing the guanamine by using a borane-tetrahydrofuran complex; or, in addition, a method of reacting a p-alkoxybenzyl aldehyde with the diamine compound A method in which an imine is synthesized and separated, and the imine is reduced by sodium borohydride. Among these methods, a method of synthesizing via an imine is preferred.

作為所述二羧酸，例如可列舉：間苯二甲酸、對苯二甲酸、2,2-雙(4-羧基苯基)-1,1,1,3,3,3-六氟丙烷、4,4'-二羧基聯苯、4,4'-二羧基二苯基醚、4,4'-二羧基四苯基矽烷、雙(4-羧基苯基)碸、2,2-雙(對羧基苯基)丙烷、5-第三丁基間苯二甲酸、5-溴間苯二甲酸、5-氟間苯二甲酸、5-氯間苯二甲酸、2,6-萘二羧酸等芳香族系二羧酸等。該些二羧酸可單獨使用一種或將兩種以上組合使用。Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, and 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane. 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylnonane, bis(4-carboxyphenyl)anthracene, 2,2-dual ( P-carboxyphenyl)propane, 5-t-butylisophthalic acid, 5-bromosisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalene dicarboxylic acid An aromatic dicarboxylic acid or the like. These dicarboxylic acids may be used alone or in combination of two or more.

N-保護基聚醯胺樹脂例如可使所述N-保護基二胺化合物、與所述二羧酸的二鹵化物衍生物反應而獲得。具體而言，首先，使鹵化劑作用於二羧酸而合成二鹵化物衍生物。二鹵化物衍生物較佳為二氯化物衍生物。於獲得二氯化物衍生物的情況下，鹵化劑可為通常的羧酸的醯氯化反應中使用的亞硫醯氯、氯化磷醯（phosphoryl chloride）、***（phosphorus oxychloride）、五氯化磷等。The N-protecting polyamine resin can be obtained, for example, by reacting the N-protected diamine compound with a dihalide derivative of the dicarboxylic acid. Specifically, first, a halogenating agent is allowed to act on a dicarboxylic acid to synthesize a dihalide derivative. The dihalide derivative is preferably a dichloride derivative. In the case of obtaining a dichloride derivative, the halogenating agent may be a sulfinium chloride, a phosphoryl chloride, or a phosphorous oxychloride used in a hydrazine chlorination reaction of a usual carboxylic acid. Phosphorus pentachloride, etc.

合成二氯化物衍生物的方法可為如下方法：使二羧酸與鹵化劑於溶媒中反應、或於過剩的鹵化劑中添加二羧酸並進行反應後，將過剩的成分蒸餾去除的方法。作為反應溶媒，可使用N-甲基-2-吡咯啶酮、N-甲基-2-吡啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、甲苯、苯等。The method for synthesizing the dichloride derivative may be a method in which a dicarboxylic acid and a halogenating agent are reacted in a solvent or a dicarboxylic acid is added to an excess halogenating agent and reacted, and then the excess component is distilled off. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, N,N-dimethylformamide, toluene can be used. Benzene, etc.

關於該些鹵化劑的使用量，相對於二羧酸1莫耳，於在溶媒中反應的情況下，較佳為1.5莫耳～3.0莫耳，更佳為1.7莫耳～2.5莫耳，於在鹵化劑中反應的情況下，較佳為4.0莫耳～50莫耳，更佳為5.0莫耳～20莫耳。反應溫度較佳為-10℃～70℃，更佳為0℃～20℃。The amount of the halogenating agent used is preferably from 1.5 mol to 3.0 mol, more preferably from 1.7 mol to 2.5 mol, in the case of reacting in a solvent with respect to 1 mol of the dicarboxylic acid. In the case of the reaction in the halogenating agent, it is preferably from 4.0 mol to 50 mol, more preferably from 5.0 mol to 20 mol. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

N-保護基二胺化合物與二氯化物衍生物的反應較佳為於脫鹵化氫劑的存在下、在有機溶媒中進行。作為脫鹵化氫劑，例如使用吡啶、三乙胺等有機鹼。作為有機溶媒，可使用N-甲基-2-吡咯啶酮、N-甲基-2-吡啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺等。反應溫度較佳為-10℃～30℃，更佳為0℃～20℃。The reaction of the N-protecting diamine compound with the dichloride derivative is preferably carried out in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, for example, an organic base such as pyridine or triethylamine is used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, N,N-dimethylformamide or the like can be used. The reaction temperature is preferably -10 to 30 ° C, more preferably 0 to 20 ° C.

[光酸產生劑] 光酸產生劑（亦稱為光感應性酸產生劑）為藉由光化射線等的照射而產生酸的化合物。藉由自光酸產生劑產生的酸的催化效果，N-保護基聚醯胺樹脂的保護基脫離，可於樹脂組成物中將N-保護基聚醯胺樹脂轉換為聚醯胺樹脂。[Photoacid generator] The photoacid generator (also referred to as a photo-sensitive acid generator) is a compound which generates an acid by irradiation with actinic rays or the like. The protective group of the N-protecting polyamine resin is desorbed by the catalytic effect of the acid generated from the photoacid generator, and the N-protecting polyamine resin can be converted into a polyamide resin in the resin composition.

光酸產生劑若為藉由光化射線的照射而產生酸的化合物，則並無特別限定，例如可列舉：鎓鹽化合物、含有鹵素的化合物、重氮酮化合物、碸化合物、磺酸化合物、磺醯亞胺化合物、重氮甲烷化合物等。該些中，就獲得的容易性的觀點而言，較佳為使用鎓鹽化合物或磺醯亞胺化合物，特佳為使用鎓鹽化合物。光酸產生劑可單獨使用該些的一種或將該些的兩種以上組合使用。以下，示出該些化合物的具體例。The photoacid generator is not particularly limited as long as it is an acid which generates an acid by irradiation with actinic rays, and examples thereof include an onium salt compound, a halogen-containing compound, a diazoketone compound, an anthraquinone compound, and a sulfonic acid compound. Sulfonimide compounds, diazomethane compounds, and the like. Among these, from the viewpoint of easiness of obtaining, it is preferred to use an onium salt compound or a sulfonium imide compound, and particularly preferably an onium salt compound. The photoacid generator may be used alone or in combination of two or more kinds thereof. Specific examples of these compounds are shown below.

作為鎓鹽化合物，例如可列舉：錪鹽、鋶鹽、鏻鹽、重氮鎓鹽及吡啶鎓鹽。作為較佳的鎓鹽化合物的具體例，可列舉：二苯基錪三氟甲磺酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽、二苯基錪六氟磷酸鹽、二苯基錪四氟硼酸鹽等二芳基錪鹽；三苯基鋶三氟甲磺酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽等三芳基鋶鹽；4-第三丁基苯基-二苯基鋶三氟甲磺酸鹽；4-第三丁基苯基-二苯基鋶對甲苯磺酸鹽；4,7-二-正丁氧基萘基四氫噻吩鎓三氟甲磺酸鹽等。Examples of the onium salt compound include a phosphonium salt, a phosphonium salt, a phosphonium salt, a diazonium salt, and a pyridinium salt. Specific examples of the preferable onium salt compound include diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, and diphenylphosphonium. a diarylsulfonium salt such as fluorophosphate or diphenylphosphonium tetrafluoroborate; triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, etc. Triarylsulfonium salt; 4-tert-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-tert-butylphenyl-diphenylsulfonium p-toluenesulfonate; 4,7-di- n-Butoxynaphthyltetrahydrothiophene trifluoromethanesulfonate and the like.

鎓鹽化合物較佳為具有三氟甲磺酸鹽、九氟丁磺酸鹽、六氟銻酸鹽、六氟磷酸鹽、四氟硼酸鹽、三(五氟乙基)三氟磷酸鹽或四(五氟苯基)硼酸鹽作為陰離子的化合物。The onium salt compound preferably has a triflate, a nonafluorobutanesulfonate, a hexafluoroantimonate, a hexafluorophosphate, a tetrafluoroborate, a tris(pentafluoroethyl)trifluorophosphate or a tetra (Pentafluorophenyl) borate as an anionic compound.

作為含有鹵素的化合物，例如可列舉：含有鹵代烷基的烴化合物及含有鹵代烷基的雜環式化合物。作為較佳的含有鹵素的化合物的具體例，可列舉：1,10-二溴正癸烷、1,1-雙(4-氯苯基)-2,2,2-三氯乙烷；苯基-雙(三氯甲基)-均三嗪、4-甲氧基苯基-雙(三氯甲基)-均三嗪、苯乙烯基-雙(三氯甲基)-均三嗪、萘基-雙(三氯甲基)-均三嗪等均三嗪衍生物。Examples of the halogen-containing compound include a hydrocarbon compound containing a halogenated alkyl group and a heterocyclic compound containing a halogenated alkyl group. Specific examples of the preferred halogen-containing compound include 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane; and benzene. Base-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, a s-triazine derivative such as naphthyl-bis(trichloromethyl)-s-triazine.

作為重氮酮化合物，例如可列舉：1,3-二酮基-2-重氮化合物、重氮苯醌化合物、重氮萘醌化合物等。作為具體例，可列舉：酚類的1,2-萘醌二疊氮-4-磺酸酯化合物。Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzene compound, and a diazonaphthoquinone compound. Specific examples thereof include a phenolic 1,2-naphthoquinonediazide-4-sulfonate compound.

作為碸化合物，例如可列舉：β-酮基碸化合物、β-磺醯基碸化合物及該些化合物的α-重氮化合物。作為具體例，可列舉：4-甲苯基苯甲醯甲基碸、均三甲苯基苯甲醯甲基碸、雙(苯甲醯甲基磺醯基)甲烷等。Examples of the ruthenium compound include a β-keto oxime compound, a β-sulfonyl fluorene compound, and an α-diazonium compound of these compounds. Specific examples thereof include 4-methylphenylbenzhydrylmethylhydrazine, mesitylene benzhydrylmethylhydrazine, and bis(benzhydrylmethylsulfonyl)methane.

作為磺酸化合物，例如可列舉：烷基磺酸酯類、鹵代烷基磺酸酯類、芳基磺酸酯類、亞胺基磺酸鹽類等。作為較佳的具體例，可列舉：安息香對甲苯磺酸鹽、鄰苯三酚三-三氟甲烷磺酸鹽、鄰硝基苄基三氟甲烷磺酸鹽、鄰硝基苄基對甲苯磺酸鹽等。Examples of the sulfonic acid compound include alkylsulfonates, haloalkylsulfonates, arylsulfonates, and imidosulfonates. Preferred examples of the benzoic acid p-toluenesulfonate, pyrogallol tri-trifluoromethanesulfonate, o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl p-toluenesulfonate Acid salt, etc.

作為磺醯亞胺化合物的具體例，可列舉：N-(三氟甲基磺醯氧基)琥珀醯亞胺、N-(三氟甲基磺醯氧基)鄰苯二甲醯亞胺、N-(三氟甲基磺醯氧基)二苯基馬來醯亞胺、N-(三氟甲基磺醯氧基)雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺、N-(三氟甲基磺醯氧基)萘二甲醯亞胺、N-(對甲苯磺醯氧基)-1,8-萘二甲醯亞胺、N-(10-樟腦磺醯氧基)-1,8-萘二甲醯亞胺等。Specific examples of the sulfonium imine compound include N-(trifluoromethylsulfonyloxy) succinimide, N-(trifluoromethylsulfonyloxy) phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimine, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(trifluoromethylsulfonyloxy)naphthylimine, N-(p-toluenesulfonyloxy)-1,8-naphthylimine, N-(10 - camphorsulfonyloxy)-1,8-naphthyldimethylimine and the like.

作為重氮甲烷化合物的具體例，可列舉：雙(三氟甲基磺醯基)重氮甲烷、雙(環己基磺醯基)重氮甲烷及雙(苯基磺醯基)重氮甲烷。Specific examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(phenylsulfonyl)diazomethane.

就N-保護基聚醯胺樹脂的保護基的脫離容易性的觀點而言，相對於N-保護基聚醯胺樹脂100質量份，光酸產生劑的含量可為1質量份以上、5質量份以上、或10質量份以上，可為100質量份以下、90質量份以下、70質量份以下、或50質量份以下，較佳為1質量份～100質量份，更佳為5質量份～90質量份，進而佳為5質量份～70質量份，特佳為10質量份～50質量份。再者，本說明書中，所謂N-保護基聚醯胺樹脂100質量份，是指N-保護基聚醯胺樹脂的固體成分100質量份。The content of the photoacid generator may be 1 part by mass or more and 5 parts by mass with respect to 100 parts by mass of the N-protecting polyamine resin, from the viewpoint of easiness of removal of the protective group of the N-protecting polyamine resin. The amount may be 100 parts by mass or less, 90 parts by mass or less, 70 parts by mass or less, or 50 parts by mass or less, preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 5% by mass or more. 90 parts by mass, and more preferably 5 parts by mass to 70 parts by mass, particularly preferably 10 parts by mass to 50 parts by mass. In the present specification, 100 parts by mass of the N-protecting polyamine resin means 100 parts by mass of the solid content of the N-protecting polyamine resin.

[溶劑] 為了提高感光性樹脂組成物的操作性、或調節黏度及保存穩定性，感光性樹脂組成物可進而含有溶劑。溶劑較佳為有機溶劑。該有機溶劑的種類只要可發揮所述性能，則並無特別限制，例如可列舉：乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯等乙二醇單烷基醚乙酸酯化合物；丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚等丙二醇單烷基醚化合物；丙二醇二甲醚、丙二醇二***、丙二醇二丙醚、丙二醇二丁醚等丙二醇二烷基醚化合物；丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、丙二醇單丁醚乙酸酯等丙二醇單烷基醚乙酸酯化合物；乙基溶纖劑、丁基溶纖劑等溶纖劑化合物；丁基卡必醇等卡必醇化合物；乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸異丙酯等乳酸酯化合物；乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙酸異戊酯、丙酸異丙酯、丙酸正丁酯、丙酸異丁酯等脂肪族羧酸酯化合物；3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯等其他酯化合物；甲苯、二甲苯等芳香族烴化合物；2-丁酮、2-庚酮、3-庚酮、4-庚酮、環己酮等酮化合物；N,N-二甲基甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等醯胺化合物；γ-丁內酯等內酯化合物等。有機溶劑可單獨使用一種或將兩種以上混合使用。[Solvent] The photosensitive resin composition may further contain a solvent in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. The solvent is preferably an organic solvent. The type of the organic solvent is not particularly limited as long as it exhibits the above properties, and examples thereof include ethylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. An ester compound; a propylene glycol monoalkyl ether compound such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether and the like propylene glycol II Alkyl ether compound; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. propylene glycol monoalkyl ether acetate compound; ethyl cellosolve Agent, cellosolve compound such as butyl cellosolve; carbitol compound such as butyl carbitol; lactate compound such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, acetic acid An aliphatic carboxy group such as n-propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate Acid ester compound; 3-methoxypropane Other ester compounds such as methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; toluene, An aromatic hydrocarbon compound such as toluene; a ketone compound such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or cyclohexanone; N,N-dimethylformamide, N-methylethyl a guanamine compound such as guanamine, N,N-dimethylacetamide or N-methylpyrrolidone; a lactone compound such as γ-butyrolactone. The organic solvent may be used alone or in combination of two or more.

相對於將溶劑除外的感光性樹脂組成物的成分總量100質量份，溶劑的含量可為50質量份以上或1000質量份以上，可為3000質量份以下或2000質量份以下，較佳為50質量份～3000質量份，更佳為1000質量份～2000質量份。The content of the solvent may be 50 parts by mass or more or 1000 parts by mass or more, and may be 3,000 parts by mass or less or 2,000 parts by mass or less, preferably 50%, based on 100 parts by mass of the total amount of the components of the photosensitive resin composition excluding the solvent. The parts by mass to 3,000 parts by mass, more preferably from 1,000 parts by mass to 2,000 parts by mass.

[N-保護基聚醯胺樹脂的利用酸性溶液的脫保護方法] N-保護基聚醯胺樹脂例如是藉由保護基於使用酸性溶液的酸性條件下脫離（脫保護）而轉換為聚醯胺樹脂。酸性溶液若可進行脫保護則並無特別限制，較佳為包含鹽酸、硫酸、硝酸、甲磺酸、三氟甲磺酸、三氟乙酸等的pKa為0以下的酸性溶液。使該些酸作用於N-保護基聚醯胺樹脂，藉此脫保護反應進行而獲得聚醯胺樹脂。[N-protecting polyamine resin using deprotection method using an acidic solution] N-protecting polyamine resin is converted to polyamine by, for example, protection under detachment (deprotection) under acidic conditions using an acidic solution Resin. The acidic solution is not particularly limited as long as it can be deprotected, and preferably contains an acidic solution having a pKa of 0 or less such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, trifluoromethanesulfonic acid or trifluoroacetic acid. The acid is allowed to act on the N-protecting polyamine resin, whereby the deprotection reaction proceeds to obtain a polyamine resin.

[N-保護基聚醯胺樹脂的利用曝光的脫保護方法] N-保護基聚醯胺樹脂例如亦藉由對感光性樹脂組成物進行曝光而轉換為聚醯胺樹脂。具體而言，首先，於基材（帶有樹脂的銅箔、覆銅積層板、矽晶圓、氧化鋁基板、鋁箔等）上配置感光性樹脂組成物而形成感光層。作為該感光層的形成方法，可列舉藉由棒塗佈、旋轉塗佈等於基材上形成感光層的方法等。[Deprotection Method by Exposure Using N-Protected Polyamide Compound] The N-protecting polyamine resin is also converted into a polyamide resin by, for example, exposing the photosensitive resin composition. Specifically, first, a photosensitive resin composition is placed on a substrate (a copper foil with a resin, a copper-clad laminate, a tantalum wafer, an alumina substrate, an aluminum foil, or the like) to form a photosensitive layer. As a method of forming the photosensitive layer, a method of forming a photosensitive layer on a substrate by bar coating or spin coating may be mentioned.

其次，對所述感光層進行曝光。作為曝光所使用的光化射線，例如可列舉：g射線步進機（stepper）的光線；低壓水銀燈、高壓水銀燈、金屬鹵化物燈（metal halide lamp）、i射線步進機等的紫外線；電子束；雷射光線等。曝光量可根據使用的光源及感光層的厚度等而適宜選定，例如於照射來自高壓水銀燈的紫外線的情況下，在感光層的厚度為0.1 μm～10 μm時，曝光量為100 mJ/cm2 ～10000 mJ/cm2 左右。Next, the photosensitive layer is exposed. Examples of the actinic rays used for the exposure include: light of a g-ray stepper; ultraviolet rays of a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an i-ray stepper, and the like; Beam; laser light, etc. The exposure amount can be appropriately selected depending on the light source used and the thickness of the photosensitive layer, for example, when irradiating ultraviolet rays from a high pressure mercury lamp, when the thickness of the photosensitive layer is 0.1 μm to 10 μm, the exposure amount is 100 mJ/cm 2 . ~10000 mJ/cm 2 or so.

進而，對曝光後的感光層進行加熱（曝光後烘烤）。藉由進行曝光後烘烤，可促進自光酸產生劑產生的酸引起的N-保護基聚醯胺樹脂的脫保護反應。曝光後烘烤的條件視感光性樹脂組成物的組成、各成分的含量、感光層的厚度等而不同，例如較佳為於70℃～200℃下加熱1分鐘～60分鐘，更佳為於80℃～150℃下加熱1分鐘～60分鐘。Further, the exposed photosensitive layer is heated (post-exposure baking). By performing post-exposure baking, the deprotection reaction of the N-protecting polyamine resin caused by the acid generated by the photoacid generator can be promoted. The conditions of the post-exposure baking differ depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like. For example, it is preferably heated at 70 to 200 ° C for 1 minute to 60 minutes, more preferably Heat at 80 ° C ~ 150 ° C for 1 minute to 60 minutes.

＜抗蝕劑圖案的形成方法＞ 本實施形態的抗蝕劑圖案的形成方法包括：於基材上配置所述感光性樹脂組成物而形成感光層的步驟；以及對感光層利用規定的圖案進行曝光後，進行加熱的步驟。形成感光層的具體的方法、對感光層進行曝光及加熱的具體的方法可與所述N-保護基聚醯胺樹脂的利用曝光的脫保護方法中的方法相同。即，該抗蝕劑圖案的形成方法中，於形成感光層後，對該感光層進行曝光及加熱，藉此使N-保護基聚醯胺樹脂脫保護，並且形成抗蝕劑圖案。<Method for Forming Resist Pattern> The method for forming a resist pattern according to the present embodiment includes a step of forming the photosensitive layer on the substrate to form a photosensitive layer, and performing a predetermined pattern on the photosensitive layer. After the exposure, the step of heating is performed. A specific method of forming the photosensitive layer, and a specific method of exposing and heating the photosensitive layer may be the same as those in the deprotection method using the N-protecting polyamine resin by exposure. That is, in the method of forming a resist pattern, after the photosensitive layer is formed, the photosensitive layer is exposed and heated, whereby the N-protecting polyamine resin is deprotected, and a resist pattern is formed.

該抗蝕劑圖案的形成方法中，因使用所述感光性樹脂組成物，因此藉由進行曝光及加熱可獲得對水的潤濕性提高了的感光層，並且可形成較佳的抗蝕劑圖案。另外，可於使用所述感光性樹脂組成物而獲得的抗蝕劑圖案上較佳地實施無電解電鍍。 [實施例]In the method for forming a resist pattern, since the photosensitive resin composition is used, a photosensitive layer having improved wettability to water can be obtained by exposure and heating, and a preferable resist can be formed. pattern. Further, electroless plating can be preferably performed on the resist pattern obtained by using the photosensitive resin composition. [Examples]

以下，示出實施例對本發明進行詳細說明，但本發明並不受該些實施例的任何限定。The invention is described in detail below with reference to examples, but the invention is not limited thereto.

＜合成例1-1：N-保護基（甲氧基苄基）二胺（i）的合成＞ 向50 mL茄形燒瓶中添加3,4'-二胺基二苯基醚4.0034 g（19.98 mmol）後，進而添加4-甲氧基苯甲醛12 mL（100 mmol）。將其於70℃下攪拌10分鐘。繼而，添加乾燥乙醇30 mL並對固體進行過濾，利用乙醇進行3次清洗。其後，於乾燥器（desiccator）中，在減壓下進行乾燥，獲得作為粗產物的白色固體的亞胺體8.3564 g（粗產率96%）。<Synthesis Example 1-1: Synthesis of N-protecting group (methoxybenzyl) diamine (i)> To a 50 mL eggplant-shaped flask, 3,4'-diaminodiphenyl ether 4.0034 g (19.98) was added. After mmol), further added 4-methoxybenzaldehyde 12 mL (100 mmol). It was stirred at 70 ° C for 10 minutes. Then, 30 mL of dry ethanol was added, and the solid was filtered, and washed with ethanol three times. Thereafter, drying was carried out under reduced pressure in a desiccator to obtain 8.3564 g (yield 96%) of the imine of a white solid as a crude product.

其次，向200 mL茄形燒瓶中添加該亞胺體3.01 g（6.6 mmol）與乾燥四氫呋喃（tetrahydrofuran，THF）60 mL後，於0℃下攪拌20分鐘。其後，添加甲醇30 mL，進而添加硼氫化鈉764.2 mg（27.0 mmol），於0℃下攪拌21小時。向其中添加二氯甲烷，利用飽和碳酸氫鈉水溶液進行清洗，並利用無水硫酸鎂進行乾燥。繼而，進行過濾，在減壓下將溶媒蒸餾去除後，在減壓下進行乾燥，獲得作為粗產物的黃色黏性液體3.0092 g（粗產率104%）。使其於甲苯：己烷=1：3（體積比）的混合溶媒中再結晶，獲得作為白色結晶的二胺（i）2.3394 g（產率80.4%）。Next, 3.01 g (6.6 mmol) of the imine body and 60 mL of dry tetrahydrofuran (THF) were added to a 200 mL eggplant-shaped flask, followed by stirring at 0 ° C for 20 minutes. Thereafter, 30 mL of methanol was added, and then sodium borohydride 764.2 mg (27.0 mmol) was added thereto, and the mixture was stirred at 0 ° C for 21 hours. Methylene chloride was added thereto, washed with a saturated aqueous sodium hydrogencarbonate solution, and dried over anhydrous magnesium sulfate. Then, filtration was carried out, and the solvent was distilled off under reduced pressure, and then dried under reduced pressure to obtain 3.0092 g (yield: 104%) of a yellow viscous liquid as a crude product. This was recrystallized from a mixed solvent of toluene:hexane = 1:3 (volume ratio) to obtain 2.3394 g (yield 80.4%) of a diamine (i) as a white crystal.

將所得的二胺（i）的1 H核磁共振（1 H Nuclear Magnetic Resonance，1 H NMR）的測定結果示於以下。1 H NMR（600MHz, CDCl3 ） δ7.30 (d, J=8.2Hz, 2H), 7.24 (d, J=7.9Hz, 2H), 7.04 (t, J=8.0Hz, 1H), 6.89-6.85 (m-3H), 6.60 (d, J=6.0Hz, 1H), 6.28 (dd, J=2.5與6.0Hz, 1H), 6.25 (dd, J=2.5與6.5Hz, 1H), 6.20 (s1H), 4.23 (s, 2H), 4.18 (s, 2H), 3.80 (s, 3H), 3.80 (s, 3H).The resulting diamine (i) a 1 H nuclear magnetic resonance (1 H Nuclear Magnetic Resonance, 1 H NMR) measurement results are shown below. 1 H NMR (600MHz, CDCl 3 ) δ 7.30 (d, J = 8.2 Hz, 2H), 7.24 (d, J = 7.9 Hz, 2H), 7.04 (t, J = 8.0 Hz, 1H), 6.89-6.85 (m-3H), 6.60 (d, J=6.0Hz, 1H), 6.28 (dd, J=2.5 and 6.0Hz, 1H), 6.25 (dd, J=2.5 and 6.5Hz, 1H), 6.20 (s1H) , 4.23 (s, 2H), 4.18 (s, 2H), 3.80 (s, 3H), 3.80 (s, 3H).

＜合成例1-2：N-保護基（辛基氧基苄基）二胺（ii）的合成＞ 向100 mL茄形燒瓶中添加3,4'-二胺基二苯基醚2.003 g（10.01 mmol）後，進而添加4-正辛基氧基苯甲醛12.0 mL（50 mmol）。將其於70℃下攪拌10分鐘。繼而，添加乾燥乙醇30 mL並對固體進行過濾，利用己烷進行3次清洗。其後，於乾燥器中，在減壓下進行乾燥，獲得作為粗產物的白色固體的亞胺體5.8379 g（粗產率92%）。<Synthesis Example 1-2: Synthesis of N-protecting group (octyloxybenzyl) diamine (ii)> To a 100 mL eggplant-shaped flask was added 3,4'-diaminodiphenyl ether 2.003 g ( After 10.01 mmol), 12.0 mL (50 mmol) of 4-n-octyloxybenzaldehyde was further added. It was stirred at 70 ° C for 10 minutes. Then, 30 mL of dry ethanol was added, and the solid was filtered, and washed with hexane three times. Thereafter, drying was carried out under reduced pressure in a desiccator to obtain 5.8379 g (yield: 92%) of the imine of a white solid as a crude product.

其次，向200 mL茄形燒瓶中添加該亞胺體4.956 g（7.831 mmol）與乾燥THF 120 mL後，於0℃下攪拌20分鐘。其後，添加乾燥甲醇61 mL，進而添加硼氫化鈉1.286 g（34.00 mmol），於0℃下攪拌21小時。向其中添加二氯甲烷，利用飽和碳酸氫鈉水溶液進行清洗，並利用無水硫酸鎂進行乾燥。繼而，進行過濾，在減壓下將溶媒蒸餾去除後，在減壓下進行乾燥，獲得作為粗產物的黃色固體3.251 g（粗產率65%）。使其於己烷中再結晶，獲得作為黃色固體的二胺（ii）1.950 g（產率39%）。Next, 4.956 g (7.831 mmol) of the imine body and 120 mL of dry THF were added to a 200 mL eggplant-shaped flask, followed by stirring at 0 ° C for 20 minutes. Thereafter, 61 mL of dry methanol was added, and then 1.286 g (34.00 mmol) of sodium borohydride was added thereto, and the mixture was stirred at 0 ° C for 21 hours. Methylene chloride was added thereto, washed with a saturated aqueous sodium hydrogencarbonate solution, and dried over anhydrous magnesium sulfate. Then, filtration was carried out, and the solvent was distilled off under reduced pressure, and then dried under reduced pressure to obtain 3.251 g (yield: 65%) as a crude solid. It was recrystallized from hexane to obtain 1.950 g (yield 39%) of diamine (ii) as a yellow solid.

將所得的二胺（ii）的1 H NMR的測定結果示於以下。1 H NMR（600MHz, CDCl3 ） δ7.28 (d, J=8.6Hz, 2H), 7.23 (d,J=8.6Hz, 2H), 7.04 (t, J=7.9Hz, 1H), 6.81-6.89 (m, 6H), 6.60 (d, J=8.5Hz, 2H), 6.29 (dd, J=1.9與9.9Hz, 1H), 6.25 (dd, J=8.0與1.7Hz, 1H), 6.21-6.22 (m, 1H), 4.21 (s, 2H), 4.18 (s, 2H), 3.92-3.95 (m, 6H), 1.74-1.79 (m, 4H), 1.42-1.46 (m, 4H), 1.23-1.35 (m, 16H), 0.87-0.90 (m, 6H)The measurement results of 1 H NMR of the obtained diamine (ii) are shown below. 1 H NMR (600MHz, CDCl 3 ) δ 7.28 (d, J = 8.6 Hz, 2H), 7.23 (d, J = 8.6 Hz, 2H), 7.04 (t, J = 7.9 Hz, 1H), 6.81-6.89 (m, 6H), 6.60 (d, J=8.5Hz, 2H), 6.29 (dd, J=1.9 and 9.9Hz, 1H), 6.25 (dd, J=8.0 and 1.7Hz, 1H), 6.21-6.22 ( m, 1H), 4.21 (s, 2H), 4.18 (s, 2H), 3.92-3.95 (m, 6H), 1.74-1.79 (m, 4H), 1.42-1.46 (m, 4H), 1.23-1.35 ( m, 16H), 0.87-0.90 (m, 6H)

＜合成例1-3：N-保護基（第三丁氧基羰基）二胺（iii）的合成＞ 向50 mL茄形燒瓶中添加3,4'-二胺基二苯基醚1.005 g（5.02 mmol）並利用氬進行置換，添加乾燥THF 5.0 mL。向茄形燒瓶中於氮氣流下添加包含二-第三丁基二碳酸酯2.734 g（12.53 mmol）與乾燥THF 10.0 mL的溶液。將其攪拌1天后，添加水並停止反應，利用無水硫酸鎂對利用乙酸乙酯進行了3次提取的有機層進行乾燥。其後，對有機層進行過濾，在減壓下將溶媒蒸餾去除，獲得作為粗產物的淡褐色固體。使用作為良溶媒的乙醇、作為不良溶媒的己烷而使粗產物再結晶。利用抽吸過濾回收經精製的結晶，在減壓下進行乾燥而獲得淡褐色固體的二胺（iii）0.9342 g（產率46%）（mp 138.4℃-142.4℃）。<Synthesis Example 1-3: Synthesis of N-protecting group (t-butoxycarbonyl) diamine (iii)> To a 50 mL eggplant-shaped flask was added 3,4'-diaminodiphenyl ether 1.005 g ( 5.02 mmol) was replaced with argon and 5.0 mL of dry THF was added. A solution containing 2.734 g (12.53 mmol) of di-t-butyldicarbonate and 10.0 mL of dry THF was added to an eggplant-shaped flask under a nitrogen stream. After stirring this for 1 day, water was added and the reaction was stopped, and the organic layer extracted three times with ethyl acetate was dried over anhydrous magnesium sulfate. Thereafter, the organic layer was filtered, and the solvent was distilled away under reduced pressure to obtain a pale brown solid as a crude product. The crude product was recrystallized using ethanol as a good solvent and hexane as a poor solvent. The purified crystals were recovered by suction filtration, and dried under reduced pressure to give a pale-brown solid, diamine (iii) 0.9342 g (yield 46%) (mp 138.4 ° C - 142.4 ° C).

將所得的二胺（iii）的1 H NMR的測定結果示於以下。1 H NMR（600MHz, CDCl3 ） δ7.31-7.32 (m, 2H), 7.20 (t, J=7.6Hz, 1H), 7.09 (d, J=7.6Hz, 1H), 6.95-6.97 (m, 3H), 6.61 (dd, J=2.4與8.2Hz, 1H), 1.57 (s, 9H), 1.49 (s, 9H)The measurement result of 1 H NMR of the obtained diamine (iii) is shown below. 1 H NMR (600MHz, CDCl 3 ) δ7.31-7.32 (m, 2H), 7.20 (t, J=7.6Hz, 1H), 7.09 (d, J=7.6Hz, 1H), 6.95-6.97 (m, 3H), 6.61 (dd, J=2.4 and 8.2Hz, 1H), 1.57 (s, 9H), 1.49 (s, 9H)

[樹脂的合成] ＜合成例2-1：N-保護基（甲氧基苄基）聚醯胺（I）的合成＞ 對30 mL茄形燒瓶在減壓下使用熱風器（heat gun）進行加熱乾燥後，利用氬進行置換。於氮氣流下向燒瓶中添加使N-保護基（甲氧基苄基）二胺（i）0.6991 g（1.587 mmol）與吡啶0.30 mL（3.5 mmol）溶解於乾燥N-甲基-2-吡咯啶酮（N-methyl-2-pyrrolidone，NMP）1.4 mL中而成的溶液，於0℃下攪拌10分鐘。向其中於氮氣流下添加使間苯二甲醯氯0.3218 g（1.585 mmol）溶解於乾燥NMP 1.4 mL中而成的溶液，於室溫下使其聚合。自開始聚合2天后，添加乾燥甲醇0.5 mL並停止反應，對反應溶液利用4 mL的NMP進行淡化並滴加至20倍的水中，使聚合物沈澱。利用桐山漏斗對沈澱物進行過濾並回收，在減壓下進行乾燥，獲得包含下述式（I）所表示結構單元的白色固體的N-保護基（甲氧基苄基）聚醯胺（I）0.8995 g（粗產率94%）。N-保護基（甲氧基苄基）聚醯胺（I）的藉由GPC法（凝膠滲透層析法（Gel Permeation Chromatography））標準聚苯乙烯換算求出的重量平均分子量為13,503，分散度為1.57。 [化14] [Synthesis of Resin] <Synthesis Example 2-1: Synthesis of N-protecting group (methoxybenzyl) polydecylamine (I)> A 30 mL eggplant-shaped flask was used under reduced pressure using a heat gun. After heating and drying, it was replaced with argon. The N-protecting group (methoxybenzyl) diamine (i) 0.6991 g (1.587 mmol) and pyridine 0.30 mL (3.5 mmol) were dissolved in dry N-methyl-2-pyrrolidine under a nitrogen stream. A solution of ketone (N-methyl-2-pyrrolidone, NMP) in 1.4 mL was stirred at 0 ° C for 10 minutes. A solution obtained by dissolving 0.3218 g (1.585 mmol) of m-xylylene chloride in 1.4 mL of dry NMP was added thereto under a nitrogen stream, and polymerization was carried out at room temperature. Two days after the start of the polymerization, 0.5 mL of dry methanol was added and the reaction was stopped, and the reaction solution was diluted with 4 mL of NMP and added dropwise to 20 times of water to precipitate a polymer. The precipitate was filtered and recovered using a Kiriyama funnel, and dried under reduced pressure to obtain an N-protecting group (methoxybenzyl) polydecylamine (I) containing a white solid represented by the following formula (I). ) 0.8995 g (94% crude yield). The weight average molecular weight of the N-protecting group (methoxybenzyl) polydecylamine (I) determined by GPC method (Gel Permeation Chromatography) standard polystyrene conversion is 13,503, dispersed The degree is 1.57. [Chemistry 14]

＜合成例2-2：N-保護基（甲氧基苄基）聚醯胺（II）的合成＞ 對30 mL茄形燒瓶在減壓下使用熱風器進行加熱乾燥後，利用氬進行置換。向燒瓶中添加N-保護基（甲氧基苄基）二胺（i）0.6996 g（1.588 mmol）與吡啶0.30 mL（3.5 mmol）的乾燥NMP 1.4 mL的混合溶液，於0℃下攪拌10分鐘。向其中於氮氣流下添加使對苯二甲醯氯0.3220 g（1.586 mmol）溶解於乾燥NMP 1.4 mL中而成的溶液，並於室溫下使其聚合。自開始聚合2天后，添加乾燥甲醇0.5 mL並停止反應，對反應溶液利用4 mL的NMP進行淡化並滴加至20倍的水中，使聚合物沈澱。利用桐山漏斗對沈澱物進行過濾並回收，在減壓下進行乾燥，獲得包含下述式（II）所表示結構單元的黃色固體的N-保護基（甲氧基苄基）聚醯胺（II）0.8697 g（粗產率91%）。N-保護基（甲氧基苄基）聚醯胺（II）的藉由GPC法標準聚苯乙烯換算求出的重量平均分子量為7,066，分散度為1.36。 [化15] <Synthesis Example 2-2: Synthesis of N-protecting group (methoxybenzyl) polydecylamine (II)> A 30 mL eggplant-shaped flask was heated and dried under reduced pressure using a hot air blower, and then replaced with argon. A mixed solution of N-protecting group (methoxybenzyl) diamine (i) 0.6996 g (1.588 mmol) and pyridine 0.30 mL (3.5 mmol) in dry NMP 1.4 mL was added to the flask, and stirred at 0 ° C for 10 min. . A solution obtained by dissolving 0.3220 g (1.586 mmol) of p-xylylene chloride in 1.4 mL of dry NMP was added thereto under a nitrogen stream, and polymerization was carried out at room temperature. Two days after the start of the polymerization, 0.5 mL of dry methanol was added and the reaction was stopped, and the reaction solution was diluted with 4 mL of NMP and added dropwise to 20 times of water to precipitate a polymer. The precipitate was filtered and recovered using a Kiriyama funnel, and dried under reduced pressure to obtain an N-protecting group (methoxybenzyl) polydecylamine (II) containing a yellow solid represented by the following formula (II). ) 0.8697 g (crude yield 91%). The weight average molecular weight of the N-protecting group (methoxybenzyl) polydecylamine (II) determined by GPC standard polystyrene conversion was 7,066, and the degree of dispersion was 1.36. [化15]

＜合成例2-3：N-保護基（辛基氧基苄基）聚醯胺（III）的合成＞ 對30 mL茄形燒瓶在減壓下使用熱風器進行加熱乾燥後，利用氬進行置換。於氮氣流下向燒瓶中添加使N-保護基（辛基氧基苄基）二胺（ii）1.0032 g（1.575 mmol）與吡啶0.30 mL（3.45 mmol）溶解於乾燥NMP 1.4 mL中而成的溶液，於0℃下攪拌20分鐘。向其中於氮氣流下添加使間苯二甲醯氯0.3200 g（1.576 mmol）溶解於乾燥NMP 1.4 mL中而成的乾燥溶液，於室溫下使其聚合。自開始聚合2天后，添加乾燥甲醇0.5 mL並停止反應，對反應溶液利用4 mL的NMP進行淡化並滴加至20倍的水中，使聚合物沈澱。利用桐山漏斗對沈澱物進行過濾並回收，在減壓下進行乾燥，獲得包含下述式（III）所表示結構單元的黃色固體的N-保護基（辛基氧基苄基）聚醯胺（III）1.2079 g（粗產率96%）。N-保護基（辛基氧基苄基）聚醯胺（III）的藉由GPC法標準聚苯乙烯換算求出的重量平均分子量為23,246，分散度為1.56。 [化16] <Synthesis Example 2-3: Synthesis of N-protecting group (octyloxybenzyl) polydecylamine (III)> A 30 mL eggplant-shaped flask was heated and dried using a hot air blower under reduced pressure, and then replaced with argon. . A solution of N-protecting group (octyloxybenzyl) diamine (ii) 1.0032 g (1.575 mmol) and pyridine 0.30 mL (3.45 mmol) dissolved in dry NMP 1.4 mL was added to the flask under a nitrogen stream. Stir at 0 ° C for 20 minutes. A dry solution obtained by dissolving 0.3200 g (1.576 mmol) of m-xylylene chloride in 1.4 mL of dry NMP was added thereto under a nitrogen stream, and polymerization was carried out at room temperature. Two days after the start of the polymerization, 0.5 mL of dry methanol was added and the reaction was stopped, and the reaction solution was diluted with 4 mL of NMP and added dropwise to 20 times of water to precipitate a polymer. The precipitate was filtered and recovered using a Kiriyama funnel, and dried under reduced pressure to obtain an N-protecting group (octyloxybenzyl) polydecylamine containing a yellow solid of the structural unit represented by the following formula (III) ( III) 1.2079 g (crude yield 96%). The weight average molecular weight of the N-protecting group (octyloxybenzyl) polydecylamine (III) determined by GPC standard polystyrene conversion was 23,246, and the degree of dispersion was 1.56. [Chemistry 16]

＜合成例2-4：N-保護基（辛基氧基苄基）聚醯胺（IV）的合成＞ 對30 mL茄形燒瓶在減壓下使用熱風器進行加熱乾燥後，利用氬進行置換。於氮氣流下向燒瓶中添加使N-保護基（辛基氧基苄基）二胺（ii）1.0032 g（1.575 mmol）與吡啶0.30 mL（3.45 mmol）溶解於乾燥NMP 1.4 mL中而成的溶液，於0℃下攪拌10分鐘。向其中於氮氣流下添加使對苯二甲醯氯0.3200 g（1.576 mmol）溶解於乾燥NMP 1.4 mL中而成的溶液，於室溫下使其聚合。自開始聚合2天后，添加乾燥甲醇0.5 mL並停止反應，對反應溶液利用4 mL的NMP進行淡化並滴加至20倍的水中，使聚合物沈澱。利用桐山漏斗對沈澱物進行過濾並回收，進行減壓乾燥，獲得包含下述式（IV）所表示結構單元的黃色固體的N-保護基（辛基氧基苄基）聚醯胺（IV）0.9685 g（粗產率77%）。N-保護基（辛基氧基苄基）聚醯胺（IV）的藉由GPC法標準聚苯乙烯換算求出的重量平均分子量為9,753，分散度為1.30。 [化17] <Synthesis Example 2-4: Synthesis of N-protecting group (octyloxybenzyl) polydecylamine (IV)> A 30 mL eggplant-shaped flask was heated and dried using a hot air blower under reduced pressure, and then replaced with argon. . A solution of N-protecting group (octyloxybenzyl) diamine (ii) 1.0032 g (1.575 mmol) and pyridine 0.30 mL (3.45 mmol) dissolved in dry NMP 1.4 mL was added to the flask under a nitrogen stream. Stir at 0 ° C for 10 minutes. A solution obtained by dissolving 0.3200 g (1.576 mmol) of p-xylylene chloride in 1.4 mL of dry NMP was added thereto under a nitrogen stream, and the mixture was polymerized at room temperature. Two days after the start of the polymerization, 0.5 mL of dry methanol was added and the reaction was stopped, and the reaction solution was diluted with 4 mL of NMP and added dropwise to 20 times of water to precipitate a polymer. The precipitate was filtered and recovered by a Kiriyama funnel, and dried under reduced pressure to obtain an N-protecting group (octyloxybenzyl) polydecylamine (IV) containing a yellow solid represented by the following formula (IV). 0.9685 g (yield 77%). The weight average molecular weight of the N-protecting group (octyloxybenzyl) polydecylamine (IV) determined by GPC standard polystyrene conversion was 9,753, and the degree of dispersion was 1.30. [化17]

＜合成例2-5：N-保護基（辛基氧基苄基）聚醯胺（V）的合成＞ 於200 mL可分離式燒瓶中使N-保護基（辛基氧基苄基）二胺（ii）1.911 g（3 mmol）與吡啶0.48 mL（6 mmol）溶解於乾燥NMP 10mL中。其後於氮氣流下以0℃攪拌10分鐘。向其中添加4,4'-二苯基醚二甲醯氯0.890 g（3 mmol），於室溫下攪拌1天。將該反應溶液滴加至20倍的水中，使聚合物沈澱。利用桐山漏斗對沈澱物進行過濾並回收，進行減壓乾燥，獲得包含下述式（V）所表示結構單元的黃色固體的N-保護基（辛基氧基苄基）聚醯胺（V）2.42 g（粗產率91%）。N-保護基（辛基氧基苄基）聚醯胺（V）的藉由GPC法標準聚苯乙烯換算求出的重量平均分子量為24,636，分散度為1.35。 [化18] <Synthesis Example 2-5: Synthesis of N-protecting group (octyloxybenzyl) polydecylamine (V) > N-protecting group (octyloxybenzyl) II in a 200 mL separable flask Amine (ii) 1.911 g (3 mmol) and pyridine 0.48 mL (6 mmol) were dissolved in dry NMP 10 mL. Thereafter, the mixture was stirred at 0 ° C for 10 minutes under a nitrogen stream. To this was added 0.890 g (3 mmol) of 4,4'-diphenylether dimethylhydrazine chloride, and the mixture was stirred at room temperature for 1 day. The reaction solution was added dropwise to 20 times of water to precipitate a polymer. The precipitate was filtered and recovered by a Kiriyama funnel, and dried under reduced pressure to obtain an N-protecting group (octyloxybenzyl) polydecylamine (V) containing a yellow solid of the structural unit represented by the following formula (V). 2.42 g (crude yield 91%). The weight average molecular weight of the N-protecting group (octyloxybenzyl) polydecylamine (V) determined by GPC standard polystyrene conversion was 24,636, and the degree of dispersion was 1.35. [化18]

＜合成例2-6：N-保護基（第三丁氧基羰基）聚醯胺（VI）的合成＞ 向5 mL茄形燒瓶中添加N-保護基（第三丁氧基羰基）二胺（iii）0.0810 g（0.202 mmol）與N,N-二甲基-4-胺基吡啶0.1148 g（0.940 mmol）並利用氬進行置換，於氮氣流下添加乾燥二氯甲烷0.2 mL與乾燥三乙胺0.11 mL（0.790 mmol）並進行攪拌。將包含間苯二甲醯氯0.422 g（0.217 mmol）與乾燥二氯甲烷0.2 mL的溶液添加至茄形燒瓶中。將該溶液於室溫下攪拌19小時後，利用1 M鹽酸、飽和氯化鈉水溶液、及飽和碳酸氫鈉水溶液分別進行2次清洗，並利用無水硫酸鎂進行乾燥。繼而，在減壓下將溶媒蒸餾去除，獲得0.0642 g（粗產率60%）的包含下述式（VI）所表示的結構單元的黃色固體的N-保護基（第三丁氧基羰基）聚醯胺（VI）。N-保護基（第三丁氧基羰基）聚醯胺（VI）的藉由GPC法標準聚苯乙烯換算求出的重量平均分子量為3,200，分散度為1.29。 [化19] <Synthesis Example 2-6: Synthesis of N-protecting group (t-butoxycarbonyl) polydecylamine (VI)> Adding N-protecting group (t-butoxycarbonyl)diamine to a 5 mL eggplant-shaped flask (iii) 0.0810 g (0.202 mmol) and N,N-dimethyl-4-aminopyridine 0.1148 g (0.940 mmol) were replaced with argon, and dry dichloromethane (0.2 mL) and dry triethylamine were added under a nitrogen stream. 0.11 mL (0.790 mmol) and stirred. A solution containing 0.422 g (0.217 mmol) of m-xylylene chloride and 0.2 mL of dry dichloromethane was added to the eggplant-shaped flask. This solution was stirred at room temperature for 19 hours, and then washed twice with 1 M hydrochloric acid, a saturated aqueous sodium chloride solution and a saturated aqueous sodium hydrogen carbonate solution, and dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure to obtain 0.0642 g (yield 60%) of a N-protecting group (tris-butoxycarbonyl) of a yellow solid containing a structural unit represented by the following formula (VI). Polyamine (VI). The weight average molecular weight of the N-protecting group (t-butoxycarbonyl) polydecylamine (VI) determined by GPC standard polystyrene conversion was 3,200, and the degree of dispersion was 1.29. [Chemistry 19]

＜合成例2-7：N-保護基（辛基氧基苄基）聚醯胺（VII）的合成＞ 對5 mL茄形燒瓶在減壓下使用熱風器進行加熱乾燥後，利用氬進行置換。向其中添加聚丁二烯（日本PTI（PTI JAPAN）製造，商品名西普洛（Hypro）CTB 2000×162，數量平均分子量4200）1.00 g（0.23 mmol）與亞硫醯氯0.034 mL（0.47 mmol），於室溫下攪拌1小時。對該反應溶液進行減壓乾燥，獲得聚丁二烯的二羧酸二氯化物。其次，對10 mL茄形燒瓶在減壓下使用熱風器進行加熱乾燥後，利用氬進行置換。向其中添加N-保護基（辛基氧基苄基）二胺（ii）0.097 g（0.15 mmol）與乾燥吡啶0.09 mL（1.11 mmol）及乾燥NMP 0.5 mL，於0℃下攪拌20分鐘。向其中添加聚丁二烯的二羧酸二氯化物0.063 g與間苯二甲醯氯0.028 g（0.136 mmol），於氮氣流下添加乾燥NMP 3.6 mL，於室溫下攪拌2天。其後，添加乾燥甲醇0.05 mL並停止反應，利用1.1 mL的NMP進行稀釋並滴加至200 mL的水中，使聚合物沈澱。利用桐山漏斗對沈澱物進行過濾，進行減壓乾燥，獲得包含下述式（VII-1）所表示結構單元及下述式（VII-2）所表示的結構單元的淡黃色黏性固體的N-保護基（辛基氧基苄基）聚醯胺（VII）0.079 g（粗產率42%）。N-保護基（辛基氧基苄基）聚醯胺（VII）的藉由GPC法標準聚苯乙烯換算求出的重量平均分子量為17,000，分散度為2.54。 [化20]式（VII-1）中，Z11 為包含下述式（3-1）所表示的結構單元及下述式（3-2）所表示的結構單元的二價基。 [化21] <Synthesis Example 2-7: Synthesis of N-protecting group (octyloxybenzyl) polydecylamine (VII)> A 5 mL eggplant-shaped flask was heated and dried using a hot air blower under reduced pressure, and then replaced with argon. . Polybutadiene (manufactured by PTI JAPAN, Japan, trade name: Hypro CTB 2000×162, number average molecular weight 4200) 1.00 g (0.23 mmol) and sulfoxide chloride 0.034 mL (0.47 mmol) were added thereto. ), stirred at room temperature for 1 hour. The reaction solution was dried under reduced pressure to obtain a dicarboxylic acid dichloride of polybutadiene. Next, the 10 mL eggplant-shaped flask was heated and dried using a hot air blower under reduced pressure, and then replaced with argon. N-protecting group (octyloxybenzyl) diamine (ii) 0.097 g (0.15 mmol) and dry pyridine 0.09 mL (1.11 mmol) and dry NMP 0.5 mL were added thereto, and stirred at 0 ° C for 20 minutes. 0.063 g of dicarboxylic acid dichloride of polybutadiene and 0.028 g (0.136 mmol) of m-xylylene chloride were added thereto, and 3.6 mL of dry NMP was added under a nitrogen stream, and the mixture was stirred at room temperature for 2 days. Thereafter, 0.05 mL of dry methanol was added and the reaction was stopped, diluted with 1.1 mL of NMP, and added dropwise to 200 mL of water to precipitate a polymer. The precipitate was filtered through a Kiriyama funnel, and dried under reduced pressure to obtain a yellowish-yellow solid N containing a structural unit represented by the following formula (VII-1) and a structural unit represented by the following formula (VII-2). - Protecting group (octyloxybenzyl) polydecylamine (VII) 0.079 g (crude yield 42%). The weight average molecular weight of the N-protecting group (octyloxybenzyl) polydecylamine (VII) determined by GPC standard polystyrene conversion was 17,000, and the degree of dispersion was 2.54. [Chemistry 20] In the formula (VII-1), Z 11 is a divalent group containing a structural unit represented by the following formula (3-1) and a structural unit represented by the following formula (3-2). [Chem. 21]

＜合成例3-1：聚醯胺（VIII）的合成＞ 向30 mL茄形燒瓶中加入氯化鋰0.2730 g（6.393 mmol），在減壓下使用熱風器進行加熱乾燥後，利用氬進行置換。於氮氣流下向燒瓶中添加使3,4'-二胺基二苯基醚0.5004 g（2.499 mmol）與吡啶0.50 mL（5.8 mmol）溶解於乾燥NMP 2.5 mL中而成的溶液，於0℃下攪拌20分鐘。向其中於氮氣流下添加使間苯二甲醯氯0.5065 g（2.495 mmol）溶解於乾燥NMP 2.5 mL中而成的溶液，於室溫下使其聚合。自開始聚合2天后，添加乾燥甲醇0.5 mL並停止反應，對反應溶液利用4 mL的NMP進行淡化並滴加至20倍的水中，使聚合物沈澱。利用桐山漏斗對沈澱物進行過濾並回收，在減壓下進行乾燥，獲得包含下述式（VIII）所表示結構單元的淡黃色固體的聚醯胺（VIII）1.9587 g（粗產率218%）。聚醯胺（VIII）的藉由GPC法標準聚苯乙烯換算求出的重量平均分子量為52,500，分散度為1.84。 [化22] <Synthesis Example 3-1: Synthesis of Polydecylamine (VIII)> To a 30 mL eggplant-shaped flask, 0.2730 g (6.393 mmol) of lithium chloride was added, and the mixture was heated and dried using a hot air blower under reduced pressure, and then replaced with argon. . A solution of 0.5004 g (2.499 mmol) of 3,4'-diaminodiphenyl ether and 0.50 mL (5.8 mmol) of pyridine dissolved in dry NMP 2.5 mL was added to the flask under a nitrogen stream at 0 ° C. Stir for 20 minutes. A solution obtained by dissolving 0.5065 g (2.495 mmol) of m-xylylene chloride in 2.5 mL of dry NMP was added thereto under a nitrogen stream, and polymerization was carried out at room temperature. Two days after the start of the polymerization, 0.5 mL of dry methanol was added and the reaction was stopped, and the reaction solution was diluted with 4 mL of NMP and added dropwise to 20 times of water to precipitate a polymer. The precipitate was filtered and recovered using a Kiriyama funnel, and dried under reduced pressure to obtain a polyamine (VIII) 1.9587 g (crude yield: 218%) of a pale yellow solid containing a structural unit represented by the following formula (VIII). . The weight average molecular weight of the polyamine (VIII) obtained by the GPC standard polystyrene conversion was 52,500, and the degree of dispersion was 1.84. [化22]

＜合成例3-2：聚醯胺（VIV）的合成＞ 向30 mL茄形燒瓶中加入氯化鋰0.2726 g（6.392 mmol），在減壓下使用熱風器進行加熱乾燥後，利用氬進行置換。於氮氣流下向燒瓶中添加使3,4'-二胺基二苯基醚0.5011 g（2.503 mmol）與吡啶0.50 mL（5.8 mmol）溶解於乾燥NMP 2.5 mL中而成的溶液，於0℃下攪拌20分鐘。向其中於氮氣流下添加使對苯二甲醯氯0.5065 g（2.495 mmol）於乾燥NMP 2.5 mL中溶解而成的溶液，於室溫下使其聚合。自開始聚合2天后，添加乾燥甲醇0.5 mL並停止反應，對反應溶液利用4 mL的NMP進行淡化並滴加至20倍的水中，使聚合物沈澱。利用桐山漏斗對沈澱物進行過濾並回收，在減壓下進行乾燥，獲得包含下述式（VIV）所表示結構單元的淡黃色固體的聚醯胺（VIV）0.9929 g（粗產率110%）。聚醯胺（VIV）的藉由GPC法標準聚苯乙烯換算求出的重量平均分子量為25,900，分散度為2.13。 [化23] <Synthesis Example 3-2: Synthesis of Polyamine (VIV)> To a 30 mL eggplant-shaped flask, 0.2726 g (6.392 mmol) of lithium chloride was added, and the mixture was heated and dried using a hot air blower under reduced pressure, and then replaced with argon. . A solution of 0.5011 g (2.503 mmol) of 3,4'-diaminodiphenyl ether and 0.50 mL (5.8 mmol) of pyridine dissolved in dry NMP 2.5 mL was added to the flask under a nitrogen stream at 0 ° C. Stir for 20 minutes. A solution obtained by dissolving 0.5065 g (2.495 mmol) of p-xylylene chloride in 2.5 mL of dry NMP was added thereto under a nitrogen stream, and polymerization was carried out at room temperature. Two days after the start of the polymerization, 0.5 mL of dry methanol was added and the reaction was stopped, and the reaction solution was diluted with 4 mL of NMP and added dropwise to 20 times of water to precipitate a polymer. The precipitate was filtered and recovered using a Kiriyama funnel, and dried under reduced pressure to obtain a polyamine (VIV) of 0.929 g (yield 110%) of a pale yellow solid containing a structural unit represented by the following formula (VIV). . The weight average molecular weight of the polyamine (VIV) obtained by the GPC standard polystyrene conversion was 25,900, and the degree of dispersion was 2.13. [化23]

[於有機溶劑中的溶解性] 對合成的N-保護基聚醯胺（I）～N-保護基聚醯胺（IV）及聚醯胺（VIII）、聚醯胺（VIV）的固體分別添加表1所示的有機溶劑並評價溶解性。具體而言，相對於有機溶劑10 mL而添加固體0.1 g後，以目視進行確認，將固體完全溶解者評價為「A」，將並未溶解者評價為「B」。將結果示於表1中。[Solubility in organic solvent] The solids of the synthesized N-protected polyamines (I) to N-protected polyamines (IV) and polyamines (VIII) and polyamines (VIV) The organic solvents shown in Table 1 were added and the solubility was evaluated. Specifically, 0.1 g of a solid was added to 10 mL of an organic solvent, and it was visually confirmed, and when the solid was completely dissolved, it was evaluated as "A", and when it was not dissolved, it was evaluated as "B". The results are shown in Table 1.

[表1] [Table 1]

根據以上的結果得知，N-保護基聚醯胺（I）～N-保護基聚醯胺（VII）與聚醯胺（VIII）、聚醯胺（VIV）相比，於有機溶劑中的溶解性優異。According to the above results, it is known that the N-protecting group polyamine (I) to N-protecting group polyamine (VII) is in an organic solvent compared with polyamine (VIII) and polyamine (VIV). Excellent solubility.

＜感光性樹脂組成物的製備＞ 以表2所示的量（質量份）調配N-保護基聚醯胺（I）～N-保護基聚醯胺（V）、下述光酸產生劑（A）～光酸產生劑（C）及甲基乙基酮（和光純藥工業股份有限公司製造，商品名：2-丁酮），製備感光性樹脂組成物。 光酸產生劑（A）：三芳基鋶鹽（聖阿普羅（San-Apro）股份有限公司製造，商品名：CPI-110A） 光酸產生劑（B）：三芳基鋶鹽（聖阿普羅（San-Apro）股份有限公司製造，商品名：CPI-310A） 光酸產生劑（C）：三芳基鋶鹽（聖阿普羅（San-Apro）股份有限公司製造，商品名：CPI-310B）<Preparation of photosensitive resin composition> The N-protecting group polyamine (I) to N-protecting group polyamine (V) and the following photoacid generator were blended in an amount (parts by mass) shown in Table 2. A) - Photoacid generator (C) and methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone), and a photosensitive resin composition was prepared. Photoacid generator (A): triarylsulfonium salt (manufactured by San-Apro Co., Ltd., trade name: CPI-110A) Photoacid generator (B): triarylsulfonium salt (St. Apollo ( Manufactured by San-Apro Co., Ltd., trade name: CPI-310A) Photoacid generator (C): Triaryl sulfonium salt (manufactured by San-Apro Co., Ltd., trade name: CPI-310B)

＜光脫保護反應的評價＞ 以濕厚度為22 μm的方式利用棒塗佈將各感光性樹脂組成物塗佈於鋁箔（8079材，厚度20 μm，東洋鋁業股份有限公司製造）上，於80℃的加熱板上進行5分鐘加熱，使溶劑揮發，形成厚度為0.5 μm的感光層。其次，對感光層，使用UV照射裝置（牛尾（USHIO）股份有限公司製造，SP-500D），以曝光量5 J/cm2 光照射i射線（波長365 nm）。光照射後，對感光層於130℃下加熱15分鐘（曝光後烘烤）。對如此所得的樣品，藉由紅外衰減全反射（attenuated total reflectance，ATR）法測定紅外吸收光譜。將可觀測到波數3400 cm-1 附近的源自由N-保護基聚醯胺的脫保護產生的醯胺的NH鍵的信號者評價為「A」，將並未觀測到者評價為「B」。將結果示於表2中。<Evaluation of Photodeprotection Reaction> Each photosensitive resin composition was applied to an aluminum foil (8079 material, thickness: 20 μm, manufactured by Toyo Aluminum Co., Ltd.) by bar coating so that the wet thickness was 22 μm. The plate was heated on a hot plate at 80 ° C for 5 minutes to volatilize the solvent to form a photosensitive layer having a thickness of 0.5 μm. Next, the photosensitive layer was irradiated with i-rays (wavelength 365 nm) at a light exposure amount of 5 J/cm 2 using a UV irradiation device (manufactured by USHIO Co., Ltd., SP-500D). After the light irradiation, the photosensitive layer was heated at 130 ° C for 15 minutes (baked after exposure). The infrared absorption spectrum of the sample thus obtained was measured by an infrared attenuated total reflectance (ATR) method. The signal of the NH bond of the guanamine produced by the deprotection of the source free N-protected polyamine at a wave number of 3400 cm -1 was evaluated as "A", and the unobserved person was evaluated as "B". "." The results are shown in Table 2.

[表2] [Table 2]

如表2所示，於N-保護基聚醯胺（I）～N-保護基聚醯胺（V）與光酸產生劑（A）～光酸產生劑（C）的組合中，確認到N-保護基聚醯胺（I）～N-保護基聚醯胺（V）的光脫保護反應進行。As shown in Table 2, in the combination of the N-protecting polyamine (I) to the N-protecting polyamine (V) and the photoacid generator (A) to the photoacid generator (C), it was confirmed The photodeprotection reaction of the N-protecting group polyamine (I) to the N-protecting group polyamine (V) is carried out.

＜與水的接觸角的評價＞ 將實施例7、實施例9的感光性樹脂組成物旋轉塗佈於矽晶圓上，於80℃的加熱板上進行5分鐘加熱，形成加熱後的厚度為0.5 μm的感光層。對感光層，使用UV照射裝置（牛尾（USHIO）股份有限公司製造，SP-500D），以曝光量5 J/cm2 光照射i射線（波長365 nm）。光照射後，於130℃下加熱15分鐘（曝光後烘烤）。對如此所得的樣品，於並未曝光的未曝光部、與進行了曝光及曝光後烘烤的曝光·烘烤部的各自中，測定與水的接觸角。將結果示於表3中。<Evaluation of contact angle with water> The photosensitive resin compositions of Example 7 and Example 9 were spin-coated on a ruthenium wafer, and heated on a hot plate at 80 ° C for 5 minutes to form a thickness after heating. 0.5 μm photosensitive layer. For the photosensitive layer, an i-ray (wavelength 365 nm) was irradiated with light at an exposure amount of 5 J/cm 2 using a UV irradiation device (manufactured by USHIO Co., Ltd., SP-500D). After light irradiation, it was heated at 130 ° C for 15 minutes (bake after exposure). The sample thus obtained was measured for the contact angle with water in each of the unexposed portions which were not exposed, and the exposure/baking portions which were subjected to exposure and post-exposure baking. The results are shown in Table 3.

[表3] [table 3]

如表3所示，實施例7及實施例9的感光層中，藉由光照射及曝光後烘烤，與水的接觸較變小（對水的潤濕性提高）。As shown in Table 3, in the photosensitive layers of Example 7 and Example 9, the contact with water was reduced by light irradiation and post-exposure baking (the wettability to water was improved).

＜圖案化性的評價＞ 將實施例7的感光性樹脂組成物旋轉塗佈於矽晶圓上，於80℃的加熱板上進行5分鐘加熱，形成加熱後的厚度為0.5 μm的感光層。對感光層，使用UV照射裝置（牛尾（USHIO）股份有限公司製造，SP-500D），介隔遮罩以曝光量5 J/cm2 光照射i射線（波長365 nm）。光照射後，於130℃下加熱15分鐘（曝光後烘烤）。將該所獲得的樣品於丙酮中浸漬10秒。結果，確認到可以顯影後膜厚0.3 μm形成線/空間：25 μm/25 μm的圖案。將該圖案的掃描型電子顯微鏡照片示於圖1中。<Evaluation of Patterning Property> The photosensitive resin composition of Example 7 was spin-coated on a ruthenium wafer, and heated on a hot plate at 80 ° C for 5 minutes to form a photosensitive layer having a thickness of 0.5 μm after heating. For the photosensitive layer, a UV irradiation device (manufactured by USHIO Co., Ltd., SP-500D) was used, and the i-ray (wavelength 365 nm) was irradiated with light at an exposure amount of 5 J/cm 2 through a mask. After light irradiation, it was heated at 130 ° C for 15 minutes (bake after exposure). The obtained sample was immersed in acetone for 10 seconds. As a result, it was confirmed that a film thickness of 0.3 μm after development could be formed into a line/space: 25 μm / 25 μm pattern. A scanning electron micrograph of the pattern is shown in Fig. 1.

＜無電解電鍍密接性的評價＞ 使N-保護基聚醯胺（VIV）0.045 g與光酸產生劑（A）0.005 g溶解於乙酸2-甲氧基-1-甲基乙基酯0.25 g中，獲得感光性樹脂溶液。將該感光性樹脂溶液旋轉塗佈於矽晶圓上，於80℃的加熱板上進行5分鐘加熱，形成加熱後的厚度為1.2 μm的感光層。對感光層，使用UV照射裝置（牛尾（USHIO）股份有限公司製造，SP-500D），以曝光量5 J/cm2 光照射i射線（波長365 nm）。光照射後，於130℃下加熱15分鐘（曝光後烘烤），獲得樣品。關於所獲得的樣品，製備二乙二醇單丁醚：200 mL/L、氫氧化鈉：5 g/L的水溶液作為膨潤液，加溫至70℃並進行5分鐘浸漬處理。其次，將包含氯化鉛的日本阿托科技（atotech Japan）公司製造的無電解電鍍用觸媒活化劑耐奧甘特（Activator Neoganth）834 加溫至35℃並進行5分鐘浸漬處理後，於室溫下在無電解鍍銅用的日本阿托科技（atotech Japan）公司製造的鍍覆液普林特甘特（Printoganth）MSK-DK中浸漬15分鐘，獲得厚度約0.1 μm的Cu種子層。將形成有種子層的樣品於硫酸Cu鍍覆液中以電流密度1.89 A/dm2 處理60分鐘，使Cu鍍層析出約25 μm。其後，於180 ℃下進行60分鐘退火處理。藉由濕式蝕刻製作5 mm寬的銅箔線，製成試驗片。使用島津製作所製造的自動繪圖儀（autograph）AGS-X 100N，依照JIS-C-6481於90°方向上以拉伸速度5 mm/min的條件撕下銅箔，測定鍍敷剝離強度。結果，示出剝離強度為0.15 kN/m，為比較高的值。<Evaluation of Electroless Plating Adhesion> Dissolving N-protecting polyamine (VIV) 0.045 g and photoacid generator (A) 0.005 g in 2-methoxy-1-methylethyl acetate 0.25 g In the middle, a photosensitive resin solution was obtained. The photosensitive resin solution was spin-coated on a ruthenium wafer, and heated on a hot plate at 80 ° C for 5 minutes to form a photosensitive layer having a thickness of 1.2 μm after heating. For the photosensitive layer, an i-ray (wavelength 365 nm) was irradiated with light at an exposure amount of 5 J/cm 2 using a UV irradiation device (manufactured by USHIO Co., Ltd., SP-500D). After the light irradiation, it was heated at 130 ° C for 15 minutes (post-exposure baking) to obtain a sample. With respect to the obtained sample, an aqueous solution of diethylene glycol monobutyl ether: 200 mL/L, sodium hydroxide: 5 g/L was prepared as a swelling liquid, and the mixture was heated to 70 ° C and immersed for 5 minutes. Next, Activator Neoganth 834, a catalyst activator for electroless plating, manufactured by Atotech Japan Co., Ltd. containing lead chloride, was heated to 35 ° C and immersed for 5 minutes. The coating was immersed in a plating solution of Printoganth MSK-DK manufactured by Atotech Japan Co., Ltd. for electroless copper plating for 15 minutes at room temperature to obtain a Cu seed layer having a thickness of about 0.1 μm. The sample in which the seed layer was formed was treated in a Cu plating solution of sulfuric acid at a current density of 1.89 A/dm 2 for 60 minutes to subject Cu plating to about 25 μm. Thereafter, annealing treatment was performed at 180 ° C for 60 minutes. A test piece was prepared by wet etching a 5 mm wide copper foil wire. The copper foil was peeled off in a 90° direction at a tensile speed of 5 mm/min in accordance with JIS-C-6481 using an autograph AGS-X 100N manufactured by Shimadzu Corporation, and the plating peel strength was measured. As a result, the peel strength was shown to be 0.15 kN/m, which was a relatively high value.

無no

圖1是表示實施例中的圖案化性的評價結果的電子顯微鏡照片。Fig. 1 is an electron micrograph showing the results of evaluation of patterning properties in Examples.

Claims (4)

一種感光性樹脂組成物，其含有具有下述式（1）所表示的結構單元的樹脂、以及光酸產生劑；（式中，R1 及R2 分別獨立地表示於酸性條件下脫保護的一價保護基，X1 及Z1 分別獨立地表示二價有機基）。A photosensitive resin composition containing a resin having a structural unit represented by the following formula (1), and a photoacid generator; (wherein R 1 and R 2 each independently represent a monovalent protecting group which is deprotected under acidic conditions, and X 1 and Z 1 each independently represent a divalent organic group). 如申請專利範圍第1項所述的感光性樹脂組成物，其中所述保護基為於pKa為0以下的酸性條件下脫保護的保護基。The photosensitive resin composition according to claim 1, wherein the protecting group is a protecting group deprotected under acidic conditions having a pKa of 0 or less. 如申請專利範圍第1項或第2項所述的感光性樹脂組成物，其中相對於所述樹脂100質量份，所述光酸產生劑的含量為1質量份～100質量份。The photosensitive resin composition according to the first or second aspect of the invention, wherein the photoacid generator is contained in an amount of from 1 part by mass to 100 parts by mass per 100 parts by mass of the resin. 一種抗蝕劑圖案的形成方法，其包括：於基材上配置如申請專利範圍第1項至第3項中任一項所述的感光性樹脂組成物而形成感光層的步驟；以及 對所述感光層利用規定的圖案進行曝光後，進行加熱的步驟。A method of forming a resist pattern, comprising: a step of forming a photosensitive layer by disposing a photosensitive resin composition according to any one of claims 1 to 3 on a substrate; and The step of heating after the photosensitive layer is exposed by a predetermined pattern.
TW107114324A 2017-04-26 2018-04-26 Photosensitive resin composition and method for forming resist pattern TW201843526A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-087467 2017-04-26
JP2017087467 2017-04-26

Publications (1)

Publication Number Publication Date
TW201843526A true TW201843526A (en) 2018-12-16

Family

ID=63920166

Family Applications (1)

Application Number Title Priority Date Filing Date
TW107114324A TW201843526A (en) 2017-04-26 2018-04-26 Photosensitive resin composition and method for forming resist pattern

Country Status (3)

Country Link
JP (1) JP6733813B2 (en)
TW (1) TW201843526A (en)
WO (1) WO2018199247A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114488693A (en) * 2021-12-24 2022-05-13 苏州理硕科技有限公司 Polymer, photoresist containing the polymer and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7119997B2 (en) * 2018-12-28 2022-08-17 信越化学工業株式会社 Photosensitive resin composition, laminate, and pattern forming method
TW202208511A (en) * 2020-08-27 2022-03-01 日商富士軟片股份有限公司 Method for manufacturing cured product, resin composition, developing solution, method for manufacturing layered body, and method for manufacturing semiconductor device

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6951682B1 (en) * 1998-12-01 2005-10-04 Syntrix Biochip, Inc. Porous coatings bearing ligand arrays and use thereof
JP3353292B2 (en) * 1999-03-29 2002-12-03 日本電気株式会社 Chemically amplified resist
EP1636648B1 (en) * 2003-06-05 2015-08-12 FujiFilm Electronic Materials USA, Inc. Novel positive photosensitive resin compositions
CN102428121B (en) * 2009-03-10 2014-05-28 日产化学工业株式会社 Polyimide precursor, polyimide, and liquid crystal aligning agent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114488693A (en) * 2021-12-24 2022-05-13 苏州理硕科技有限公司 Polymer, photoresist containing the polymer and application thereof

Also Published As

Publication number Publication date
JP6733813B2 (en) 2020-08-05
JPWO2018199247A1 (en) 2019-11-07
WO2018199247A1 (en) 2018-11-01

Similar Documents

Publication Publication Date Title
EP3275940B1 (en) Energy-sensitive resin composition
KR20120003870A (en) Base-generating agent photosensitive resin composition patterning material comprising the photosensitive resin composition patterning method and article using the photosensitive resin composition
TW201921114A (en) Photosensitive resin composition
TW201843526A (en) Photosensitive resin composition and method for forming resist pattern
Hsu et al. A novel positive photosensitive polybenzoxazole precursor for microelectronic applications
JP2007186680A (en) Amide derivative, polymer, chemical amplification type photosensitive resin composition and method for forming pattern
JP3968886B2 (en) Photosensitive composition
JP5768348B2 (en) Thermal base generator, polymer precursor composition, and article using the composition
WO2020080207A1 (en) Photosensitive insulating film composition
TWI629311B (en) Embossed pattern film, method for producing embossed pattern film, electronic component or optical article containing embossed pattern film, and adhesive containing photosensitive resin composition
JP2003238683A (en) Positive photosensitive resin composition
JP4154954B2 (en) Photosensitive resin composition, relief pattern and heat-resistant coating film production method using the same, and electronic component having the same
JP6767470B2 (en) Photosensitive resin composition, dry film, cured product, printed wiring board and photobase generator
WO2010001779A1 (en) Photosensitive insulating resin composite and pattern forming method using the same
JP4487981B2 (en) Polyimide and process for producing the same
JP4811162B2 (en) Polyimide and process for producing the same
KR102679410B1 (en) Photosensitive resin compositions, dry films, cured products, printed wiring boards, and photobase generators
WO2021117764A1 (en) Compound, method for producing same, resin composition, resin sheet, multilayer printed wiring board, and semiconductor device
WO2009099083A1 (en) Acrylamide polymers, acrylamide compounds, chemically amplified photosensitive resin compositions and pattern formation method
WO2010087195A1 (en) Positive-type photosensitive insulating resin composition, and method for forming pattern using same
JP2010243854A (en) Alkali-developable negative photosensitive resin composition, production method of cured relief pattern, and semiconductor device
JPS60178446A (en) Photosensitive material soluble in organic solvent
JP2001048950A (en) Photosensitive resin composition
JP2005173528A (en) Positive photosensitive resin composition, method for producing relief pattern and electronic component
JP2022073737A (en) Photosensitive resin composition, and manufacturing method of cured film