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TW201111911A - Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern - Google Patents

Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern Download PDF

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Publication number
TW201111911A
TW201111911A TW099125162A TW99125162A TW201111911A TW 201111911 A TW201111911 A TW 201111911A TW 099125162 A TW099125162 A TW 099125162A TW 99125162 A TW99125162 A TW 99125162A TW 201111911 A TW201111911 A TW 201111911A
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Taiwan
Prior art keywords
photosensitive resin
group
mass
compound
resin composition
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TW099125162A
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Chinese (zh)
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TWI491979B (en
Inventor
Go Nishizawa
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Asahi Kasei E Materials Corp
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    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask
    • H10P76/20—
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
    • H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Abstract

Disclosed is a photosensitive resin composition which enables a good contrast right after exposure to light. Specifically disclosed is a photosensitive resin composition which contains (a) 20-80% by mass of an alkali-soluble polymer that contains a carboxylic acid and has an acid equivalent weight of 100-600 and a weight average molecular weight of 5,000-500,000, (b) 5-60% by mass of an ethylenically unsaturated addition polymerizable monomer that contains at least one compound having an acrylic group, (c) 0.1-20% by mass of photopolymerization initiator that contains an N-aryl-a-amino acid compound, (d) 0.1-10% by mass of a leuco dye, and (e) 0.01-5% by mass of a mercaptothiadiazole compound that is represented by general formula (I). (In the formula, R1 represents one group that is selected from the group consisting of alkyl groups having 1-9 carbon atoms, alkoxyl groups having 1-9 carbon atoms, alkylthio groups having 1-16 carbon atoms, mercapto groups, amino groups, and alkyl amino groups having 1-9 carbon atoms.)

Description

201111911 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種能夠利用鹼性水溶液顯影之感光性樹 C 脂組合物、將該感光性樹脂組合物積層於支持體上而形成 • 之感光性樹脂積層體、使用該感光性樹脂積層體於基板上 形成光阻圖案之方法、及該光阻圖案之用途。更詳細而 言，係關於在以下製造中可賦予較佳之光阻圖案的感光性 樹脂組合物：印刷線路板之製造、可撓性印刷線路板之製 造、1C晶片搭載用導線架（以下稱為導線架）之製造、以金 屬掩模製造為代表之金屬箔精密加工、.以BGA(Ball Array，球柵陣列）及CSP(Chip Size package，晶片尺寸封 裝）為代表之半導體封裝體之製造、以TAB(Tape Am〇mated B〇nding，捲帶式自動接合）及COF(Chip on Fiim，薄膜覆 晶：將半導體1C搭載於膜狀微細線路板上者）為代表之捲 π基板之製造、半導體凸塊之製造、以平板顯示器⑺ panel display)領域中之IT〇(Indium 丁化〇以心，氧化銦錫） 電極、定址電極及電磁波遮罩為代表之隔離壁構件之製 造、以及藉由喷砂工法加工基材時之保護掩模構件之製造 * 中。 【先前技術】 先前，印刷線路板係藉由光微影法（ph〇t〇Hth〇graphy meth〇d)而製造。作為光微影法，例如可列舉以下方法： 於負型之情形時，將感光性樹脂組合物塗佈於基板上，進 行圖案曝光而使該感光性樹脂組合物之曝光部分聚合硬 149481.doc 201111911 化’並藉由顯影液去除未曝光部分而於基板上形成光阻圖 案，實施餘刻或鑛敷處理而形成導體圖案後，將該光阻圖 案自該基板上剝離去&，藉此於基板上形《導體圖案。 於上述光微影法中可使用以下方法中之任一者：將感光 性樹脂組合物塗佈於基板上時，將感光性樹脂組合物溶液 作為光阻溶液塗佈於基板上並使之乾燥的方法；或使將支 ，體、包含感光性樹脂組合物之層（以下亦稱為「感光性 樹脂層」）、及視需要之保護層依序積層而成之感光性樹 脂積層體（以下亦稱為「乾膜光阻」）積層於基板上的方 法。並且，於印刷線路板之製造中，多數情況係使用後者 之乾膜光阻。 以下對使用上述乾膜光阻而製造印刷線路板之方法進行 簡單闡述。 首先，於乾膜光阻具有保護層、例如聚乙烯膜之情形 時，自感光性樹脂層將其剝離。繼而，使用貼合機於基板 (例如銅箔積層板）上以該基板、感光性樹脂層、支持體（例 如聚對苯二甲酸乙二酯）之順序積層感光性樹脂層及支持 體。繼而經由具有線路圖案之光罩，利用超高壓水銀燈發 出之1射線（波長365 nm)等紫外線對該感光性樹脂層進行曝 光，藉此使曝光部分聚合硬化。繼而將支持體剝離。接著 藉由顯影液、例如具有弱鹼性之水溶液將感光性樹脂層之 未曝光部分溶解或分散去除，而於基板上形成光阻圖案。 作為使用以上述方式形成之基板上的光阻圖案而製作金 屬導體圖案之方法，大致分為2種方法，有藉由蝕刻而去 149481.doc 201111911 除未經光阻被覆之金屬部分之方法、及藉由鍍敷而敷設金 屬之方法。特別是最近，就步驟之簡便性而言，大多使用 前者之方法。 於藉由蚀刻而去除金屬部分之方法中，通常利用硬化光 阻膜覆蓋基板之貫通孔（throUgh hole)及用於層間連接之通 孔（via hole)，而使孔内之金屬不受到蝕刻。將該工法稱為 蓋孔法。於蚀刻步驟中，例如可使用氯化銅溶液、氯化鐵 溶液或銅氨錯合物溶液。 最近’隨著印刷線路板之生產量增加，而要求應對高生 產之高感度乾膜光阻。又存在以下傾向：於曝光後導入檢 測機而於生產線之早期階段發現例如由異物所致之缺陷， 藉此欲使生產性提高。曝光後之缺陷檢測機之判定通常係 識別未曝光部分與曝光部分而進行者，因此現狀為要求剛 曝光後之感光性樹脂層具有極為良好的剛曝光後之對比 度。 又，另一方面，於印刷線路板製造技術中，可見藉由雷 射所進行之直接刻寫、即無需光罩之無光罩曝光在近年迅 速推廣。作為無光罩曝光之光源，多數情況係使用波長為 350〜410 nm之光、特別是丨射線或匕射線（波長4〇5 nm)。於 無光罩曝光中，為於曝光時對準基板而需要對準標記 (alignment mark)。該對準標記係藉由在圖案曝光前僅預先 使對準標記曝光而製作。因此，若於剛曝光後感光性樹脂 層不具有良好的剛曝光後之對比度，則至圖案曝光為止之 節拍時間（takt time)變長，單位時間之生產量變差。因 S. 149481.doc 201111911 此’現狀為要求剛曝光後之感光性樹脂層具有極為良好的 剛曝光後之對比度。 迄今為止’已揭示有大量關於感光性樹脂組合物及感光 性樹脂積層體之文獻，關於提高剛曝光後之對比度之文獻 亦大量存在（參照專利文獻^3)。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開2000-241971號公報 [專利文獻2]曰本專利特開2002-053 621號公報 [專利文獻3]曰本專利特開200 1-209 177號公報 [專利文獻4]曰本專利特開2008-287227號公報 【發明内容】 [發明所欲解決之問題] 但是’現狀為即便利用上述文獻所提出之技術，剛曝光. 後之對比度仍不充分。本發明之目的在於提供一種能夠克 服上述問題、於剛曝光後具有極為良好的對比度、解像度 及感度優異、進而於特定態樣中可抑制剝離時殘膜性降低 的感光性樹脂組合物；以及使用其之感光性樹脂積層體及 光阻圖案之形成方法。 [解決問題之技術手段] 為解決上述課題而反覆銳意研究之結杲發現，藉由使用 特定嗟二唑化合物作為感光性樹脂組合物之成分，可解決 上述課題，從而完成本發明。即本發明如以下所述。 (1) 一種感光性樹脂組合物，其包含：（a)含有叛酸、酸[Technical Field] The present invention relates to a photosensitive tree C-fat composition which can be developed with an aqueous alkaline solution, and which is formed by laminating the photosensitive resin composition on a support. A resin laminated body, a method of forming a photoresist pattern on a substrate using the photosensitive resin laminate, and use of the photoresist pattern. More specifically, it relates to a photosensitive resin composition which can provide a preferable photoresist pattern in the following production: manufacture of a printed wiring board, manufacture of a flexible printed wiring board, and lead frame for 1C wafer mounting (hereinafter referred to as Fabrication of a lead frame, fabrication of a metal foil represented by a metal mask, and fabrication of a semiconductor package represented by a BGA (Ball Array) and a CSP (Chip Size Package) Manufacture of a roll π substrate typified by TAB (Tape Am〇mated B〇nding) and COF (Chip on Fiim, film-on-film: a semiconductor 1C mounted on a film-shaped micro-board) Manufacture of semiconductor bumps, fabrication of spacers represented by IT〇 (Indium, indium tin oxide) electrodes, address electrodes, and electromagnetic wave masks in the field of flat panel displays (7) Manufacturing of protective mask members in the processing of substrates by the blasting method*. [Prior Art] Previously, printed wiring boards were manufactured by photolithography (ph〇t〇Hth〇graphy meth〇d). Examples of the photolithography method include the following methods: in the case of a negative type, a photosensitive resin composition is applied onto a substrate, and pattern exposure is performed to polymerize the exposed portion of the photosensitive resin composition. 149481.doc And forming a photoresist pattern on the substrate by removing the unexposed portion by the developer, performing a residual or mineralization treatment to form a conductor pattern, and then stripping the photoresist pattern from the substrate, thereby A conductor pattern is formed on the substrate. In the photolithography method, any of the following methods may be used: when the photosensitive resin composition is applied onto a substrate, the photosensitive resin composition solution is applied as a photoresist solution to the substrate and dried. Or a photosensitive resin laminate in which a layer containing a photosensitive resin composition (hereinafter also referred to as "photosensitive resin layer") and an optional protective layer are sequentially laminated (hereinafter) Also known as "dry film photoresist") is a method of laminating on a substrate. Moreover, in the manufacture of printed wiring boards, the dry film photoresist of the latter is often used. Hereinafter, a method of manufacturing a printed wiring board using the above dry film photoresist will be briefly described. First, when the dry film photoresist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Then, a photosensitive resin layer and a support are laminated on the substrate (e.g., a copper foil laminate) in the order of the substrate, the photosensitive resin layer, and the support (e.g., polyethylene terephthalate) using a laminator. Then, the photosensitive resin layer is exposed to ultraviolet rays such as 1 ray (wavelength 365 nm) emitted from an ultrahigh pressure mercury lamp through a mask having a line pattern, whereby the exposed portion is polymerized and cured. The support is then peeled off. Then, the unexposed portion of the photosensitive resin layer is dissolved or dispersed by a developing solution, for example, an aqueous solution having a weak alkalinity, to form a photoresist pattern on the substrate. A method of fabricating a metal conductor pattern using a photoresist pattern on a substrate formed as described above is roughly classified into two methods, and a method of removing a metal portion not covered by a photoresist by etching, 149481.doc 201111911, And a method of laying metal by plating. Especially recently, the method of the former is mostly used in terms of the simplicity of the steps. In the method of removing the metal portion by etching, the through hole (throUgh hole) of the substrate and the via hole for interlayer connection are usually covered by the cured photoresist film, so that the metal in the hole is not etched. This method is called the cover hole method. In the etching step, for example, a copper chloride solution, a ferric chloride solution or a copper ammonia complex solution can be used. Recently, as the production of printed wiring boards has increased, it has been required to cope with high-sensitivity dry film photoresists of high production. Further, there is a tendency to introduce a tester after exposure and to find defects such as foreign matter at an early stage of the production line, thereby improving productivity. The determination of the defect detecting machine after the exposure is usually performed by identifying the unexposed portion and the exposed portion. Therefore, it is required that the photosensitive resin layer immediately after exposure has an extremely good contrast immediately after exposure. On the other hand, in the printed circuit board manufacturing technology, it can be seen that the direct writing by laser, that is, the maskless exposure without a mask, has been rapidly promoted in recent years. As a light source for the reticle exposure, in many cases, light having a wavelength of 350 to 410 nm, particularly xenon rays or xenon rays (wavelength 4 〇 5 nm), is used. In the maskless exposure, an alignment mark is required to align the substrate during exposure. The alignment mark is produced by exposing only the alignment mark in advance before pattern exposure. Therefore, if the photosensitive resin layer does not have a good contrast immediately after exposure immediately after exposure, the takt time until the pattern exposure becomes long, and the throughput per unit time is deteriorated. In view of the fact that the photosensitive resin layer immediately after exposure has an extremely good contrast immediately after exposure, S. 149481.doc 201111911. A large number of documents relating to photosensitive resin compositions and photosensitive resin laminates have been disclosed so far, and there has been a large amount of literature on improving the contrast immediately after exposure (see Patent Document ^3). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-241971 [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A No. 2002-053 621 (Patent Document 3) [Patent Document 4] [Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-287227 [Draft of the Invention] [Problems to be Solved by the Invention] However, the status quo is just exposure using the technique proposed in the above documents. The contrast is still insufficient. An object of the present invention is to provide a photosensitive resin composition which can overcome the above-mentioned problems, has excellent contrast, excellent resolution and sensitivity after exposure, and can suppress a decrease in residual film property in peeling in a specific aspect; A method of forming a photosensitive resin laminate and a photoresist pattern. [Means for Solving the Problems] In order to solve the above problems, it has been found that the above problems can be solved by using a specific oxadiazole compound as a component of the photosensitive resin composition, and the present invention has been completed. That is, the present invention is as follows. (1) A photosensitive resin composition comprising: (a) containing a tickic acid, an acid

149481.doc • 6 - S 201111911 當量為100〜600、重量平均分子量為5,〇〇〇〜5〇〇 〇〇〇之鹼溶 性咼分子：20〜80質量。/〇 ; 含有至少1種具有丙烯醯基之 化合物的乙烯性不飽和加成聚合性單體：5〜6〇質量。/。；（c) 含有N-芳基-α-胺基酸化合物之光聚合起始劑：〇丨〜2〇質量 % ; (d)隱色染料：〇·ι〜1〇質量％ ;及⑷下述通式⑴所示之 疏基°塞二唾化合物：〇 · 〇 1〜5質量〇/0 : [化1] HSxVRi N—N ⑴ {式中’尺丨表示選自由碳數1〜9之烷基、碳數1〜9之烷氧 基、碳數1〜16之烷硫基、巯基、胺基及碳數1〜9之烷基胺 基所組成之群中之1種基}。 (2)如上述（1)之感光性樹脂組合物，其中上述（b)含有至 少1種具有丙烯醯基之化合物的乙烯性不飽和加成聚合性 單體中之具有丙烯醯基的化合物係下述通式（II)所示之化 合物： [化2]149481.doc • 6 - S 201111911 Equivalent 100~600, weight average molecular weight 5, 〇〇〇~5〇〇 碱 alkali soluble 咼 molecule: 20~80 mass. /?; an ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group: 5 to 6 Å by mass. /. (c) a photopolymerization initiator containing an N-aryl-α-amino acid compound: 〇丨~2〇% by mass; (d) a leuco dye: 〇·ι~1〇% by mass; and (4) The sulphate-salt compound represented by the formula (1): 〇· 〇1 to 5 mass 〇/0: [Chemical 1] HSxVRi N-N (1) {wherein the ruler indicates that it is selected from the carbon number 1 to 9 An alkyl group, an alkoxy group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amine group, and a group of the alkyl group having 1 to 9 carbon atoms. (2) The photosensitive resin composition according to the above (1), wherein the (b) ethylenically unsaturated addition polymerizable monomer having at least one compound having an acrylonitrile group has a propylene group-containing compound a compound represented by the following formula (II): [Chemical 2]

H2C=C-CH2C=C-C

II 0 149481.doc 201111911 {式中，R2、R3、R4及R5表示Η，X及Y分別獨立表示碳數 2〜4之伸烷基，X及Υ互不相同，p1、p2、p3、p4、D5、6、 p7及P8分別獨立為0或正整數，p1、P2、P3、p4、P5、p6、P7 及p8之合計為0〜2〇的整數}。 (3) 如上述（1)或（2)之感光性樹脂組合物，其中上述（e) 酼基噻二唑化合物為選自由5-甲硫基-2-巯基4,3,4-嘆二 唑、2-胺基-5-疏基-1，3,4-噻二唑、5-甲基胺基_2-巯基-1，3,4-嗟二哇及2,5-二疏基_1，3,4-°塞二°坐所組成之群中之至 少1種化合物。 (4) 如上述（1)至（3)中任一項之感光性樹脂組合物，其中 上述（c)光聚合起始劑所含有之上述N_芳基_α_胺基酸化合 物為Ν-笨基甘胺酸。 (5) 如上述（1)至（4)中任—項之感光性樹脂組合物，其中 上述（b)含有至少1種具有丙烯醯基之化合物的乙烯性不飽 和加成聚合性單體包含選自由下述通式（ΠΙ)所示之能夠光 聚合之不飽和化合物中的至少丨種： [化3]II 0 149481.doc 201111911 {wherein, R2, R3, R4 and R5 represent Η, X and Y respectively represent an alkylene group having a carbon number of 2 to 4, and X and Υ are different from each other, p1, p2, p3, p4 , D5, 6, p7, and P8 are each independently 0 or a positive integer, and the total of p1, P2, P3, p4, P5, p6, P7, and p8 is an integer of 0 to 2 }}. (3) The photosensitive resin composition according to (1) or (2) above, wherein the (e) mercaptothiadiazole compound is selected from the group consisting of 5-methylthio-2-indenyl 4,3,4-anthracene Azole, 2-amino-5-mercapto-1,3,4-thiadiazole, 5-methylamino 2-indenyl-1,3,4-indenyl and 2,5-diyl _1, 3, 4-° The at least one compound of the group consisting of two sittings. (4) The photosensitive resin composition according to any one of the above (1), wherein the (N) photopolymerization initiator contains the above-mentioned N_aryl-α-amino acid compound - Stupid glycine acid. (5) The photosensitive resin composition of any one of (1) to (4) above, wherein the (b) ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group contains At least one of the photopolymerizable unsaturated compounds represented by the following formula (ΠΙ) is selected: [Chemical 3]

o-(a-〇Kb-o)-c-c=ch n2 n4|l I o r7 (HI) 149481.doc 201111911 (式中，R6及I分別獨立表示Η或CH3，A表示C2H4，B表示 3H6 nl+n2為2〜30之整數，n3+n4為〇〜3〇之整數，ni及n2 分別獨立為1〜29之整數，n3及n4分別獨立為〇〜3〇之整數， 並且-(A-O)-及之重複單元的排列既可為無規亦可 為嵌段}。 (6) —種感光性樹脂積層體，其係於包含基材膜之支持 體上積層包含如上述⑴至（5)中任—項之感光性樹脂組合 物之感光性樹脂層而成。 (7) —種光阻圖案之形成方法，其包括如下步驟： 積層步驟，將如上述⑹之感光性樹脂積層體積層於基 板上； 曝光步驟，對感光性樹脂積層體中之感光性樹 曝光；及 顯影步驟，將感光性樹脂層之未曝光部分顯影去除。 ⑻如上述⑺之光阻圖案之形成方法，纟中藉㈣㈣ 案之直接刻寫而進行上述曝光步驟。 [發明之效果] 根據本發明，提供—種於剛曝光後具有極為良好的對比 =、·解像度及感度優異、進而於特定態樣中能夠抑制剥離 時殘膜性降低的感光性樹脂組合物；以及使用其之感 樹脂積層體及光阻圖案之形成方法。 【實施方式】 以下，對本發明進行具體說明。 &lt;感光性樹脂組合物&gt; 149481 .doc 201111911 本發明提供一種感光性樹脂組合物，其包含：（a)含有幾 酸、酸當量為100〜600、重量平均分子量為5 〇〇〇〜5〇〇 〇〇〇 之驗ί谷性尚分子（於本說明書中稱為（a)驗溶性高分子）： 20〜80質量％ ; (b)含有至少1種具有丙烯醯基之化合物的乙 烯性不飽和加成聚合性單體（於本說明書中稱為（b)乙烯性 不飽和加成聚合性單體）：5〜60質量％ ; (c)含有N_芳基_α_ 胺基酸化合物之光聚合起始劑（於本說明書中稱為（c)光聚 合起始劑）：0.1〜20質量％ ; (d)隱色染料：〇卜⑺質量0/〇 ; 及（e)下述通式（I)所示之巯基噻二唑化合物（於本說明書中 稱為（e)威基。塞二唾化合物）：〇 〇 1〜$質量％ : [化4] HS^rVRi N-N (1) {式中，1表示選自由碳數^之烷基、碳數丨〜9之烷氧 基、碳數1〜16之烷硫基、巯基、胺基、及碳數1〜9之烷基 胺基所組成之群中之1種基}。 (a)驗溶性高分子 本毛月之感光性樹脂組合物中之（a)驗溶性高分子係含有 叛酉义@义田量為100〜600、重量平均分子量為5,000〜500,000 之驗溶性高分子。 +為使感光性樹脂組合物對包含驗性水溶液之顯影液及剝 +液八有.’、、員〜性及剝離性，（a)鹼溶性高分子之羧基係必需 者(a)驗'合性高分子之酸當量為100〜600，較佳為 149481.doc 201111911 250〜450。就確保與溶劑、或感光性樹脂組合物中之其他 成分、特別是後述（b)含有至少1種具有丙稀醯基之化合物 的乙烯性不飽和加成聚合性單體之相溶性的觀點而言，上 述酸當量為100以上，又，就維持顯影性及剝離性之觀點 而言，為600以下。此處所謂酸當量，係指於其中具有1當 量羧基之鹼溶性高分子之質量（克）。再者，酸當量之測定 係使用 Hiranuma Reporting Titrator(COM-555)，利用 0.1 mol/L·之NaOH水溶液藉由電位差滴定法進行。 (a)鹼溶性高分子之重量平均分子量為5,000〜500,000。 就均勻地維持感光性樹脂層之厚度、獲得對顯影液之耐性 的觀點而言，為5,000以上，又，就維持顯影性之觀點而 言，為500,000以下。更好的是重量平均分子量為 20,000〜100,000。於本說明書中，所謂重量平均分子量， 係指藉由凝膠滲透層析儀（GPC，Gel Permeation Chromatography)，使用聚苯乙烯（例如昭和電工股份有限 公司製造之Shodex STANDARD SM-105)之校準曲線所測 定之重量平均分子量。該重量平均分子量更典型的是可使 用曰本分光股份有限公司製造之凝膠滲透層析儀，按以下 條件進行測定。 示差折射儀：RI-1530 泵：PU-1580 除氣器：DG-9-80-50 管柱烘箱：CO-1560 管柱：依序為 KF-802.5、KF-806Mx2、KF-807 149481.doc • 11 - 201111911O-(a-〇Kb-o)-cc=ch n2 n4|l I o r7 (HI) 149481.doc 201111911 (wherein R6 and I respectively represent Η or CH3, A represents C2H4, and B represents 3H6 nl +n2 is an integer of 2 to 30, n3+n4 is an integer of 〇~3〇, ni and n2 are each an integer of 1 to 29, and n3 and n4 are each an integer of 〇~3〇, and -(AO) And the arrangement of the repeating units may be either random or block. (6) A photosensitive resin laminate which is laminated on a support comprising a substrate film and contains (1) to (5) as described above (7) A method for forming a resist pattern, comprising the steps of: a laminating step of depositing a volume layer of the photosensitive resin as in the above (6) On the substrate; an exposure step for exposing the photosensitive tree in the photosensitive resin laminate; and a developing step of developing and removing the unexposed portion of the photosensitive resin layer. (8) A method for forming a photoresist pattern according to (7) above, (4) (4) The above exposure step is carried out by direct writing of the case. [Effect of the Invention] According to the present invention, it is provided that The photosensitive resin composition which is excellent in the contrast ratio and the sensitivity, and which can suppress the fall of the residual film property at the time of peeling in a specific aspect, and the formation method of the photosensitive resin laminated body and the photoresist pattern using this. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described. <Photosensitive Resin Composition> 149481 .doc 201111911 The present invention provides a photosensitive resin composition comprising: (a) a certain acid and an acid equivalent of 100 to 600 The weight average molecular weight is 5 〇〇〇 5 5 验 谷 性 性 分子 分子 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( An ethylenically unsaturated addition polymerizable monomer having a compound having an acrylonitrile group (referred to as (b) an ethylenically unsaturated addition polymerizable monomer in the present specification): 5 to 60% by mass; (c) containing N Photopolymerization initiator of _aryl_α_ amino acid compound (referred to as (c) photopolymerization initiator in the present specification): 0.1 to 20% by mass; (d) leuco dye: 〇b (7) mass 0 /〇; and (e) 巯 represented by the following general formula (I) The thiadiazole compound (referred to in the present specification as (e) weiji. sedation compound): 〇〇1 to $% by mass: [Chemical 4] HS^rVRi NN (1) {wherein, 1 means a group consisting of an alkyl group having a free carbon number, an alkoxy group having a carbon number of 丨~9, an alkylthio group having 1 to 16 carbon atoms, an anthracenyl group, an amine group, and an alkylamine group having 1 to 9 carbon atoms; (a) A solvent-soluble polymer in the photosensitive resin composition of the hair-soluble polymer (a) The test-soluble polymer contains a rebel-free @义田 amount of 100 to 600, and a weight average molecular weight of 5,000 〜 500,000 test soluble polymers. + In order to make the photosensitive resin composition to the developer containing the aqueous solution and the peeling liquid, the carboxy group of the alkali-soluble polymer is required (a) The acid equivalent of the conjugated polymer is from 100 to 600, preferably from 149481.doc 201111911 250 to 450. From the viewpoint of ensuring compatibility with the solvent or other components in the photosensitive resin composition, particularly the ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group (b) described later. In addition, the acid equivalent is 100 or more, and it is 600 or less from the viewpoint of maintaining developability and peelability. The acid equivalent herein means the mass (gram) of the alkali-soluble polymer having 1 equivalent of a carboxyl group. Further, the acid equivalent was measured by a potentiometric titration method using a Hiranuma Reporting Titrator (COM-555) using a 0.1 mol/L NaOH aqueous solution. (a) The alkali-soluble polymer has a weight average molecular weight of 5,000 to 500,000. From the viewpoint of maintaining the thickness of the photosensitive resin layer uniformly and obtaining the resistance to the developer, it is 5,000 or more, and is 500,000 or less from the viewpoint of maintaining developability. More preferably, the weight average molecular weight is 20,000 to 100,000. In the present specification, the weight average molecular weight refers to a calibration curve using polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.) by gel permeation chromatography (GPC, Gel Permeation Chromatography). The weight average molecular weight determined. The weight average molecular weight is more typically measured by a gel permeation chromatography apparatus manufactured by Sakamoto Optical Co., Ltd. under the following conditions. Differential Refractometer: RI-1530 Pump: PU-1580 Deaerator: DG-9-80-50 Column oven: CO-1560 Column: KF-802.5, KF-806Mx2, KF-807 149481.doc • 11 - 201111911

溶離液：THF ⑷鹼溶性高分子較佳為後述第-單體之i種以上與後述 第二單體之1種以上的共聚物。 第單體係刀子中具有1個聚合性不飽和基之缓酸或缓 酸酐。例如可列舉：（曱基）丙烯酸、反丁烯二酸、肉桂 酉欠、丁烯酸、衣康酸、順丁烯二酸酐及順丁烯二酸半酯。 其中特佳為（曱基）丙烯酸。 第一單體係非酸性、且於分子中具有至少i個聚合性不 飽和基之單體。例如可列舉：（曱基)丙烯酸曱自旨、（甲基) 丙烯酸乙酯、（曱基）丙烯酸正丙酯、（曱基）丙烯酸異丙 酯、（曱基）丙烯酸正丁酯、（曱基）丙烯酸異丁酯、（曱基）丙 烯S文第—丁 g曰、（甲基）丙婦酸2_羥基乙酯、（甲基）丙烯酸 蛵基丙酯、（曱基）丙烯酸2_乙基己酯、（曱基）丙烯酸苄 酯、乙烯醇之酯類、例如乙酸乙烯酯、（曱基）丙烯腈、苯 乙烯、及旎夠聚合之苯乙稀衍生物。其中特佳為（曱基）丙 稀酸f醋、（甲基）丙烤酸正丁_、苯乙烯、（甲基）丙烯酸 苄醋。 再者，於本說明書中，所謂（曱基）丙烯醯基，係指丙烯 醯基及/或曱基丙烯醯基。 (a)鹼溶性高分子於感光性樹脂組合物中之含有比例為 20〜80質量％之範圍，較佳為3〇〜7〇質量％之範圍。就藉由 曝光、顯影所形成之光阻圖案具有作為光阻之特性、例如 蓋孔、蝕刻及各種鍍敷步驟中的充分耐性之觀點而言， 述含有比例為20質量％以上80質量％以下。 149481.doc 201111911 (b)含有至少1種具有丙稀醢基之化合物的乙稀性不飽和 加成聚合性單體 本發明之感光性樹脂組合物中的（b)含有至少1種具有丙 烯醯基之化合物的乙烯性不飽和加成聚合性單體係具有1 個以上乙烯性不飽和鍵之單體。藉由含有至少1種具有丙 烯醯基之化合物，可賦予剛曝光後之對比度提高效果。作 為具有两烯醯基之化合物，可列舉：1，6-己二醇二丙烯酸 酷、1,4-環己二醇二丙稀酸酯、聚丙二醇二丙烯酸醋、聚 乙二醇二丙烯酸酯、2-二（對羥基苯基）丙烷二丙烯酸酯、 甘油三丙烯酸酯、三羥曱基丙烷三丙烯酸酯、聚氧丙基三 經甲基丙烷三丙烯酸酯、聚氧乙基三羥甲基丙烷三丙烯酸 酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、三羥 曱基丙燒三縮水甘油醚三丙烯酸酯、雙酚A二縮水甘油醚 二丙烯酸酯、β-羥基丙基_β·-(丙烯醯氧基）丙基鄰苯二甲酸 酯、苯氧基聚乙二醇丙烯酸酯、壬基苯氧基聚乙二醇丙烯 酉欠S曰、壬基苯氧基聚烷二醇丙烯酸酯、聚丙二醇單丙烯酸 S曰、雙盼Α之環氧烧加成物（例如於兩端各加成平均$莫耳 之裱氧乙烷而成的加成物、於兩端各加成平均2莫耳之環 氧丙烷及於兩端各加成平均15莫耳之環氧乙烷而成的加成 物）之一丙烯酸酯、三乙二醇十二丙二醇、於加成環氧丙 烷而成之聚丙二醇上進而於兩端加成環氧乙烷（於加成平 均12莫耳之環氧丙烷而成之聚丙二醇的兩端分別各加成平 均3莫耳之環氧乙烷）而得之聚烷二醇之二丙烯酸酯。其 中，較佳為季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸 14948l.doc -13- 201111911 酯、雙酚A二縮水甘油醚二丙烯酸酯、雙酚A之環氧烷加 成物之二丙婦酸酯。 特別是就平衡性良好地達成剛曝光後之對比度性、感 度、解像度及殘膜率之觀點而言，最佳為具有丙烯醯基之 化合物係下述通式（II)所示之化合物： [化5] H2〇4iThe elution liquid: THF (4) The alkali-soluble polymer is preferably a copolymer of one or more kinds of the above-mentioned first monomers and one or more of the second monomers described later. The first system knives have a slow acid or a slow anhydride of a polymerizable unsaturated group. For example, (fluorenyl)acrylic acid, fumaric acid, cinnamyl pentoxide, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester can be mentioned. Among them, it is particularly preferred as (fluorenyl) acrylic acid. The first single system is a monomer which is non-acidic and has at least i polymerizable unsaturated groups in the molecule. For example, (meth)acrylic acid, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (曱Isobutyl acrylate, (mercapto) propylene S-di-butyl ketone, (methyl) propyl benzoate 2-hydroxyethyl ester, (meth) methacrylate, (mercapto) acrylic acid 2_ Ethylhexyl ester, benzyl (meth) acrylate, esters of vinyl alcohol, such as vinyl acetate, (mercapto) acrylonitrile, styrene, and styrene-polymerized styrene derivatives. Among them, particularly preferred are (mercapto) acrylic acid f vinegar, (methyl) propylene succinic acid n-butyl styrene, styrene, and (meth)acrylic acid benzyl vinegar. Further, in the present specification, the "fluorenyl" acrylonitrile group means an acryl fluorenyl group and/or a decyl acryl fluorenyl group. (a) The content of the alkali-soluble polymer in the photosensitive resin composition is in the range of 20 to 80% by mass, preferably in the range of 3 to 7 % by mass. The resist pattern formed by exposure and development has a property as a photoresist, for example, a cap hole, etching, and sufficient resistance in various plating steps, and the content ratio is 20% by mass or more and 80% by mass or less. . 149481.doc 201111911 (b) Ethylene unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group (b) in the photosensitive resin composition of the present invention contains at least one kind of acrylonitrile The ethylenically unsaturated addition polymerizable single system of the compound of the group has a monomer having one or more ethylenically unsaturated bonds. By containing at least one compound having a propylene group, it is possible to impart a contrast-improving effect immediately after exposure. Examples of the compound having a dienol group include 1,6-hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, polypropylene glycol diacrylate, and polyethylene glycol diacrylate. , 2-bis(p-hydroxyphenyl)propane diacrylate, glycerol triacrylate, trihydroxydecyl propane triacrylate, polyoxypropyl trimethylpropane triacrylate, polyoxyethyl trimethylol Propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, trishydroxypropylpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, β-hydroxypropyl_β·- (Propylene methoxy) propyl phthalate, phenoxy polyethylene glycol acrylate, nonyl phenoxy polyethylene glycol propylene oxime S 曰, nonyl phenoxy polyalkylene glycol acrylic acid Ester, polypropylene glycol monoacrylic acid S 曰, 双 Α Α 环氧 环氧 ( ( ( ( ( ( ( ( ( ( ( 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧 环氧2 molar propylene oxide and an adduct formed by adding an average of 15 moles of ethylene oxide at both ends One of acrylate, triethylene glycol dodecanol, and polypropylene glycol added to propylene oxide and further added ethylene oxide at both ends (added to an average of 12 moles of propylene oxide) A dialkyl acrylate diacrylate is obtained by adding an average of 3 moles of ethylene oxide to each end of the polypropylene glycol. Among them, preferred are pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate 14948l.doc -13-201111911 ester, bisphenol A diglycidyl ether diacrylate, bisphenol A alkylene oxide adduct dipropionate . In particular, from the viewpoint of achieving good contrast, sensitivity, resolution, and residual film ratio immediately after exposure, the compound having an acrylonitrile group is preferably a compound represented by the following formula (II): 5] H2〇4i

{式中，R2、I、尺4及尺5表示Η，χ及γ分別獨立表示碳數 2〜4之伸烷基，ΧΛγ互不相同，p,、p2、p3、〆 ' 卩5、〆、 P7及P8分別獨立為〇或正整數，ρι、p2、p3、p4、p5 '〆、p7 及p8之合計為0〜2〇的整數}。 本發明之感光性樹脂組合物中之具有丙烯醯基之化合物 的含有比例，較佳為i 而較佳為5〜20質量％。 一45質量％，更佳為1〜30質量％，進 就於剛曝光後具有良好之對比度性 之觀而Q，上述含有比例較佳為i質量％以上，更佳為5 貝1%以上。又，就抑制剝離時殘膜性降低之觀點而言， 較佳為45質量％以下，更佳為3〇質量％以下。 (b)含有至少1種具有丙烯醯基之化合物的乙烯性不飽和 加成聚合性單體， 就解像度方面而言’較佳為含有選自由 14948l.doc 201111911 下述通式（III)所示之能夠光聚合之不飽 的至少 π化合物中 1種： [化6] 〇 r6In the formula, R2, I, 4 and 5 represent Η, χ and γ each independently represent an alkylene group having a carbon number of 2 to 4, and ΧΛγ are different from each other, p, p2, p3, 〆' 卩5, 〆 , P7 and P8 are each independently 正 or a positive integer, and the total of ρι, p2, p3, p4, p5 '〆, p7, and p8 is an integer of 0 to 2 }}. The content of the compound having an acrylonitrile group in the photosensitive resin composition of the present invention is preferably i and preferably 5 to 20% by mass. A content of 45% by mass, more preferably 1 to 30% by mass, has a good contrast ratio immediately after exposure, and the content ratio is preferably i% by mass or more, more preferably 5% by weight or more. Moreover, from the viewpoint of suppressing a decrease in residual film property at the time of peeling, it is preferably 45 mass% or less, more preferably 3 mass% or less. (b) an ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group, and in terms of resolution, preferably contains a compound selected from the group consisting of 14948l.doc 201111911 represented by the following formula (III) One of at least π compounds capable of photopolymerization: 化r6

0-(A-0}-(B-0)-C-C=CH2 I n1 n3 h3c- -CH,0-(A-0}-(B-0)-C-C=CH2 I n1 n3 h3c- -CH,

o-{a-〇Hb-o)-c-c=ch2 n2 n4j|丄 匕 〇 r7 (in)O-{a-〇Hb-o)-c-c=ch2 n2 n4j|丄 匕 〇 r7 (in)

{式中’ R6及R?分別獨立表示H或CH3，A夹TT 衣不C2H4，B表示 C3H6，nl+n2為2〜30之整數，n3+n4為〇〜30之整數，…及2 分別獨立為1〜29之整數，n3及n4分別獨立為〇〜3〇之整數， 並且-(A-Ο)-及-(Β·0)_之重複單元的排列既可為無規亦可 為嵌段}。 作為上述通式（III)所示之化合物，可列舉2,2-雙丙烯 醯氧基聚伸乙基氧基）苯基}丙烧及2,2_雙{(4•甲&amp;丙稀酿氧 基聚伸乙基氧基）苯基}丙烷等。上述通式（III)所示之化合 物所具有的聚伸乙基氧基較佳為選自由如下之基所組成之 群中之任一基：單伸乙基氧基、二伸乙基氧基、三伸乙基 氧基、四伸乙基氧基、五伸乙基氧基、六伸乙基氧基、七 伸乙基氧基、八伸乙基氧基、九伸乙基氧基、十伸乙基氧 基十一伸乙基氧基、十二伸乙基氧基、十三伸乙基氧 基、十四伸乙基氧基、及十五伸乙基氧基。 149481.doc •15- 201111911 又’作為上述通式（III)所示之化合物，亦可列舉2,2-雙 {(4-丙烯醯氧基聚伸烧基氧基）苯基}丙烧及2,2-雙{(4·甲基 丙烯醯氧基聚伸烷基氧基）苯基}丙烷等。作為上述通式 (III)所示之化合物所具有的聚伸烷基氧基，可列舉伸乙基 氧基與伸丙基氧基之混合物，較佳為八伸乙基氧基與二伸 丙基氧基之嵌段結構之加成物或無規結構之加成物、及四 伸乙基氧基與四伸丙基氧基之嵌段結構之加成物或無規結 構之加成物、十五伸乙基氧基與二伸丙基氧基之嵌段結構 之加成物或無規結構之加成物。該等之中，最佳為2,2-雙 {(4-曱基丙烯醯氧基五伸乙基氧基）苯基丨丙烷。 於（b)乙稀性不飽和加成聚合性單體含有上述通式（^)所 示之化合物時’本發明之感光性樹脂組合物中的上述通式 (III)所示之化合物之含有比例較佳為卜⑽質量％，更佳為 5〜30質量％。就於剛曝光後具有良好的對比度性之觀點而 言，上述含有比例較佳為丨質量％以上，又，就抑制解像 性及密接性降低之觀點而言，較佳為4〇質量％以下。 作為（b)乙烯性不飽和加成聚合性單體，可使用例如下 述所示之此夠光聚合之不飽和化合物，與上述具有丙烯醯 基之化合物及通式（ΠΙ)所示之化合物組合，或替代上述具 有丙烯醯基之化合物及通式（111)所示之化合物。即，可列 舉.1，6-己二醇二曱基丙烯酸酯、丨，4_環己二醇二曱基丙 烯酸酯、聚丙二醇二甲基丙烯酸酯、聚乙二醇二曱基丙烯 1 g曰2 — —（對备基苯基）丙院二甲基丙浠酸酯、甘油二甲 土丙烯IS曰、二赵甲基丙烧三曱基丙稀酸酯、聚氧丙某二 14948l.docIn the formula, R6 and R? respectively represent H or CH3, A clip TT clothing is not C2H4, B represents C3H6, nl+n2 is an integer of 2~30, n3+n4 is an integer of 〇~30, ... and 2 respectively Independently an integer from 1 to 29, n3 and n4 are each independently an integer of 〇~3〇, and the arrangement of the repeating units of -(A-Ο)- and -(Β·0)_ can be either random or Block}. Examples of the compound represented by the above formula (III) include 2,2-bispropenyloxypolyethyloxy)phenyl}propane and 2,2_bis{(4•甲&amp; propylene). Oxygen-polyethyloxy)phenyl}propane and the like. The polyethylidene group which the compound represented by the above formula (III) has is preferably one selected from the group consisting of a monoethyloxy group and a diethylidene group. , tri-ethyloxy, tetra-ethyloxy, penta-ethyloxy, hexaethyloxy, heptaethyloxy, octaethyloxy, hexaethyloxy, Ethyloxyethyl eleven is extended to ethyloxy, dodecylethyloxy, thirteen extended ethyloxy, tetradecylethyloxy, and pentadecylethyloxy. 149481.doc •15-201111911 Further, as the compound represented by the above formula (III), 2,2-bis{(4-propenyloxy-polyalkyleneoxy)phenyl}propene can be also mentioned. 2,2-bis{(4·methacryloxylated polyalkyleneoxy)phenyl}propane, and the like. The polyalkyleneoxy group which the compound represented by the above formula (III) has may be exemplified by a mixture of an ethyloxy group and a propyloxy group, preferably an octaethyloxy group and a di-extension propyl group. An adduct of a block structure of a oxy group or an adduct of a random structure, and an adduct of a block structure of a tetraethyl ethoxy group and a tetrapropyl propyloxy group or an adduct of a random structure An adduct of a block structure of a penta-extension ethyloxy group and a di-propyloxy group or an adduct of a random structure. Among these, 2,2-bis {(4-mercaptopropenyloxypentaethyloxy)phenyl hydrazine propane is preferred. When the (b) ethylenically unsaturated addition polymerizable monomer contains the compound represented by the above formula (^), the content of the compound represented by the above formula (III) in the photosensitive resin composition of the present invention The ratio is preferably (10)% by mass, more preferably 5 to 30% by mass. From the viewpoint of having a good contrast ratio after the exposure, the content ratio is preferably 丨% by mass or more, and is preferably 4% by mass or less from the viewpoint of suppressing the resolution and the adhesion. . As the (b) ethylenically unsaturated addition polymerizable monomer, for example, a photopolymerizable unsaturated compound shown below, a compound having an acrylonitrile group and a compound represented by the formula (ΠΙ) can be used. The compound having the propylene fluorenyl group and the compound represented by the formula (111) are combined or substituted. That is, 1,1,6-hexanediol dimercapto acrylate, hydrazine, 4_cyclohexanediol dimercapto acrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimercapto propylene 1 g曰2 — —(备备基phenyl) propyl dimethyl propyl phthalate, glycerol dimethyl propylene IS 曰, diozomethyl propyl trimethyl acrylate, polyoxy propylene 2 14948l.doc

S •16- 201111911 經甲基丙院三甲基丙婦酸酯、聚氧乙基三羥甲基丙炫三甲 基丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五曱 基丙烯酸酯、三羥甲基丙烷三縮水甘油醚三甲基丙稀酸 酯、雙酚A二縮水甘油醚二甲基丙烯酸酯、卜羥基丙基 (甲基丙烯醯氧基）丙基鄰苯二甲酸酯、苯氧基聚乙二醇甲 基丙烯酸酯、壬基苯氧基聚乙二醇甲基丙烯酸酯、壬基苯 氧基t炫一醇甲基丙烯酸醋、聚丙二醇單甲基丙烯酸酯、 雙紛A之環氧烧加成物（例如於兩端各加成平均5莫耳之環 氧乙院而成之加成物、於兩端各加成平均2莫耳之環氧丙 烷及於兩端各加成平均15莫耳之環氧乙烷而成之加成物） 之二甲基丙烯酸酯、三乙二醇十二丙二醇、於加成環氧丙 烷而成之聚丙二醇上進而於兩端加成環氧乙烷（於加成平 均12莫耳之環氧丙烷而成之聚丙二醇之兩端分別各加成平 均3莫耳之環氧乙烷）而得之聚烷二醇之二甲基丙烯酸酯。 又’作為（b)乙稀性不飽和加成聚合性單體，亦可列舉 胺醋化合物。作為胺酯化合物，例如可列舉：六亞甲基二 異氰酸S旨、曱苯二異氰酸酯及二異氰酸酯化合物、例如 2，2,4-二甲基六亞曱基二異氰酸酯與一分子中具有經基及 (甲基）丙稀酿基之化合物、例如丙烯酸2_羥基丙酯、低聚 丙二醇單曱基丙烯酸酯之胺酯化合物。具體而言有六亞甲 基二異氰酸酯與低聚丙二醇單曱基丙烯酸酯（日本油脂股 份有限公司製造、Blemmer PP1000)之反應物。胺酯化合 物既可單獨使用，亦可併用2種以上。 本电明中所使用之（b)乙;性不飽和加成聚合性單體於 j49481.doc -17- 201111911 感光性樹脂組合物中之含有比例為5〜6〇質量％之範圍，較 佳為10〜50質量％之範圍。就提高感度、解像度及密接性 之觀點而言，上述含有比例為5質量％以上，就抑制邊緣 熔融（edge fuse)之觀點而言，為6〇質量％以下。 (c)光聚合起始劑 本發明之感光性樹脂組合物中的⑷光聚合起始劑含有 N-芳基-α-胺基酸化合物作為必需成分。藉由含有N_芳基_ 心胺基酸化合物可確保良好之感度。其中，就感度方面而 言’特佳為Ν-芳基-α_胺基酸化合物為…苯基甘胺酸。 作為本發明中所使用之（c)光聚合起始劑，較佳為併用 N-芳基-α-胺基酸化合物與吖啶衍生物之系。作為吖啶衍 生物’可列舉：9_苯基。丫咬、9_σ比咬基σ丫咬、9“比哨基。丫 啶、1，2-雙（9-«丫啶基）乙烧、基）丙烷、雙 (9-吖啶基）丁烷、；!，5_雙（9_吖啶基）戊烷、丨，6-雙吖啶基） 己烷、1，7-雙（9个定基）庚燒（旭電化工業股份有限公司製 造、Ν-1717)、Μ-雙（9·α丫咬基）辛烧、雙（9十定基）壬 炫、U0-雙（9十定基）癸炫、lu雙卜丫咬基）十一院、 M2-雙（9-吖啶基）十二烷。 作為（〇光聚合起始劑，除上述所示之化合物以外，亦可 併用其他光聚合起始密丨丨。卜卜声夕土取人* 、始d。此處之先聚合起始劑係指藉由各 種活性光線、例如紫外^ω u次系外線#而活性化，開始聚合之化合 149481.docS •16- 201111911 by methyl propyl trimethyl propyl acrylate, polyoxyethyl trimethylol propyl trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentadecyl acrylate, three Hydroxymethylpropane triglycidyl ether trimethyl acrylate, bisphenol A diglycidyl ether dimethacrylate, hydroxypropyl (methacryloxy) propyl phthalate, Phenoxy polyethylene glycol methacrylate, nonylphenoxy polyethylene glycol methacrylate, nonylphenoxy t-alcohol methacrylic acid vinegar, polypropylene glycol monomethacrylate, double A epoxidized adduct of A (for example, an adduct of an average of 5 moles of epoxy enamel added at both ends, an average of 2 moles of propylene oxide at both ends and at both ends Each of the addition of an average of 15 moles of ethylene oxide to the addition of dimethacrylate, triethylene glycol dodecanide, and polypropylene glycol added to the polypropylene glycol and then at both ends Addition of ethylene oxide (addition of each of the two ends of the polypropylene glycol formed by adding 12 moles of propylene oxide to the average of 3 Diethylene glycol of polyalkylene glycol derived from ethylene oxide of the ear. Further, as the (b) ethylenically unsaturated addition polymerizable monomer, an amine vinegar compound may also be mentioned. Examples of the amine ester compound include hexamethylene diisocyanate, benzene benzene diisocyanate, and a diisocyanate compound, for example, 2,2,4-dimethylhexaadecyl diisocyanate, and one molecule thereof. A compound of a benzyl group and a (meth) propylene group, for example, an amine ester compound of 2-hydroxypropyl acrylate or propylene glycol monodecyl acrylate. Specifically, there is a reactant of hexamethylene diisocyanate and oligomeric polypropylene glycol monodecyl acrylate (manufactured by Nippon Oil Co., Ltd., Blemmer PP1000). The urethane compound may be used singly or in combination of two or more. The content of the (b) B; unsaturated unsaturated addition polymerizable monomer used in the present invention is in the range of 5 to 6 % by mass in the photosensitive resin composition of j49481.doc -17 - 201111911, preferably. It is in the range of 10 to 50% by mass. In view of the improvement of the sensitivity, the resolution, and the adhesion, the content ratio is 5% by mass or more, and from the viewpoint of suppressing the edge fuse, it is 6% by mass or less. (c) Photopolymerization initiator The (4) photopolymerization initiator in the photosensitive resin composition of the invention contains an N-aryl-α-amino acid compound as an essential component. Good sensitivity is ensured by the inclusion of the N_aryl-cardamine acid compound. Among them, in terms of sensitivity, it is particularly preferable that the Ν-aryl-α-amino acid compound is phenylglycine. As the (c) photopolymerization initiator used in the present invention, a combination of an N-aryl-α-amino acid compound and an acridine derivative is preferably used in combination. As the acridine derivative, a 9-phenyl group can be mentioned. Bite, 9_σ than biting base σ bite, 9" than whistle. Acridine, 1,2-bis(9-«acridinyl)ethene, yl)propane, bis(9-acridinyl)butane ,;,,5_bis(9-acridinyl)pentane, hydrazine, 6-bisacridinyl) hexane, 1,7-bis (9 fixed) gypsum (manufactured by Asahi Kasei Kogyo Co., Ltd., Ν-1717), Μ-double (9·α丫 基 base) Xin Shao, double (9 ten fixed base) 壬 Hyun, U0-double (9 ten fixed base) 癸 Hyun, lu double 丫 丫 bite base) M2-bis(9-acridinyl)dodecane. As a (tanning polymerization initiator), in addition to the above-mentioned compounds, other photopolymerization initiations may be used in combination. *, start d. Here, the first polymerization initiator refers to the activation by a variety of active light, such as ultraviolet ^ω u-external line #, to start the polymerization of 149481.doc

S -18- 201111911 '琳，靦類、例如2-乙基葱醒及2·第三丁編，芳香族 ^ :如二苯甲明及安息香’安息香趟類、例如安息香 醚及安息香乙醚…丫啶化合物、例如9·苯基α丫啶，苯偶 酿縮_、例如苯偶醯二甲基_及苯偶醯二乙基縮明。 又’作為上述其他光聚合起始劑，亦可併用9_氧硫‘星 星類、例如9-氧硫•星、2,4_二乙基氧硫㈣或2_氣_9 乳硫叫與級胺化合物、例如二甲基胺基苯甲酸 合物。 又，作為上述其他光聚合起始劑，亦可列舉：肪醋類、 例如1-苯基-1，2-丙二酮_2_〇_苯甲酿基將及卜苯基-工，2-丙二 酮-2-(〇-乙氧基羰基）肟。 (c) 光聚合起始劑於感光性樹脂組合物中之含有比例為 〇·ι質量。〜2〇質量％之範圍。若上述含有比例未達〇1質量 %，則無法獲得‘充分之感度。又，若上述含有比例超過2〇 貝1 /〇，則於曝光時容易產生由通過光罩之光的繞射所引 起之灰霧，其結果解像性惡化。上述含有比例更佳為 〇.1〜15質量％之範圍，進而較佳為〇丨〜⑺質量％之範圍β (d) 隱色染料 作為本發明之感光性樹脂組合物中之（句隱色染料，可 列舉隱色結晶紫、熒烷染料等。其中，於使用隱色結晶紫 時，剛曝光後之對比度良好而較佳。作為熒烷染料，例如 可列舉：3-二乙基胺基-6-曱基-7-苯胺基熒烷、3-二丁基胺 基-6-曱基-7-苯胺基熒烷、2-(2-氯苯胺基）-6-二丁基胺基熒 烷、2-溴-3-曱基-6-二丁基胺基熒烷、2-Ν,Ν-二苄基胺基- 14948l.doc 19 201111911 6-二乙基胺基熒烷、3-二乙基胺基-7-氣膦基熒烷、3,6-二 甲氧基熒烷、3-二乙基胺基-6-甲氧基-7-胺基熒烷等。 (d) 隱色染料於感光性樹脂組合物中之含有比例為 0.1〜10質量％之範圍，較佳為0.1〜5質量％之範圍，更佳為 0.5〜3質量％之範圍。就表現充分之岡，J曝光後之對比度的觀 點而言，上述含有比例為0.1質量％以上，又，就維持保存 穩定性之觀點而言，為1〇質量％以下。 (e) 毓基噻二唑化合物 本發明之感光性樹脂組合物中之（e)巯基噻二唑化合物係 下述通式（I)所示之化合物： [化7]S -18- 201111911 'Lin, scorpion, such as 2-ethyl onion and 2 · third butyl, aromatic ^: such as dibenzamine and benzoin 'benzoin, such as benzoin ether and benzoin ether...丫A pyridine compound, for example, 9 phenyl alpha acridine, benzoin condensed _, such as benzoin dimethyl _ and benzoin diethyl condensed. In addition, as the other photopolymerization initiators mentioned above, 9-oxysulfide 'stars, such as 9-oxo-sulfur-star, 2,4-diethyloxysulfide (tetra) or 2_gas--9 thiol is also used together. Amine compound, such as dimethylaminobenzoic acid. Further, examples of the other photopolymerization initiator include a fatty vinegar such as 1-phenyl-1,2-propanedione-2-indole benzoyl and phenyl-based, 2 - Malondione-2-(anthracene-ethoxycarbonyl) hydrazine. (c) The photopolymerization initiator is contained in the photosensitive resin composition in a proportion of 〇·ι mass. ~2〇% by mass range. If the above content ratio is less than 1% by mass, "sufficient sensitivity" cannot be obtained. Further, when the content ratio exceeds 2 〇 1 / 〇, fogging caused by diffraction of light passing through the reticle is likely to occur during exposure, and as a result, the resolution is deteriorated. The content ratio is more preferably in the range of from 1 to 15% by mass, further preferably in the range of from 〇丨 to (7)% by mass. (d) a leuco dye is used as the photosensitive resin composition of the present invention. Examples of the dye include leuco crystal violet, a fluoran dye, etc. Among them, when leuco crystal violet is used, the contrast immediately after exposure is good, and preferred is a fluoran dye, for example, 3-diethylamino group. -6-mercapto-7-anilinofluoran, 3-dibutylamino-6-mercapto-7-anilinofluoran, 2-(2-chloroanilino)-6-dibutylamino Fluorane, 2-bromo-3-indolyl-6-dibutylaminofluoran, 2-indole, fluorenyl-dibenzylamino- 14948l.doc 19 201111911 6-diethylaminofluoran, 3 2-Diethylamino-7-phosphinylfluoran, 3,6-dimethoxyfluoran, 3-diethylamino-6-methoxy-7-aminofluoran, etc. (d The content of the leuco dye in the photosensitive resin composition is in the range of 0.1 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass. From the viewpoint of the contrast after exposure of J, the above content ratio is 0.1 mass. In addition, it is 1% by mass or less from the viewpoint of maintaining storage stability. (e) Mercaptothiadiazole compound (e) a mercapto thiadiazole compound in the photosensitive resin composition of the present invention a compound of the formula (I): [Chemical 7]

HS 會 (I) {式中，Ri表示選自由碳數^之烷基、碳數1〜9之烷氧 基、碳數1〜16之烷硫基、巯基、胺基、及碳數id之烷基 胺基所組成之群中之1種基}。 作為（e)锍基噻二唑化合物，例如可列舉：5_曱基_2酼 基]，3,4-噻二唑、5_乙基_2·巯基-1，3,4-噻二唑、5_正丙基_ 2-巯基-1，3,4-噻二唑、5_異丙基_2_巯基·^乒噻二唑、弘 甲氧基-2-疏基-l，3，m %乙氡基_2_疏基嗟二 。坐、5_正丙氧基疏基-1，3,4-。塞二唑、5-異丙氧基_2·魏 基-1，3,4嘆一坐、5-甲硫基_2_疏基-1,3,4_。塞二唑、5-乙硫 基-2-魏基-1，3,4-嗟二D坐、5_正丙硫基_2_毓基山^·嗟二 149481.doc 2〇HS (I) wherein R represents an alkyl group selected from the group consisting of a carbon number, an alkoxy group having 1 to 9 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an anthracenyl group, an amine group, and a carbon number id. One of the groups consisting of alkylamino groups}. As the (e) mercaptothiadiazole compound, for example, 5-indenyl-2-indenyl, 3,4-thiadiazole, 5-ethyl-2-indolyl-1,3,4-thiadi Azole, 5_n-propyl-2-nonyl-1,3,4-thiadiazole, 5-isopropyl-2-ylidene thiophene, hydrolyzyl-2-sulfonyl-l, 3, m % ethyl hydrazino 2 _ base 嗟 two. Sit, 5_-n-propoxy-based 1,3,4-. Seoxadiazole, 5-isopropoxy-2-ribulin-1,3,4 sigh, 5-methylthio-2-disyl-1,3,4_. Saidazole, 5-ethylthio-2-weiry-1,3,4-anthracene 2D, 5_n-propylthio 2 毓 山 山 149 149481.doc 2〇

S 201111911 唑、5-異丙硫基_2_酼基_ι，3,4-噻二唑、2_胺基_5_巯基_ 1，3,4塞一唾、5-曱基胺基_2·疏基— 嚷二唾、2,5_二疏 基-1，3,4-。塞二β坐等。 特別是5-甲硫基-2-巯基噻二唑、2_胺基·5_酼基_ 1，3,4塞—唾、5-甲基胺基_2-疏基_ι，3,4_0塞二唑及2,5-二疏 基-1，3,4-噻二唑因感度、密接性及剛曝光後之對比度性能 較高而可較佳地使用。該等可單獨使用或將2種以上組合 使用。 (e)巯基噻二唑化合物於感光性樹脂組合物中之含有比 例為0.01〜5質里％之範圍，較佳為〇〇5〜3質量。/◦之範圍，最 佳為0.1〜2質量％之範圍。就獲得充分之感度及密接性、以 及對比度之觀點而言，上述含有比例為〇 〇1質量％以上， 又，就維持保存穩定性之觀點而言，為5質量％以下。再 者由於（e)巯基噻二唑化合物於常溫下為粉體，因此上述含 有比例典型的是固體成分比例。 於本奴明中，較佳為於感光性樹脂組合物中含有鹵化 物。於此情形下，藉由將（句隱色染料與南化物組合使用， 可使密接性及剛曝光後之對比度更加良好。 作為鹵化物，例如可列舉：溴戊烷、溴異戊烷、溴異丁 烷、1，2-二溴乙烷、溴二苯基甲烷、二溴▼苯、二溴甲 烷、二溴甲基苯基硬、四溴化碳、磷酸三（2,3-二溴丙基） 酯、三氯乙醯胺、碘戊烷、碘異丁烷、i，】，卜三氯_2,2_雙 (對氣苯基）乙烷、六氯乙烷、鹵化三畊化合物等。 於本發明中使用自化物時，感光性樹脂組合物令之鹵化S 201111911 oxazole, 5-isopropylthio 2-indolyl_ι, 3,4-thiadiazole, 2-amino- 5-fluorenyl-1,3,4-salt, 5-nonylamino _2·Sparing-based — sputum, 2,5_di-salaki-1,3,4-. Sai II β waits. In particular, 5-methylthio-2-mercaptothiadiazole, 2-amino-5-indenyl-1,3,4-salt-salt, 5-methylamino-2-sulfoyl-ι,3, 4_0 stopper diazole and 2,5-dioxa-1,3,4-thiadiazole are preferably used because of their high sensitivity, adhesion, and contrast performance immediately after exposure. These may be used alone or in combination of two or more. The content of the (e) mercapto thiadiazole compound in the photosensitive resin composition is in the range of 0.01 to 5 % by mass, preferably 〇〇 5 to 3 by mass. The range of /◦ is preferably in the range of 0.1 to 2% by mass. The content ratio is 〇 质量 1% by mass or more, and 5% by mass or less from the viewpoint of maintaining storage stability from the viewpoint of obtaining sufficient sensitivity, adhesion, and contrast. Further, since the (e) mercaptothiadiazole compound is a powder at normal temperature, the above content ratio is typically a solid content ratio. In Benno, it is preferred to contain a halogenated product in the photosensitive resin composition. In this case, by using a combination of a leuco dye and a sulphate, the adhesion and the contrast immediately after exposure can be made better. Examples of the halide include bromopentane, bromoisopentane, and bromine. Isobutane, 1,2-dibromoethane, bromodiphenylmethane, dibromo-tert-benzene, dibromomethane, dibromomethylphenyl hard, carbon tetrabromide, tris(2,3-dibromopropyl phosphate) Ester, trichloroacetamide, iodopentane, iodoisobutane, i,], trichloro-2,2_bis(p-phenylphenyl)ethane, hexachloroethane, halogenated tri-grid compound The photosensitive resin composition is halogenated when the self-chemical is used in the present invention.

149481.doc •21· 201111911 物之含量較佳為0.01〜5質量％，更佳為〇.〇5~3質量％。 於本發明中，為提高感光性樹脂組合物之操作性，除上 述（d)隱色染料外，亦可使感光性樹脂組合物中含有著色物 質。作為著色物質’例如可列舉：品紅（fuchsin)、酿菁綠 (phthalocyanine green)、金黃胺驗（auramine base)、對品紅 (paramagenta)、結晶紫（crystal vi〇let)、甲基橙、尼羅藍 (Nile blue)-2B、維多利亞藍（vict〇ria blue)、孔雀綠 (malachite green)(例如保土 谷化學（H〇d〇gaya Chemicai)股 份有限公司製造之AIZEN(註冊商標）MALACmTE GREEN)、驗性藍（basic blue)_2〇、鑽石綠（d — green)(例如保土谷化學股份有限公司製造之aizen(註冊 商標）DIAMOND GREEN GH)等。 於使用上述著色物質時，感光性樹脂組合物中之著色物 質之含有比例較佳為❹川^〜丨質量％，更佳為〇 〇1〜〇丨質量 %。於上述含有比例為〇.〇〇1質量％以上時，操作性提高之 效果良好，於為1質量％以下時，維持保存穩定性之效果 良好。 又，為提高本發明中之感光性樹脂組合物之熱穩定性及 保存穩定性，亦可使感光性樹脂組合物中含有穩定劑。作 為穩定劑，例如可列舉：對甲氧基苯酚、對苯二酚、鄰苯 一酴;胺、弟二丁基鄰苯二盼、氯化亞鋼、26-二_第：： 丁基-對甲酚、2,2，·亞甲基雙(4_乙基_6_第三丁基苯酚 2,2’-亞甲基雙(&quot;基_6_第三丁基苯酚)、n_亞硝基二苯胺 等。又，.亦可列舉：苯并三唑、羧基苯并三唑、^(2二烷 J 49481 .doc149481.doc •21·201111911 The content of the substance is preferably 0.01 to 5% by mass, more preferably 〇.〇5 to 3% by mass. In the present invention, in order to improve the handleability of the photosensitive resin composition, in addition to the above (d) leuco dye, the photosensitive resin composition may contain a coloring matter. Examples of the coloring matter include fuchsin, phthalocyanine green, auramine base, paramagenta, crystal vi〇let, and methyl orange. Nile blue-2B, Victium blue, malachite green (eg AIZEN (registered trademark) MALACmTE GREEN manufactured by H〇d〇gaya Chemicai Co., Ltd. ), blue (2), diamond green (d-green) (for example, aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). In the case of using the above-mentioned coloring matter, the content ratio of the coloring matter in the photosensitive resin composition is preferably ❹川^丨% by mass, more preferably 〇1 to 〇丨% by mass. When the content ratio is 〇.〇〇1% by mass or more, the effect of improving workability is good, and when it is 1% by mass or less, the effect of maintaining storage stability is good. Moreover, in order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, a stabilizer may be contained in the photosensitive resin composition. Examples of the stabilizer include p-methoxyphenol, hydroquinone, o-benzoquinone; amine, dibutyl phthalate, chlorinated steel, 26-di-:: butyl- P-cresol, 2,2,·methylenebis(4_ethyl_6_t-butylphenol 2,2'-methylenebis(&quot;yl_6_t-butylphenol), n _Nitroso-diphenylamine, etc. Also, may also be listed as: benzotriazole, carboxybenzotriazole, ^ (2 dioxane J 49481 .doc

S -22- 201111911S -22- 201111911

基胺基）羧基苯并三唑、季戊四醇_3,5二_第三丁基_4_羥基 苯基丙酸四酯等。 A 於使用上述穩定劑時，感光性樹脂組合物中之穩定劑之 含有比例4父佳為0.01〜3質量％，更佳為0 05H質量％。上述 含有比例為0.01質量％以上時，對感光性樹脂組合物賦予 保存穩定性之效果良好，於為3質量％以下時，維持感度 之效果良好。 進而於本發明之感光性樹脂組合物中，視需要亦可含有 塑化劑。作為塑化劑，可列舉：鄰苯二甲酸酯類例如鄰苯 二甲酸二乙酯、鄰甲苯磺醯胺、對甲苯磺醯胺、檸檬酸三 丁酯、檸檬酸三乙酯、乙醯基檸檬酸三乙酯、乙醯基檸檬 酸三正丙酯、乙醯基檸檬酸三正丁酯、聚丙二醇、聚乙二 醇、聚乙二醇烷基醚、聚丙二醇烷基醚等。於含有上述塑 化劑時’感光性樹脂組合物中之塑化劑之含有比例較佳為 5〜50質量％，更佳為5〜30質量％。於上述含有比例為⑽質 量％以下時，抑制顯影時間之延遲並對硬化膜賦予柔軟性 之效果良好，於為5質量％以上時，抑制硬化不足或冷流 (cold fl〇w)之效果良好。 &lt;感光性樹脂積層體&gt; 本發明亦提供一種於包含基材膜之支持體上積層包含上 述本發明之感光性樹脂組合物之感光性樹脂層而成的感光 性樹脂積層體。本發明之感光性樹脂積層體具有感光性樹 脂層、及支持該感光性樹脂層之包含基材膜的支持體，視 需要亦可於感光性樹脂層之與支持體相對側之表面具有保 149481.doc -23- 201111911 護層。 作為基材膜’較理想的是使自曝光光源射出之光透過的 透明基材膜。作為此種基材膜，例如可列舉：聚對苯二曱 酸乙二醋膜、聚乙稀醇膜、聚氯乙婦膜、氯乙婦共聚物 膜、聚偏二氯乙烯膜、偏二氣乙烯共聚物膜、”基丙烯 酸曱醋共聚物膜、聚笨乙烯膜、聚丙烯腈膜'苯乙稀共聚 物膜、聚酿胺膜、纖維素衍生物膜等。該等膜視需要亦可 使用經延伸者。基材膜之霧度較佳為5以下。雖然膜之厚 度較薄者於圖像形成性及經濟性方面有利，但由於需要維 持強度，因此較佳為10〜30 μηι。 又，關於在感光性樹脂積層體中視需要而使用之保護層 的重要特性，與支持體相比保護層與感光性樹脂層之密接 力足夠小，可容易地剝離。例如聚乙烯膜及聚丙烯膜可較 好地用作保護層。又，例如可使用日本專利特開昭59_ 202457號公報中揭示之剝離性優異之膜。保護層之膜厚較 佳為10〜1〇〇4111，更佳為1〇〜5()^1111。 本發明之感光性樹脂積層體中之感光性樹脂層的厚度根 據用途而不同，較佳為5〜1〇〇 μιη，更佳為7〜6〇 ，越薄 則解像度越提高，又，越厚則膜強度越提高。 作為依序積層支持®、感光性樹脂I、及視需要之保護 層而製作本發明之感光性樹脂積層體的方法，可採用先前 已去之方;{列如使感光性樹脂層甲所使用之感光性樹脂 組合物與溶解其之溶劑混合而製成均勻之溶液，首先使用 棒塗機或缝缺支㈣上塗㈣錢錢行乾燥，而於 149481.docAminoamino)carboxybenzotriazole, pentaerythritol _3,5-di-tert-butyl-4-hydroxy phenylpropionic acid tetraester, and the like. When the above stabilizer is used, the content ratio of the stabilizer in the photosensitive resin composition is preferably from 0.01 to 3% by mass, more preferably from 00.5 % by mass. When the content is 0.01% by mass or more, the effect of imparting storage stability to the photosensitive resin composition is good, and when it is 3% by mass or less, the effect of maintaining sensitivity is good. Further, the photosensitive resin composition of the present invention may contain a plasticizer as needed. Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, and ethyl hydrazine. Triethyl citrate, tri-n-propyl ethyl citrate, tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. When the plasticizer is contained, the content of the plasticizer in the photosensitive resin composition is preferably from 5 to 50% by mass, more preferably from 5 to 30% by mass. When the content ratio is (10)% by mass or less, the effect of suppressing the delay of the development time and imparting flexibility to the cured film is good, and when the content is 5 mass% or more, the effect of suppressing insufficient hardening or cold flow is good. . &lt;Photosensitive Resin Laminate&gt; The present invention also provides a photosensitive resin laminate in which a photosensitive resin layer containing the photosensitive resin composition of the present invention is laminated on a support comprising a substrate film. The photosensitive resin laminate of the present invention has a photosensitive resin layer and a support comprising a base film which supports the photosensitive resin layer, and may have a surface on the opposite side of the photosensitive resin layer from the support, if necessary. .doc -23- 201111911 Cover. The substrate film ' is preferably a transparent substrate film that transmits light emitted from the exposure light source. Examples of such a substrate film include a polyethylene terephthalate film, a polyethylene glycol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, and a second embodiment. a gas ethylene copolymer film, a "acrylic ruthenium vinegar copolymer film, a polystyrene film, a polyacrylonitrile film" styrene copolymer film, a polyamine film, a cellulose derivative film, etc. The stretcher may be used. The haze of the base film is preferably 5 or less. Although the thickness of the film is thin, it is advantageous in terms of image formability and economy, but it is preferably 10 to 30 μm because it is required to maintain strength. In addition, as for the important characteristics of the protective layer which is used as needed in the photosensitive resin laminate, the adhesion between the protective layer and the photosensitive resin layer is sufficiently smaller than that of the support, and can be easily peeled off. For example, polyethylene film and poly The propylene film can be preferably used as a protective layer. For example, a film having excellent releasability as disclosed in JP-A-59-202457 can be used. The film thickness of the protective layer is preferably 10 to 1 〇〇 4111. Preferably, it is 1〇~5()^1111. The photosensitive resin product of the present invention The thickness of the photosensitive resin layer in the layer differs depending on the application, and is preferably 5 to 1 μm, more preferably 7 to 6 Å. The thinner the resolution is, the thicker the film strength is. As a method of producing the photosensitive resin laminate of the present invention as a sequential build-up support®, a photosensitive resin I, and an optional protective layer, a method which has been previously used can be used; {column is used for a photosensitive resin layer A The photosensitive resin composition is mixed with the solvent in which it is dissolved to prepare a homogeneous solution, firstly dried by using a bar coater or a slit (4) coating (4), and 149481.doc

S •24· 201111911 支持體上積層包含感光性樹脂組合物之感光性樹脂層。繼 而’視需要於感光性樹脂層上貼合保護層，藉此可製作感 光性樹脂積層體。 作為上述溶劑，可列舉：以甲基乙基酮（MEK)為代表之 嗣類，及以甲醇、乙醇及異丙醇為代表之醇類。以塗佈於 支持體上之感光性樹脂組合物之溶液的黏度於饥下成為 5〇〇〜侧mPa. s之方式，於感光性樹脂組合物中添加溶 劑。 &lt;光阻圖案之形成方法&gt; 上述本發明之感純樹脂組合物及感光性樹脂積層體可 用於形成負型光阻圖案。本發明亦提供—種光阻圖案之形 成方法，纟包括以下步驟：積層步驟，將上述本發明之感 光性樹脂積層體積層於基板上；曝光步驟，對感光性樹脂 積層體中之感光性樹脂層進行曝光；及顯影步驟，將感光 性樹脂層之未曝光部分顯影去除。以下表示具體方法之一 例0 作為基板，於以製造印職路板為目㈣，可列舉㈣ 積屬板’ X，於以製造凹凸基材為目的時，可列舉：塗佈 有玻璃肋漿料之玻璃基板、例如電漿顯示面板用基板、表 面電解顯示器基板、有機EL密封蓋用基板、形成有貫通孔 之矽晶圓及陶瓷基板。所謂電漿顯示器用基板，係於玻璃 上形成電極後，塗佈介電體層，繼而塗佈隔離壁用玻璃衆 料’並對隔離㈣玻璃漿料部分實施切加工而形成隔離壁 之基板。對該等基板實施喷砂步驟而成者成為凹凸基材。 149481.doc •25- 201111911 [積層步驟] 於積層步驟中，使用例如貼合機等將感光性樹脂積層體 積層於基板上。於感光性樹脂積層體具有保護層時，將保 «•蒦層剝離後，藉由貼合機將感光性樹脂層加熱壓接於基板 表面而積層。此時，感光性樹脂層可僅積層於基板表面之 單面上，亦可積層於兩面。此時之加熱溫度通常為 40〜160 C。又，錯由進行2次以上該加熱壓接可提高密接 性及耐化學藥品性。此時，壓接可使用具備二聯輥之二段 式貼合機，亦可使感光性樹脂積層體與基板反覆幾次通過 輥進行壓接。 [曝光步驟] 繼而，於曝光步驟中，使用曝光機對感光性樹脂積層體 中之感光性樹脂層進行曝光。若有必要則於曝光前將支持 體剝離，通過光罩藉由活性光進行曝光。曝光量藉由光源 照度及曝光時間而決定，可使用光量計進行測定。又，曝 光步驟亦可藉由刻寫圖案之直接刻寫而進行。直接刻寫曝 光方法係不使用光罩而於基板上直接刻寫並曝光之方法。 作為光源，例如可使用波長為35〇〜41〇 nm2半導體雷射或 超高壓水銀燈。刻寫圖案藉由計算機來控制，此時之曝光 ®藉由光源照度及基板之移動速度而決定。 [顯影步驟] 於顯影步驟中，使用顯影裝置將感光性樹脂層之未曝光 部分顯影去除。曝光後，於感光性樹脂層上具有支持體 寺視而要將其去除，繼而使用鹼性水溶液之顯影液將未 149481 .docS • 24· 201111911 A photosensitive resin layer containing a photosensitive resin composition is laminated on the support. Then, a protective layer is bonded to the photosensitive resin layer as needed, whereby a photosensitive resin laminate can be produced. Examples of the solvent include an anthracene represented by methyl ethyl ketone (MEK), and an alcohol represented by methanol, ethanol and isopropyl alcohol. The solvent is added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied to the support is 5 〇〇 to mPa. s. &lt;Method of Forming Photoresist Pattern&gt; The above-described sensible resin composition and photosensitive resin laminate of the present invention can be used to form a negative resist pattern. The present invention also provides a method for forming a photoresist pattern, comprising the steps of: laminating a layer of the photosensitive resin layer of the present invention on a substrate; and exposing the photosensitive resin in the photosensitive resin laminate The layer is exposed; and the developing step is performed to remove the unexposed portion of the photosensitive resin layer. In the following, an example of a specific method is shown as a substrate. For the purpose of producing a printed circuit board (four), (4) a laminated board 'X is used. For the purpose of producing a textured substrate, a glass rib paste is applied. The glass substrate, for example, the substrate for a plasma display panel, the surface electrolytic display substrate, the substrate for an organic EL sealing cover, the tantalum wafer in which the through holes are formed, and the ceramic substrate. In the substrate for a plasma display, after forming an electrode on a glass, a dielectric layer is applied, and then the glass material for the partition wall is applied, and the insulating (four) glass paste portion is subjected to a cutting process to form a substrate of the partition wall. The blasting step is performed on the substrates to form an uneven substrate. 149481.doc •25-201111911 [Laminating step] In the lamination step, a photosensitive resin layer is laminated on a substrate using, for example, a laminator. When the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heated and pressure-bonded to the surface of the substrate by a bonding machine to be laminated. In this case, the photosensitive resin layer may be laminated only on one surface of the substrate surface, or may be laminated on both surfaces. The heating temperature at this time is usually 40 to 160 C. Further, by performing the thermocompression bonding twice or more, the adhesion and the chemical resistance can be improved. In this case, a two-stage laminating machine having a double roll can be used for the pressure bonding, and the photosensitive resin laminate can be pressure-bonded by a roller several times over the substrate. [Exposure Step] Then, in the exposure step, the photosensitive resin layer in the photosensitive resin laminate is exposed using an exposure machine. If necessary, the support is peeled off before exposure, and exposure is performed by active light through a photomask. The amount of exposure is determined by the illuminance of the light source and the exposure time, and can be measured using a light meter. Further, the exposing step can also be performed by direct writing of the writing pattern. The direct writing exposure method is a method of directly writing and exposing on a substrate without using a mask. As the light source, for example, a semiconductor laser or an ultrahigh pressure mercury lamp having a wavelength of 35 〇 to 41 〇 nm 2 can be used. The engraving pattern is controlled by a computer, and the exposure ® at this time is determined by the illumination of the light source and the moving speed of the substrate. [Developing Step] In the developing step, the unexposed portion of the photosensitive resin layer is developed and removed using a developing device. After exposure, the support is removed on the photosensitive resin layer, and then the developer using an alkaline aqueous solution will not be 149481.doc

S -26- 201111911 曝光部分顯影去除’而獲得光阻圖案。作為驗性水溶液， 例如可使用ΝΜΧ&gt;3或K2C〇&lt;水溶液。該等可根據感光性 樹脂層之特性而進行選擇，通常為濃度〇_2〜2質量％、溫度 20〜40C之Na2C〇3水溶液。該驗性水溶液中亦可混入表面 活性劑、消泡劑、用以促進顯影之少量有機溶劑等。 雖然可藉由上述㈣而獲得光阻㈣，但根據情況亦可 進一步進行⑽〜·。C之加熱步驟。藉由實施該加熱步 驟，可進-步提高耐化學藥品性。加熱可使用熱風、紅外 線或遠紅外線之方式的加熱爐。 〈導體圖案之製造方法及印刷線路板之製造方法〉 本:明可較好地應用於導體圓案之製造方法及印刷線路 板之製造方法。例如使用銅箱積層板或可撓性基板作為基 板’藉由繼上述光阻圖案之形成方法後經由以下步驟，可 製造導體圖案及印刷線路板。 首先，利用先前公知之方法，對藉由上述本發明之光阻 形成方法中的顯影而露出之基板之銅面進行蝕刻或鍍敷， 而形成導體圖案。 /、後H由具有強於顯影液之驗性之水溶液將光阻圖案 自基板剝離而獲得所f之印刷線路板。剝㈣㈣水溶液 (以下亦稱為「剝離液」）並無特別限制，通常使用濃度為 2〜5質量％、溫度為4〇〜7〇t2Na〇H或k〇h之水溶液。剝 離液中亦可添加少量水溶性溶劑。 〈導線架之製造方法&gt; 具體而 本發明亦可較好地應用於導線架之製造方法 149481.doc 5 -27- 201111911 吕，使用金屬板、例如銅、銅合金或鐵系合金之板作為基 板，繼上述光阻圖案之形成方法後經由以下步騾，而製造 導線架。 首先，對藉由光阻圖案之形成方法中之顯影而露出之基 板進行蝕刻而形成導體圖案。其後，以與上述印刷線路板 之製造方法相同之方法剝離光阻圖案，而獲得所需之導線 架。 &lt;半導體封裝體之製造方法&gt; 本發明亦可較好地應用於半導體封裝體之製造方法。具 體而言，使用作為LSI(large sca丨e integrated circuh，大型 積體電路）之電路形成完畢之晶圓作為基板，繼上述光阻 圖案之形成方法後經由以下步驟，藉此可製造半導體封裝 體。 首先，對藉由光阻圖案之形成方法中之顯影而露出之開 口部實施例如銅或焊錫之柱狀鍍敷，形成導體圖案。其 後，以與上述印刷線路板之製造方法相同之方法剝離光阻 圖案’進而藉由餘刻而去除柱狀鍍敷以外之部分的較薄之 金屬層’藉此獲得所需之半導體封裝體。 〈具有凹凸圖案之基材之製造方法&gt; 本發明亦可較好地應用於具有凹凸圖案之基材之製造方 法。在使用本發明之感純樹脂積層體作為乾膜光阻藉由 噴砂工法對基板實施加卫時，使用塗佈有玻璃肋漿料之玻 璃基板作為基板，以與上述方法相同之方法於基板上積層 感光性樹脂積層體，並實施曝光及顯影。 149481.docS -26-201111911 The exposed portion is developed to remove 'to obtain a photoresist pattern. As the aqueous test solution, for example, ΝΜΧ&gt;3 or K2C〇&lt;aqueous solution can be used. These may be selected depending on the characteristics of the photosensitive resin layer, and are usually a Na2C〇3 aqueous solution having a concentration of 〇 2 to 2% by mass and a temperature of 20 to 40C. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the aqueous test solution. Although the photoresist (4) can be obtained by the above (4), (10) ~ can be further carried out depending on the situation. The heating step of C. By carrying out this heating step, the chemical resistance can be further improved. Heating can be done by means of hot air, infrared or far infrared. <Method for Producing Conductor Pattern and Method for Manufacturing Printed Wiring Board> This is a good method for producing a conductor round case and a method for producing a printed wiring board. For example, a copper box laminate or a flexible substrate is used as the substrate. By following the method of forming the photoresist pattern, the conductor pattern and the printed wiring board can be manufactured through the following steps. First, a copper pattern of a substrate exposed by development in the above-described photoresist forming method of the present invention is etched or plated by a conventionally known method to form a conductor pattern. /, After H, the photoresist pattern is peeled off from the substrate by an aqueous solution having an inferiority to the developer to obtain a printed wiring board of the f. The peeling (four) (iv) aqueous solution (hereinafter also referred to as "peeling liquid") is not particularly limited, and an aqueous solution having a concentration of 2 to 5% by mass and a temperature of 4 Torr to 7 Torr 2 Na 〇 H or k 〇 h is usually used. A small amount of water-soluble solvent may also be added to the stripping solution. <Method of Manufacturing Lead Frame> Specifically, the present invention can also be preferably applied to a method of manufacturing a lead frame 149481.doc 5 -27- 201111911, using a metal plate such as a plate of copper, copper alloy or iron alloy as a plate. The substrate is fabricated through the following steps after the method of forming the photoresist pattern. First, a conductor pattern is formed by etching a substrate exposed by development in a photoresist pattern forming method. Thereafter, the photoresist pattern is peeled off in the same manner as in the above-described method of manufacturing a printed wiring board to obtain a desired lead frame. &lt;Manufacturing Method of Semiconductor Package&gt; The present invention can also be preferably applied to a method of manufacturing a semiconductor package. Specifically, a wafer formed as a circuit of an LSI (large sca-e integrated circuit) is used as a substrate, and after the method of forming the photoresist pattern, the semiconductor package can be manufactured through the following steps. . First, a columnar plating such as copper or solder is applied to the opening portion exposed by the development in the photoresist pattern forming method to form a conductor pattern. Thereafter, the photoresist pattern is peeled off in the same manner as in the above-described method of manufacturing a printed wiring board, and a thin metal layer other than the pillar plating is removed by the remainder to thereby obtain a desired semiconductor package. . <Method for Producing Substrate Having Concavo-Concave Pattern> The present invention can also be preferably applied to a method for producing a substrate having a concavo-convex pattern. When the substrate is cured by the sandblasting method using the sensible resin laminate of the present invention as a dry film photoresist, a glass substrate coated with a glass rib slurry is used as a substrate, and the substrate is applied to the substrate in the same manner as the above method. The photosensitive resin laminate is laminated and exposed and developed. 149481.doc

-28- S 201111911 進而’經由自所形成之光阻圖案上吹时擊材料而切削 W度的噴办處理步驟、利用驗性剝離液將殘存於基 上之樹月曰部分自基4去除之剥離步驟，可於基材上加工 微細之凹凸圖荦0竹或4 i , 〃 為上述噴砂處理步驟中所使用之喷擊 材料，可使用公知者，例如可使用以_、叫、Ai2〇3、-28- S 201111911 Further, 'the spraying process step of cutting the W degree by blowing the material from the formed resist pattern, and removing the remaining part of the tree scorpion remaining on the base by the test stripping liquid In the stripping step, a fine uneven pattern 荦0 bamboo or 4 i can be processed on the substrate, and 喷 is used for the blasting material used in the blasting step, and a known material can be used, for example, _, 、, Ai2 〇 3 can be used. ,

CaC〇3、Zr〇、玻璃或不鏽鋼為材質之粒徑為2〜_ _左 右之微粒子。 [實施例] 以下’藉由實施例對本發明之實施形態之例進行詳細說 明。 1.評價用樣品之製作 實知例及比例巾之感光性樹脂積層體藉由如下方 作。 〈感光性樹脂積層體之製作〉 準備表1所示之化合物’將表2及3所示之組成比例之感 光性樹脂組合物充分地攪拌、混合，並使用棒塗機均勻地 塗佈於作為支持體的19 _厚之聚對苯二甲酸乙二酯膜之 表面於95 C之乾燥機中乾燥3分鐘而形成感光性樹脂 層。感光性樹脂層之厚度為3〇 μπι。繼而’於感光性樹脂 層之未積層聚對苯二甲酸乙二自旨膜之表面上，貼合Μ _ 厚之聚乙烯膜作為保護層’而獲得感光性樹脂積層體。再 者，表1中，「Ρ」對應於⑷驗溶性高分子，「Μ1」及「Μ_ 2」對應於（b).乙雜殘和加成聚合性單體巾之能夠光聚 合之不飽和化合物’「M_3」對應於（b)乙稀性不飽和加成 149481.doc -29- 201111911 聚σ丨生單體中之具有丙烯醯基之化合物，「I-1」對應於（c) 光聚合起始劑中之吖啶衍生物，「1-2」對應於（C)光聚合起 始劑中之N-芳基_α_胺基酸化合物，「μ」、「1-4」及「[ 5」對應於（e)巯基噻二唑化合物，「D_i」對應於（d)隱色染 料。又，表2及3中之p之質量份係包含甲基乙基酮之值Q &lt;銅箔積詹板之整面&gt; 使用積層有35 μπΐ壓延銅箔之〇·4 mm厚之銅箔積層板， 藉由喷射洗滌器（jet scrubber)(石井表記股份有限公司製 造）對表面進行研磨。 &lt;積層&gt; 一面將感光性樹脂積層體之聚乙烯膜剝離，一面於作為 預熱至60°C之基板的銅箔積層板上藉由加熱輥貼合機（旭 化成股份有限公司公司製造、AL-70)於親溫度1 05。(：下積 層感光性樹脂積層體。將氣壓設為0·35 MPa，將積層速度 設為 1.5 m/min。 &lt;曝光：直接刻寫方法&gt; 藉由直接刻寫式曝光裝置（曰立比亞機械（Hitachi ViaCaC〇3, Zr〇, glass or stainless steel is a particle with a particle size of 2~_ _ left and right. [Examples] Hereinafter, examples of the embodiments of the present invention will be described in detail by way of examples. 1. Preparation of sample for evaluation The photosensitive resin laminate of the known example and the proportioned towel was produced as follows. <Preparation of Photosensitive Resin Laminate> Preparation of the compound shown in Table 1 The photosensitive resin composition of the composition ratio shown in Tables 2 and 3 was sufficiently stirred and mixed, and uniformly applied as a coating machine using a bar coater. The surface of the 19-thick polyethylene terephthalate film of the support was dried in a 95 C drier for 3 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 3 〇 μπι. Then, a photosensitive resin laminate was obtained by laminating a polyethylene film having a thickness of Μ _ as a protective layer on the surface of the uncoated polyethylene terephthalate film of the photosensitive resin layer. In addition, in Table 1, "Ρ" corresponds to (4) a testable polymer, and "Μ1" and "Μ_2" correspond to (b). Photopolymerizable unsaturated of the ethylidene residue and the addition polymerizable monomer towel. The compound 'M_3' corresponds to (b) the ethylenic unsaturated addition 149481.doc -29- 201111911 polypyroxene monomer having a propylene fluorenyl group, and "I-1" corresponds to (c) light The acridine derivative in the polymerization initiator, "1-2" corresponds to (N) the N-aryl_α-amino acid compound in the photopolymerization initiator, "μ", "1-4" and "[5" corresponds to (e) a mercaptothiadiazole compound, and "D_i" corresponds to (d) a leuco dye. Further, the mass parts of p in Tables 2 and 3 include the value of methyl ethyl ketone Q &lt; the entire surface of the copper foil sheet; &gt; the use of laminated 35 μπΐ rolled copper foil 〇·4 mm thick copper The foil laminate was ground by a jet scrubber (manufactured by Ishii Kee Co., Ltd.). &lt;Laminating&gt; The polyethylene film of the photosensitive resin laminate is peeled off, and is laminated on a copper foil laminate which is a substrate preheated to 60 ° C by a heating roll laminator (Asahi Kasei Co., Ltd., AL-70) is at a temperature of 0.05. (: Lower laminated photosensitive resin laminate. The gas pressure was set to 0·35 MPa, and the lamination speed was set to 1.5 m/min. &lt;Exposure: Direct engraving method&gt; By direct writing exposure apparatus (曰立比亚Machinery (Hitachi Via

Mechanics)股份有限公司製造' DI曝光機de-1 AH、光 源：GaN藍紫二極體、主波長4〇7±3 nm)，以20 mJ/cm2之 曝光量’對積層於銅箔積層板上之感光性樹脂積層體進行 曝光。 &lt;顯影&gt; 將聚對苯二甲酸乙二酯膜剝離後，使用鹼性顯影機 (FUJI KIKO製造、乾膜用顯影機），將30°C之1質量％ 149481.doc 201111911Mechanics) Co., Ltd. manufactures 'DI exposure machine de-1 AH, light source: GaN blue-violet diode, main wavelength 4〇7±3 nm), with an exposure of 20 mJ/cm2 'on layer of copper foil laminate The photosensitive resin laminate was exposed to light. &lt;Development&gt; After the polyethylene terephthalate film was peeled off, an alkaline developing machine (manufactured by FUJI KIKO, a dry film developing machine) was used, and 1% by mass of 30 ° C was used. 149481.doc 201111911

Na2C〇3水溶液噴霧特定時 一 最小顯影時間之2倍時間 洛解去除感光性樹脂層之未 八“…丄 禾曝光#分。此時，將未曝光部 刀之感光性樹脂層完全溶解 m 螂所而要之取少時間作為最小顯 影時間。 2·評價方法 (1) 剛曝光後之對比度評價法 將感光性樹脂層曝光後分別30秒後及i分鐘後，藉由測 色色差計（曰本電色股份有限公司製造之Σ80)，對未曝光 部分與曝光部分之感光性樹脂層敎色差Μ。曝光後川秒 後及1分鐘後之對比度分別如下分級。 ΑΑΑ :厶丑為2.5以上 ΑΑ : ΔΕ為1以上且未達2 5 Β : ΔΕ未達1 (2) 解像度之評價方法 藉由直接曝光而刻寫曝光部分與未曝光部之寬度為ι:ι 之比率的線圖案’並進行顯影。將硬化光阻線未缺失或剝離 而正^形成之最小寬度作為解像度之值。解像度如下分級。 A A : 35 μηι 以下 Α .超過 35 μηι (3) 感度之評價方法 使用明度分21階段自透明變化成黑色之St〇uffer製造之 2 1格階段式曝光表進行曝光並顯影。根據顯影後光阻膜完 王殘存之階段式曝光表格數，如下分級。 AA :光阻膜完全殘存之階段式曝光表格數為5格以上 14948 丨.doc -31 · 201111911 :光阻膜完全殘存之階段式曝光表格數未達5格 (4)殘膜率之評價方法 自聚對苯二曱酸乙二酯膜侧對感光性樹脂積層體進行曝 光’自曝光後之感光性樹脂積層體剝離聚對苯二甲酸乙二 酯膜及聚乙烯膜，並測定硬化膜之質量，然後於5(rc之3 質！ ％ NaOH溶液中攪拌3小時。繼而將Na〇I^#液過濾，使 殘存於濾紙上之硬化膜乾燥並測定質量。將殘存之硬化骐之 質里相對於授拌前之硬化膜之質量之比例作為殘膜率。 AA :殘膜率為25%以上 A :殘膜率未達25% 3·評價結果 將實施例及比較例之評價結果示於表2及3 [表1]The Na2C〇3 aqueous solution is sprayed at a specific time twice as long as the minimum development time to remove the photosensitive resin layer. The photosensitive resin layer of the unexposed portion is completely dissolved. It takes a small amount of time as the minimum development time. 2. Evaluation method (1) The contrast evaluation method immediately after exposure exposes the photosensitive resin layer after 30 seconds and after i minutes, respectively, by colorimetric color difference meter (曰Σ80) manufactured by the Electro-Color Co., Ltd., the color difference between the unexposed portion and the exposed portion of the photosensitive resin layer is Μ. The contrast ratio after the exposure and after 1 minute is respectively classified as follows. ΑΑΑ : 厶 为 is 2.5 or more ΑΑ : ΔΕ is 1 or more and less than 2 5 Β : ΔΕ is less than 1 (2) Evaluation method of resolution The direct line is used to write a line pattern of the ratio of the exposed portion to the unexposed portion with a width of ι:ι and develop The minimum width of the hardened photoresist line is not missing or peeled off and is formed as the resolution. The resolution is graded as follows: AA : 35 μηι or less Α. More than 35 μηι (3) Sensitivity evaluation method using brightness score 21 The segment is exposed and developed by a 2-stage stage exposure meter manufactured by St〇uffer, which is transparent to black. According to the number of staged exposure tables of the photoresist film remaining after development, it is classified as follows. AA: The photoresist film completely remains. The number of staged exposure tables is 5 or more. 14948 丨.doc -31 · 201111911 : The number of staged exposure tables in which the photoresist film completely remains is less than 5 (4) Evaluation method of residual film rate Self-polymerization of terephthalic acid The photosensitive resin laminate is exposed on the ethylene glycol film side. The photosensitive resin laminate after self-exposure is peeled off the polyethylene terephthalate film and the polyethylene film, and the quality of the cured film is measured, and then 5 (rc) 3 !! Stir in the NaOH solution for 3 hours. Then filter the Na〇I^# solution to dry the cured film remaining on the filter paper and measure the quality. The hardened enamel in the remaining material is hardened before the mixing. The ratio of the mass of the film is the residual film rate. AA: Residual film rate is 25% or more A: Residual film rate is less than 25% 3. Evaluation results The evaluation results of the examples and comparative examples are shown in Tables 2 and 3 [Table 1 ]

溶液 干勺刀子$為50,000的共聚物之43質量％(固體成分)曱基乙基酮 甲 之:分環氧乙烧而成的聚乙三 ^丙‘酸酯〈氧丙烷之末*而各加成3莫耳之環氧乙烷而成的聚乙二醇之二 M-3 ^酸酯土 之環氳乙烷而成的聚乙二⑤^ 9-笨基吖咬 基土 二疏基 _隱色結晶紫 3石綠 基苯基灵 l4948l.d〇cThe solution dry spoon knife is 43% by mass of the copolymer of 50,000 (solid content) mercaptoethyl ketone: the end of the epoxy bromide, the poly(tris-propyl) ester, the end of the oxypropane* Addition of 3 moles of ethylene oxide to polyethylene glycol 2 M-3 ^ ester soil ring 氲 ethane to form a polyethylene 2 5 9 - stupid base bite base disulfide _ leuco crystal violet 3 stone green phenyl spirit l4948l.d〇c

S -32 - 201111911S -32 - 201111911

【ϊι——I 149481.doc 實施例9 〇 m in m ο CN o κη O ο 0.04 卜 ο 20 mJ/cm2 1 AAA 1 &lt; AA 實施例8 〇 CO fS o m 〇 气 c&gt; 0.04 r- ο 20 mJ/cm2 1 AAA AAA AA AA &lt; 實施例7 Ο ΓΛ 〇 cn (N 〇 in 〇 d 0-04 卜 ο 20 mJ/cm2 1 AAA AAA ί AA 實施例6 Ο »~Η uo ri CN o 〇 o 0.04 ο 20 mJ/cm2 丨 AAA AAA AA AA AA 實施例5 Ο cn vn r—H (N 〇 o o 0.04 卜 ο 20 mJ/cm2 AAA AAA AA AA 實施例4 Ο m 〇 to F_嶙 (N 〇 o o 0.04 j ο 20 mJ/cm2 ' AA AA AA AA AA 實施例3 Ο m 〇 CN 〇 〇 o 0.04 1 ο 20 mJ/cm2 1 AA AAA AA AA 實施例2 ο m 1—Η o &lt;N 〇 o 寸 o 0.04 r- ο 20 mJ/cm2 AA AAA AA AA 實施例1 ο m cn o (N 〇 o 寸 o 0.04 _1 卜 ο 20 mJ/cm2] AA AAA AA AA AA PL, 1 2 Μ^Π M-3 &lt;N HH m 寸 二 κη 1 Q ㈣ D-3 曝光量 ___________j 對比度(曝光後30秒） 對比度(曝光後1分鐘） 感度 解像度 殘膜率 感光性樹脂組合物(質量份） -33- 201111911 [表3][ϊι——I 149481.doc Example 9 〇m in m ο CN o κη O ο 0.04 ο ο 20 mJ/cm 2 1 AAA 1 &lt; AA Example 8 〇CO fS om 〇气 c&gt; 0.04 r- ο 20 mJ/cm2 1 AAA AAA AA AA &lt;Example 7 Ο 〇 〇cn (N 〇in 〇d 0-04 Bu ο 20 mJ/cm2 1 AAA AAA ί AA Example 6 Ο »~Η uo ri CN o 〇o 0.04 ο 20 mJ/cm2 丨AAA AAA AA AA AA Example 5 Ο cn vn r—H (N 〇oo 0.04 ο ο 20 mJ/cm 2 AAA AAA AA AA Example 4 Ο m 〇to F_嶙 (N 〇oo 0.04 j ο 20 mJ/cm2 ' AA AA AA AA AA Example 3 Ο m 〇CN 〇〇o 0.04 1 ο 20 mJ/cm2 1 AA AAA AA AA Example 2 ο m 1—Η o &lt;N 〇o inch o 0.04 r- ο 20 mJ/cm2 AA AAA AA AA Example 1 ο m cn o (N 〇o inch o 0.04 _1 ο ο 20 mJ/cm2] AA AAA AA AA AA PL, 1 2 Μ^Π M-3 &lt;N HH m Inch 2 κη 1 Q (4) D-3 Exposure amount ___________j Contrast (30 seconds after exposure) Contrast (1 minute after exposure) Sensitivity resolution residual film ratio photosensitive resin composition (parts by mass) -33- 201111911 [table 3]

比較例1 比較例2 比較例3 比較例4 感光性樹脂組合物 (質量份） P 130 130 130 130 M-1 45 45 45 35 M-2 M-3 10 1-1 1 1 1 1 1-2 0.2 0.2 0.2 1-3 0.5 0.5 1-4 1-5 D-1 0.4 0.4 0.4 0.4 D-2 0.04 0.04 0.04 0.04 D-3 0.7 0.7 0.7 0.7 曝光量 20 mJ/cm2 20 mJ/cm2 20 mJ/cm2 20 mJ/cm2 對比度(曝光後30秒） B B B B 對比度(曝光後1分鐘） B B B B 感度 AA A AA AA 解像度 AA AA AA AA 殘膜率 AA AA AA AA *P為投入MEK之質量 [產業上之可利用性] 本發明可較好地用於例如印刷線路板之製造、1C晶片搭 載用導線架之製造、以金屬掩模製造為代表之金屬箔精密 加工、以BGA及CSP為代表之封裝體之製造、以COF及 TAB為代表之捲帶基板之製造、半導體凸塊之製造、以 ITO電極、定址電極及電磁波遮罩為代表之平板顯示器的 隔離壁之製造、以及具有利用噴砂工法所產生之凹凸圖案 的基材之製造。Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Photosensitive resin composition (parts by mass) P 130 130 130 130 M-1 45 45 45 35 M-2 M-3 10 1-1 1 1 1 1 1-2 0.2 0.2 0.2 1-3 0.5 0.5 1-4 1-5 D-1 0.4 0.4 0.4 0.4 D-2 0.04 0.04 0.04 0.04 D-3 0.7 0.7 0.7 0.7 Exposure 20 mJ/cm2 20 mJ/cm2 20 mJ/cm2 20 mJ/cm2 Contrast (30 seconds after exposure) BBBB Contrast (1 minute after exposure) BBBB Sensitivity AA A AA AA Resolution AA AA AA AA Residual film rate AA AA AA AA *P is the quality of input MEK [Industrial Applicability] The present invention can be preferably used, for example, in the manufacture of a printed wiring board, the manufacture of a lead frame for 1C wafer mounting, the precision processing of a metal foil represented by a metal mask manufacturing, and the manufacture of a package represented by BGA and CSP. Manufacture of a tape substrate represented by COF and TAB, manufacture of a semiconductor bump, manufacture of a partition wall of a flat panel display represented by an ITO electrode, an address electrode, and an electromagnetic wave mask, and a concave-convex pattern produced by a sand blasting method The manufacture of substrates.

149481.doc -34- S149481.doc -34- S

Claims (1)

201111911 七、申請專利範圍： 1 · 一種感光性樹脂組合物，其包含：（a)含有缓酸、酸當量 為100〜600、重量平均分子量為5,〇〇〇〜500,000之鹼溶性 高分子：20〜80質量％ ; (b)含有至少2種具有丙烯醯基之 化合物的乙烯性不飽和加成聚合性單體：5〜6〇質量％ ; (c)含有N-芳基-α-胺基酸化合物之光聚合起始劑：〇1〜2〇 質量°/〇 ; (d)隱色染料：0.1〜1〇質量％ ;及（6)下述通式⑴ 所示之Μ基°塞二°坐化合物：0. 〇 1〜5質量％ : [化1] HS、VRi N—N (I) {式中’ 1^表示選自由碳數1〜9之烷基、碳數1〜9之烷氧 基 '碳數1〜16之烷硫基、巯基、胺基及碳數1〜9之烷基 胺基所組成之群中之1種基}。 2.如請求項1之感光性樹脂組合物，其中上述（b)含有炱少1 種具有丙烯醯基之化合物的乙烯性不飽和加成聚合性單 體中之具有丙烯醯基的化合物係下述通式（H)所示之化 合物： [化2] CH2〇{x-〇^Y-〇J-C-C=CH2 p3 p4〇 Η2〇^-ρ&lt;〇-γχ〇-χ}〇Η2(：«Η20·(χ-〇)(γ-〇]·〇-έ=〇Η 0 p2 P1 ^ pS p6〇 ch2o^x-〇^y-〇|c-c=ch2 p7 p8〇 149481.doc (II) 201111911 {式中，尺2、Rq、R ΤΛ _U 尺4及Rs表示Η ’ X及Υ分別獨立表示碳 數2〜4之伸規基，Χ及Υ互不相同，Ρ1、Ρ2、Ρ3、〆、ρ5、 ρ6/ Ρ7及Ρ8分別獨立為G或正整數，ρ]、ρ2、ρ3、ρ4、ρ5、 Ρ、Ρ及ρ8之合計為〇〜2〇的整數 3. 如凊求項1或2之感光性樹脂組合物，其中上述⑷疏基嘆 二唑化合物為選自由5-曱硫基-2-巯基-1，3,4-噻二唑、2_ 胺基-5·疏基·ΐ，3,44:唾、5_甲基胺基_2遵基]，3,4_售 二吐及2,5-二疏基-^4.嘆二唾所組成之群中之至少^ 化合物。 4·如請求項1或2之感光性樹脂組合物，其中上述（c)光聚合 起始劑所含有之上述N_芳基_α_胺基酸化合物為N_苯基甘 胺酸。 5 _如請求項1或2之感光性樹脂組合物，其中上述含有至 少1種具有丙烯醯基之化合物的乙烯性不飽和加成聚合 性單體包含選自由下述通式（111)所示之可光聚合之不飽 和化合物中的至少1種： [化3] 0 r6201111911 VII. Patent application scope: 1 . A photosensitive resin composition comprising: (a) an alkali-soluble polymer containing a slow acid, an acid equivalent of 100 to 600, a weight average molecular weight of 5, and a 〇〇〇~500,000: 20 to 80% by mass; (b) an ethylenically unsaturated addition polymerizable monomer containing at least two compounds having an acrylonitrile group: 5 to 6 % by mass; (c) containing an N-aryl-α-amine Photopolymerization initiator of basic acid compound: 〇1 to 2 〇 mass ° / 〇; (d) leuco dye: 0.1 to 1 〇 mass%; and (6) thiol ° plug shown by the following formula (1) 2° sitting compound: 0. 〇1 to 5 mass%: [Chemical 1] HS, VRi N-N (I) {wherein 1^ represents an alkyl group selected from carbon numbers 1 to 9, carbon number 1 to 9 The alkoxy group is a group of a group consisting of an alkylthio group having 1 to 16 carbon atoms, a mercapto group, an amine group and an alkylamine group having 1 to 9 carbon atoms. 2. The photosensitive resin composition of claim 1, wherein (b) the compound having an acryl oxime group in the ethylenically unsaturated addition polymerizable monomer containing one compound having an acryl fluorenyl group The compound represented by the general formula (H): [Chemical 2] CH2〇{x-〇^Y-〇JCC=CH2 p3 p4〇Η2〇^-ρ&lt;〇-γχ〇-χ}〇Η2(:«Η20 ·(χ-〇)(γ-〇)·〇-έ=〇Η 0 p2 P1 ^ pS p6〇ch2o^x-〇^y-〇|cc=ch2 p7 p8〇149481.doc (II) 201111911 {式Medium, ruler 2, Rq, R ΤΛ _U ruler 4 and Rs indicate that Η 'X and Υ respectively represent the extension number of carbon number 2~4, and Χ and Υ are different from each other, Ρ1, Ρ2, Ρ3, 〆, ρ5, Ρ6/ Ρ7 and Ρ8 are each independently G or a positive integer, and the total of ρ], ρ2, ρ3, ρ4, ρ5, Ρ, Ρ, and ρ8 is an integer of 〇~2〇 3. If the sensitivity of the item 1 or 2 is sought a resin composition wherein the above (4) thiol oxadiazole compound is selected from the group consisting of 5-nonylthio-2-mercapto-1,3,4-thiadiazole, 2-amino-5-sulfenyl hydrazine, 3, 44 : saliva, 5_methylamino 2 compliant, 3, 4 _ sell two spit and 2,5-di-salt-^4. The photosensitive resin composition of claim 1 or 2, wherein the above-mentioned N_aryl_α-amino acid compound contained in the above (c) photopolymerization initiator is N-phenylgan The photosensitive resin composition according to claim 1 or 2, wherein the ethylenically unsaturated addition polymerizable monomer containing at least one compound having an acrylonitrile group is selected from the group consisting of the following formula (111) At least one of the photopolymerizable unsaturated compounds shown: [Chemical 3] 0 r6 o-{a-o}-(b-〇}-c-c=ch2 H3C- -ch3O-{a-o}-(b-〇}-c-c=ch2 H3C- -ch3 CKA-〇KB-〇hi?_?=CH2 02 n〇 r7 (III) 149481.doc 201111911 {式中，R6及R7分別獨立表示11或(：113 , A表示C2H4，]8表 示CsH6 πΐ+η2為2〜30之整數，n3+n4為0〜30之整數，ηι 及n2分別獨立為1〜29之整數，n3及n4分別獨立為〇〜3〇之 in·數並且及-(B-O)-之重複單元的排列既可為無 規亦可為嵌段}。 6. 一種感光性樹脂積層體’其係於包含基材膜之支持體上 積層包含如請求項1或2之感光性樹脂組合物之感光性樹 脂層而成。 7. 一種光阻圖案之形成方法，其包括如下步驟： 積層步驟，將如請求項6之感光性樹脂積層體積層於 基板上； 曝光步驟，對感光性樹脂積層體中之感光性樹脂層進 行曝光；及 顯影步驟，將感光性樹脂層之未曝光部分顯影去除。 8·如請求項7之光阻圖案之形成方法，其中藉由刻寫圖案 之直接刻寫而進行上述曝光步驟。 S 149481.doc 201111911 四、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： HSCKA-〇KB-〇hi?_?=CH2 02 n〇r7 (III) 149481.doc 201111911 {wherein, R6 and R7 respectively represent 11 or (:113, A represents C2H4,]8 represents CsH6 πΐ+η2 An integer of 2 to 30, n3+n4 is an integer of 0 to 30, and ηι and n2 are each independently an integer of 1 to 29, and n3 and n4 are respectively in the number of 〇~3〇 and -(BO)- The arrangement of the repeating units may be either random or block}. A photosensitive resin laminate which is laminated on a support comprising a substrate film and comprises a photosensitive resin combination according to claim 1 or 2. A photosensitive resin layer formed by the method. 7. A method for forming a photoresist pattern, comprising the steps of: laminating a layer of a photosensitive resin layer as claimed in claim 6 on a substrate; and exposing step to a photosensitive resin The photosensitive resin layer in the laminate is exposed; and the developing step is performed to remove the unexposed portion of the photosensitive resin layer. 8. The method for forming a photoresist pattern according to claim 7, wherein the direct writing of the pattern is performed by writing Perform the above exposure steps. S 149481.doc 201111911 IV. Designated representative Figure: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: HS (I) 149481.doc(I) 149481.doc
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