TWI299043B - - Google Patents

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TWI299043B
TWI299043B TW090125377A TW90125377A TWI299043B TW I299043 B TWI299043 B TW I299043B TW 090125377 A TW090125377 A TW 090125377A TW 90125377 A TW90125377 A TW 90125377A TW I299043 B TWI299043 B TW I299043B
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Taiwan
Prior art keywords
film
resin composition
photosensitive
photosensitive resin
polyimine
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TW090125377A
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Chinese (zh)
Inventor
Okada Koji
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Kaneka Corp
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Priority claimed from JP2000315946A external-priority patent/JP2002121207A/en
Priority claimed from JP2000356492A external-priority patent/JP2002162740A/en
Priority claimed from JP2000360199A external-priority patent/JP2002164642A/en
Priority claimed from JP2001078201A external-priority patent/JP4981215B2/en
Priority claimed from JP2001163470A external-priority patent/JP2002258474A/en
Application filed by Kaneka Corp filed Critical Kaneka Corp
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Publication of TWI299043B publication Critical patent/TWI299043B/zh

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    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Description

1299043 A7 _____ B7_____ 五、發明說明（/ ) 〔技術領域〕 本發明係關於加工性、接著劑良好的感光性樹脂組成 物，使用其之感光性膜、防焊膜，以及使用其等之感光性 被覆膜、印刷配線板。本發明之被覆膜，係具有充分的機 械強度，且在較低溫下的加工性、接著性良好，又硬化後 的彈性模數低，而適用於作爲印刷基板用、或硬碟用的被 覆膜。 〔背景技術〕 近年，隨著電子機器之高機能化、高性能化、小型化 的快速進展，對其所使用的電子零件也要求更加小型、輕 量化。因此，關於構裝電子零件用的配線板，相較於通常 的硬質印刷配線板，富可撓性之軟性印刷基板（以下稱 FPC)的需要也急劇地增加。 然而，基於保護形成有電路（銅箔等的導體所構成）之 導體面之目的，FPC會在電路表面貼合聚醯亞胺等所構成 之稱作被覆膜的薄膜。該被覆膜的接著方法，係將單面塗 有接著劑之被覆膜加工成既定形狀，重疊並定位在形成有 電路之銅面積層板(以下稱CCL)後，利用壓機等來進行熱 壓合，此乃一般採用的方法。然而，所使用的接著劑是以1299043 A7 _____ B7_____ V. OBJECT OF THE INVENTION (Technical Field) The present invention relates to a photosensitive resin composition having good processability and an adhesive, a photosensitive film using the same, a solder resist film, and photosensitivity thereof. Coating film, printed wiring board. The coating film of the present invention has sufficient mechanical strength, has good workability and adhesion at a relatively low temperature, and has a low modulus of elasticity after hardening, and is suitable for use as a printed substrate or a hard disk. Laminating. [Background Art] In recent years, with the rapid development of high-performance, high-performance, and miniaturization of electronic equipment, electronic components used for them are required to be smaller and lighter. Therefore, with respect to the wiring board for arranging electronic components, the demand for a flexible flexible printed circuit board (hereinafter referred to as FPC) is drastically increased as compared with a conventional hard printed wiring board. However, for the purpose of protecting the conductor surface on which a circuit (conductor made of a copper foil or the like) is formed, the FPC bonds a film called a coating film made of polyimide or the like to the surface of the circuit. In the method of attaching the coating film, the coating film coated with the adhesive agent on one side is processed into a predetermined shape, and is superposed and positioned on a copper-area laminate (hereinafter referred to as CCL) in which a circuit is formed, and then is carried out by a press or the like. Hot pressing, this is the commonly used method. However, the adhesive used is

I 環氧系、丙烯酸系接著劑爲主流。因此，會有焊接耐熱性 、高溫時的接著強度等之耐熱性差、又缺乏可撓性之問題 ，並無法使聚醯亞胺膜充分發揮其作爲被覆膜來使用的性 能。 又，以往之使用接著劑來接著被覆膜和CCL的情形， 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂--- 1299043 B7 五、發明說明（2 ) (請先閱讀背面之注意事項再填寫本頁) 接著前須先對被覆膜之電路端子部或零件接合部進行鑽孔 或開窗等的加工。然而，不僅在極薄的被覆膜上進行鑽孔 等相當困難，且將鑽孔後的被覆膜在CCL既定位置上進行 定位之定位作業幾乎是採手工作業的狀態，因此，位置精 度低，貼合時的作業性差，且成本變高。 又，亦可在被覆膜和CCL接著後再用雷射或電漿蝕刻 進行鑽孔作業，雖位置精度極佳，但反而會產生鑽孔費時 、裝置本身的成本和運轉成本非常高的問題。 爲了改善前述作業性、鑽孔之位置精度等，已開發出 將感光性組成物塗佈於導體面，藉以形成保護層之方法。 進一步開發出的感光性被覆膜，係貼合在FPC上後，藉由 曝光顯影來形成圖案，即可在必要位置上進行精度良好的 鑽孔。因此作業性及位置精度均有改善。 然而，上述感光性被覆膜，由於是使用一般的丙烯酸 系樹脂，故面臨耐熱溫度低、膜強度低的難題。因此要求 進一步的改善。 然而，作爲具耐熱性且膜本身有強度之感光性素材， 雖有聚醯亞胺，但將感光性聚醯亞胺應用於被覆膜時，由 於聚醯亞胺難溶於一般的溶劑，且難溶於鹼性顯影液，必 須以其前驅物之聚醯胺酸狀態積層在FPC上，經曝光顯影 後使其醯亞胺化。爲進行醯亞胺化，必須250°C以上的溫 度，由於在此高溫下會使以使用環氧樹脂爲主之FPC基板 產生熱劣化，故要將聚醯亞胺適用於FPC會有困難。 雖有開發出溶劑可溶解之感光性聚醯亞胺，例如曰本 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 ___B7_ 五、發明說明（$ ) 特開平6 - 27667號公報中揭示在高分子側鏈具有乙烯醚基 之組成物，但其顯影特性差。 又，隨著硬碟之高記憶容量化和高速化，配線變得更 細，磁頭也不斷的朝小型化發展，而通常是採用在組裝磁 頭之懸吊具上直接形成電路之方法(參照特開昭48 - 16620 號）。例如，硬碟用懸吊具之電路形成用基板或電路基板， 係在長帶狀的不銹鋼箔上形成聚醯亞胺層，用電漿蝕刻或 雷射來進行乾蝕刻後，或用肼等有害的化學品進行濕蝕刻 後，依序形成導體層，經由如此般複雜的製程來作出，由 於製程多且複雜，故成本極高。 於是本發明之目的係提供一感光性樹脂組成物，其可 溶於有機溶劑故處理容易，耐熱性、加工性及接著性良好 ’所得塗膜具有充分的機械強度；並提供使用該感光性樹 脂組成物之防焊劑、具有絕緣被覆膜的效果之被覆膜、及 積層該膜而成之印刷配線板。 〔發明之揭示〕 本發明之感光性樹脂組成物之必須成份爲(A)沸點120 °c以下的溶劑中可溶之可溶性聚醯亞胺，（B)1分子中具有 1個以上芳香環、2個以上雙鍵之化合物；可溶性聚醯亞胺 ，至少可使用 具有1〜6個芳香環之酸酐或脂環式酸二酐、及/或具有 1〜6個二胺而製得。 本發明的感光性樹脂組成物之其他樣態之必須成份爲 (A)沸點120°C以下的溶劑中可溶之可溶性聚醯亞胺，（B)l ^尺度適用(CN^^各（21^2_9;公爱「 --- -------------·1111111 ^«1 — (請先閱讀背面之注意事項再填寫本頁) ♦ 1299043 A7 _ _ B7 五、發明說明（f ) 分子中具有1個以上芳香環、2個以上雙鍵之化合物；（C) 光反應起始劑及/或增感劑；可溶性聚醯亞胺，至少可使用 具有1〜6個芳香環之酸酐或脂環式酸二酐、及/或具有 1〜6個二胺而製得。 前述(A)成份，可包含通式（1)I epoxy-based and acrylic-based adhesives are the mainstream. Therefore, there is a problem that solder heat resistance, heat resistance at the time of high temperature, and the like are poor, and the flexibility is lacking, and the polyimine film cannot sufficiently exhibit its performance as a coating film. In addition, in the past, when an adhesive was used to coat the film and the CCL, 4 the paper size was applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note and fill out this page) -------- Order --- 1299043 B7 V. Invention Description (2) (Please read the note on the back and fill in this page.) Then, the circuit terminal or part joint of the coating must be carried out beforehand. Machining of drilling or windowing. However, it is quite difficult not only to drill holes on an extremely thin coating film, but also to position the coated film after drilling at a predetermined position in the CCL, which is almost a manual operation state, and therefore, the positional accuracy is low. The workability at the time of bonding is poor, and the cost becomes high. In addition, the coating film and the CCL may be followed by laser or plasma etching, and the positional accuracy is excellent, but the problem of time-consuming drilling, cost of the device itself, and high running cost may occur. . In order to improve the workability, the positional accuracy of the drilled hole, and the like, a method of applying a photosensitive composition to a conductor surface to form a protective layer has been developed. Further, the photosensitive coating film which has been developed is bonded to the FPC, and then formed into a pattern by exposure and development, whereby the precision drilling can be performed at a necessary position. Therefore, workability and positional accuracy are improved. However, since the above-mentioned photosensitive coating film is a general acrylic resin, it has a problem that the heat resistance temperature is low and the film strength is low. Therefore, further improvement is required. However, as a photosensitive material having heat resistance and strength of the film itself, although polyimine is used, when a photosensitive polyimide is applied to a coating film, since polyimide is hardly soluble in a general solvent, Moreover, it is difficult to dissolve in an alkaline developing solution, and it must be laminated on the FPC in the polylysine state of its precursor, and after exposure and development, the oxime is imidized. In order to carry out the imidization, it is necessary to have a temperature of 250 ° C or higher, and since the FPC substrate mainly composed of an epoxy resin is thermally deteriorated at this high temperature, it is difficult to apply the polyimide to the FPC. Although a solvent-soluble photosensitive polyimide has been developed, for example, the size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1299043 A7 ___B7_ V. Invention Description ($) JP-A-6-27667 discloses a composition having a vinyl ether group in a polymer side chain, but has poor development characteristics. Moreover, with the high memory capacity and high speed of the hard disk, the wiring becomes finer, and the magnetic head is continuously developed toward miniaturization, and a method of directly forming a circuit on a suspension for assembling a magnetic head is generally used. Kai Zhao 48 - 16620). For example, a substrate for forming a circuit for a hard disk suspension or a circuit substrate is formed by forming a polyimide layer on a long strip of stainless steel foil, dry etching by plasma etching or laser, or using a crucible or the like. After the wet chemical is wet-etched, the conductor layer is sequentially formed, which is made through such a complicated process, and the cost is extremely high due to the complicated and complicated process. Accordingly, an object of the present invention is to provide a photosensitive resin composition which is soluble in an organic solvent, is easy to handle, and has good heat resistance, processability and adhesion. The resulting coating film has sufficient mechanical strength; and the use of the photosensitive resin is provided. A solder resist for a composition, a coating film having an effect of an insulating coating film, and a printed wiring board formed by laminating the film. [Disclosure of the Invention] The essential component of the photosensitive resin composition of the present invention is (A) a soluble polyimine which is soluble in a solvent having a boiling point of 120 ° C or less, and (B) one or more aromatic rings in one molecule. A compound of two or more double bonds; a soluble polyimine, which can be obtained by using at least an acid anhydride having 1 to 6 aromatic rings or an alicyclic acid dianhydride, and/or having 1 to 6 diamines. The other essential components of the photosensitive resin composition of the present invention are (A) soluble polyimine in a solvent having a boiling point of 120 ° C or less, and (B) 1 ^ scale is applicable (CN ^ ^ each (21 ^2_9; 公爱" --- -------------·1111111 ^«1 — (Please read the notes on the back and fill out this page) ♦ 1299043 A7 _ _ B7 V. Invention (f) a compound having one or more aromatic rings and two or more double bonds in the molecule; (C) a photoreaction initiator and/or a sensitizer; and a soluble polyimine having at least 1 to 6 An aromatic ring anhydride or an alicyclic acid dianhydride, and/or having 1 to 6 diamines. The above component (A) may comprise the general formula (1)

N、 R1 NV V -R2 N R1N, R1 NV V -R2 N R1

C R4\ N —R3 、C II Ο η (式中R1爲4價有機基，R2爲2價有機基，R3爲3價有機 基，R4爲羧基或羥基)所代表之聚醯亞胺。 前述通式（1)所代表之聚醯亞胺，可包含COOH當量 200〜3000之可溶性聚醯亞胺。 前述可溶性聚醯亞胺，可用通式（1)代表：C R4 \ N —R 3 , C II Ο η (wherein R 1 is a tetravalent organic group, R 2 is a divalent organic group, R 3 is a trivalent organic group, and R 4 is a carboxyl group or a hydroxyl group). The polyimine represented by the above formula (1) may contain a soluble polyimine having a COOH equivalent of 200 to 3,000. The aforementioned soluble polyimine can be represented by the general formula (1):

NN

Λ -R3- η (式中R1爲4價有機基，R2爲2價有機基，R3爲3價有機 基，R4爲擇自羧基、羥基或群(I) R5 一 R5 -C一 〇 II ΟΛ -R3- η (wherein R1 is a tetravalent organic group, R2 is a divalent organic group, R3 is a trivalent organic group, R4 is selected from a carboxyl group, a hydroxyl group or a group (I) R5-R5-C-〇II Ο

Η 0Η 0

Η 一0—C 一R5 (請先閱讀背面之注意事項再填寫本頁)Η One 0—C one R5 (please read the notes on the back and fill out this page)

· n ·ϋ smmmMm i i ί n 一：OJI n n ϋ ϋ an ϋ ϋ I 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公楚） 1299043 A7 B7 五、發明說明（女） 一C- 〇 II Ο· n ·ϋ smmmMm ii ί n I: OJI nn ϋ ϋ an ϋ ϋ I This paper scale applies to China National Standard (CNS) A4 specification (210 x 297 public Chu) 1299043 A7 B7 V. Invention description (female) One C- 〇II Ο

R5 η〕οη 0R5 η]οη 0

Η R5 I) (式中R5爲具有擇自環氧基、碳-碳三鍵、碳-碳雙鍵所 構成群中之至少一種以上之1價有機基)之有機基）。 前述通式（1)所代表之聚醯亞胺，可使用二胺（包含分 子內具有2個以上COOH基之二胺)而製得。 前述(A)成份，可使用具有矽氧烷鍵之二胺而得之聚醯 亞胺， 前述可溶性聚醯亞胺，可包含通式(2) ίλΗ R5 I) (wherein R5 is an organic group having at least one or more monovalent organic groups selected from the group consisting of an epoxy group, a carbon-carbon triple bond, and a carbon-carbon double bond). The polyimine represented by the above formula (1) can be produced by using a diamine (containing a diamine having two or more COOH groups in a molecule). The above (A) component may be a polyimine obtained by using a diamine having a siloxane coupling, and the above-mentioned soluble polyimine may comprise the general formula (2) λ

ϊ L v〇 R6 γΝ -R7十h2) 十一〒i —(ch2 n (式中R6爲4價有機基，R7爲2價有機基，R8爲1價有機 基，X爲1以上的整數，y爲1以上的整數，z爲1〜40的 整數，η爲1〜5的整數）。 ，前述可溶性聚醯亞胺，可包含在全部二胺中，使用 5〜95莫耳％之擇自通式(3) R8 H2I^CH2)-Si8-ϊ L v〇R6 γΝ -R7 十h2) eleven 〒i —(ch2 n (wherein R6 is a tetravalent organic group, R7 is a divalent organic group, R8 is a monovalent organic group, and X is an integer of 1 or more, y is an integer of 1 or more, z is an integer of 1 to 40, and η is an integer of 1 to 5). The soluble polyimine may be contained in all diamines, using 5 to 95 mol%. General formula (3) R8 H2I^CH2)-Si8-

PH2 卜 NH2 η (式中R8爲碳數1〜η之烷基、苯基、甲氧基，ζ爲1〜4〇之PH2 卜 NH2 η (wherein R8 is an alkyl group having a carbon number of 1 to η, a phenyl group, a methoxy group, and a hydrazine is 1 to 4 Å.

Aw ^--------^-------- (請先閱讀背面之注意事項再填寫本頁) ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公复） 1299043 A7 _B7______ 五、發明說明（έ ) 整數，η分別爲獨立的1〜20之整數)之矽氧烷二胺而得之 聚醯亞胺。 前述可溶性聚醯亞胺，可包含在全部二胺中，使用 5〜99莫耳％之擇自通式(4)Aw ^--------^-------- (Please read the notes on the back and fill out this page) ^Paper scale applies to China National Standard (CNS) A4 specification (210 X 297) 1299043 A7 _B7______ V. Inventive Note (έ) An integer, η is an independent 1 to 20 integer) of a polyoxyalkylene diamine. The aforementioned soluble polyimine may be included in all diamines, using 5 to 99 mol% of the formula (4)

(式中 R1 爲- 0-、- CH2-、- CO -、-、- C(CF3)2 -、一 C(CH3)2 -、- COO -、- S02 -，R1G 爲氫、鹵素、甲 氧基、- OH、- COOH、Cl - C5 之烷基，I 爲 0、1、2、3 、4，m爲0、1、2、3)之二胺而得之聚醯亞胺。 前述可溶性聚醯亞胺，可包含在全部酸二酐中，使用 ί0〜100莫耳％之擇自通式(5)、通式(6) (請先閱讀背面之注意事項再填寫本頁) --------^------(wherein R1 is -0-, -CH2-, -CO-, -, -C(CF3)2-, -C(CH3)2-, -COO-, -S02-, R1G is hydrogen, halogen, A A polyalkylenimine obtained by oxy, -OH, -COOH, an alkyl group of Cl - C5, and I is 0, 1, 2, 3, 4, m is a diamine of 0, 1, 2, 3). The above-mentioned soluble polyimine may be contained in all acid dianhydrides, and is selected from the general formula (5) and the general formula (6) using ί0 to 100 mol% (please read the back of the back sheet and fill in this page) --------^------

(V) (VI) (式中 R11 爲-、- CQ -、- Q -、- C(CF3)2 -、- S〇2 -、-C(CH3)2_，R12爲2價有機基)之酸二酐而得之聚醯亞 胺。 前述可溶性聚醯亞胺，可包含在全部酸二酐中，使用 5〜95莫耳％之通式(6)中R12爲擇自群(II) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐〉 1 1299043 A7 B7 五、發明說明（7 )(V) (VI) (wherein R11 is -, -CQ-, -Q-, -C(CF3)2-, -S〇2-, -C(CH3)2_, and R12 is a divalent organic group) A polydiimine obtained from an acid dianhydride. The above-mentioned soluble polyimine may be contained in all acid dianhydrides, using 5 to 95 mol% of the general formula (6), and R12 is selected from the group (II). The paper size is applicable to the Chinese National Standard (CNS) A4 specification. (210 X 297 mm) 1 1299043 A7 B7 V. Description of invention (7)

r^n ι^ϊιr^n ι^ϊι

l^!J ’ ~ Tl^!J ’ ~ T

_!·〇 一 1丨- ri^ A -r^_ rs-0 1--· I I I (請先閱讀背面之注意事項再填寫本頁) 訂--- Φ. 八八CF3八_!·〇 1 1丨- ri^ A -r^_ rs-0 1--· I I I (please read the notes on the back and fill out this page) Order --- Φ. 八八 CF3八

Oi；〇-°-〇 -p^>， —CPH2 〇·^〇*〇·〇·ΰΌ~,Oi;〇-°-〇 -p^>, —CPH2 〇·^〇*〇·〇·ΰΌ~,

ρπ2ρ ， (P爲1〜20之整數) 群（II) “·〇〇以分 (T代表Η、F、a、Br、I、MeO -、碳數1〜20之焼基) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公t ) A7 1299043 五、發明說明（e?) 之酸二酐而得之聚醯亞胺。 前述酸二酐，可爲通式(7\ (請先閱讀背面之注意事項再填寫本頁) 0 (式中，R13 爲-Ο -、- CO -、-、- C(CF3)厂、一 c(ch3)2-、- coo-、- so2 -) 〇 前述(Α)可溶性聚醯亞胺之Tg可爲100〜30(TC。 硬化後的彈性模數可爲100〜3000MPa。 硬化後的熱分解開始溫度可爲300°C以上。 本發明之感光性樹脂組成物之硬化溫度可爲200°C以 下。 硬化後之焊接耐熱性(300°C)可爲3分以上。 硬化後之熱膨脹係數可爲20ppm〜500ppm。 本發明之樹脂組成物所含之光反應起始劑，可藉由g 線或I線之至少一方來產生游離基。 硬化後的Tg可爲50°C〜300°C。 前述(B)成份可爲具有碳-碳雙鍵之共聚單體。 前述(B)成份，可爲多官能(甲基）丙烯酸系化合物及/ 或其類似體之多官能（甲基)丙烯酸系化合物類。 在此，前述多官能（甲基）丙烯酸系化合物類，可爲2 官能，且具有（-0 - CH2CH2-)的反覆單位。 本發明之感光性樹脂組成物，其(B)成份，可爲擇自雙 酚F EO變性二丙烯酸酯、雙酚A EO變性二丙烯酸酯、雙 酚S EO變性二丙烯酸酯中之至少一種二丙烯酸酯。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 B7 — ----------------------------- ------------------ 五、發明說明（7 ) 本發明之感光性樹脂組成物之必續成份爲(A)成份1〇〇 重量份、（B)成份1〜200重量份。或以(A)可溶性聚醯亞胺 :1〇〇重量份，及 (B) l分子中具有1個以上芳香環、2個以上雙鍵之化 合物1〜200重量份，及 (C) 光反應起始劑及/或增感劑0·1〜50重量份， 爲必須成份。 或是，本發明之感光性樹脂組成物爲（Α)可溶性聚醯 亞胺，（B)l分子中具有1個以上芳香環、2個以上雙鍵之 化合物，（C)光反應起始劑及/或增感劑所構成，當(Α)及(Β) 的合計含量爲100重量份，（Α)成份爲30〜90重量份、(Β) 成份爲10〜70重量份、（C)成份爲0.01〜10重量份。 本發明之感光性膜係由上述樹脂組成物所構成，且能 在150°C以下的溫度下進行積層。 本發明之感光性膜，其B階狀態的膜之可壓接溫度爲 20〇C 〜150〇C 〇 本發明之感光性膜之製造方法包含，將上述感光性樹 脂組成物的有機溶劑溶液塗佈於底膜上並進行乾燥之製程 〇 本發明之防焊劑，係至少由上述感光性樹脂組成物所 構成，在未曝光時爲可溶，曝光後因產生聚合反應而變得 不溶於鹼性水溶液中。 本發明之被覆膜，係至少由上述感光性樹脂組成物所 構成，其可壓接溫度爲20°C〜150°C。 12___ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) · I------^--------- 1299043 A7 ___Β7_____ 五、發明說明（Ρ ) (請先閱讀背面之注意事項再填寫本頁) 本發明之被覆膜，係由上述感光性樹脂組成物所構成 ，在未曝光時爲可溶，曝光後因產生聚合反應而變得不溶 於驗性水溶液中。 本發明之被覆膜，具有線寬/線距寬= 100/100/zm以下 之解析度。 本發明之被覆膜之其他態樣，係將底膜、申請專利範 圍第29項之感光性膜、保護膜依序積層而成之三層構造薄 片，保護膜係由（a)聚乙烯和乙烯-乙烯醇樹脂的共聚物膜 、及(b)聚乙烯膜之積層膜所組成，且(a)共聚物膜側係形成 感光性膜接合面。 在此，前述感光性膜厚爲5〜75 # m。 構成保護膜之(a)共聚物膜厚爲2〜50# m，（b)聚乙烯 膜厚爲10〜50//m。前述底膜可爲聚對苯二甲酸乙二醇酯膜 〇 本發明之被覆膜，可用於軟性印刷配線板、硬碟用懸 吊具、或硬碟記憶裝置之磁頭部分。 本發明之印刷配線板，可積層上述被覆膜來形成。 〔圖式之簡單說明〕 圖1係本發明的被覆膜之示意截面圖。 圖2係顯示使用本發明的被覆膜的軟性印刷基板之局 部製程。（a)製程爲剝離被覆膜的保護膜，.和形成有電路之 銅面積層板貼合；（b)製程將形成有本發明的被覆膜和電路 之銅面積層板實施熱壓接而進行積層；（c)製程是放置光罩 圖案進行曝光；（d)製程是剝離PET膜並進行顯影。 13 _ ____ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 1299043 B7 五、發明說明（Η ) 圖3係顯示本發明實施例之線寬/線距寬=2〇〇//m/2〇〇 /zm 之 10cm2 方形 FPC。 〔用以實施本發明之最佳形態〕 本發明之感光性樹脂組成物所含的必須成份爲(A)可 溶性聚釀亞胺’（B)l分子中具有1個以上芳香環、2個以 .上雙鍵之化合物。 首先說明可丨谷性聚醯亞胺之製法。可溶性聚醯亞胺， 可賦予含有其之樹脂組成物所構成的薄膜耐熱性及良好的 機械特性。 本發明之感光性樹脂組成物所含的可溶性聚醯亞胺之 「可溶性」’係指在沸點120 °C以下的有機溶劑中，於室 溫〜100°C的溫度範圍呈可溶。作爲有機溶劑，例如可列舉 N，N_二甲基甲醯胺、N，N_二乙基甲醯胺等之甲醯胺系溶 劑，N，N-二甲基乙醯胺、N，N_二乙基乙醯胺等之乙醯胺 系溶劑’ N -甲基_2-|]比略院酮、N -乙燦基- 2_P比略垸 酮等之毗咯烷酮系溶劑，酚、鄰-、間-或對—甲酸、二 甲苯酚、鹵素化酚、兒茶酚等之酚系溶劑，四氫呋喃、二 噁院、一惡茂垸等的醚系溶劑，甲醇、乙醇、丁醇等之醇 系溶劑，丁基溶纖劑等之溶纖系劑系或六甲基磷醯胺、r -丁內酯等的溶劑，氯仿、二氯甲烷等的鹵素系溶劑等等 。具體而言，所稱「可溶性」是指溶劑l〇〇g中，於2(rc 〜50°c能溶解lg以上者。較佳爲在上述溶劑中，於2〇ι 〜50°C能溶解5g以上，更佳爲溶解i〇g以上者。 本發明之可溶性聚醯亞胺，係至少使用具有1〜6個芳 14 尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " (請先閱讀背面之注意事項再填寫本頁) 裝--------訂--- 1299043 A7 _______ B7_ __ 五、發明說明（θ ) 香環之酸二酐或脂環式的酸二酐，及/或具有1〜6個芳香環 之二胺而製得者。 具體而言，（A)成份之可溶性聚醯亞胺包含通式（1)Ρπ2ρ , (P is an integer from 1 to 20) Group (II) "· 〇〇 分 (T stands for Η, F, a, Br, I, MeO -, carbon number 1 to 20 焼) This paper scale applies China National Standard (CNS) A4 specification (210 X 297 metric tons) A7 1299043 V. Inventions (e?) Polydiimide derived from acid dianhydride. The aforementioned acid dianhydride may be of the general formula (7\ ( Please read the notes on the back and fill out this page.) (where R13 is -Ο -, - CO -, -, - C (CF3), one c(ch3)2-, - coo-, - so2 -) The Tg of the above (Α) soluble polyimine may be 100 to 30 (TC. The elastic modulus after hardening may be 100 to 3000 MPa. The thermal decomposition initiation temperature after hardening may be 300 ° C or more. The curing temperature of the photosensitive resin composition may be 200 ° C or less. The solder heat resistance after curing (300 ° C) may be 3 or more. The thermal expansion coefficient after hardening may be 20 ppm to 500 ppm. The resin composition of the present invention The photoreaction initiator contained therein may generate a radical by at least one of a g-line or an I-line. The Tg after hardening may be from 50 ° C to 300 ° C. The component (B) may have a carbon-carbon. Comonomer of double bond. The component (B) may be a polyfunctional (meth)acrylic compound of a polyfunctional (meth)acrylic compound and/or the like. Here, the polyfunctional (meth)acrylic compound may be used. It is a bifunctional and has a repeating unit of (-0 - CH2CH2-). The photosensitive resin composition of the present invention, the component (B), may be selected from bisphenol F EO denatured diacrylate, bisphenol A EO denatured Diacrylate, bisphenol S EO denatured at least one diacrylate. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 B7 — ------- ---------------------- ------------------ V. Invention Description (7) The present invention The indispensable component of the photosensitive resin composition is (A) component 1 part by weight, (B) component 1 to 200 parts by weight, or (A) soluble polyimine: 1 part by weight, and (B) 1 to 200 parts by weight of a compound having one or more aromatic rings and two or more double bonds in the molecule, and (C) a photoreaction initiator and/or a sensitizer of 0.1 to 50 parts by weight, which are essential components Or, the photosensitive tree of the present invention The lipid composition is (Α) soluble polyimine, (B) a compound having one or more aromatic rings and two or more double bonds in one molecule, and (C) a photoreaction initiator and/or a sensitizer. When the total content of (Α) and (Β) is 100 parts by weight, the (Α) component is 30 to 90 parts by weight, the (Β) component is 10 to 70 parts by weight, and the (C) component is 0.01 to 10 parts by weight. The photosensitive film of the present invention is composed of the above resin composition, and can be laminated at a temperature of 150 ° C or lower. In the photosensitive film of the present invention, the pressure-bondable temperature of the film in the B-stage state is 20 〇C to 150 〇C. The method for producing the photosensitive film of the present invention comprises coating the organic solvent solution of the photosensitive resin composition. A process for depositing on a base film and drying it. The solder resist of the present invention is composed of at least the above-mentioned photosensitive resin composition, is soluble when not exposed, and becomes insoluble in alkali due to polymerization reaction after exposure. In an aqueous solution. The coating film of the present invention is composed of at least the above-mentioned photosensitive resin composition, and its pressure-bondable temperature is 20 ° C to 150 ° C. 12___ This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) · I------^-------- - 1299043 A7 ___Β7_____ V. INSTRUCTIONS (Ρ) (Please read the precautions on the back side and fill out this page.) The coating film of the present invention is composed of the above-mentioned photosensitive resin composition, and is soluble when not exposed. After the exposure, it becomes insoluble in the aqueous test solution due to the polymerization reaction. The coating film of the present invention has a resolution of line width/line width = 100/100/zm or less. The other aspect of the coating film of the present invention is a three-layer structural sheet in which a base film, a photosensitive film of claim 29, and a protective film are sequentially laminated, and the protective film is made of (a) polyethylene and A copolymer film of an ethylene-vinyl alcohol resin and (b) a laminated film of a polyethylene film are formed, and (a) a photosensitive film joint surface is formed on the side of the copolymer film. Here, the photosensitive film thickness is 5 to 75 #m. The (a) copolymer film constituting the protective film has a film thickness of 2 to 50 #m, and (b) the polyethylene film has a film thickness of 10 to 50/m. The base film may be a polyethylene terephthalate film. The film of the present invention can be used for a flexible printed wiring board, a hard disk suspension, or a magnetic head portion of a hard disk memory device. The printed wiring board of the present invention can be formed by laminating the above-mentioned coating film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view of a coating film of the present invention. Fig. 2 is a partial process showing a flexible printed circuit board using the coated film of the present invention. (a) The process is a protective film for peeling off the coating film, and is bonded to the copper-area laminate having the circuit formed; (b) the process is to perform thermocompression bonding on the copper-area laminate on which the coating film and the circuit of the present invention are formed. And (c) the process is to place a reticle pattern for exposure; (d) the process is to peel the PET film and perform development. 13 _ ____ This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1299043 B7 V. Inventive Note (Η) Figure 3 shows the line width/line width = 2〇〇 of the embodiment of the present invention 10cm2 square FPC of //m/2〇〇/zm. [Best Mode for Carrying Out the Invention] The essential component contained in the photosensitive resin composition of the present invention is (A) soluble polyamidiamine (B)1 having one or more aromatic rings in the molecule, and two . Compounds with double bonds. First, the method for preparing the glutinous polyimine can be described. The soluble polyimine can impart heat resistance and good mechanical properties to a film composed of a resin composition containing the same. The "soluble" of the soluble polyimine contained in the photosensitive resin composition of the present invention means that it is soluble in a temperature range of room temperature to 100 ° C in an organic solvent having a boiling point of 120 ° C or lower. Examples of the organic solvent include a carbamide solvent such as N,N-dimethylformamide or N,N-diethylformamide, and N,N-dimethylacetamide, N,N. _Ethylacetamide-based solvent, acetaminophen-based solvent, N-methyl-2-|] is a pyrrolidone solvent such as leucovorin, N-ethylcanyl-2P or fluorenone, phenol , o-, m- or p-carboxylic acid, xylenol, halogenated phenol, catechol and other phenolic solvents, tetrahydrofuran, dioxins, mono- oxime, etc., ether, methanol, ethanol, butanol A solvent such as an alcohol solvent such as a butyl cellosolve or a solvent such as hexamethylphosphonamide or r-butyrolactone, a halogen solvent such as chloroform or dichloromethane, or the like. Specifically, the term "soluble" means that the solvent is 1 rcg, and it can dissolve lg or more at 2 (rc ~ 50 °c). It is preferably dissolved in 2 〇 〜 50 ° C in the above solvent. More than 5g, more preferably dissolved above i〇g. The soluble polyimine of the present invention is used at least 1 to 6 fangs 14 scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) &quot (Please read the note on the back and fill out this page) Pack------- 1299043 A7 _______ B7_ __ V. Description of invention (θ) Acid dianhydride or alicyclic Produced by acid dianhydride, and/or diamine having 1 to 6 aromatic rings. Specifically, the soluble polyimine of component (A) contains formula (1)

(式中R1爲4價有機基，R2爲2價有機基，R3爲3價有機 基，R4爲羧基或羥基)所代表之聚醯亞胺。 通式（1)所代表的可溶性聚醯亞胺中，導入有羥基及/ 或竣基。 若在可溶性聚醯亞胺中導入羥基及/或羧基，可期待鹼 液中溶解性的提昇，而能使用鹼性溶液來作爲顯影液。該 具有羥基及/或羧基之聚醯亞胺，可藉由使二胺成份(部分 爲具有羥基及/或羧基的二胺）和酸二酐成份進行聚合反應 而製得。 本發明所用之可溶性聚醯亞胺，其COOH當量可爲 200〜3000。該聚醯亞胺之COOH當量，係相當於聚醯亞胺 分子量除以存在於聚醯亞胺分子的羧基數的値（平均値）。 如此般具有COOH當量200〜3000之聚醯亞胺，例如藉由 將具有羧基之二胺當作可溶性聚醯亞胺的原料之至少一部 分來使用即可實現。可溶性聚醯亞胺之較佳COOH當量， 係250〜2500，更佳爲300〜2000。COOH當量超過3000時 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ： " " (請先閲讀背面之注意事項再填寫本頁) --------訂--------- 1299043 A7 ^__B7 ___ 五、發明說明（β ) ，含聚醯亞胺的樹脂組成物變得不易溶解於水溶液系之鹼 性顯影液中，而有顯影時間變長的傾向。若考慮到調製可 溶性聚醯亞胺所用的原料之酸二酐構造及分子量，可溶性 聚醯亞胺的COOH當量通常爲上述般之200以上。例如， —較單純的模式之式(V)所示的化合物(R11爲單鍵）和二胺 基苯二甲基所合成出之聚醯亞胺的COOH當量爲227。使 用R9爲-C(CF3)2 -之上述式(V)的化合物時，COOH當量 爲 299 〇 爲實現前述COOH當量，較佳爲使用分子內具有2個 以上羧基之二胺。藉由倂用該二胺與其他二胺，可容易地 設計出具有既定羧酸當量、具有既定物性之聚醯亞胺。 可溶性聚醯亞胺(A)可用通常的聚醯亞胺之製法來製 得。例如，在有機溶劑中令酸二酐和二胺反應成聚醯胺酸 後，進行脫水反應使其醯亞胺化之方法；或在溶劑中令酸 二酐和二異氰酸酯反應的方法。其等中較適用的方法，係 令酸二酐和二胺反應成聚醯胺酸後，進行脫水反應使其醯 亞胺化之前者的方法。 在分子內具有2個以上羧基(COOH基)之二胺，或在 分子內具有2個以上羧基(COOH基)之二胺和其他二胺的 組合均可選用。藉此可獲得具有羧基之可溶性聚醯亞胺。 上述分子內具有2個以上羧基之二胺並沒有特別的限 定。例如可列舉以下化合物：2,5 -二胺基對苯二甲酸等的 二胺基苯二甲酸類；3,3’ -二胺基-4,4’ _二羧基聯苯基、 4,4’ -二胺基-3,3’ -二羧基聯苯基、4,4’ -二胺基-2,2’ - 16 表紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)(wherein R1 is a tetravalent organic group, R2 is a divalent organic group, R3 is a trivalent organic group, and R4 is a carboxyl group or a hydroxyl group). A hydroxyl group and/or a thiol group is introduced into the soluble polyimine represented by the formula (1). When a hydroxyl group and/or a carboxyl group are introduced into the soluble polyimine, an increase in solubility in the alkali solution can be expected, and an alkaline solution can be used as the developer. The polyiminoimine having a hydroxyl group and/or a carboxyl group can be obtained by polymerizing a diamine component (partially a diamine having a hydroxyl group and/or a carboxyl group) and an acid dianhydride component. The soluble polyimine used in the present invention may have a COOH equivalent of 200 to 3,000. The COOH equivalent of the polyimine is equivalent to the molecular weight of the polyimine divided by the number of carboxyl groups present in the polyimine molecule (average enthalpy). The polyimine having a COOH equivalent of 200 to 3,000 as described above can be obtained, for example, by using a diamine having a carboxyl group as at least a part of a raw material of a soluble polyimine. The preferred COOH equivalent of the soluble polyimine is from 250 to 2,500, more preferably from 300 to 2,000. The COOH equivalent exceeds 3000. 15 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm): "" (Please read the notes on the back and fill out this page) ------- -Order--------- 1299043 A7 ^__B7 ___ V. Inventive Note (β), the resin composition containing polyimine has become difficult to dissolve in an aqueous solution of an aqueous solution, and has been developed. The tendency to get longer. The COOH equivalent of the soluble polyimine is usually 200 or more as described above in consideration of the structure and molecular weight of the acid dianhydride of the raw material used for the preparation of the soluble polyimide. For example, the compound represented by the formula (V) in a simple mode (R11 is a single bond) and the polyamidiamine synthesized by the diaminobenzenedimethyl group have a COOH equivalent of 227. When a compound of the above formula (V) wherein R9 is -C(CF3)2- is used, the COOH equivalent is 299 〇. To achieve the COOH equivalent, it is preferred to use a diamine having two or more carboxyl groups in the molecule. By using the diamine and other diamines, a polyimine having a predetermined carboxylic acid equivalent and having a predetermined physical property can be easily designed. The soluble polyimine (A) can be produced by the usual method of polyimine. For example, a method in which an acid dianhydride and a diamine are reacted to form a polyamic acid in an organic solvent, followed by a dehydration reaction to imidize the oxime; or a method in which an acid dianhydride and a diisocyanate are reacted in a solvent. A more suitable method is a method in which an acid dianhydride and a diamine are reacted to form a polyamic acid, and then subjected to a dehydration reaction to cause imidization. A diamine having two or more carboxyl groups (COOH groups) in the molecule or a combination of a diamine having two or more carboxyl groups (COOH groups) in the molecule and another diamine may be used. Thereby, a soluble polyimine having a carboxyl group can be obtained. The diamine having two or more carboxyl groups in the above molecule is not particularly limited. For example, the following compounds may be mentioned: diamino phthalic acid such as 2,5-diaminoterephthalic acid; 3,3'-diamino-4,4'-dicarboxybiphenyl, 4,4 '-Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-2,2' - 16 Table paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back and fill out this page)

---— — — — — ^ ------I I I 1299043 A7 ___ Β7__ 五、發明說明（W ) 二羧基聯苯基、4,4’ -二胺基—2,2’，5,5’ -四羧基聯苯基等 的羧基聯苯基化合物類；3,3’ -二胺基-4，f -二羧基聯苯 基甲烷、2,2 -雙〔3 -胺基—4 -羧基苯基〕丙烷、2,2 -雙〔4 -胺基-3 -羧基苯基〕丙烷、2,2 -雙〔3 -胺基- 4 -羧基苯基〕六氟丙烷、4,4’ -二胺基-2,2\5,5’ -四羧基 二苯基甲烷等的羧基二苯基鏈烷類；3,3f -二胺基-4,4’ -二羧基二苯醚、4,4’-二胺基-3,3f-二羧基二苯醚、4,4’-二胺基-2,2’ -二羧基二苯醚、4,4·-二胺基-2,2f，5,5f -四 羧基二苯醚等的羧基二苯醚化合物；3,3’-二胺基-4,4’-二羧基二苯楓、4,4’ -二胺基-3,3’ -二羧基二苯硼、4,4’ -二胺基-2,2’ -二羧基二苯碾、4,4’ -二胺基-2,2’，5β -四 羧基二苯硼等的羧基二苯硼化合物；2,2 -雙〔4 - (4-胺 基-3 -羧基苯氧）苯基〕丙烷等的雙〔（羧基苯氧）苯基〕 鏈烷化合物類；2,2 -雙〔4 - (4 -胺基-3 -羧基苯氧)苯基 〕碾等的雙〔（羧基苯氧)苯基〕楓化合物。. 上述其他二胺(分子內不具羧基或具有1個羧基之二胺 )，可列舉分子內具有1個羥基或羧基之二胺、矽氧烷二胺 、其等以外的二胺。 上述分子內具有1個羥基或羧基之二胺，可列舉以下 的化合物：2,4 -二胺基酚等的二胺基酚類；3,3f -二胺基 - 4,4f -二羥基聯苯基、4,4·-二胺基_ 3,3’ -二羥基聯苯基 、4,4·-二胺基-2,2’ -二羥基聯苯基、4,4’ -二胺基-2,2’，5,5’-四羥基聯苯基等的羥基聯苯化合物類；3,3’-二 胺基-4,4,-二羥基聯苯基甲烷、4,4’-二胺基-3,3’-二羥 17 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 --訂-----1 _ 1299043 A7 ____B7_ 五、發明說明（rr ) 基聯苯基甲烷、4,4’ -二胺基-2,2f -二羥基聯苯基甲烷、 2,2 -雙〔3 -胺基一 4 -羥基苯基〕丙烷、2,2 -雙〔4 -胺 基一3 -羥基苯基〕丙烷、2,2 -雙〔3 -胺基_ 4 -羥基苯 基〕六氟丙烷、4,4’ -二胺基-2,2’，5,5’ -四羥基聯苯基甲 烷等的羥基二苯基鏈烷類；3,3’-二胺基-4,4’-二羥基二 苯醚、4,4夂二胺基_ 3,3’ -二羥基二苯醚、4,4’ -二胺基-2,2’ -二羥基二苯醚、4,4·-二胺基-2,2’，5,5f -四羥基二苯 醚等的羥基二苯醚化合物；3,3’-二胺基-4,4’-二羥基二 苯硼、4,4’ -二胺基-3,3’ -二羥基二苯硼、4,4’ -二胺基-2,2·-二羥基二苯硼、4,4’ -二胺基-2,2’，5,5’ -四羥基二苯 硼等的羥基二苯碾化合物；2,2 -雙〔4 - (4 _胺基-3 -羥 基苯氧）苯基〕丙烷等的雙〔（羥基苯氧）苯基〕鏈烷化合物 類；4,4’ -雙(4 -胺基-3 -羥基苯氧）聯苯基〕等的雙（羥 基苯氧)聯苯基化合物類；2,2 -雙〔4 _ (4 -胺基-3 -羥基 苯氧)苯基〕碾等的雙〔（羥基苯氧)苯基〕碾化合物；3,5 -二胺基苯甲酸等的二胺基苯甲酸類；4,4’-二胺基-3,3·-二羥基二苯基甲烷、4,4’_二胺基-2,2，-二羥基二苯基甲 烷、2,2 -雙〔3 -胺基-4 -羧基苯基〕丙烷、4,4f -雙(4 -胺基-3 -羥基苯氧）聯苯等的雙（羥基苯氧）聯苯化合物 基於確保膜柔軟性而降低彈性模數之觀點，本發明之 感光性樹脂組成物之可溶性聚醯亞胺中，可進一步包含通 式⑺ 18 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 訂----— 11! 1299043 A7 B7 五、發明說明（---------^ ------III 1299043 A7 ___ Β7__ V. Description of invention (W) Dicarboxybiphenyl, 4,4'-diamino-2,2',5,5 '-Carboxybiphenyl compounds such as tetracarboxybiphenyl; 3,3'-diamino-4,f-dicarboxybiphenylmethane, 2,2-bis[3-amino-4-carboxyl Phenyl]propane, 2,2-bis[4-amino-3-carboxyphenyl]propane, 2,2-bis[3-amino-4-carboxyphenyl]hexafluoropropane, 4,4' - a carboxydiphenylalkane of diamino-2,2\5,5'-tetracarboxydiphenylmethane; 3,3f-diamino-4,4'-dicarboxydiphenyl ether, 4, 4'-Diamino-3,3f-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4.-diamino-2,2f, a carboxydiphenyl ether compound such as 5,5f-tetracarboxydiphenyl ether; 3,3'-diamino-4,4'-dicarboxydiphenyl maple, 4,4'-diamino-3,3' -dicarboxydiphenylboron, 4,4'-diamino-2,2'-dicarboxydiphenyl milling, 4,4'-diamino-2,2',5β-tetracarboxydiphenylboron Carboxy diphenyl boron compound; 2,2-bis[4-(4-amino-3-carboxyphenyloxy)phenyl]propane Carboxyphenoxy)phenyl]alkane compounds; bis[(carboxyphenoxy)phenyl] maple compounds such as 2,2-bis[4-(4-amino-3-carboxyphenyloxy)phenyl] . The other diamine (diamine having no carboxyl group or one carboxyl group in the molecule) may, for example, be a diamine having a hydroxyl group or a carboxyl group in the molecule, a decane diamine, or a diamine other than the above. Examples of the diamine having one hydroxyl group or a carboxyl group in the molecule include the following compounds: diaminophenols such as 2,4-diaminophenol; and 3,3f-diamino-4,4f-dihydroxyl linkage. Phenyl, 4,4·-diamino-3,3'-dihydroxybiphenyl, 4,4·-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamine Hydroxybiphenyl compounds such as benzyl-2,2',5,5'-tetrahydroxybiphenyl; 3,3'-diamino-4,4,-dihydroxybiphenylmethane, 4,4' -Diamino-3,3'-dihydroxyl 17 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) ----1 _ 1299043 A7 ____B7_ V. Description of the invention (rr) phenylbiphenyl, 4,4'-diamino-2,2f-dihydroxybiphenylmethane, 2,2-bis[3- Amino-4-hydroxyphenyl]propane, 2,2-bis[4-amino-3-hydroxyphenyl]propane, 2,2-bis[3-amino-4-tetrahydroxyphenyl]hexafluoropropane a 4,4'-diamino-2,2',5,5'-tetrahydroxybiphenylmethane hydroxydiphenylalkane; 3,3'-diamino-4,4'- Dihydroxydiphenyl ether, 4,4夂2 Base 3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, 4,4.-diamino-2,2',5,5f a hydroxydiphenyl ether compound such as tetrahydroxydiphenyl ether; 3,3'-diamino-4,4'-dihydroxydiphenylboron, 4,4'-diamino-3,3'-dihydroxyl Diphenylboron, 4,4'-diamino-2,2.-dihydroxydiphenylboron, 4,4'-diamino-2,2',5,5'-tetrahydroxydiphenylboron Hydroxydiphenyl milling compound; bis[(hydroxyphenoxy)phenyl]alkane compound such as 2,2-bis[4-(4-amino-3-hydroxyphenyloxy)phenyl]propane; 4,4 Bis(hydroxyphenoxy)biphenyl compounds such as '-bis(4-amino-3-hydroxyphenyloxy)biphenyl); 2,2-bis[4 _(4-amino-3-hydroxyl) Bis[(hydroxyphenoxy)phenyl]trimium compound such as phenoxy)phenyl]mill; diaminobenzoic acid such as 3,5-diaminobenzoic acid; 4,4'-diamino-3 ,3·-dihydroxydiphenylmethane, 4,4′-diamino-2,2,-dihydroxydiphenylmethane, 2,2-bis[3-amino-4-carboxyphenyl]propane Bis(hydroxyphenoxy) linkage of 4,4f-bis(4-amino-3-hydroxyphenyloxy)biphenyl The compound is based on the viewpoint of ensuring the softness of the film and lowering the modulus of elasticity. The soluble polyimide composition of the photosensitive resin composition of the present invention may further comprise the general formula (7) 18 The paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) (Please read the notes on the back and fill out this page) Binding----- 11! 1299043 A7 B7 V. Description of invention (

0 〇 R8 〇 〇0 〇 R8 〇 〇

(式中R6爲4價有機基，R7爲2價有機基’ r8爲1價有機 基，X爲1以上的整數，y爲1以上的整數，z爲1〜40的 整數，η爲1〜5的整數)所代表的構造。 包含通式（2)所代表之聚醯亞胺中，可使用擇自通式 (3) R8 Η2Ν~((：Η2)η1 R8 Λ -Si τ〇 —ΡΗ2)-ΝΗ2 (請先閱讀背面之注意事項再填寫本頁) (式中R8爲碳數1〜12之烷基、苯基、甲氧基，ζ爲1〜40之 整數，η分別爲獨立的1〜20之整數)之矽氧烷二胺。 由於使用矽氧烷二胺可製得高柔軟性及溶解性之可溶 性聚醯亞胺，故相當適用。通式(3)的化合物中R1之較佳 例爲甲基、乙基、苯基’更佳爲甲基。π較佳爲2〜1〇,更 佳爲2〜5，ζ較佳爲4〜30，更佳爲5〜20，特佳爲8〜15。z 値的範圍對物性的影響很大，ζ値越小所得聚醯亞胺變得 缺乏可撓性，但過大時會有損及聚醯亞胺耐熱性之傾向。 通式(3)所代表的砂氧垸二胺，爲減低膜的彈性模數， 用量較佳爲全胺中之5〜95莫耳％，少於5莫耳％時添加效 果不足，比95莫耳％多時膜變得過軟而有熱膨膜變大之傾 19 1299043 A7 —_______Β7____ 五、發明說明（卩） 向。上述矽氧烷二胺，在原料所用之全二胺中，較佳爲以 5〜70莫耳％的比例來含有，更佳爲以10〜50莫耳％的&例 來含有。 上述以外之本發明的可溶性聚醯亞胺原料之二胺，可 要是二胺並沒有特別的限定，例如可列舉以下化合物：對 苯撐二胺、間苯撐二胺、4,4, _二胺基二苯基甲烷、4,4, -二胺基二苯基硫醚、4,4,-二胺基二苯碾、丨，5 _二胺基萘 、3,3 -二甲基-4,4f _二胺基聯苯、5 _胺基_丨_ (4'-胺 基苯基）-1，3,3 -三甲基茚滿、6 -胺基-1 - (4,-胺基苯基 )-1，3,3 _三甲基茚滿、4,4，-二胺基苯醯苯胺、3,5 -二胺 基-3^三氟甲基苯醯苯胺、3,5 —二胺基—4,—三氟甲基 苯醯苯胺、3,4f -二胺基二苯醚、2,7 -二胺基芴、2,2 -二 (4-胺基苯基）六氟丙烷、4,4,-甲撐-雙（2-氯苯胺）、 2,2、5,5’-四氯-4,4,-二胺基聯苯、2,2,—二氯—4,4,-二 胺基-5,5’ -二甲氧基聯苯、3,3,—二甲氧基—4,4,-二胺基 聯苯、4,4’-二胺基- 2,2，_雙(三氟甲基)聯苯、2,2 -雙〔4 _ (4 -胺基苯氧)苯基〕丙烷、2,2 -雙〔4 - (4 -胺基苯氧） 苯基〕 六 氟丙烷、1，4 -雙(4 -胺基苯氧）苯、4,4,-雙(4 -胺基苯氧）-聯苯、1，3,-雙(4 _胺基苯氧)苯、9,9,-雙(4 -胺基苯基)芴、4,4f -(對苯撐異丙叉)雙苯胺、4,4，-(間苯撐 異丙叉）雙苯胺、2,2, _雙〔4 _ (4 _胺基_ 2 _三氟甲基苯 氧）苯基〕六氟丙烷、4,4,-雙〔4 _ (4 -胺基-2 -三氟甲 基）苯氧〕八氟聯苯等的芳香族二胺（不帶雜環之芳香族二 胺）；一胺基四苯基噻吩等之帶雜環的芳香族二胺；以及， 20 衣纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） '" ' (請先閱讀背面之注意事項再填寫本頁) — - — — III — — 一-°4·111111. .參 1299043 A7 B7(wherein R6 is a tetravalent organic group, R7 is a divalent organic group, r8 is a monovalent organic group, X is an integer of 1 or more, y is an integer of 1 or more, z is an integer of 1 to 40, and η is 1~ The construction represented by the integer of 5). Including the polyimine represented by the general formula (2), it can be selected from the general formula (3) R8 Η2Ν~((:Η2)η1 R8 Λ -Si τ〇-ΡΗ2)-ΝΗ2 (please read the back Note: Please fill in this page again) (wherein R8 is an alkyl group having a carbon number of 1 to 12, a phenyl group, a methoxy group, and an an integer of 1 to 40, and η is an independent integer of 1 to 20, respectively). Alkyldiamine. It is quite suitable because it can produce highly flexible and soluble soluble polyimine by using a nonoxyldiamine. A preferred example of R1 in the compound of the formula (3) is a methyl group, an ethyl group or a phenyl group. More preferably, it is a methyl group. The π is preferably 2 to 1 Torr, more preferably 2 to 5, more preferably 4 to 30, still more preferably 5 to 20, and particularly preferably 8 to 15. The range of z 値 has a great influence on the physical properties, and the smaller the ruthenium, the less polyphenyleneimine becomes flexible, but when it is too large, it tends to impair the heat resistance of the polyimide. The molybdenum diamine represented by the formula (3) is used to reduce the elastic modulus of the film, and the amount is preferably from 5 to 95 mol% in the total amine. When the amount is less than 5 mol%, the addition effect is insufficient, and the ratio is less than 95. When the mole is too much, the film becomes too soft and the hot expanded film becomes larger. 19 1299043 A7 —_______Β7____ V. Description of invention (卩). The above-mentioned nonoxyldiamine is preferably contained in a proportion of 5 to 70 mol%, more preferably 10 to 50 mol%, based on the total diamine used in the raw material. The diamine of the soluble polyimine raw material of the present invention other than the above may be a diamine, and is not particularly limited, and examples thereof include the following compounds: p-phenylenediamine, m-phenylenediamine, 4, 4, and _ Aminodiphenylmethane, 4,4,-diaminodiphenyl sulfide, 4,4,-diaminodiphenyl milling, hydrazine, 5-diaminonaphthalene, 3,3-dimethyl- 4,4f _diaminobiphenyl, 5-amino-indole_(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1 - (4,- Aminophenyl)-1,3,3-trimethylindan, 4,4,-diaminobenzidine, 3,5-diamino-3^trifluoromethylbenzoanilide, 3, 5-diamino-4,-trifluoromethylbenzoanilide, 3,4f-diaminodiphenyl ether, 2,7-diaminopurine, 2,2-bis(4-aminophenyl) Hexafluoropropane, 4,4,-methylene-bis(2-chloroaniline), 2,2,5,5'-tetrachloro-4,4,-diaminobiphenyl, 2,2,-dichloro —4,4,-Diamino-5,5′-dimethoxybiphenyl, 3,3,-dimethoxy-4,4,-diaminobiphenyl, 4,4′-diamine -2,2,_bis(trifluoromethyl)biphenyl, 2,2-bis[4 _(4-aminophenoxy)phenyl]propane, 2,2-bis[4- (4-amine Phenyloxy) benzene Hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 4,4,-bis(4-aminophenoxy)-biphenyl, 1,3,-bis(4-amino Phenoxy)benzene, 9,9,-bis(4-aminophenyl)anthracene, 4,4f-(p-phenylene isopropylidene) bisaniline, 4,4,-(m-phenylene isopropylidene) double Aniline, 2,2, bis[4 _(4 _amino 2 _trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4,-bis[4 _ (4-amino-2) An aromatic diamine such as trifluoromethyl)phenoxy]octafluorobiphenyl (aromatic diamine without a heterocyclic ring); a heterocyclic aromatic diamine such as monoaminotetraphenylthiophene; 20 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) '" ' (Please read the note on the back and fill out this page) — — — — III — — 一-°4· 111111. .参1299043 A7 B7

R 15 五、發明說明（f? U -間苯一甲基二胺、丨，3 —丙烷二胺、四甲撐二胺、五 甲撐一胺、A甲撐：胺、九甲撐二胺、4,4_三胺基七甲撐 一胺、1，4_ 一胺基環己烷、異佛爾酮二胺、四氫二環戊二 烯基一胺、/、氫-4J〜間茚滿烯二甲撐二胺、三環〔 6,2，1，0 〕十—碳烯一甲基二胺、4，# —甲撐雙（環己胺)等 的脂肪族二胺或脂環式二胺。除上述化合物外，作爲芳香 族一胺也能利用通式（8)所代表之具有類固醇基的苯撐二胺 類： h2n-C4rh 所代表之單取代苯撐二胺類（式中R14爲擇自—〇_、一 COO -、- OCO -、- CQNH -、- CO-之 2 價有機基， R15爲具有類固醇骨架之1價有機基)等的化合物。這些化 合物可單獨使用或組合2種以上來使用。 使用芳香族二胺時，若使用其2個胺基位於芳香環的 對位(3位)之二胺，在g線及i線區域會有可溶性醯亞胺本 身之光吸收變小的傾向，在設計感光性樹脂時是有利的。 又，基於求取耐熱性和可溶性的平衡之觀點’較佳爲 使用擇自通式(4) 10 (請先閱讀背面之注意事項再填寫本頁) - — — III — — ^ ---------.« h2n^5(R10)R 15 V. Description of the invention (f? U-m-phenyl-methyldiamine, anthracene, 3-propanediamine, tetramethylenediamine, pentamethylamine, A-methyl: amine, nonamethylenediamine 4,4_triaminoheptamethylamine, 1,4-aminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylamine, /, hydrogen-4J~ An aliphatic diamine or an alicyclic ring such as a fullerene diamine, a tricyclo[6,2,1,0]decacarbene monomethyldiamine, a 4,#-methylene bis(cyclohexylamine) In addition to the above compounds, as the aromatic monoamine, it is also possible to use a phenylene diamine having a steroid group represented by the general formula (8): a monosubstituted phenylene diamine represented by h2n-C4rh R14 is a compound selected from the group consisting of -〇_, a COO-, -OCO-, -CQNH-, -CO-, and a monovalent organic group having a steroid skeleton. These compounds can be used alone. It is used in combination of two or more. When an aromatic diamine is used, if the diamine in which the two amine groups are located at the para position (3 position) of the aromatic ring, the soluble quinone imine itself is present in the g-line and the i-line region. The tendency of light absorption to become smaller, It is advantageous to measure the photosensitive resin. Further, based on the viewpoint of determining the balance between heat resistance and solubility, it is preferable to use the formula (4) 10 (please read the back of the back sheet and fill out this page) - — III — — ^ ---------.« h2n^5(R10)

一 R 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐） 1299043 A7 _______B7__ 五、發明說明（/7 ) (式中，R9 爲 - CH2 _、- CO -、_、- C(CF3)2 - 、- C(CH3)2 -、- COO -、- S〇2 -，R10 爲氫、鹵素、甲 氧基、-OH、- COOH、C1 - C5 之烷基，I 爲 0、1、2、3 、4，m 爲 0、1、2、3)之二胺。 通式(4)所代表的二胺，基於使所得聚醯亞胺的可溶性 提高之觀點，較佳爲在全二胺中使用5〜99莫耳％，更佳爲 全二胺中之10〜70莫耳％。 可溶性聚醯亞胺(A)的原料所用之酸二酐並沒有特別 的限制，例如可使用以下化合物：2,2’ -六氟丙叉二苯二甲 酸二酐、2,2-雙(4-羥基苯基）丙烷二苯甲酸酯-3,3’，4,4’ -四羧酸二酐、丁烷四羧酸二酐、1，2,3,4-環丁烷四羧酸 二酐、1，3 -二甲基-1，2,3,4 -環丁烷四羧酸二酐、1，2,3,4 -環戊烷四羧酸二酐、2,3,5 -三羧基環戊基醋酸二酐、 3,5,6 -三羧基降冰片烷-2 -醋酸二酐、2,3,4,5 -四氫呋喃 四羧酸二酐、5 - (2,5 _二氧四氫呋喃基）_ 3 -甲基-3 -環 己烷-1，2 -二羧酸二酐、雙環〔2,2,2〕-八-7 -烯-2,3,5,6-四羧酸二酐等的脂肪族或脂環式四羧酸二酐；均 苯四甲酸二酐、3,3f，4,4’_二苯甲酮四羧酸二酐、3,3’，4,4’ -聯苯碾四羧酸二酐、1，4,5,8 -萘四羧酸二酐、2,3,6,7 -萘四羧酸二酐、3,3’，4,4·-聯苯醚四羧酸二酐、3,3’，4,4’-二甲基聯苯矽烷四羧酸二酐、3,3f，4,4’-四苯基矽烷四羧酸 二酐、1，2,3,4 -呋喃四羧酸二酐、4,4’ -雙（3,4 -二羧基苯 氧）二苯基硫醚二酐、4,4’-雙(3,4一二羧基苯氧）二苯碾二 22 木紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------^--------- 1299043 ____B7_ 五、發明說明（Y) 酐、4,4’ -雙（3,4 -二羧基苯氧）二苯基丙烷二酐、3,3，，4,4’ -全氟異丙叉二苯二甲酸二酐、3,3’，4,4f-聯苯四羧酸二酐 、雙（苯二甲酸)苯基氧化膦二酐、對苯撐-雙（三苯基苯二 甲酸)二酐、間苯撐-雙(三苯基苯二甲酸)二酐、雙(三苯基 苯二甲酸）-4,4’ -二苯基醚二酐、雙（三苯基苯二甲酸）-4,4’ -二苯基甲烷二酐等的芳香族四羧酸二酐；以及， l，3,3a，4,5,9b -六氫- 2,5 - 二氧- 3 -咲喃基）-萘〔1，2 - c 〕呋喃- 1，3 - 二酮、1，3,3&，4,5,91^-六氫-5-甲基-5-( 四氫-2,5 -二氧-3 -呋喃基）_萘〔1，2 - c〕呋喃-1，3 -二酮、l，3,3a，4,5,9b -六氫-8-甲基 - 5 -（四氫-2,5 -二 氧- 3 -呋喃基）-萘〔1，2- c〕呋喃_ 1，3 -二酮，通式(9) 所代表的化合物：A R 9 paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1299043 A7 _______B7__ V. Invention description (/7) (where R9 is - CH2 _, - CO -, _, - C(CF3)2 - , -C(CH3)2 -, -COO -, -S〇2 -, R10 is hydrogen, halogen, methoxy, -OH, -COOH, C1 - C5 alkyl, I is 0, 1, 2, 3, 4, m are diamines of 0, 1, 2, 3). The diamine represented by the formula (4) is preferably used in an amount of from 5 to 99 mol% in the total diamine, more preferably from 10 to 99 mol% in the total diamine, from the viewpoint of improving the solubility of the obtained polyimine. 70% by mole. The acid dianhydride used for the raw material of the soluble polyimine (A) is not particularly limited, and for example, the following compounds can be used: 2,2'-hexafluoropropanedicarboxylic dianhydride, 2,2-bis (4) -hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid Dihydride, 1,3 -dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5 -tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5 - (2,5 _ Dihydrotetrahydrofuranyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-octa-7-ene-2,3,5,6- An aliphatic or alicyclic tetracarboxylic dianhydride such as tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3f, 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl-tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4 , 4·-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethylbiphenylnonane tetracarboxylic dianhydride, 3,3f,4,4'-tetraphenyl Alkane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4' -Bis(3,4-dicarboxyphenoxy)diphenyl mill 2 22 Wood paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back and fill out this page) - -------^--------- 1299043 ____B7_ V. INSTRUCTIONS (Y) Anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride ,3,3,,4,4'-perfluoroisopropylidene di phthalic anhydride, 3,3',4,4f-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide Dihydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4' - An aromatic tetracarboxylic dianhydride such as diphenyl ether dianhydride or bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride; and, l, 3, 3a, 4, 5, 9b-hexahydro-2,5-dioxo-3-(indolyl)-naphthalene[1,2-c]furan-1,3-diketone, 1,3,3&,4,5,91^- Hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene 1,2-c]furan-1,3-dione, l,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 - Furyl)-naphthalene [1,2-c]furan-1,3-dione, compound represented by the formula (9):

(式中R10爲具有芳香環之2價有機基，R17及R18分別爲氫 原子或烷基）， (請先閱讀背面之注意事項再填寫本頁) H-----------------.(wherein R10 is a divalent organic group having an aromatic ring, and R17 and R18 are each a hydrogen atom or an alkyl group), (Please read the back of the note first and then fill in this page) H---------- -------.

(式中R19爲具有芳香環之2價有機基，R2()及R21分別爲氫 23 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 1299043 A7 ^____B7 ___五、發明說明（）丨） 原子或烷基）， 所代表的化合物等之具有芳香環的脂肪族四羧酸二酐等。 這些酸二酐中，基於耐熱性的觀點，較佳爲使用具有1〜6 個芳香環之酸二酐或脂環式酸二酐。這些四羧酸二酐可單 獨使用或組合2種以上來使用。 爲求取耐熱性和可溶性的平衡、並展現高度的機械特 性，較佳爲擇自通式(5)、通式(6)(wherein R19 is a divalent organic group having an aromatic ring, R2() and R21 are respectively hydrogen 23. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public) 1299043 A7 ^____B7 ___ five The invention is an aliphatic tetracarboxylic dianhydride having an aromatic ring, such as an atom or an alkyl group, or a compound represented by the invention. Among these acid dianhydrides, acid dianhydride or alicyclic acid dianhydride having 1 to 6 aromatic rings is preferably used from the viewpoint of heat resistance. These tetracarboxylic dianhydrides can be used singly or in combination of two or more. In order to obtain a balance between heat resistance and solubility, and exhibit high mechanical properties, it is preferred to select from the general formula (5) and the general formula (6).

(式中，R"爲-、-CO -、- Ο -、- C(CF3)2 -、- S02 -、-C(CH3)2-，R12 爲 2 價有機基）。 特別是，爲獲得溶解性，較佳爲在酸二酐的一部分使 用2,2，-六氟丙叉二苯二甲酸二酐、2,3,3，，4，-聯苯四羧酸 二酐。特別是，上述 R16 爲-CH2C(CH3)2 _、- CnH2n -（η 爲1〜20之整數），R12爲擇自下述(II)群 24 B氏張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 裝(wherein R" is -, -CO -, - Ο -, -C(CF3)2 -, -S02 -, -C(CH3)2-, and R12 is a divalent organic group). In particular, in order to obtain solubility, it is preferred to use 2,2,-hexafluoropropanedicarboxylic dianhydride, 2,3,3,4,-biphenyltetracarboxylic acid in a part of the acid dianhydride. anhydride. In particular, R16 is -CH2C(CH3)2 _, -CnH2n - (η is an integer from 1 to 20), and R12 is selected from the following (II) group 24 B-slice scale applicable Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) (Please read the notes on the back and fill out this page)

I 1 I I 訂.—---— II 0. 1299043 A7 B7 五、發明說明（ c- -0-I 1 I I 订.——————— II 0. 1299043 A7 B7 V. Description of invention ( c- -0-

cf3]h〇2 〇-，~CH-0' CF3Cf3]h〇2 〇-,~CH-0' CF3

，Ό_〇 - O-，~0 -cH2 O~^ ^ ’ ~,Ό_〇 - O-,~0 -cH2 O~^ ^ ’ ~

jT^LjT^L

CF3 >-〇τ Μ--------^— (請先閱讀背面之注意事項再填寫本頁) -〇-〇ί>—Os-γΘ-， rT%n V〇CF3 >-〇τ Μ--------^— (Please read the notes on the back and fill out this page) -〇-〇ί>—Os-γΘ-, rT%n V〇

•Hi-于0 CF•Hi- at 0 CF

S02 一~CpH2p (P爲1〜20之整數) -〇-L°-〇-°^-0-, 群(⑴〇·δ-〇ΌΌ"ο_δΌ~ (Τ代表Η、F、C卜Br、I、MeO -、碳數1〜20之焼基） 25 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 B7 五、發明說明（/ ) (T代表Η、F、a、Bi·、I、MeO -、碳數1〜20之烷基） 之二價有機基。 (請先閱讀背面之注意事項再填寫本頁) 上述(Π)群所代表的化合物，基於將所得聚醯亞胺的 溶解性提高之觀點，在全酸二酐中較佳爲10〜100莫耳％。 特別是，爲獲得對有機溶劑的溶解性高之聚醯亞胺， 更佳爲一部分是使用通式(7)S02~~CpH2p (P is an integer from 1 to 20) -〇-L°-〇-°^-0-, group ((1)〇·δ-〇ΌΌ"ο_δΌ~ (Τ stands for Η, F, C卜 Br, I, MeO -, carbon number 1~20 )) 25 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 B7 V. Invention description (/ ) (T stands for Η, F, a divalent organic group of a, Bi·, I, MeO -, alkyl having 1 to 20 carbon atoms. (Please read the notes on the back and fill out this page.) The compounds represented by the above (Π) group are based on The viewpoint of improving the solubility of the obtained polyimine is preferably from 10 to 100 mol% in the total acid dianhydride. Particularly, in order to obtain a polyimine having high solubility in an organic solvent, it is more preferably a part. Is using the general formula (7)

C(CH3)2 -、_ COO -、- S〇2 -） 的構造所代表之具有4個芳香環之酯酸二酐。 本發明之感光性樹脂組成物所含之可溶性聚醯亞胺， 可將其前驅物之聚醯胺酸經醯胺化而製得。聚醯胺酸，可 在有機溶劑中令二胺與酸二酐反應而得。該聚醯胺酸，例 如在氬、氮等的非活性環境氣氛中，將二胺以溶解於有機 溶劑中或擴散成糊狀的狀態、將酸二酐以溶解於有機溶劑 中或擴散成糊狀的狀態、或以固體狀態來添加。 只要上述二胺之1種與酸二酐之1種爲實質上等莫耳 ，即構成酸成份1種、二胺成份1種之聚醯胺酸。又分別 使用2種以上的酸二酐成份及二胺成份，將二胺成份全量 與酸二酐成份全量的莫耳比調整成實質上等莫耳，即可得 出任意的聚醯胺酸共聚物。 例如，可先將二胺成份-1及二胺成份-2加入有機 __ 26 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） '' 1299043 A7 —___B7___ 五、發明說明（>4) 極性溶劑中，接著加入酸二酐成份，以作成聚醯胺酸聚合 物的溶液。或先將二胺成份-1加入有機極性溶劑中，再 加入酸二酐成份，攪拌一段時間後加入二胺成份-2，以製 成聚醯胺酸聚合物的溶液。或是，先將酸二酐成份加入有 機極性溶劑中，再加入二胺成份-1，攪拌一段時間後加入 二胺成份-2，再攪拌一段時間後加入二胺成份-3，以製 成聚醯胺酸聚合物的溶液。 和上述添加方法剛好相反，先加入酸二酐，後加入二 胺成份的作法，實質上也是同樣的。 聚醯胺酸合成時的反應溫度較佳爲-20°C〜90°C。反 應時間爲30分〜24小時。所得聚醯胺酸的平均分子量(重 量平均分子量）較佳爲5000〜1000000。平均分子量未滿 5000時，從聚醯胺酸製得的可溶性聚醯亞胺的分子量變低 。若使用含有該可溶性聚醯亞胺之感光性樹脂組成物’例 如所得乾膜光阻本身有變脆的傾向。另一方面’當分子量 超過1000000時，含有聚醯胺酸的溶液(淸漆)粘度過高而 有處理困難的傾向。 聚醯胺酸的生成反應所使用之有機極性溶劑，例如可 列舉二甲亞碾、二乙亞碾等的亞硼系溶劑，N，N-二甲基 甲醯胺、N，N-二乙基甲醯胺等之甲醯胺系溶劑，N，N-二 甲基乙醯胺、N，N-二乙基乙醯胺等之乙醯胺系溶劑，N-甲基-2 -吡咯烷酮、N -乙烯基-2_吡咯烷酮等之吡咯 烷酮系溶劑，酚、鄰-、間-或對-甲酚、二甲苯酚、鹵 素化酚、兒茶酚等之酚系溶劑，四氫呋喃、二噁烷、二惡 27 _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝The ester acid dianhydride having four aromatic rings represented by the structure of C(CH3)2 -, _COO -, -S〇2 -). The soluble polyimine contained in the photosensitive resin composition of the present invention can be obtained by subjecting the precursor polyamine to amidoxime. Polylysine can be obtained by reacting a diamine with an acid dianhydride in an organic solvent. The polyamic acid is dissolved in an organic solvent or diffused into a paste by dissolving the diamine in an organic solvent or in a paste-like state in an inert atmosphere such as argon or nitrogen. It is added in a state of a solid state or in a solid state. As long as one of the above-mentioned diamines and one of the acid dianhydrides are substantially equal to each other, that is, one of the acid components and one polyamine component of the diamine component. Further, two or more kinds of acid dianhydride components and diamine components are used, and the molar ratio of the total amount of the diamine component to the total amount of the acid dianhydride component is adjusted to substantially equimolar, thereby obtaining any polyglycolic acid copolymerization. Things. For example, the diamine component-1 and the diamine component-2 can be first added to the organic __ 26 paper scale applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) '' 1299043 A7 —___B7___ V. Description of the invention (>4) The polar dianhydride component is added to the polar solvent to form a solution of the polyglycolic acid polymer. Alternatively, the diamine component-1 is first added to the organic polar solvent, and then the acid dianhydride component is added. After stirring for a while, the diamine component-2 is added to prepare a solution of the polyaminic acid polymer. Alternatively, the acid dianhydride component is first added to the organic polar solvent, and then the diamine component-1 is added. After stirring for a while, the diamine component-2 is added, and after stirring for a while, the diamine component-3 is added to form a poly A solution of a proline polymer. In contrast to the above-described addition method, the addition of the acid dianhydride and the addition of the diamine component are substantially the same. The reaction temperature at the time of polyamic acid synthesis is preferably from -20 ° C to 90 ° C. The reaction time is 30 minutes to 24 hours. The average molecular weight (weight average molecular weight) of the obtained polyamic acid is preferably from 5,000 to 1,000,000. When the average molecular weight is less than 5,000, the molecular weight of the soluble polyimine prepared from polyamic acid is lowered. When a photosensitive resin composition containing the soluble polyimine is used, for example, the obtained dry film resist itself tends to become brittle. On the other hand, when the molecular weight exceeds 1,000,000, the solution containing polylysine (the lacquer) has a high viscosity and tends to be difficult to handle. Examples of the organic polar solvent used in the formation reaction of the polyproline include, for example, a boronic solvent such as dimethyl yam or yam, N,N-dimethylformamide, N,N-diethyl A mercaptoamine solvent such as carbamide or an acetamide solvent such as N,N-dimethylacetamide or N,N-diethylacetamide, N-methyl-2-pyrrolidone, a pyrrolidone solvent such as N-vinyl-2_pyrrolidone, a phenol solvent such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol or catechol, tetrahydrofuran, dioxane, Dioxin 27 _ This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page)

ϋ n n n^eJ« ϋ n ϋ I n n I 1299043 Λ7 ____B7 _ 五、發明説明（β ) 茂烷等的醚系溶劑’甲醇、乙醇、丁醇等之醇系溶劑，丁 基溶纖劑等之溶纖系劑系或六甲基磷醯胺、r - 丁內酯等 的溶劑等等，這些可單獨或作爲混合物來使用，二甲苯、 甲苯般之芳香族烴也能使用。溶劑可只是能溶解聚醯胺酸 者即可，並沒有特別的限定。聚醯胺酸合成後，由於是將 該聚醯胺酸的溶液實施加熱減壓，而同時進行去溶劑和醯 亞胺化，故儘量選擇能溶解聚醯胺酸之低沸點者，在製程 上較有利。其次說明將聚醯胺酸醯亞胺化的製程。 上述所得的聚醯胺酸，係經由脫水反應變換成聚醯亞 胺。醯亞胺化的方法並沒有特別的限定，適用的方法，係 將上述進行聚醯胺酸的合成後之反應混合物在減壓下加熱 。依據該方法，由於能將醯亞胺化所生成的水積極地除去 ，故能抑制水所造成之聚醯亞胺的加水分解，而能避免分 子量的降低。一般所用的原料之酸二酐中，混入有因加水 分解而開環後的四羧酸、或酸二酐的一方經加水開環而成 者等的情形，聚醯胺酸的的聚合反應會停止，而無法獲得 高分子量的聚醯亞胺。然而，若採用上述減壓下加熱的方 法，因加熱會使開環後的酸二酐再度閉環而形成酸二酐， 並和殘留的胺進行反應。這時，由於處於減片條件下，將 能有效地除去反應系內的水，而能避免水所造成之加水分 解。因此，可獲得更高分子量的聚醯亞胺。 除上述方法外，也能採用一般的醯亞胺化方法。例如 ，在上述進行聚醯胺酸合成後的反應混合物中，加入甲苯 、二甲苯等的共沸溶劑並實施加熱，以同時進行醯亞胺化 28 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) I--------t---------— 1299043 A7 ___B7___ 五、發明說明（以） 和利用共沸來除去水的方法。以及，在上述進行聚醯胺酸 合成後的反應混合物中，加入醋酸酐等的脂肪族二酐、三 乙胺、吡啶、甲基毗啶、喹啉等的3級胺，以同時進行醯 亞胺化和脫水的方法。 然而，前者之利用共沸來除去水，由於反應系中會有 水的存在，會有產生水所造成的水解之可能性。後者之化 學醯亞胺化法，由於將生成的水，藉由脂肪族酸二酐之變 化成脂肪族酸而以化學手段來除去，在加水分解這點比前 者的反應系爲有利。然而，由於反應系內有脂肪族酸二酐 和3級胺的殘留，故其等的除去製程將變爲必要。這些方 法由於存在著上述問題點，故須視目的來選擇醯亞胺化的 方法。而以上述減壓下加熱的方法特別適用。 採用減壓下加熱之醯亞胺化方法時，加熱溫度較佳爲 80〜400°C。這種溫度下能高效率的進行醯亞胺化。高效率 的除去水之溫度爲100°C以上，更佳爲120°C以上的溫度。 最高溫較佳爲設定成所用聚醯亞胺的熱分解溫度以下。通 常在200〜350°C左右醯亞胺化就會大致完成，亦可將最高 溫度設定在這個程度。ϋ nnn^eJ« ϋ n ϋ I nn I 1299043 Λ7 ____B7 _ V. OBJECTS OF THE INVENTION (β) An ether solvent such as a motenane, an alcohol solvent such as methanol, ethanol or butanol, or a solubilized cellulose such as butyl cellosolve. A solvent or a solvent such as hexamethylphosphoniumamine or r-butyrolactone or the like may be used singly or as a mixture, and an aromatic hydrocarbon such as xylene or toluene may also be used. The solvent may be only one which can dissolve the polyaminic acid, and is not particularly limited. After the synthesis of polylysine, the solution of the poly-proline is heated and decompressed, and at the same time, the solvent is removed and the imidization is carried out. Therefore, the low-boiling point capable of dissolving the poly-proline is selected as much as possible in the process. More favorable. Next, a process for imidizing polyphosphonium citrate will be described. The polylysine obtained above is converted into a polyimine by a dehydration reaction. The method for the imidization of hydrazine is not particularly limited, and a suitable method is to heat the reaction mixture obtained by synthesizing the above polyamic acid under reduced pressure. According to this method, since the water produced by the imidization can be actively removed, the hydrolysis of the polyimine by water can be suppressed, and the decrease in the molecular weight can be avoided. In the case where the acid dianhydride used in the raw material is mixed with a tetracarboxylic acid or an acid dianhydride which is opened by hydrolysis and is opened by adding water, the polymerization reaction of polyglycine is carried out. Stopping, and high molecular weight polyimine is not available. However, according to the above method of heating under reduced pressure, the acid dianhydride after ring opening is closed by heating to form an acid dianhydride, and reacts with the residual amine. At this time, since the water in the reaction system is effectively removed under the conditions of the film reduction, the hydrolysis caused by the water can be avoided. Therefore, a higher molecular weight polyimine can be obtained. In addition to the above methods, a general oxime imidization method can also be employed. For example, in the reaction mixture after the polyamic acid synthesis described above, an azeotropic solvent such as toluene or xylene is added and heated to simultaneously carry out the oxime imidization. 28 The paper scale applies the Chinese National Standard (CNS) A4 specification. (210 X 297 mm) (Please read the notes on the back and fill out this page) I--------t--------- 1299043 A7 ___B7___ V. Description of invention (I) And a method of removing water by azeotropy. Further, a tertiary amide such as an aliphatic dianhydride such as acetic anhydride, triethylamine, pyridine, methylpyridin or quinoline is added to the reaction mixture after the polyamic acid synthesis described above, and simultaneously A method of amination and dehydration. However, the former uses azeotrope to remove water, and there is a possibility that hydrolysis due to water may occur due to the presence of water in the reaction system. The latter chemical imidization method is advantageous in that the water to be produced is removed by chemical means by changing the aliphatic acid dianhydride to an aliphatic acid, and the hydrolysis is more advantageous than the former. However, since the reaction system has residues of aliphatic acid dianhydride and tertiary amine, the removal process of these will become necessary. Since these methods have the above problems, it is necessary to select the method of imidization according to the purpose. The method of heating under the above reduced pressure is particularly suitable. When the hydrazine imidization method is carried out under reduced pressure, the heating temperature is preferably from 80 to 400 °C. At this temperature, ruthenium imidization can be carried out efficiently. The high-efficiency water removal temperature is 100 ° C or higher, more preferably 120 ° C or higher. The maximum temperature is preferably set to be lower than the thermal decomposition temperature of the polyimine used. Generally, the imidization at about 200 to 350 ° C is substantially completed, and the maximum temperature can be set to this extent.

反應系的壓力，雖如上述般採低壓較佳，但只要是在 上述加熱條件下，能高效率地除去醯亞胺化時所生成的水 之壓力即可。具體而言，反應系內的壓力爲1〇〇〜9.2 X 104Pa，較佳爲 1〇〇〜8.2Xl04Pa，更佳爲 1000〜7.2xi〇4pa 〇 具體而言，本發明所用之可溶性聚醯亞胺，例如將聚 29 尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) « — — — III— « — — — — — — I — Φ. A7 1299043 ______B7_ 五、發明說明（>7 ) (請先閱讀背面之注意事項再填寫本頁) 醯胺酸溶液在減壓下加熱乾燥而直接醯亞胺化，如此可有 利的調製出。例如，作爲批式的方法，係使用真空泵，作 '爲連續式的方法，係使用附減壓裝置之雙軸或三軸擠製機 來達成聚醯亞胺化反應。這些方式，能依據生產量來作適 當的選擇。在此所稱之附減壓裝置之雙軸或三軸擠製機， 係在一般進行熱塑性樹脂的加熱熔融擠出之熔融擠製機上 ，附加藉減壓來除去溶劑之裝置者。聚醯胺酸溶液，係藉 由該擠製機進行加熱、混練，以除去溶劑和醯亞胺化時所 產生的水。如此般來形成可溶性聚醯亞胺。 又，本發明之感光性樹脂組成物，除上述成份外，亦 可含有各種有機添加劑、有機或無機塡料類、各種強化材 、各種有機溶劑等等。 上述具有羥基及/或羧基之聚醯亞胺，可導入其他官能 基來賦予所望的特性。例如，藉由讓聚醯亞胺(具有羥基及 /或羧基)和具有環氧基之化合物反應所得之聚醯亞胺(本發 明稱環氧變性聚醯亞胺），基於可賦予所得組成物反應性及 硬化性之觀點，是較佳的。 以下，對環氧變性聚醯亞胺作說明。環氧變性聚醯亞 胺，以通式（1)The pressure of the reaction system is preferably as low as described above, but the pressure of the water generated during the imidization can be efficiently removed under the above heating conditions. Specifically, the pressure in the reaction system is from 1 9.2 to 9.2 X 104 Pa, preferably from 1 〇〇 to 8.2 X 10 4 Pa, more preferably from 1000 to 7.2 xi 〇 4 kPa. Specifically, the soluble poly phthalate used in the present invention Amines, for example, will be calibrated to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) (please read the notes on the back and fill out this page) « — — — III — « — — — — — — I — Φ. A7 1299043 ______B7_ V. INSTRUCTIONS (>7) (Please read the notes on the back and then fill out this page) The proline solution is heated and dried under reduced pressure and directly imidized, which can be advantageously modulated. Out. For example, as a batch method, a vacuum pump is used as a continuous method, and a biaxial or triaxial extruder equipped with a pressure reducing device is used to achieve a polyfluorene imidization reaction. These methods can make the right choice based on production volume. The biaxial or triaxial extruder to which the pressure reducing device is attached is referred to as a device which is generally subjected to a hot melt extrusion of a thermoplastic resin, and a device for removing a solvent by decompression. The polyaminic acid solution is heated and kneaded by the extruder to remove the solvent and the water produced by the imidization of the hydrazine. So as to form soluble polyimine. Further, the photosensitive resin composition of the present invention may contain, in addition to the above components, various organic additives, organic or inorganic materials, various reinforcing materials, various organic solvents and the like. The above polyiminoimine having a hydroxyl group and/or a carboxyl group can be introduced into another functional group to impart desired properties. For example, a polyfluorene imine obtained by reacting a polyimine (having a hydroxyl group and/or a carboxyl group) with a compound having an epoxy group (referred to as an epoxy-modified polyimine in the present invention) is based on the composition which can be imparted to the composition. The viewpoint of reactivity and hardenability is preferred. Hereinafter, the epoxy-modified polyimine will be described. Epoxy-denatured polyamidiamine with the general formula (1)

30 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 1299043 ____B7 _30 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 1299043 ____B7 _

五、發明說明（>MV. Description of the invention (>M

(式中R1爲4價有機基，R2爲2價有機基，R3爲3價有機 基，R4爲羧基、羥基或擇自群⑴ (請先閱讀背面之注意事項再填寫本頁) (式中R5爲具有擇自環氧基、碳-碳三鍵、碳-碳雙鍵所 構成群中之至少一種以上之1價有機基)之有機基)來代表 〇 環氧變性聚醯亞胺，可將具有羥基或羧基之可溶性聚 醯亞胺溶解於有機溶劑，再和具有環氧基之化合物反應而 製得。 具有環氧基之化合物，較佳爲具有2個以上環氧基之 環氧樹脂，和環氧基形成雙鍵或三鍵結合之化合物。 具有2個以上環氧基之環氧樹脂，只要在分子內具有 2個以上的環氧基即可，並沒有特別的限定，可使用以下 所例示者。 例如，Epikote 828(油化殻牌公司製)等的雙酚樹脂， 180S65(油化殼牌公司製）等的鄰甲酚酚醛淸漆樹脂， 157S70(油化殼牌公司製）等的雙酚A酚醛淸漆樹脂， 1032H60(油化殼牌公司製)等的三羥基苯基甲烷酚醛淸漆樹 脂，ESN375等的萘芳烷基酚醛淸漆樹脂，四酚乙烷 1031S(油化殼牌公司製），YGD414S(東都化成），三羥基苯 基甲烷EPPN502H(日本化藥），特殊雙酚VG3101L(三井化 31 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 -------Β7 _ 五、發明說明（彳） 學），特殊萘酚NC7000(日本化藥），TETRAD - X， TETRAD - C(三菱瓦斯化學公司製）等的縮水甘油胺型樹脂 等。 和環氧基形成雙鍵結合的化合物，只要在分子內具有 和環氧基形成的雙鍵結合即可，並沒有特別的限定，可舉 例如稀丙基縮水甘油醚、縮水甘油丙烯酸酯、縮水甘油甲 基丙烯酸酯、縮水甘油乙烯醚等。 和環氧基形成三鍵結合的化合物，只要在分子內具有 和環氧基形成的三鍵結合即可，並沒有特別的限定，可舉 例如炔丙基縮水甘油醚、縮水甘油丙炔酯、乙炔基縮水甘 油醚等。 反應所用的溶劑，只要不和環氧基反應，能溶解具有 羥基或羧基之聚醯亞胺者即可，並沒有特別的限定。例如 可使用二甲亞碾、二乙亞碉等的亞硼系溶劑，N，N-二甲 基甲醯胺、N，N-二乙基甲醯胺等之甲醯胺系溶劑，N，N -二甲基乙醯胺、N，N-二乙基乙醯胺等之乙醯胺系溶劑，N -甲基-2 -吡咯烷酮、N -乙烯基-2 -吡咯烷酮等之吡 咯烷酮系溶劑，四氫呋喃、二噁烷等的醚系溶劑，甲醇、 乙醇、丁醇等之醇系溶劑，丁基溶纖劑等之溶纖系劑系或 六甲基磷醯胺、T - 丁內酯等的溶劑等等，二甲苯、甲苯 般之芳香族烴也能使用，這些可單獨或作爲混合物來使用 〇 由於之後要進行溶劑的除去，故以選擇可溶解熱塑性 聚醯亞胺（具有羥基或羧基）之沸點儘量低者，在製程上較 32 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝 -----訂ί 1299043 A7 ___B7_ 五、發明說明（？。） 有利。 關於反應溫度，環氧基和羥基/羧基的反應較佳爲在 40〜130°C的溫度下進行。特別是關於和環氧基形成雙鍵結 合或和環氧基形成三鍵結合的化合物，較佳的反應溫度爲 使雙鍵結合或三鍵結合不致因熱而分解或交聯的溫度。具 體而言爲40〜100°C ’較佳爲50〜80°C。反應時間爲數分 〜15小時左右。 如此般，即製得環氧變性聚醯亞胺的溶液。爲提高和 銅箔的接著性及顯影性，可在該環氧變性聚醯亞胺溶液中 ，適當地混入環氧樹脂、丙烯酸樹脂等的熱固性樹脂，聚 酯、聚醯胺、聚氨酯、聚碳酸酯等的熱塑性樹脂。 又，和環氧樹脂以外的熱固性樹脂混合，以獲得良好 的物性亦可。在此所用的熱固性樹脂，可列舉雙馬來醯亞 胺、雙烯丙基雙醯亞胺、酚樹脂、氰酸酯樹脂等等。 將該環氧變性聚醯亞胺溶液直接塗佈於待接合的部分 再使其乾燥亦可，或以塗佈乾燥而成的片狀來使用。 乾燥條件較佳爲，使殘存的環氧基、雙鍵結合、三鍵 結合不致因熱而分解、交聯左右的較低溫條件。 若將本發明之環氧變性聚醯亞胺和通常的環氧樹脂硬 化劑混合’由於能獲得良好物性的硬化物故較佳。只要是 環氧樹脂硬化劑即可，可使用胺系、咪唑系、酸酐系、酸 系等，也能混合各種的偶合劑。也能使用環氧變性聚醯亞 胺以外的可溶性聚醯亞胺。 上述般所得的可溶性聚醯亞胺之玻璃轉移溫度Tg雖 ____ 33 T紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐) "~—- (請先閱讀背面之注意事項再填寫本頁) -^--------^--------- 1299043 A7 ___B7 _ 五、發明說明（Η ) 越高越好，但基於溶解性和硬化物物性間的平衡，係定爲 100〜30〇。〇，較佳爲120〜300°C，更佳爲140〜280°C。 本發明之感光性樹脂組成物所含之(B)成份’係具有碳 -碳雙鍵之共聚物單體，較佳爲多官能（甲基）丙烯酸系化 合物及/或其類似物之多官能（甲基)丙烯酸系化合物類。所 謂「多官能（甲基）丙烯酸系化合物」，是指多官能丙烯酸 系化合物及多官能甲基丙烯酸系化合物中之至少1種。所 謂多官能丙烯酸系化合物，係至少有2個丙烯醯基 (CH2=CHCO -)之化合物；所謂多官能甲基丙烯酸系化合 物，係一分子中有4〜40個-(CHR- CH2 - 0)-所代表的 反覆單位（其中，R爲氫或甲基或乙基）之化合物。藉由選 擇這種化合物，硬化前的單體易溶解於鹼性水溶液中，曝 光部的樹脂硬化後未曝光部的樹脂能迅速溶解於鹼性水溶 液中，故能在短時間內賦予良好的解析度。 作爲易溶解於鹼性水溶液的構造之二（甲基)丙烯酸酯 (請先閱讀背面之注意事項再填寫本頁) 裝--------訂---------^__w((wherein R1 is a tetravalent organic group, R2 is a divalent organic group, R3 is a trivalent organic group, R4 is a carboxyl group, a hydroxyl group or a selected group (1) (please read the back of the back sheet and fill out this page) R5 is an organic group having at least one or more monovalent organic groups selected from the group consisting of an epoxy group, a carbon-carbon triple bond, and a carbon-carbon double bond, and represents an oxime epoxy-modified polyimine. A soluble polyimine having a hydroxyl group or a carboxyl group is dissolved in an organic solvent and then reacted with a compound having an epoxy group. The compound having an epoxy group is preferably an epoxy resin having two or more epoxy groups, and a compound in which an epoxy group forms a double bond or a triple bond. The epoxy resin having two or more epoxy groups is not particularly limited as long as it has two or more epoxy groups in the molecule, and the following examples can be used. For example, a bisphenol resin such as Epikote 828 (manufactured by Oiled Shell Co., Ltd.), an o-cresol novolac lacquer resin such as 180S65 (manufactured by Hosei Shell Co., Ltd.), and bisphenol A phenolic resin such as 157S70 (manufactured by Hosei Shell Co., Ltd.) Lacquer resin, trishydroxyphenylmethane phenolic enamel resin such as 1032H60 (manufactured by Hosei Shell Co., Ltd.), naphthyl aryl phenolic enamel resin such as ESN375, tetraphenol ethane 1031S (manufactured by Oil Chemical Shell Co., Ltd.), YGD414S (Dongdu Huacheng), Trihydroxyphenylmethane EPPN502H (Nippon Chemical), special bisphenol VG3101L (Mitsuihua 31 paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 ---- --- Β7 _ 5, invention description (彳)), special naphthol NC7000 (Nippon Chemical), TETRAD-X, TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.) and other glycidylamine resin. The compound which forms a double bond with an epoxy group is not particularly limited as long as it has a double bond formed with an epoxy group in the molecule, and examples thereof include a propylene glycol glycidyl ether, a glycidyl acrylate, and a shrinkage. Glycerol methacrylate, glycidyl vinyl ether, and the like. The compound which forms a triple bond with an epoxy group is not particularly limited as long as it has a triple bond formed with an epoxy group in the molecule, and examples thereof include propargyl glycidyl ether and glycidyl propargyl ester. Acetylene glycidyl ether and the like. The solvent to be used in the reaction is not particularly limited as long as it does not react with an epoxy group and can dissolve a polyimine having a hydroxyl group or a carboxyl group. For example, a boronic solvent such as dimethyl sulfite or diethyl hydrazine, a carbamide solvent such as N,N-dimethylformamide or N,N-diethylformamide can be used, N, An acetamide solvent such as N-dimethylacetamide or N,N-diethylacetamide, or a pyrrolidone solvent such as N-methyl-2-pyrrolidone or N-vinyl-2-pyrrolidone. An ether solvent such as tetrahydrofuran or dioxane; an alcohol solvent such as methanol, ethanol or butanol; a cellosolve such as butyl cellosolve; a solvent such as hexamethylphosphonamide or T-butyrolactone; Etc., xylene, toluene-like aromatic hydrocarbons can also be used. These can be used singly or as a mixture. Since the solvent is removed afterwards, the boiling point of the soluble thermoplastic polyimine (having a hydroxyl group or a carboxyl group) can be selected. As low as possible, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied to the 32 paper scales in the process (please read the note on the back and fill out this page). Pack-----订ί 1299043 A7 ___B7_ V. Invention description (?.) Favorable. With respect to the reaction temperature, the reaction of the epoxy group and the hydroxyl group/carboxy group is preferably carried out at a temperature of from 40 to 130 °C. In particular, regarding a compound which forms a double bond with an epoxy group or a triple bond with an epoxy group, a preferred reaction temperature is a temperature at which double bond bonding or triple bond bonding does not cause decomposition or crosslinking by heat. Specifically, it is 40 to 100 ° C ', preferably 50 to 80 ° C. The reaction time is several minutes to about 15 hours. In this way, a solution of epoxy-modified polyimine was prepared. In order to improve the adhesion and developability of the copper foil, a thermosetting resin such as an epoxy resin or an acrylic resin, polyester, polyamide, polyurethane, or polycarbonate may be appropriately blended in the epoxy-modified polyimine solution. And other thermoplastic resins. Further, it may be mixed with a thermosetting resin other than an epoxy resin to obtain good physical properties. The thermosetting resin used herein may, for example, be bismaleimide, bisallylbisimide, phenol resin, cyanate resin or the like. The epoxy-modified polyimine solution is applied directly to the portion to be joined, and dried, or used in the form of a sheet which is coated and dried. The drying condition is preferably a lower temperature condition in which residual epoxy groups, double bonds, and triple bonds are not decomposed by heat and crosslinked. When the epoxy-modified polyimine of the present invention is mixed with a usual epoxy resin hardener, it is preferred because a cured product having good physical properties can be obtained. Any epoxy resin curing agent may be used, and an amine type, an imidazole type, an acid anhydride type, an acid type, or the like may be used, and various coupling agents may be mixed. Soluble polyimine other than epoxy-modified polyimine can also be used. The glass transition temperature Tg of the above-mentioned soluble polyimine is ____ 33 T paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 public meals) "~-- (Please read the back note first) Fill in this page again) -^--------^--------- 1299043 A7 ___B7 _ V. Invention description (Η) The higher the better, but based on the solubility and hardening properties The balance is set at 100~30〇. Preferably, it is from 120 to 300 ° C, more preferably from 140 to 280 ° C. The component (B) contained in the photosensitive resin composition of the present invention is a copolymer monomer having a carbon-carbon double bond, preferably a polyfunctional (meth)acrylic compound and/or the like thereof. (Meth)acrylic compounds. The term "polyfunctional (meth)acrylic compound" means at least one of a polyfunctional acrylic compound and a polyfunctional methacrylic compound. The polyfunctional acrylic compound is a compound having at least two acryl(enyl) groups (CH2=CHCO-); the polyfunctional methacrylic compound is 4 to 40-(CHR-CH2 - 0) in one molecule. - a compound of the reciprocal unit (wherein R is hydrogen or methyl or ethyl). By selecting such a compound, the monomer before curing is easily dissolved in the alkaline aqueous solution, and the resin in the unexposed portion can be quickly dissolved in the alkaline aqueous solution after the resin in the exposed portion is cured, so that good analysis can be imparted in a short time. degree. As a structure of bis(meth) acrylate which is easily soluble in an alkaline aqueous solution (please read the back of the page and fill out this page) 装--------Book---------^ __w(

本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1299043

五、發明說明（β) (式中R22爲氫基或甲基或乙基，R23爲2價有機基，S及t 爲2〜40的整數） 所代表之具有二個芳香環之二（甲基)丙烯酸酯化合物。當 通式（Π)中的s及t爲0或1時，組成物對鹼性水溶液的溶 解性變差，而有無法獲得良好的顯影性之傾向，s及t爲 41以上的化合物，在材料的取得上會有困難。 作爲(B)成份較佳爲，將通式（11)中s及t爲2〜10的二 (甲基)丙烯酸酯化合物、和通式（11)中s及t爲11〜20的二（ 甲基)丙烯酸酯化合物混合使用。更佳爲，將通式（11)中s 及t爲2〜5的二（甲基)丙烯酸酯化合物、和通式（11)中s及 t爲11〜16的二（甲基)丙烯酸酯化合物混合使用。 其混合比，相對於前者1重量份，後者較佳爲 0.1〜100重量份。若僅使用通式（11)中s及t爲2〜10的二（ 甲基)丙烯酸酯化合物，組成物對鹼性水溶液的溶解性變差 ，而有無法獲得良好的顯影性之傾向。 作爲(B)成份，可使用1種通式（11)所示的化合物，或 將2種以上的化合物混合使用。 作爲上述多官能（甲基)丙烯酸系化合物類(B)，可列舉 以下的化合物，但不限於這些化合物：雙酚F E0變性雙 丙烯酸酯(n=2〜50)(EO爲環氧乙烷、η爲環氧乙院的加成莫 耳數，以下相同），雙酚A ΕΟ變性雙丙烯酸酯(η=2〜50)， 雙酚S ΕΟ變性雙丙烯酸酯(η=2〜50)，雙酚F ΕΟ變性雙甲 基丙烯酸酯(η=2〜50)，雙酚S ΕΟ變性雙甲基丙烯酸酯 35 (請先閱讀背面之注意事項再填寫本頁) --------訂------I--. 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 1299043 A7 _B7__ 五、發明說明（η ) (11=2〜50)，雙酚A EO變性雙甲基丙烯酸酯(n=2〜50)，1，6 -己二醇二丙烯酸酯，新戊二醇二丙烯酸酯，乙二醇二丙 烯酸酯，季戊四醇二丙烯酸酯，三羥甲基丙烷三丙烯酸酯 ，季戊四醇三丙烯酸酯，二季戊四醇六丙烯酸酯，四羥甲 基丙烷四丙烯酸酯，四乙二醇二丙烯酸酯，1，6_己二醇二 甲基丙烯酸酯，新戊二醇二甲基丙烯酸酯，乙二醇二甲基 丙烯酸酯，季戊四醇二甲基丙烯酸酯，三羥甲基丙烷三甲 基丙烯酸酯，季戊四醇三甲基丙烯酸酯，二季戊四醇六甲 基丙烯酸酯，四羥甲基丙烷四甲基丙烯酸酯，四乙二醇二 甲基丙烯酸酯，甲氧基二乙二醇甲基丙烯酸酯，甲氧基聚 乙二醇甲基丙烯酸酯，/3 -甲基丙烯醯羥乙基氫化苯二甲 酸酯，/3 -甲基丙烯醯羥乙基氫化琥珀酸酯，3_氯-2-羥丙基甲基丙烯酸酯，硬脂基甲基丙烯酸酯，苯氧基乙基 丙烯酸酯，苯氧基二乙二醇丙烯酸酯，苯氧基聚乙二醇丙 烯酸酯，/3 _丙烯醯基羥乙基氫化琥珀酸酯，月桂基丙烯 酸酯，乙二醇二甲基丙烯酸酯，二乙二醇二甲基丙烯酸酯 ，三乙二醇二甲基丙烯酸酯，聚乙二醇二甲基丙烯酸酯， 1，3 _ 丁二醇二甲基丙烯酸酯，1，6 -己二醇二甲基丙烯酸 酯，新戊二醇二甲基丙烯酸酯，聚丙二醇二甲基丙烯酸酯 ，2 -羥基_ 1，3-二甲基丙烯醯基羥基丙烷，聚乙二醇二 丙烯酸酯，三丙二醇二丙烯酸酯，聚丙二醇二丙烯酸酯:，2 -羥基-1 -丙烯醯氧-3 -甲基丙烯醯氧丙烷，三羥甲基 丙烷三甲基丙烯酸酯，四羥甲基甲烷三丙烯酸酯，四羥甲 基甲烷四丙烯酸酯，甲氧基二丙二醇甲基丙烯酸酯，甲氧 36 本纸張尺度適用中國國家標準（CNS)A4規格（210x 297公釐） -----------^--------1--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ____B7____ 五、發明說明（W) 基三乙二醇丙烯酸酯，壬基苯氧基聚乙二醇丙烯酸酯，壬 基苯氧基聚丙二醇丙烯酸酯，1-丙烯醯氧丙基-2 -苯二 甲酸酯，異硬脂基丙烯酸酯，聚氧乙烯烷基醚丙烯酸酯， 壬基苯氧基乙二醇丙烯酸酯，聚丙二醇二甲基丙烯酸酯， 1，4- 丁二醇二甲基丙烯酸酯，3 -甲基-1，5 -戊二醇二甲 基丙烯酸酯，1，6_己二醇二甲基丙烯酸酯，1，9 -壬二醇 二甲基丙烯酸酯，2,4 _二乙基-1，5 -戊二醇二甲基丙烯 酸酯，1，4_環已烷二甲醇二甲基丙烯酸酯，二丙二醇二甲 基丙烯酸酯，三環癸烷二甲醇二丙烯酸酯，2,2 -加氫雙酚 A EO變性二丙烯酸酯(n=2〜50)，雙酚A PO變性二丙烯酸 酯(n=2〜50)(PO爲環氧丙烷，η爲環氧丙烷之加成莫耳數) ，2,4 -二乙基-1，5 -戊二醇二丙烯酸酯，乙氧化三羥甲 基丙烷三丙烯酸酯，丙氧化三羥甲基丙烷三丙烯酸酯，異 氰尿酸ΕΟ變性三丙烯酸酯，季戊四醇四丙烯酸酯，乙氧 化季戊四醇四丙烯酸酯，丙氧化季戊四醇四丙烯酸酯，雙 三羥甲基丙烷四丙烯酸酯，雙季戊四醇聚丙烯酸酯，異氰 尿酸三烯丙酯，縮水甘油甲基丙烯酸酯，縮水甘油烯丙醚 ，1，3,5 -三丙烯醯基六羥基-s -三嗪，三烯丙基-1，3,5 -苯羧酸酯，三烯丙胺，三烯丙基檸檬酸酯，三烯丙基磷酸 酯，別巴比妥(allobarbitone)，二嫌丙基二甲基砂院，二燦 丙基二硫醚，二烯丙醚，二烯丙基氰尿酸酯，二烯丙基異 苯二甲酸酯，二烯丙基對苯二甲酸酯，1，3_二烯丙氧基-2 -丙醇，二烯丙基硫醚，二烯丙基馬來酸酯，4,4’ -異丙 叉二酚二甲基丙烯酸酯，4,4’-異丙叉二苯氧基二丙烯酸酯 37 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1 I 111— Aw ·1111111 ^ · I------- (請先閱讀背面之注意事項再填寫本頁) A7 1299043 ___B7 ___ 五、發明說明uo 等等。這些多官能（甲基)丙烯酸系化合物類(B)，可使用1 種化合物，或混合數種來使用。 爲使本發明之感光性樹脂組成物所製得之感光性膜能 展現柔軟性，作爲上述多官能（甲基)丙烯酸系化合物類(B) ，較佳爲使用雙酚F EO變性二丙烯酸酯’雙酚A EO變性 二丙烯酸酯，雙酚S EO變性二丙烯酸酯’雙酚F EO變性 二甲基丙烯酸酯，雙酚S EO變性二甲基丙烯酸酯，雙酚A EO變性二甲基丙烯酸酯等等。較佳爲二丙烯酸酯或二甲基 丙烯酸酯的一分子中所含之E〇反覆單位有2〜5〇個，特佳 爲4〜40個的範圍之化合物。藉由EO的反覆單位，由於能 提高其對鹼性水溶液的溶解性，將能縮短所製得樹脂組成 物在曝光後的顯影時間’且解析度會變高。超過50時，所 得樹脂組成物的耐熱性有變差的傾向。 上述(B)成份，相對於本發明之上述可溶性聚醯亞胺 (A)100重量份，較佳爲含有1〜20〇重量份。少於1重量份 時，可壓接的溫度變高’且有解析度變差的傾向。超過 200重量份時，B階狀態的膜有參差產生，熱壓接時樹脂 變得易滲出，硬化物有變脆的傾向。較佳爲20〜1〇〇重量份 的範圍，更佳爲5〇〜80重量份。 特別是，當(A)和(B)的合計重量爲1〇〇重量份，（八)成 份較佳爲30〜90重量份，B成份較佳爲1〇〜7〇重量份。 藉由改變其等的h合比例’即可調整感光性膜的耐熱 性和可壓接溫度。 本發明之感光性樹脂組成物，除上述认）、（B)成份外 38 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） (請先閱讀背面之注意事項再填寫本頁) · I I I I I ! I « — — — — — — — I. 1299043 A7 B7 五、發明說明（Μ ) ，也能把(C)之光反應起始劑及/或增感劑當作必要成份。 作爲(C)成份之光反應起始劑，並沒有特別的限定。適 用的化合物，係利用波長爲g線左右的光能產生游離基者 。較佳爲，利用g線及I線之至少一方能產生游離基者。 這種化合物可列舉如：3,3’，4,4’-四（特丁基過氧竣基）二苯 甲酮、通式（I2)及（Π)所代表的醯基氧化膦化合物等。一般 所用的增感劑，或增感劑與光聚合助劑的組合，也能當作 上述光反應起始劑(C)來使用。光反應起始劑（(：)所產:之 游離基，會和具有雙鍵之反應基（乙烯基、丙烯酸基生甲基 丙烯醯基、烯丙基)反應。因此，多官能（甲基)芮烯酸系化 合物類(B)會進行聚合反應而促進交聯。 ’、 |25 0V. Description of the invention (β) (wherein R22 is a hydrogen group or a methyl group or an ethyl group, R23 is a divalent organic group, and S and t are integers of 2 to 40), and two of the two aromatic rings are represented. Base) acrylate compound. When s and t in the formula (Π) are 0 or 1, the solubility of the composition in the alkaline aqueous solution is deteriorated, and there is a tendency that good developability is not obtained, and the compound having s and t of 41 or more is There will be difficulties in obtaining materials. As the component (B), a di(meth)acrylate compound in which s and t in the formula (11) are 2 to 10, and a s in the formula (11) and t in the formula (11) of 11 to 20 are preferably used. A methyl acrylate compound is used in combination. More preferably, a di(meth) acrylate compound of the formula (11) wherein s and t are 2 to 5, and a di(meth) acrylate of the formula (11) wherein s and t are 11 to 16 are used. The compounds are used in combination. The mixing ratio thereof is preferably from 0.1 to 100 parts by weight based on 1 part by weight of the former. When only the bis (meth) acrylate compound of the formula (11) and t of 2 to 10 are used, the solubility of the composition in the alkaline aqueous solution is deteriorated, and there is a tendency that good developability cannot be obtained. As the component (B), one compound represented by the formula (11) or two or more compounds may be used in combination. Examples of the polyfunctional (meth)acrylic compound (B) include the following compounds, but are not limited to these compounds: bisphenol F E0 denatured diacrylate (n = 2 to 50) (EO is ethylene oxide) η is the addition mole number of the epoxy epoxide, the same below), bisphenol A oxime denatured diacrylate (η=2~50), bisphenol S oxime denatured diacrylate (η=2~50), Bisphenol F deuterated dimethacrylate (η=2~50), bisphenol S deuterated dimethacrylate 35 (please read the notes on the back and fill out this page) -------- Order ------I--. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1299043 A7 _B7__ V. Invention description (η) (11=2~50), bisphenol A EO denatured dimethacrylate (n=2~50), 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trishydroxyl Propane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol Acrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol Hexamethyl acrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxy polyethylene glycol methacrylate , /3 - methacryl oxime hydroxyethyl hydrogen phthalate, /3 - methacryl oxime hydroxyethyl hydrogen succinate, 3 chloro-2-hydroxypropyl methacrylate, stearyl Methacrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, /3 _ propylene hydroxyethyl hydride succinate, lauryl acrylate Ester, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 _ butanediol Acrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethyl Polyacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-1,3-methylpropenylhydroxypropane, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate: 2-hydroxy-1-propenyloxy-3-methylpropane oxirane, trimethylolpropane trimethacrylate, tetramethylolethane triacrylate, tetramethylolmethane tetraacrylate, methoxy Dipropylene glycol methacrylate, methoxy 36 This paper scale applies to China National Standard (CNS) A4 specification (210x 297 mm) -----------^-------- 1--------- (Please read the note on the back and fill out this page) 1299043 A7 ____B7____ V. Description of invention (W) Base triethylene glycol acrylate, nonylphenoxy polyethylene glycol Acrylate, mercaptophenoxy polypropylene glycol acrylate, 1-propenyl methoxypropyl-2-phthalate, isostearyl acrylate, polyoxyethylene alkyl ether acrylate, mercaptophenoxy Ethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethyl propylene Ethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate 1,4_cyclohexanediethanol dimethacrylate, dipropylene glycol dimethacrylate, tricyclodecane dimethanol diacrylate, 2,2-hydrogenated bisphenol A EO denatured diacrylate (n =2~50), bisphenol A PO modified diacrylate (n=2~50) (PO is propylene oxide, η is the molar addition of propylene oxide), 2,4-diethyl-1 , 5-pentanediol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, isocyanuric acid decyl triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol IV Acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3 ,5-tripropylene decyl hexahydroxy-s-triazine, triallyl-1,3,5-benzenecarboxylate, triallylamine, triallyl citrate , triallyl phosphate, allobarbitone, dipropyl dimethyl dimethyl sand, di-glycidyl disulfide, diallyl ether, diallyl cyanurate, diene Propyl isophthalate, diallyl terephthalate, 1,3-dipropoxy-2-propanol, diallyl sulfide, diallyl maleate ,4,4'-isopropylidene diphenol dimethacrylate, 4,4'-isopropylidene diphenoxy diacrylate 37 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 PCT) 1 I 111— Aw ·1111111 ^ · I------- (Please read the notes on the back and fill out this page) A7 1299043 ___B7 ___ V. Invention description uo etc. These polyfunctional (meth)acrylic compound (B) can be used as one type of compound or a mixture of several types. In order to exhibit flexibility in the photosensitive film obtained by the photosensitive resin composition of the present invention, as the above polyfunctional (meth)acrylic compound (B), it is preferred to use bisphenol F EO denatured diacrylate. 'Bisphenol A EO denatured diacrylate, bisphenol S EO denatured diacrylate' bisphenol F EO denatured dimethacrylate, bisphenol S EO denatured dimethacrylate, bisphenol A EO denatured dimethacrylate Ester and so on. Preferably, the E 〇 reversing unit contained in one molecule of the diacrylate or dimethacrylate has 2 to 5 Å, particularly preferably 4 to 40. By the EO reversal unit, since the solubility in the alkaline aqueous solution can be improved, the development time of the obtained resin composition after exposure can be shortened and the resolution becomes high. When it exceeds 50, the heat resistance of the obtained resin composition tends to be deteriorated. The component (B) is preferably contained in an amount of from 1 to 20 parts by weight based on 100 parts by weight of the above-mentioned soluble polyimine (A) of the present invention. When the amount is less than 1 part by weight, the temperature at which the pressure can be applied becomes high, and the resolution tends to be deteriorated. When the amount is more than 200 parts by weight, the film in the B-stage state is staggered, and the resin tends to bleed out during thermocompression bonding, and the cured product tends to become brittle. It is preferably in the range of 20 to 1 part by weight, more preferably 5 to 80 parts by weight. In particular, when the total weight of (A) and (B) is 1 part by weight, the (eight) component is preferably 30 to 90 parts by weight, and the component B is preferably 1 to 7 parts by weight. The heat resistance and the crimpable temperature of the photosensitive film can be adjusted by changing the ratio of h to the same. The photosensitive resin composition of the present invention, in addition to the above-mentioned components, and (B), the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) (please read the precautions on the back and fill in the form) Page) · IIIII ! I « — — — — — — — I. 1299043 A7 B7 V. INSTRUCTIONS (Μ) The photoreaction initiator and/or sensitizer of (C) can also be used as an essential component. The photoreaction initiator of the component (C) is not particularly limited. A suitable compound is one which generates a radical by using light energy having a wavelength of about g line. Preferably, at least one of the g line and the I line is capable of generating a radical. Examples of such a compound include 3,3', 4,4'-tetrakis(t-butylperoxyfluorenyl)benzophenone, fluorenylphosphine oxide compounds represented by the general formula (I2) and (fluorene), and the like. . A sensitizer generally used, or a combination of a sensitizer and a photopolymerization aid, can also be used as the photoreaction initiator (C). The photoreaction initiator ((:) produces a free radical which reacts with a reactive group having a double bond (vinyl group, acryloyl methacryloyl group, allyl group). Therefore, polyfunctional (methyl) The terpene-based compound (B) undergoes a polymerization reaction to promote crosslinking. ', |25 0

P-R (式中，R24 代表 C6H5_、C6H4(CH3)_、C6H2(Cil3)3 (CH3)3C-、C6H3C12 ; R25 及 R26 分別獨立地代袠 甲氧基、乙氧基、C6H4(CH3)-、c6h2(ch3)3-。） ι28 -----------AW --------訂------1— (請先閱讀背面之注意事項再填寫本頁) 26PR (wherein R24 represents C6H5_, C6H4(CH3)_, C6H2(Cil3)3(CH3)3C-, C6H3C12; R25 and R26 are independently substituted for methoxy, ethoxy, C6H4(CH3)-, c6h2 (ch3)3-.) ι28 -----------AW -------- order ------1— (Please read the notes on the back and fill out this page) 26

R 24.R 24.

R 27一 0R 27 - 0

P-R 29 (式中，R27及以28分別獨立地表（：6115-、（：6札〇：：%)_ 39 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 _____ B7__ 五、發明說明（W ) C6H2(CH3)3-、（CH3)3C-、C6H3C12 ; R29 代表 C6H5-、甲 氧基、乙氧基、c6h4(ch3)_、C6H2(CH3)3-。） 通式（12)代表的醯基氧化膦，會產生二個游離基；通 式（13)代表的醯基氧化膦，會依據α分裂而產生四個游離 基。以通式（13)代表的醯基氧化膦爲較佳。 在環氧變性聚醯亞胺的情形，爲了使附在聚醯亞胺樹 脂側鏈上的環氧基硬化，可取代上述游離基產生劑，而使 用光陽離子產生劑。例如可使用二甲氧基憩醌磺酸的二苯 基碘鎗鹽等之二苯基碘鎗鹽類，三苯銃鹽類，吡喃鎗鹽類 ，三苯鎗鹽類，重氮鎗鹽類等等。這時，較佳爲混合高陽 離子硬化性之脂環式環氧或乙烯醚化合物。 或者是，爲了使附於側鏈之環氧基硬化，也能使用光 鹼產生劑。例如可例示出：硝基苄醇或二硝基苄醇和異氰 酸酯反應所得之氨酯化合物，硝基-1-苯基乙醇或二硝基 -1 -苯基乙醇和異氰酸酯反應所得之氨酯化合物，二甲氧 基-2 -苯基-2 -丙醇和異氰酸酯反應所得之氨酯化合物 等等。 作爲游離基起始劑，也能使用各種過氧化物和下述增 感劑的組合。較佳的組合，係3,3’，4,4’ -四(特丁基過氧羧 基)二苯甲酮和以下增感劑的組合。 作爲增感劑，雖可列舉下述化合物，但不限於此：米 希勒酮、雙-4,4’-二甲基胺基二苯甲酮、苄基、4,4’-二 甲基胺基苄基、3,5 -雙（二乙基胺基苄叉）-Ν -甲基-4 -呢啶酮、3,5 -雙（二甲基胺基苄叉卜Ν-甲基-4 -锨啶酮 40 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------»^9. (請先閱讀背面之注意事項再填寫本頁) A7 1299043 _B7 _ 五、發明說明（) 、3,5 -雙（二乙基胺基苄叉）-N -乙基-4 -派啶酮、3,3f -羰基雙（7-二乙基胺基）香豆素、核黃素四丁酸酯、2 -甲基-1-〔4-(甲基硫代）苯基〕-2-嗎啉丙烷-1-酮 、2,4_二甲基噻噸酮、2,4-二乙基噻噸酮、2,4_二異丙 基噻噸酮、3,5 -二甲基噻噸酮、3,5 -二異丙基噻噸酮、1 -苯基-2 -(乙氧基羰基）羥基亞氨丙烷-1 _酮、苯偶因 醚、苯偶因異丙醚、苯並憩酮、5 -硝基厄、2 -硝基芴、 憩酮、1，2 -苯並憩醌、1 -苯基-5 -锍基-1H -四唑、噻 噸- 9 -酮、10 -噻噸酮、3 -乙醯基吲D朵、2,6 -二(p -二 甲基胺基苄叉）-4 -羧基環己酮、2,6 -二(p-二甲基胺基 苄叉）-4-羥基環己酮、2,6 -二(p-二乙基胺基苄叉）- 4 -羧基環己酮、2,6 -二(p -二乙基胺基苄叉）_ 4_羥基環 己酮、4,6 -二甲基-7 -乙基胺基香豆素、7 -二乙基胺基 - 4 -甲基香豆素、7-二乙基胺基-3-(1-甲基苯並咪唑 基)香豆素、3- (2-苯並噻唑）-7-二乙基胺基香豆素、2 -(p-二甲基胺基苯乙烯基）苯並噁哇、2 - (p-二甲基胺 基苯乙烯基)喹啉、4- (P-二甲基胺基苯乙烯基）喹啉、2 -(p-二甲基胺基苯乙烯基）苯並噻唑、2 - (p-二甲基胺 基苯乙烯基）-3,3-二甲基-3H- D引D朵等等。 (C)光反應起始劑及/或增感劑，相對於可溶性聚醯亞 胺樹脂(A)100重量份，較佳爲以0.1〜50重量份的比例存在 於組成物中，更佳爲以0.3〜20重量份的比例來存在。若脫 離0.1〜50重量份的範圍，可能無法獲得增感效果，或對顯 影性產生不佳的影響。作爲增感劑，可使用1種化合物， 41 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------1-----訂---------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ___ B7____ 五、發明說明（？？） 也能混合數種來使用。 上述光聚合助劑，係用來提高本發明的感光性樹脂組 成物之感光度。作爲光聚合助劑可列舉以下化合物，但不 限於此：4-二乙基胺基乙基苯甲酸酯、4-二甲基胺基乙 基苯甲酸酯、4 -二乙基胺基丙基苯甲酸酯、4_二甲基胺 基丙基苯甲酸酯、4-二甲基胺基異戊基苯甲酸酯、N-苯 基甘氨酸、N -甲基_ N -苯基甘氨酸、N - (4-氰基苯基) 甘氨酸、4-二甲基胺基苯甲腈、乙二醇二锍基乙酸酯、乙 二醇雙(3 -锍基丙酸酯）、三羥甲基丙烷锍基乙酸酯、三羥 甲基丙烷三(3-锍基丙酸酯）、季戊四醇四锍基乙酸酯、季 戊四醇三（3 -巯基丙酸酯）、三羥甲基乙烷三锍基乙酸酯、 三羥甲基丙烷三锍基乙酸酯、三羥甲基乙烷三（3 -锍基丙 酸酯）、二季戊四醇六（3 -锍基丙酸酯）、锍基乙酸、α -锍基丙酸、特丁基過氧苯甲酸酯、特丁基過氧甲氧基苯甲 酸酯、特丁基過氧硝基苯甲酸酯、特丁基過氧乙基苯甲酸 酯、苯基異丙基過氧苯甲酸酯、雙特丁基二過氧苯二甲酸 酯、三特丁基三過氧偏苯三酸酯、四特丁基四過氧均苯四 甲酸酯、2,5 -二甲基-2,5 -二（苯醯過氧）己烷、3,3、4,4’ -四(特丁基過氧羰基)二苯甲酮、3,3’，4,4’_四(特戊基過氧 羰基)二苯甲酮、3,3’，4,4’-四(特己基過氧羰基)二苯甲酮、 2,6-雙(對迭氮苄叉）-4 -羥基環己酮、2,6-雙(對迭氮苄 叉）-4 -羧基環己酮、2,6_雙(對迭氮苄叉）-4 -甲氧基環 己酮、2,6 -雙（對迭氮苄叉）-4 -羥基甲基環己酮、3,5-雙(對迭氮苄叉）-1-甲基-4-哌啶酮、3,5-雙(對迭氮苄 42 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐） tI----tr--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _B7_ 五、發明說明（f。） 叉）-4 - p欣啶酮、3,5 -雙（對迭氮苄叉）-N -乙醯基-4 -派啶酮、3,5-雙(對迭氮苄叉）-N-甲氧基羰基-4-哌陡 酮、2,6-雙（對迭氮苄叉）-4 -羥基環己酮、2,6_雙（間迭 氮苄叉）-4-羧基環己酮、2,6-雙（間迭氮苄叉）-4 -甲氧 基環己酮、2,6-雙（間迭氮苄叉）-4 -羥甲基環己酮、3,5 -雙(間迭氮苄叉）_N -甲基- 4-哌啶酮、3,5-雙(間迭氮 苄叉）_ 4 - p飛啶酮、3,5 -雙（間迭氮苄叉）-N-乙醯基- 4 -呢啶酮、3,5-雙(間迭氮苄叉）- N -甲氧基羰基-4-呢 啶酮、2,6-雙（對迭氮肉桂叉）-4 -羥基環己酮、2,6-雙( 對迭氮肉桂叉）-4-羧基環己酮、2,6_雙（對迭氮肉桂叉) - 4-環己酮、3,5-雙（對迭氮肉桂叉）- N-甲基- 4-锨 啶酮、4,4f-二迭氮查耳酮、3,3f-二迭氮查耳酮、3,4’_二 迭氮查耳酮、4,3’-二迭氮查耳酮、1,3-二苯基_ 1，2,3 -丙烷三酮-2 -(鄰乙醯）胎、1，3 _二苯基-1，2,3 -丙烷三 酮_ 2 -(鄰-正丙基羰基）聘、1，3 -二苯基-1，2,3 -丙烷 三酮_2-(鄰甲氧基羰基)fl弓、1，3_二苯基-1，2,3-丙烷 三酮- 2 -(鄰乙氧羰基）目弓、1，3 -二苯基-1，2,3 -丙垸三 酮- 2 -（鄰苯醯)肟、1，3 -二苯基- 1，2,3 -丙烷三酮-2 -( 鄰苯氧基羰基)聘、1,3-雙(對甲基苯基）-1，2,3_丙烷三酮 - 2-（鄰苯醯)聘、1，3-雙(對甲基苯基）-1，2,3-丙烷三酮 - 2-(鄰乙氧羰基)聘、1-(對甲氧苯基）-3-(對硝基苯基 )-1，2,3 -丙烷三酮-2 -(鄰苯氧基羰基)肟等等。作爲以 上形式以外的助劑，也能含有三乙胺、三丁胺、三乙醇胺 等的三烷基胺類。這些光聚合助劑，可使用1種化合物， 43 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----I I I I ^ --------- (請先閱讀背面之注意事項再填寫本頁) A7 1299043 _____B7___ 五、發明說明（W ) 也能混合數種來使用。 (請先閱讀背面之注意事項再填寫本頁) 光聚合助劑，相對於可溶性聚醯亞胺樹脂(A)100重量 份，較佳爲以〇·1〜50重量份的比例存在於組成物中，更佳 爲以0.3〜20重量份的比例來存在。若脫離0.1〜50重量份 的範圔，可能無法獲得目的之增感效果，或對顯影性產生 不佳的影響。 本發明之感光性樹脂組成物，係含有上述可溶性聚醯 亞胺(Α)、多官能（甲基）丙烯酸系化合物類(Β)、（C)光反應 起始劑，視必要也能含有上述增感劑、光聚合助劑、以及 其他各種成份。作爲光聚合助劑，可使用1種化合物’也 能混合數種來使用。 又，本發明之組成物，爲達成可供實用之感光度’除 上述增感劑和光聚合助劑外，也能含有(Β)成份以外之其# 共聚單體。共聚單體是具有碳-碳雙鍵的化合物’而使光 聚合變容易。 作爲共聚單體較佳爲：二乙烯苯、1，6-己二醇二丙嫌 酸酯、新戊二醇二丙烯酸酯、乙二醇二丙烯酸酯、季戊四 醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙 烯酸酯、二季戊四醇六丙烯酸酯、四羥甲基丙烷四丙嫌酸 酯、四乙二醇二丙烯酸酯、1，6-己二醇二甲基丙烯酸酯、 新戊二醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、季戊 四醇二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、季 戊四醇三甲基丙烯酸酯、二季戊四醇六甲基丙烯酸酯、四 羥甲基丙烷四甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 ___ B7__ 五、發明說明（U) 甲氧基乙二醇甲基丙烯酸酯、甲氧基聚乙二醇甲基丙烯酸 酯、/3 _甲基丙烯醯羥乙基氫化苯二甲酸酯、沒-甲基丙 烯醯羥乙基氫化琥珀酸酯、3 -氯-2-羥丙基甲基丙烯酸 酯、硬脂基甲基丙烯酸酯、苯氧乙基丙烯酸酯、苯氧基二 乙二醇丙烯酸酯、苯氧基聚乙二醇丙烯酸酯、Θ -丙烯醯 基羥乙基氫化琥珀酸酯、月桂基丙烯酸酯、乙二醇二甲基 丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙 烯酸酯、聚乙二醇二甲基丙烯酸酯、1，3- 丁二醇二甲基丙 烯酸酯、1，6-己二醇二甲基丙烯酸酯、新戊二醇二甲基丙 烯酸酯、聚丙二醇二甲基丙烯酸酯、2 -羥基-1，3 -二甲 基丙烯氧基丙烷、2,2 -雙〔4 -(甲基丙烯氧乙氧基)苯基〕 丙烷、2,2 -雙〔4_ (甲基丙烯氧二乙氧基）苯基〕丙烷、 2,2 -雙〔4 -(甲基丙嫌氧聚乙氧基)苯基〕丙院、聚乙二醇 二丙烯酸酯、三丙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯 、2,2-雙〔4 -(丙烯氧二乙氧基)苯基〕丙烷、2,2 -雙〔4 -（丙烯氧聚乙氧基）苯基〕丙烷、2 -羥基-1 -丙烯氧基 -3-甲基丙烯氧基丙烷、三羥甲基丙烷三甲基丙烯酸酯、 四羥甲基甲烷三丙烯酸酯、四羥甲基甲烷四丙烯酸酯、甲 氧基二丙二醇甲基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、 壬基苯氧基聚乙二醇丙烯酸酯、壬基苯氧基聚丙二醇丙烯 酸酯、1 -丙烯醯基羥丙基-2 -苯二甲酸酯、異硬脂基丙 烯酸酯、聚氧乙烯烷基醚丙烯酸酯、壬基苯氧基乙二醇丙 烯酸酯、聚丙二醇二甲基丙烯酸酯、1，4- 丁二醇二甲基丙 烯酸酯、3 _甲基-1，5 -戊二醇二甲基丙烯酸酯、1，6 -己 45 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------^-------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ___jB7___ —__ 五、發明說明（μ ) 二醇二甲基丙烯酸酯、1，9 _壬二醇甲基丙烯酸酯、2,4 -二乙基-1，5-戊二醇二甲基丙烯酸酯、L4-環己烷二甲 醇二甲基丙烯酸酯、二丙二醇二丙烯酸酯' 三環癸烷三甲 醇二丙烯酸酯、2,2-加氫雙〔4-(丙烯氧基聚乙氧基)苯基 〕丙烷、2,2 _雙〔4 -(丙烯氧基聚丙氧基）苯基〕丙烷、 2,4-二乙基-1，5 -戊二醇二丙烯酸酯、乙氧化三羥甲基 丙烷三丙烯酸酯、丙氧化三羥甲基丙烷三丙烯酸酯、異氰 尿酸三（乙烷丙烯酸酯）、季戊四醇四丙烯酸酯、乙氧化季 戊四醇四丙烯酸酯、丙氧化季戊四醇四丙烯酸酯、雙三羥 甲基丙烷四丙烯酸酯、二季戊四醇聚丙烯酸酯、異氰尿酸 三烯丙基、縮水甘油甲基丙烯酸酯、縮水甘油烯丙醚、 1，3,5 -苯羧酸酯、三烯丙胺、三烯丙基檸檬酸酯、三烯丙 基磷酸酯、5,5 -二烯丙基別巴比妥酸、二烯丙胺、二烯丙 基二甲基矽烷、二烯丙基二硫醚、二烯丙醚、二烯丙基氰 尿酸酯、二烯丙基異苯二甲酸酯、二烯丙基對苯二甲酸酯 、1，3 -二烯丙氧基-2 -丙醇、二烯丙基硫醚二烯丙基馬 .來酸酯、4,4’-異丙叉雙酚二甲基丙烯酸酯等等，但不限於 此。爲提高交聯密度，更佳爲使用2官能以上的單體。 又，將本發明之感光性被覆層用樹脂組成物所製得的 被覆層積層在軟性基板上時，基於可減輕板彎的觀點，作 爲共聚單體，較佳爲使用選自雙酚F EO變性二丙烯酸酯 、雙酚A EO變性二丙烯酸酯、雙酚S EO變性二丙烯酸酯 中之至少一種以上的二丙烯酸酯。 該共聚單體，相對於本發明之聚醯亞胺1〇〇重量份， 46 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ____B7____ 五、發明說明（叫） 較佳爲以1〜200重量份的比例配合’更佳爲3〜150重量份 的範圍。若脫離1〜200重量份的範圍’可能無法獲得目的 之增感效果，或對顯影性產生不佳的影響。作爲共聚單體 ，可使用1種化合物，也能混合數種來使用。 作爲上述其他成份，可列舉可溶性聚醯亞胺(A)、多 官能（甲基)丙烯酸系化合物類(B)以外的樹脂’有機或無機 塡料類，強化材，偶合劑，各種添加劑’有機溶劑等等。 作爲可溶性聚醯亞胺(A)、多官能（甲基)丙烯酸系化合 物類(B)以外的樹脂’例如有熱固性樹脂和熱塑性樹脂。作 爲熱固性樹脂，有環氧樹脂、熱固性丙烯酸系樹脂等；作 爲熱塑性樹脂，有聚酯、聚醯胺、聚氨酯、聚碳酸酯等等 〇 上述環氧樹脂，係用來提昇感光性樹脂組成物之接著 性者。環氧樹脂的種類並沒有特別的限定，可列舉以下的 化合物·· Epikote 828(油化殼牌公司製）等的雙酚樹脂， 180S65(油化殻牌公司製）等的鄰甲酚酚醛淸漆樹脂， 157S70(油化殼牌公司製）等的雙酚A酚醛淸漆樹脂， 1032H60(油化殻牌公司製)等的三羥基苯基甲烷酚醛淸漆樹 脂，ESN375等的萘芳烷基酚醛淸漆樹脂，四酚乙院 1031S(油化殼牌公司製），YGD414S(東都化成），三羥基苯 基甲烷EPPN502H(日本化藥），特殊雙酚VG3101L(三井化 學），特殊萘酚NC7000(曰本化藥），TETRAD - X， TETRAD - C(三菱瓦斯化學公司製)等的縮水甘油胺型樹脂 等。 47 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _____B7_____ 五、發明說明Ur) 環氧樹脂可混合在分子內具有和環氧基形成的雙鍵或 三鍵結合之化合物、或其他熱固性樹脂來使用。作爲這種 化合物，可例示出烯丙基縮水甘油醚、縮水甘油丙烯酸酯 、縮水甘油甲基丙烯酸酯、縮水甘油乙烯醚、炔丙基縮水 甘油醚、縮水甘油丙炔酯、乙炔基縮水甘油醚等。作爲上 述其他熱固性樹脂，可列舉雙馬來醯亞胺、雙烯丙基雙醯 亞胺、酚樹脂、氰酸酯樹脂等等。 在本發明之感光性樹脂組成物中含有環氧樹脂時，若 進一步含有環氧樹脂的硬化劑，將能獲得具有良好物性之 硬化物。這種硬化劑並沒有特別的限定，可列舉胺系、咪 唑系、酸酐系、酸系硬化劑。 本發明之感光性組成物可含有有機溶劑。只要在溶解 於適當有機溶劑的狀態，將能以溶液(淸漆)狀態來供使用 ，而在塗佈乾燥時變得非常方便。所使用的溶劑，基於溶 解性的觀點以非質子性極性溶劑爲佳，具體而言可列舉以 下化合物：N -甲基-2 -吡咯烷酮、N -乙醯基-2 -吡咯 烷酮、N -苄基-2 -吡咯烷酮、N，N -二甲基甲醯胺、N，N -二乙基甲醯胺、N，N_二甲基乙醯胺、二甲亞碾、六甲 基磷醯胺、N_乙醯基-ε -、己內酯、二甲基咪唑烷二 酮、二乙烯基二甲醚、三乙烯基二甲醚、r -丁內酯、二 噁烷、二惡茂烷、四氫呋喃、氯仿、二氯甲烷等等。這些 可單獨使用或以混合系的形式來使用。 該有機溶劑，能使可溶性聚醯亞胺(A)的合成反應所 用之溶劑殘留來使用，或在離析後之可溶性聚醯亞胺中重 48 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---I----丨丨 ---— — III ^ · I I------ (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _B7 __ 五、發明說明（Μ ) 新添加來使用。爲改善樹脂組成物溶液之塗佈性，在不致 對聚合物的溶解性產生不佳影響的範圍內混合甲苯、二甲 苯、二乙酮、甲氧基苯、環戊酮等上述以外的溶劑亦可。 又，爲了使乾燥後的膜中殘留有一定程度的溶劑，藉以降 低可壓接溫度，亦可混合低沸點溶劑和高沸點溶劑。 本發明的組成物中所含之可溶性聚醯亞胺，由於對有 機溶劑的溶解性良好，故可溶解於以二噁烷、二惡茂烷、 四氫呋喃等的醚系溶劑，以氯仿、二氯甲烷等的鹵素系溶 劑爲首之沸點120°C以下的溶劑。特別是作爲酸二酐的主 成份，係使用2,2’-六氟丙叉二苯二甲酸二酐、2,3,3\4·-雙苯基四羧酸二酐、式(VI)所代表的酯系的酸二酐者，作 爲二胺，係使用在分子內具有2個以上羧基之二胺、在m 位具有胺基之芳香族二胺、具有碾基之二胺、通式(3)所代 表之二矽氧烷二胺等，所得可溶性聚醯亞胺(A)之溶解性極 高。由於能溶解於上述沸點12(TC以下的溶劑中，若將感 光性樹脂組成物溶解於該等溶劑所得之溶液進行塗佈、乾 燥，由於乾燥時不需要高溫，因此能防止所含的（甲基）芮 烯酸系化合物(B)之熱聚合。 本發明的感光性樹脂組成物之熱硬化後分解開始溫度 高，通常爲300°C以上，也可以是32(TC以上、340°C以上 〇 可將硬化溫度設定在200°C以下。FPC的導體層主餐 使用銅，若銅曝露在超過200°C的溫度下，銅的結晶構逭 將逐漸變化，而使強度降低。因此，本發明之感光性樹脂 49 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝--------訂--------- 1299043 A7 _B7___ 五、發明說明U7) 組成物，可當作被覆膜而用於FPC。 本發明之感光性樹脂組成物之硬化後的彈性模數可爲 10〜3000MPa。藉由具有該範圍的彈性模數，當用於被覆膜 時，可緩和被覆膜和底膜間之彈性模數、熱膨脹率之不匹 配所產生之應力。較佳爲10〜2500MPa，更佳爲 10〜2000MPa 〇 本發明之感光性樹脂組成物，硬化後之焊料耐熱性 (300°C)可爲3分以上。因此，積層銅並硬化後的樹脂具有 耐熱性，就算浸在300°C的焊料中3分鐘也看不出有發泡 或剝離等，完全不會劣化。對200°C的焊料，就算浸5分 以上也未發現劣化的情形。 本發明之感光性樹脂組成物，其硬化後的熱膨脹係數 可爲20ppm〜500ppm。因此，例如當作被覆膜而積層於銅 上時，其熱膨脹係數和銅箔差異不大，而能防止基板的板 彎。硬化後之熱膨脹係數較佳爲20〜500ppm，更佳爲 20〜400ppm，特佳爲 20〜300ppm。 如上述般，本發明之感光性樹脂組成物，由於所含的 (A)可溶性聚醯亞胺可溶於有機溶劑，因此能當作感光性防 焊劑來使用。例如，作爲感光性樹脂組成物溶液，也能直 接當作液體光阻來使用。又，藉由澆鑄等可容易地成形爲 膜狀而作成感光性膜，可作爲感光性乾膜光阻來使用。 在此之乾膜光阻，可大致分成2種，即用來形成銅電 路之伴演蝕刻劑的角色後最終須剝離之膜狀光阻，以及， 同時伴演印刷配線板等的電路之絕緣保護膜及膜狀光阻這 50 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ___J7___ 五、發明說明（# ) 2個角色之感光性被覆膜。本發明中之「被覆膜」，係同 時伴演膜狀光阻及絕緣保護膜這2個角色者。 在製造感光性膜時，首先是將感光性樹脂組成物(含有 (A)成份之可溶性聚醯亞胺、（B)成份之1分子中具有1個 以上芳香環且具有2個以上碳-碳間雙鍵結合之化合物、 (C)成份之光反應起始劑及/或增感劑)及其他成份均一溶解 於有機溶劑中。在此所用的有機溶劑，只要是能溶解感光 性樹脂組成物之溶劑即可，例如可使用四氫呋喃、二噁烷 、二惡茂院等的醚系溶劑，丙酮、甲基乙基酮等的酮系溶 劑，甲醇、乙醇等之醇系溶劑等。這些溶劑可單獨使用或 混合2種以上來使用。因之後須進行溶劑的除去，故儘量 選擇可溶解(A)、（B)、（C)成份等之低沸點者，在製程上較 有利。 將所得的感光性樹脂組成物之溶液均一塗佈於支持膜 上後使其乾燥，而製成膜狀的感光性膜。將其當作被覆膜 來使用。這時，可塗佈在金屬或PET膜等的支持體上，使 其乾燥後，從支持體剝下而單獨以膜的狀態來處理。又， 如圖1所示般，也能以保持積層在PET等膜16上的形態 使用。也能在感光性聚醯亞胺14的表面積層保護膜16來 使用。該感光性樹脂組成物之乾燥溫度之較佳溫度範圍， 是在不致因熱而使多官能（甲基)丙烯酸系化合物(B)所具有 的雙鍵、或組成物所含之其他化合物的雙鍵、三鍵、環氧 基等反應而變得非活性化之溫度，具體而言爲180°C以下 ，較佳爲150°C以下，更佳爲100°C以下。乾燥溫度從低溫 51 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----------—--------^--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 —_ B7___ 五、發明說明（叼） 分段上昇亦可。乾燥時間’只要所含的溶劑大部分能揮發 ’而使所塗佈之淸漆能薄膜化之時間即可’具體而目爲數 分〜30分，較佳爲數分〜15分。 針對本發明之被覆膜作說明。 通常FPC的製程，係在長帶狀的薄膜上塗佈接著劑， 經乾燥後連續積層銅箔，故生產性良好。然而如習知技術 所敘述般，在貼合前之被覆膜上，須進行與電路端子部或 零件接合部一致之鑽孔或開窗加工，而將被覆膜的孔等和 FPC端子部或零件接合部對準之作業是幾乎接近手工作業 ，且因是在小的工件尺寸下採批式貼合，故作業性及位置 精度低，且有耗費成本的問題。 本發明之被覆膜，由於能以膜狀來使用，故能容易地 貼合在基板導體面上。特別是，可在150°C以下的溫度積 層，不須透過接著劑即可直接積層於印刷基板。本發明之 感光性樹脂組成物，經由曝光即容易在顯影液中形成不溶 化，且未曝光部分對顯影液的溶解性高。因此’能形成高 精度的圖案。如此般，可以良好的作業效率製得位置精度 優異的被覆膜積層基板。 圖2係顯示使用本發明的被覆膜之軟性印刷基板的製 程。圖2(a)、（b)，係將銅面積層板(CCL)、和本發明之具 有PET膜和保護膜的積層板形態之感光性被覆膜貼合之製 程。該製程，係將事先藉銅箔等導體來形成電路之CCL導 電體面，用感光性乾膜（被覆膜）保護之製程。具體而言， 係將CCL和感光性乾膜(被覆膜)對準，利用熱積層、熱壓 52 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -----------•裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _B7 _ 五、發明說明（θ) 或熱真空積層來進行貼合。 積層溫度越低越好，係在150°C以下，較佳爲130°C 以下，更佳爲ll〇°C以下。 以往所用之丙烯酸系樹脂感光性膜之壓接時的溫度條 件爲80〜150°C，非感光性膜的情形通常爲18〇〜200°C。又 ，以往所用之聚醯亞胺膜的條件爲150〜300°C。然而，對 比於這些溫度條件，本發明之被覆膜之壓接，可在比上述 爲低的溫度，例如20〜150°C之溫度範圍進行成爲B階狀態 的膜之壓接，因此，可獲得解析度良好的圖案。 這時的溫度，較佳爲不致因熱而產生環氧基或雙鍵、 三鍵結合之打開的溫度範圍，具體而言爲150°C以下，較 佳爲130°C以下，更佳爲l〇〇°C以下。 又，爲了不使二（甲基)丙烯酸系化合物硬化而進行積 層，可實施積層的溫度爲150t以下，較佳爲130°C以下， 更佳爲l〇〇°C以下。該被覆膜在室溫下爲散開的薄膜，且 在積層時一受熱就會展現流動性和粘著性。 本發明之被覆膜，藉由在FPC和被覆膜的貼合後進行 曝光、顯影，即可實施用來接合FPC端子部之鑽孔，而能 改善位置精度和作業性的問題。 具體而言，藉由進行曝光顯影，可在必要處實施用來 接合基板端子部之鑽孔等。圖2(c)的步驟，係在積層體上 ，透過既定圖案的光罩圖案來照射光；圖2(d)的步驟，係 藉由鹼性溶液之溶解除去被覆膜的未曝光部之顯影處理， 而獲得所望的圖案。該顯影，可使用一般的正型光阻顯影 53 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閲讀背面之注意事項再填寫本頁) 1299043 B7 五、發明說明（幻） 裝置來進行。 曝光前，在被覆膜上載置光罩，其係具備描繪有線寬/ 線距寬= 100/100// m以下之微細的平行線、曲線、孔徑X 線寬= l〇〇#mXl〇〇//m以下之微細孔等而構成之圖案。曝 光後，經顯影來形成圖案。接著用淸洗液洗淨，除去顯影 溶劑。 如此般，可高作業效率地且位置精度優異地製得積層 有被覆膜之基板。 將該基板和其他零件用焊料接合時，通常須曝露於 200°C以上的高溫下數秒來進行接合。本發明之感光性樹脂 組成物在熱硬化後之耐熱溫度高，通常爲300°C以上，較 佳爲32(TC以上，更佳爲340°C以上。因此，硬化後之被覆 膜不致劣化，而能將被覆膜積層印刷基板接合於所望的零 件。 被覆後之本發明的被覆膜單獨的彈性模數越小越好° 此乃基於，爲了緩衝被覆膜和底膜間之彈性模數、熱膨脹 率之不匹配所產生之應力。較佳爲，硬化後之彈性模數爲 lOMPa〜3000MPa，本發明之感光性樹脂組成物則具備該特 性。 若被覆膜硬化後之彈性模數過高，將被覆膜和形成有 電路之銅面積層板(CCL)接著後進行加熱硬化時，起因於 聚醯亞胺之硬化收縮會產生樣本捲曲、彎曲的情形。該捲 曲現象，當其被當作軟性印刷基板(FPC)之被覆膜來使用時 ，會有微細銅電路之剝離或斷線容易產生之缺點。因此’ 54 __ -------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 ___B7 五、發明說明（於） 被覆膜硬化後的彈性模數較佳爲lOOMPa〜2500MPa，更佳 爲 lOOMPa〜2000MPa，特佳爲 lOOMPa〜1500MPa。 接著，在基板上所積層之被覆膜上，透過既定圖案的 光罩照光後，使用鹼性溶液之顯影液，將未曝光部溶解除 去而製得所望的圖案。該顯影步驟，可使用一般的正型光 阻顯影裝置來進行。 作爲顯影液，可使用鹼性水溶液或有機溶劑。本發明 之感光性樹脂組成物可溶解於有機溶劑和鹼性水溶液。 顯影液，係對水或甲醇等的醇類具可溶性、呈驗性之 水溶液或有機溶劑，可爲1種化合物的溶液，或2種以上 化合物的溶液。鹼性溶液，一般是將鹼性化合物溶解於水 或甲醇等醇類而成的溶液。 作爲顯影液所用之鹼性溶液所含之鹼，只要是可溶於 水或醇類、且溶液呈鹼性之化合物(鹼性化合物)即可，沒 有特別的限定。作爲這種化合物，例如可列舉鹼金屬、驗 土類金屬、銨離子之氫氧化物、碳酸鹽、胺鹽等。具體而 言可列舉以下化合物：2-二甲胺乙醇、3 -二甲胺—1 —丙 醇、4 -二甲胺-1_ 丁醇、5-二甲胺-1-戊醇、6—二甲 胺- 1 -己醇、2 -二甲胺-2 -甲基-1 —丙醇、3 -二甲胺 - 2,2-二甲基- 1 -丙醇、2 -二乙胺乙醇、3 -二乙胺 _丙醇、2 -二異丙胺乙醇、2-雙-正丁胺乙醇、n，n” 二苄基-2 -胺基乙醇、2 - (2 -二甲胺乙氧基）乙醇、2 一 (2 - 一乙胺乙氧基）乙醇、1-二甲胺-2-丙醇、~乙 胺-2 -丙醇、N-甲基二乙醇胺、N -乙基二乙醇胺、N_ 55 ^紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐1 ------------ -----------裝--------訂------ 丨！§ (請先閱讀背面之注意事項再填寫本頁) A7 1299043 ____B7_ —_ 五、發明說明（β ) (請先閱讀背面之注意事項再填寫本頁) 正丁基二乙醇胺、N_特丁基二乙醇胺、N-月桂基二乙醇 胺、3 -二乙胺- 1，2-丙二醇、三乙醇胺、三異丙醇胺、N -甲基乙醇胺、N -乙基乙醇胺、N -正丁基乙醇胺、N -特丁基乙醇胺、二乙醇胺、二異丙醇胺、2 -胺基乙醇、3 -胺基- 1 -丙醇、[胺基-卜丁醇、6 -胺基-卜己醇 、1 -胺基- 2 -丙醇、2-胺基- 2,2-二甲基厂1 -丙醇、 1 -胺基丁醇、2 -胺基-1- 丁醇、N - (2 -胺乙基）乙醇胺 、2-胺基-2-甲基- 1，3-丙—^醇、2-月女基- 2-乙基 1，3-丙二醇、3-胺基- 1，2-丙二醇、2_胺基_2-羥甲 基-1，3 -丙二醇、氫氧化鈉、氫氧化鉀、氫氧化銨、碳酸 鈉、碳酸鉀、碳酸銨、碳酸氫鈉、碳酸氫鉀、碳酸氫銨、 氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四 異丙銨、胺基甲醇、2 -胺基乙醇、3 _胺基丙醇、2 -胺基 丙醇、甲胺、乙胺、丙胺、異丙胺、二甲胺、二乙胺、二 丙胺、二異丙胺、三甲胺、三乙胺、三丙胺、三異丙胺等 這些化合物，可單獨使用，或組合2種以上來使用。 顯影液除鹼性溶液外，也能使用有機溶劑。這時，可 單獨使用有機溶劑，或使用可完全溶解感光性聚醯亞胺之 良溶劑和溶解力差的貧溶劑之混合溶劑系。具體而言，爲 改善聚醯亞胺之溶解性，可部分含有甲醇、乙醇、丙醇、 異丙醇、異丁醇、N -甲基-2 -吡咯烷酮、N，N-二甲基 甲醯胺、N，N-二甲基乙醯胺等之水溶性有機溶劑，亦可 混合2種以上的溶劑來使用。上述鹼性化合物的濃度一般 56 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 B7 五、發明說明（沙） 爲0.1〜50重量％，考慮到對支持基板等的影響，較佳爲 0.1〜30重量％。更佳爲〇·1〜1〇重量％，特佳爲0·1〜5重重 % ° 顯影所形成的圖案，經淸洗液洗淨來除去顯影液。淸 洗液的例子，有和顯影液之混合性良好之甲醇、乙醇、異 丙醇、水等等。 將具有上述處理所形成的圖案之光阻膜之基板’藉由 以20〜200°C之適當溫度實施加熱處理，使未反應的基（雙 鍵等）反應，而使該光阻完全硬化。這時的加熱溫度超過 200°C時，主要使用於基板導體層中的銅之結晶構造產生變 化，將導致強度降低故必須注意。如此般，可製得以形成 有高解析度的所望圖案之聚醯亞胺膜作爲被覆膜之基板。 膜之耐熱性高且機械特性優異。 由於本發明之感光性樹脂組成物具可溶性，因此使用 本發明之感光性乾膜光阻可容易地調製出具有被覆膜(形成 有所望圖案)之基板。 將上述處理所得的圖案，藉由在100〜200°C之範圍內 所選擇的溫度下進行加熱處理，不經塗佈乾燥製程即可製 得形成有樹脂圖案之CCL。 使用本發明的感光性樹脂組成物之被覆膜所積層而成 之CCL，基於感光性樹脂組成物的特性，其不致彎曲或捲 曲而呈平坦狀。本發明之被覆膜所製得的樹脂圖案，其耐 熱性高、機械特性優異、特別是解析度高。詳而言之，硬 化後的彈性模數爲lOOMPa〜3000MPa而具有優異的機械強 57 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） — I — Aw . I — II---t---111111 (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ___B7___ 五、發明說明（竹） 度，解析度爲線寬/線距= 100/100//m以下之高解析度。又 ，硬化後具有焊料耐熱性(300°C)3分鐘以上的高耐熱性。 和銅積層再硬化後的樹脂，具有300°C以上之焊料浴 耐熱性，即使浸在300°C的焊料中3分鐘也不會產生發泡 或剝離等，完全不會劣化。對於200°C的焊料，浸5分鐘 以上也不會產生劣化。 本發明之被覆膜可形成三層構造，係由底膜、使用本 發明的感光性樹脂組成物所製得之感光性膜、保護膜所構 成。保護膜對感光性膜具有適當的密合性和剝離性。 具體而言，係由（1)底膜、（2)本發明的感光性樹脂組 成物所構成之感光性膜、（3)保護膜依此順序所積層而成之 三層構造。該保護膜，係將聚乙稀和乙燦乙嫌醇樹脂的共 聚物膜、與拉伸聚乙烯膜經貼合而成；或將聚乙烯和乙烯 乙烯醇樹脂的共聚物膜、與拉伸聚乙烯膜經同時擠製法所 得者’且保護膜係形成感光性接著片接合面。 本發明的3層構造片中之底膜，可使用聚對苯二甲酸 乙二醇酯(PET)膜、聚苯硫醚、聚醯亞胺膜等通常市售的各 種膜’特別是在要求耐熱性的用途上，較佳爲使用聚醯亞 胺膜。關於底膜之感光性膜接合面，較佳爲實施表面處理 以使其不易剝離。 本發明之感光性膜，係將具有光硬化性及熱硬化性之 樹脂組成物保持成半硬化狀態(B階)者。係設計成，在熱 壓或積層加工時具有流動性，能追隨軟性印刷配線板上電 路的凹凸而形成密合，能藉由曝光時的光交聯反應、衝壓 ___ 58 尺度適用中_家標準（CNS)A4規格（21G X 297公爱） ~ .—裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ___^_____ 五、發明說明（以） 加工時的熱及衝壓加工後所實施之加熱硬化來使硬化完成 Ο 具體而言，作爲基底(base)聚合物，基於硬化後膜的 耐熱性、耐撓曲性的觀點，較佳爲聚醯亞胺等的樹脂，採 用聚醯亞胺寡聚物亦可，但較佳爲本發明所用的可溶性聚 醯亞胺。又，爲提高其對軟性印刷配線板的接著性，較佳 爲上述環氧變性聚醯亞胺。此外，作爲光硬化性樹脂，可 代表性地列舉具有雙鍵或三鍵之丙烯酸樹脂、甲基丙烯酸 樹脂、乙烯基樹脂等。作爲熱固性樹脂，可代表性地列舉 丙烯酸樹脂、環氧樹脂等。光硬化性樹脂和熱固性樹脂也 會有相同的情形，不須特別區別亦可。本發明中之保護膜 之特徵在於，代表性地是由「聚乙烯和乙烯乙烯醇之共聚 物膜」（簡稱(PE+EVA)共聚物膜)與「拉伸聚乙嫌膜」（簡稱 ΟΡΕ膜)之貼合體，或「聚乙烯和乙烯乙烯醇樹脂之共聚物 」與「聚乙烯」經同時擠製所得之膜（具有ρΕ膜面和 (PE+EVA)共聚物膜面）所構成，且該(pE+EVA)共聚物膜面 係形成感光片接合面。 保護膜的製法主要有二個。亦即貼合2種膜的製法， 以及將2種樹脂同時擠出的方法。 貼合製法，係將(PE+EVA)共聚物膜和ope膜貼合。 又，將乙烯乙烯醇樹脂膜和ΟΡΕ膜貼合亦可。一般是在膜 貼合面上薄塗有接著劑。這時，應與〇ρΕ膜貼合之 (PE+EVA)共聚物膜面，較佳爲實施電暈處理等之易接著化 處理。 59 ^紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐) " ^ " --------^--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ^_B7 ___ 五、發明說明（θ ) 藉由將2種樹脂同時擠出之膜製法，係將聚乙烯樹脂 、和聚乙烯與乙烯乙烯醇樹脂的共聚物所構成的樹脂’經 同時擠出並薄膜化而製作出。該方法，係獲得一面爲PE 膜面、另一面爲(PE+EVA)共聚物面之膜。 作爲該(PE+EVA)共聚物膜，較佳爲不含潤滑劑、靜電 防止劑等的添加劑。（PE+EVA)共聚物膜，由於直接和感光 性膜接觸，這些添加劑若從保護膜滲出而轉寫到感光性膜 上，可能會使感光性膜和CCL之密合性、接著性降低。因 此，在感光性膜中使用添加劑或進行表面處理時，必須充 分考慮這幾點。 (PE+EVA)共聚物膜厚度是越薄越好，基於處理性的考 量較佳爲2〜50//m。該(PE+EVA)共聚物膜的特徵在於，可 使其對感光性膜的密合性變佳，能防止感光性膜的乾燥等 變質，同時在使用感光性膜時容易剝離。 依據貼合法之保護膜中所使用的ΟΡΕ膜，係作爲 (PE+EVA)共聚物膜的補強體來貼合者，其厚度較佳爲 10〜50/zm。厚度太薄時會有易鈹的傾向。特別是較佳爲 10〜30/zm的範圍。使用該ΟΡΕ膜的一理由，係基於將薄 片做成捲取物時，其具有加滑的特徵。 貼合製法的情形，作爲將(PE+EVA)共聚物膜和ΟΡΕ 膜貼合的方法，可舉出各種例子，一般是在ΟΡΕ膜上薄塗 接著劑，經乾燥後，將接著劑面和(PE+EVA)共聚物膜之電 暈處理面用熱輥來實施積層。貼合所用的接著劑沒有特別 的限定。可使用一般市售的接著劑，特別是以使用聚氨酯 60 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---III----I Aw ·1111111 ^ · I I I--- — I <請先閱讀背面之注意事項再填寫本頁) A7 1299043 _____ B7____ 五、發明說明（β) 接著劑較有效。 藉由同時擠出製法來製作保護膜的情形，在同時擠出 時，係調整聚乙烯和乙烯乙烯醇樹脂的共聚物所構成樹脂 的量、以及聚乙烯樹脂的量。藉由該調整，可分別控制所 製作之片的（PE+EVA)共聚物膜、ΡΕ膜的厚度。這時 (PE+EVA)共聚物膜和ΡΕ膜的厚度，基於和上述同樣的理 由，分別較佳爲2〜50 # m、10〜50 # m。 可對保護膜賦予遮光性。對保護膜賦予遮光性的方法 有好幾種，本發明的情形，較佳爲將ΟΡΕ膜著色。特別是 最佳爲，著色成可吸收特定波長的光，該波長爲感光性膜 所含之光反應起始劑所能吸收的範圍。 本發明之感光性膜中，較佳爲配合光反應起始劑，以 藉由曝光顯影來描繪出所望的圖案。作爲光反應起始劑並 沒有特別的限定，只要可吸收特定波長的光而產生游離基 或產生鹼，或和具有雙鍵及/或三鍵的反應基（乙烯基、丙 烯基、甲基丙烯基、烯丙基等）反應而促進交聯、聚合者即 可，包含基底聚合物、光硬化樹脂及/或熱固性樹脂之樹脂 全體與光反應起始劑之混合比例，相對於樹脂全體100重 量份，較佳爲0.1〜5重量份，更佳爲0.5〜5重量份。 本發明之感光膜，其厚度較佳爲10〜75/zm。更佳爲 40〜70//m，最佳爲45〜65//m。若感光性膜之厚度過小， 基於軟性印刷配線板上之銅電路和底層的聚醯亞胺膜之凹 凸將無法掩埋，且無法保持貼合後表面的平坦性之觀點， 並不佳。又若厚度過大，基於細微圖案的顯影會有困難， 61 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 a7 _______B7___ 五、發明說明（巧） 又易產生樣本的彎曲之觀點，並不佳。 —般之感光性膜，係將上述具有光硬化性及熱硬化性 之接著劑組成物保持成半硬化狀態(B階）而成者，係設計 成，在熱壓或積層加工時具有流動性，能追隨軟性印刷配 線板上電路的凹凸而形成密合，能藉由曝光時的光交聯反 應、衝壓加工時的熱及衝壓加工後所實施之加熱硬化來使 硬化完成。 本發明所用之感光性膜係含有聚醯亞胺。特別是分子 內具有芳香環或脂環式之聚醯亞胺，因耐熱性高且耐撓曲 性等的機械強度良好，故較佳。較佳爲使用上述感光性樹 脂組成物所構成之膜。 以下說明本發明的3層構造被覆膜之製造方法。 將溶液狀的感光性樹脂組成物均一塗佈於PET膜等的 底膜上後，藉由加熱及/或吹熱風來除去溶劑，製得感光性 乾膜光阻。 作爲本發明之底膜，可使用聚對苯二甲酸乙二醇酯 (PET)膜、聚苯硫醚、聚醯亞胺膜等一般市售的各種膜。關 於底膜之感光性膜接合面，較佳爲實施表面處理以使其容 易剝離。基於具有相當程度的耐熱性、價廉且易取得的觀 點，較佳爲以PET膜作爲底膜。 本發明之感光性膜，厚度較佳爲5〜75m。更佳爲 10〜70/zm，最佳爲15〜40/zm。感光性膜的厚度過小時， 基於軟性印刷配線板上之銅電路和底層的聚醯亞胺膜之凹 凸將無法掩埋，且無法保持貼合後表面的平坦性之觀點， 62 ___________ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---— — — — — — — ·111111! ·11111111 (請先閱讀背面之注意事項再填寫本頁) 1299043 B7 五、發明說明（έ。） 並不佳。又若厚度過大，基於細微圖案的顯影會有困難’ 又易產生樣本的彎曲之觀點，並不佳。 (請先閱讀背面之注意事項再填寫本頁) 一般之感光性膜，係將上述具有光硬化性及熱硬化性 之接著劑組成物保持成半硬化狀態(Β階)而成者，係設計 成，在熱壓或積層加工時具有流動性，能追隨軟性印刷配 線板上電路的凹凸而形成密合’能藉由曝光時的光交聯反 應、衝壓加工時的熱及衝壓加工後所實施之加熱硬化來使 硬化完成。 本發明之三層構造片，係將上述之底膜、感光性膜、 保護膜依此順序積層而成，其重點爲保護膜之(PE+EVA)共 聚物膜面係形成接著膜接合面（脫膜面）。作爲其積層方法 ，係在底膜上塗佈感光性樹脂成份，經乾燥後，將感光性 接著膜面和保護膜之(PE+EVA)共聚物膜面實施積層，可捲 繞成圓筒狀。 可將捲繞成圓筒狀之三層構造片所構成之感光性被覆 層以捲繞的狀態來保存，在和形成有電路之CCL貼合時， 不須採以往般之批式積層，而可利用連續積層來順暢地進 行軟性印刷配線板之製程。 使用本發明之三層構造片來製造軟性印刷配線板用帔 覆膜時，在除去保護膜後，將形成有電路之軟性印刷配線 板和感光性膜藉由加熱積層來完成積層。積層時的溫度過 高會使感光性部位交聯而使膜產生硬化，由於會喪失其作 爲感光性被覆層的機能，因此積層時的溫度以低溫爲佳。 具體而言爲60〜150°C，更佳爲60〜12(TC。溫度過低時由 63 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 _ B7 _ 五、發明說明（W ) 於感光性膜的流動性變差’故要被覆在軟性印刷配線板上 的細微電路會有困難，又會有密合性變差的傾向。 使用本發明之三層構造片所構成之感光性膜時，爲提 高細微電路的掩埋性，雖可進行基板之預熱’但只要將感 光性膜如前述般加熱，則沒有事先預熱基板的必要。 如此般成爲軟性印刷配線板/感光性膜/底膜所依序積 層而成的狀態。底膜可在積層完成時再剝離，或在曝光完 成後就剝離。基於保護感光性膜的觀點’較佳爲’放上光 罩圖案經曝光後再剝離底膜。 又，該感光性膜，當積層在軟性印刷配線板上後，經 照射紫外光等的光線後，若進行加熱硬化而使膜硬化，即 構成用來對電路施以絕緣保護之被覆膜。本發明之感光性 膜也適用於，電腦的硬碟裝置之磁頭部分的電路基板用被 覆膜。 也能用於硬碟之懸吊具用，也能用於導體層之電路的 保護用。具體而言，在設有電路之懸吊具用基板上積層本 發明之被覆膜後，放上光罩經曝光顯影，即可容易地形成 配線用的圖案。因此，基於減少製程、成本的觀點是有用 的。 將本發明之感光性膜當作軟性印刷配線板或電腦硬碟 裝置之磁頭部分用的感光性被覆層來使用時.，將其接著於 電路上後，裝上光罩圖案，經曝光顯影，即可在既定位置 開孔。感光性膜所含之光反應起始劑，由於一般是吸收紫 外線區域的光，因此可使用紫外線當作有效的放射光源。 -------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 ___— _B7____ 五、發明說明（仏） 這時的顯影液，可使用上述之具有鹼性的水溶液群有 機溶劑。用來溶解鹼性化合物的溶劑可爲水或有機溶劑。 基於防止膜的損傷及對環境的影響，較佳爲使用水溶液。 特別是爲改善聚醯亞胺的溶解性，可進一步含有甲醇、乙 醇、丙醇、異丙醇、異丁醇、N -甲基-2-吡咯烷酮、 N，N-二甲基甲醯胺、N，N-二甲基乙醯胺等之水溶性有機 溶劑，亦可混合2種以上的溶劑來使用。上述鹼性化合物 的濃度一般爲〇·1〜1〇重量％，考慮到對膜等的影響，較佳 爲0.1〜5重量％。作爲上述鹼性化合物，例如可列舉鹼金 屬、鹼土金屬、或銨離子之氫氧化物或碳酸鹽、胺化合物 等等。 顯影後用蒸餾水等洗淨基板後，經乾燥、加熱硬化， 即製得耐熱性、耐化學藥品性優異的被覆層。加熱硬化是 在100〜200°C的範圍進行15〜90分左右。如此般，在印刷 配線板上製作出被覆膜，可組裝1C晶片等的電子零件。 〔實施例〕 以下，用實施例來具體說明本發明，但本發明不限於 這些實施例。 實施例中， ESDA代表2,2-雙(4-羥基苯基)丙烷二苯甲酸酯-3,3f，4,4’-四羧酸二酐，BAPS - Μ代表雙〔4 - (3-胺基苯 氧基)苯基〕硼，DMF代表Ν，Ν-二甲基甲醯胺。 (熱分解開始溫度）：藉由精工電子工業公司製熱分析 測定裝置(TG/DTA220)，以空氣中昇溫速度10°C/分測定從 65 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _____B7_ 五、發明說明（“） 室溫〜500°C之溫度範圍，以重量減少爲5%的溫度爲熱分 解開始溫度。 (熱膨脹係數） 使用精工電子製TMA裝置(型號120C)，在氮氣流下 ，以昇溫速度l〇°C/分測定室溫〜350°C之溫度範圍。 (硬化後膜之彈性模數、拉伸強度、伸長率） 根據JIS C 2318來進行測定。 關於彈性模數、拉伸強度、伸長率，係使甩島津製作 所製之拉伸試驗機(AutoGraph S - 100 - C)，如下述般進行 測定。首先，將感光性組成物溶液（淸漆）均一塗佈在銅箔 上，經乾燥而製作出25cmX25cm之被覆膜。實施全面曝 光(曝光條件：以10mJ/cm2照射3分鐘波長400nm的平行 光），以180°C硬化2小時後，經蝕刻除去銅箔。將所得的 膜掛在針架上，以100°C乾燥3分後，切出數條寬0.015m 、長0.20m之膜帶。將該膜帶之長0.10m的部分用試驗機 夾住，以一定速度拉伸，測定拉長5%時所須的力量。將該 力除去0.05，再除以膜平均厚度(m)和帶寬(0.015m)，計算 出彈性模數(MPa)。一直拉伸膜帶，將拉斷膜帶時的力（Pa • m2)除以膜平均厚度(m)和帶寬(0.015m)所得的値，爲拉 伸力（MPa)，將膜帶拉到最長之伸長星’除以原先之帶長 (0.10m)再乘1〇〇所得之數値爲伸長率(％)。 {彈性模數(MPa)} ={拉長5%時所須的力(pa· m2) } /〇·〇5Χ〔 {膜平均厚度（m)} X {帶寬（〇.〇15m)}〕 {拉伸力(1^&)}={拉斷膜帶時的力(Pa.m2)}/〔 { 66 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ______ B7____ 五、發明說明（料） 膜平均厚度(m)} X (帶寬(〇.〇15m)}〕 {伸長率(％)} =1〇〇Χ {最高伸長狀態之帶長{ 原帶長(m)} (玻璃轉移溫度Tg及5%重量損失溫度） 使用島津製作所製DSC CELL SCC- 41(示差掃描熱量 計），在氮氣流下以昇溫速度10°C/分測定從室溫〜4〇〇。(：之 溫度範圍。又，所謂5%重量損失溫度，係使用島津製作所 製TG/DTA(示差熱分析器），在空氣下以昇溫速度2(rc/分 測定從20〜600°C之溫度範圍。把樣本重量減少5%時的溫 度當作5%重量損失溫度，又該5%重量損失溫度爲顯示耐 熱性的指標。 (重量平均分子量） 使用Waters製GPC根據以下條件來測定。（管柱： Shodex製KD - 806M 2根，溫度60°C，檢測器RI，流量 :lml/分，展開液：DMF(溴化鋰0.03M，磷酸0.03M)，試 料濃度：〇.2wt%，注入量：20/zl，基準物質：聚氧化乙烯 ) (醯亞胺化率的測定) ①將聚醯胺酸溶液(DMF溶液)澆注於PET膜上，經 10(TC X 10分、130°C X 10分加熱後，從PET膜上剝下， 固定於針框，經 15〇°C X60 分、200°C X60 分、250°C X60 分加熱，製得5/zm厚之聚醯亞胺膜。②將實施例或比較例 所作成的聚醯亞胺溶解於DMF後，澆注於PET膜上，經 100°C X30分加熱後，從PET膜上剝下，固定於針框，於 67 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂-------— (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ____ B7____ 五、發明說明) 真空烘箱中，以80°C、660Pa的條件加熱乾燥12小時，製 得5# m厚之聚醯亞胺膜。分別測定各膜的IR，求取醯亞 胺吸收/苯環吸收的比値。當①所得之醯亞胺吸收/苯環吸收 爲醯亞胺化率100%時，求出②之醯亞胺吸收/苯環吸收比 相當於多少％。將該値當作醯亞胺化率。 (COOH當量之測定方法） 將約0.1N之KOH乙醇溶液用0.1N草酸水溶液來滴 定，求出正確的濃度。精確地測定可溶性聚醯亞胺的重量 ，在二惡茂烷中溶解成約2%左右。用上述KOH乙醇溶液 來滴定。滴定終點均根據酚肽溶液的發色變化來決定。根 據下式求出COOH當量。 COOH當量=(可溶性醯亞胺重量）+(κ〇Η乙醇溶液之 濃度）+(滴定量）Χ1000 其中，滴定量爲用KOH溶液滴定可溶性醯亞胺時所 需的量(ml)。 (接著強度） 根據JIS C6481之剝離強度（90度）測定方法。以寬 3mm來測定，並換算成寬lcm。 (焊料浴耐熱性之特性檢查） 將聚醯亞胺膜和銅箔的積層體，經硬化後，浸漬在 300°C的焊料中3分鐘，用目視觀察發泡或剝離等的劣化程 度。 又，根據以下的方式，進行實施例之三層構造片、保 護膜的製作及三層構造片、感光性膜的評價。 68 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---- (請先閱讀背面之注意事項再填寫本頁) ^--------t--------- 1299043 A/ _ B7 _ 五、發明說明（0 ) (1) 感光性樹脂組成物之製作 將可溶性聚醯亞胺樹脂在有機溶劑中溶解成固態成份 30重量％後，混合(B)成份之二丙烯酸酯化合物、（C)成份 之光反應起始劑及/或增感劑，調製出均勻的感光性樹脂組 成物。 (2) 三層構造片之製作 將（1)所調製成的感光性樹脂組成物之有機溶劑溶液’ 以乾燥後厚度成爲50//m的方式塗佈在PET膜(厚25//m) 上，經45°C X5分、接著65°C X5分乾燥後除去有機溶劑 ，使感光性膜成爲B階狀態。 接著，以(PE+EVA(共聚物膜面接觸感光性膜面的方式 積層下述保護膜，製成三層構造片之感光性被覆層。積層 條件爲輥溫40°C、輥點壓力1500Pa · m。 (3) 保護膜之製作 作爲ΟΡΕ膜是使用厚38#m的膜，在其上方以乾燥 後厚度成爲0.5/zm的方式塗佈聚氨酯系接著劑，於溫度 120°C乾燥5分鐘。接著，以ΟΡΕ膜的接著劑塗佈面和 (PE+EVA)共聚物膜面(積水化學(股)製，厚l〇em，單面電 暈處理)之電暈處理面接觸的方式貼合，以輥溫120°C、輥 點壓力2000Pa · m的條件進行積層。 又，將聚乙烯樹脂、聚乙烯和乙烯乙烯醇樹脂之共聚 物所構成的樹脂同時以擠製法所製得之保護膜，係使用積 水化學(股)製 PR〇TECT(#6221F)膜(厚 50/zm)。 (4) 三層構造片的評價 69 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------•裝--------訂---------^9, (請先閱讀背面之注意事項再填寫本頁) 1299043 B7 五、發明說明（W ) 對所得的三層構造片及感光性膜’依據以下方法進行 各特性的評價。 <保護膜剝離性> 將切成30mm寬的帶狀之三層構造片，用雙面膠貼在 鋁板(厚3mm)後，以朝90度拉伸保護膜之拉伸裝置來測定 。保護膜剝離性，實用上以3·3〜13.3Pa · m爲佳，取該範 圍爲合格。又33·3Ρα · m以上時因太難剝離故判定爲不合 格。 <感光性膜之顯影性〉 將三層構造片之保護膜剝離後，將感光性膜面積層於 電解銅箔的光澤面，在條件100°C、20000Pa · m下進行積 層加工。在積層品的底膜上放置光罩圖案’用波長400nm 的光曝光，經l〇〇°C X2分之加熱處理，依以下任一條件實 施顯影。 濃度1%之氫氧化鉀水溶液(液溫4〇°C)X2分 濃度1%之四甲銨之異丙醇溶液(液溫40°C)X5分 又，曝光時放置在被覆膜上的光罩圖案，係描繪有 200//mX200//m、100/zmXl00/zm 之微細孔者。顯像所 形成之圖案，用水洗淨後除去顯像溶劑，以90°C進行15 分乾燥。只要至少20〇emX200 //m的細孔能顯像，即判 定爲合格。 <感光性膜之焊料耐熱性> 將三層構造片的保護膜剝離後，將感光性膜面積層於 電解銅箔35 // m之光澤面，以l〇〇°C、20000Pa · m的條件 70 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐） " (請先閱讀背面之注意事項再填寫本頁) i裝--------訂------- 1299043 A7 :___— B7 _ 五、發明說明（W ) 實施積層。在積層品之感性膜上，透過底膜以波長400nm 的光實施曝光，剝離底膜後於180°C進行2小時加熱處理 。將該積層樣本切成25mm見方，以20°C/濕度65%的條件 進行24小時的調濕處理後，浸在300°C的熔融焊料中1分 鐘。這時，觀察樣本是否有脹起或剝落等的異常。無異常 即判定爲合格。 <感光性膜之耐折強度> 在形成有線寬/線距= l〇0/100#m之反覆圖案之銅面積 層板(CCL)的圖案上，積層剝去保護膜後的感光性膜，以 100°C、20000Pa · m的條件實施積層。使感光性膜曝光、 剝離底膜後，將該積層樣本於18〇°C進行2小時加熱處理 。將樣本裝設於MIT試驗機，以撓曲半徑1mm、撓曲角度 270° 、拉伸荷重4.9N的條件進行撓曲試驗，測定圖案所 具有的導通次數。在500次以上即判定爲合格。 該耐折強度之測定，係觀察薄膜的機械強度之指標之 一。柔軟的膜有較多的導通次數，硬且脆的膜之導通次數 少。 <感光性膜之線間絕緣電阻> 在形成有線寬/線距= 100/100的梳形圖案之銅面積 層板(CCL)之梳形圖案上，積層剝去保護膜後的感光性膜 ，以100°C、20000Pa · m的條件實施積層。根據IPC -4.8.10.2.1的標準來測定線間絕緣電阻。電阻値越高越好， 1·0Χ1013Ω以上判定爲合格。 〔實施例1〕 71 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------------^-------— (請先閱讀背面之注意事項再填寫本頁) 1299043 A/ _ ___B7_____ 五、發明說明（0) 在設有攪拌器之2000ml分離式反應器中，於激烈攪 拌下，將 BAPS - M 43.05g(0.10 莫耳）、DMF300g、ESDA 57.65g(0.10莫耳)一起加入，持續攪拌30分，製得聚醯胺 酸溶液。該聚醯胺酸之重量平均分子量(Mw)爲6.2萬。 將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空 烘箱內，以20(TC、660Pa的壓力實施2小時減壓加熱。從 真空烘箱中取出，獲得96g的熱可塑性聚醯亞胺。該聚醯 亞胺之Mw爲6.8萬，Tg爲200°C、醯亞胺化率爲1〇〇%。 讓可溶性聚醯亞胺30g溶解於二惡茂烷70g中，製得 Sc=30%之淸漆。在18.3g的淸漆中，添加新中村化學工業 公司製異氰尿酸EO變性三丙烯酸酯(A- 9300)4.5g、光反 應起始劑之伊格膠819 O.lg、聚合抑制劑之4-甲氧基苯 酚(MEHQ)O.Olg而製成溶液，經脫泡後塗佈在PET膜上， 經45°C X5分、65°C X5分、80°C X5分之乾燥後，製得感 光性聚醯亞胺之50/zm厚的薄膜。 以銅箔/聚醯亞胺膜/PET膜（剝離紙)的順序重疊，以 120°C、lOOOOPa · m的條件實施積層。積層後，裝上光罩 圖案實施3分鐘曝光(曝光條件：以10mJ/Cm2照射400nm 的平行光），剝去PET膜後於100°C進行3分鐘熱處理，用 1%之氫氧化四甲基的異丙醇溶液(液溫40°C)實施5分鐘顯 影後，以100°C X2小時、120°C X2小時、140°C X2小時 的條件進行硬化。硬化後的Tg爲290°C，硬化後的熱膨脹 係數於室溫〜100°C爲55ppm。 又，將軟性銅面板之銅箔予以蝕刻除去，留下的硬化 72 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------裝---------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _______B7 五、發明說明（7°) 後之感光性聚醯亞胺膜之彈性模數爲400Mpa、伸長率爲 2.8%，拉伸強度爲12〇MPa。 〔實施例2〕 在設有攪拌器之2000ml分離式反應器中，於激烈攪 拌下，將 BAPS - M 68.88g(0.16 莫耳）、DMF320g、ESDA 138.4g(0·24莫耳)一起加入，持續攪拌3〇分後，用冰水冷 卻再進行反應。接著，加入將二胺基苯甲酸1218g(〇.〇8莫 耳)溶於DMF120g而成者，攪拌30分，製得聚醯胺酸溶液 。該聚醯胺酸之重量平均分子量(Mw)爲5.8萬。將該聚醯 月女酸溶液倒在被覆鐵氟龍膜之盤中，於真空烘箱內，以 200°C、660Pa的壓力實施2小時減壓加熱。 從真空烘箱中取出，獲得98g的熱可塑性聚醯亞胺。 該聚醯亞胺之Mw爲6.5萬，Tg爲190。(：、醯亞胺化率爲 100%。 (環氧變性聚醯亞胺的合成） 將合成後的可溶性聚醯亞胺48.4g(56毫莫耳)溶解於 二惡茂烷ll〇g中，添加MEHQ O.lg，用50〜60°C的油浴邊 加熱邊使其溶解。將縮水甘油甲基丙烯酸酯1.42g(10毫莫 耳)溶解於二惡茂烷5g後加入前述溶液中，於60°C進行6 小時加熱攪拌。接著，將油化殼牌公司製環氧828樹脂 3-80g(10毫莫耳)溶解於二惡茂烷14g後加入前述溶液中， 於60°C進行6小時加熱攪拌，合成出環氧變性聚醯亞胺。PR 29 (wherein R27 and 28 are independent of each other (:6115-, (:6 Sapporo::%)_ 39) This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 _____ B7__ V. Description of the invention (W) C6H2(CH3)3-, (CH3)3C-, C6H3C12; R29 represents C6H5-, methoxy, ethoxy, c6h4(ch3)_, C6H2(CH3)3-. The fluorenylphosphine oxide represented by the formula (12) generates two radicals; the fluorenylphosphine oxide represented by the formula (13) generates four radicals depending on the α-cleavage, and represents the formula (13). The fluorenylphosphine oxide is preferred. In the case of the epoxy-denatured polyimine, in order to harden the epoxy group attached to the side chain of the polyimide resin, the above-mentioned radical generator may be substituted, and photocation is used. a generator, for example, a diphenyl iodonium salt such as a diphenyl iodine salt of dimethoxy sulfonium sulfonic acid, a triphenyl sulfonium salt, a pyranthene salt, a triphenyl gun salt, and a heavy Nitrogen salt, etc. At this time, it is preferred to mix a highly cationic hardening alicyclic epoxy or vinyl ether compound. Or, in order to make the epoxy attached to the side chain. For hardening, a photobase generator can also be used. For example, a urethane compound obtained by reacting nitrobenzyl alcohol or dinitrobenzyl alcohol with isocyanate, nitro-1-phenylethanol or dinitro-1-phenyl group can be exemplified. a urethane compound obtained by reacting ethanol and isocyanate, a urethane compound obtained by reacting dimethoxy-2-phenyl-2-propanol and isocyanate, etc. As a radical initiator, various peroxides and under A combination of sensitizers. A preferred combination is a combination of 3,3',4,4'-tetrakis(t-butylperoxycarboxy)benzophenone and the following sensitizers. The following compounds may be mentioned, but are not limited thereto: Michlerone, bis-4,4'-dimethylaminobenzophenone, benzyl, 4,4'-dimethylaminobenzyl, 3 ,5-bis(diethylaminobenzylidene)-indole-methyl-4-oxanthone, 3,5-bis(dimethylaminobenzylidene-p-methyl-4-acridone 40 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -----------Install--------Set--------»^ 9.  (Please read the notes on the back and fill out this page) A7 1299043 _B7 _ V. Inventions (), 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-pyridone, 3,3f-carbonylbis(7-diethylamino)coumarin, riboflavin tetrabutyrate, 2-methyl-1-[4-(methylthio)phenyl]-2-? Troprolone-1-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethylthioxanthene Ketone, 3,5-diisopropylthioxanthone, 1-phenyl-2-(ethoxycarbonyl)hydroxyiminopropane-1 ketone, benzoin ether, benzoin isopropyl ether, benzo Anthrone, 5-nitro-, 2-nitroindole, anthrone, 1,2-benzopyrene, 1-phenyl-5-mercapto-1H-tetrazole, thioxanth-9-one, 10 - thioxanthone, 3-ethylindolyl D, 2,6-bis(p-dimethylaminobenzylidene)-4-carboxycyclohexanone, 2,6-di(p-dimethylamine 4-benzylcyclohexanone, 2,6-bis(p-diethylaminobenzylidene)-4-carboxycyclohexanone, 2,6-di(p-diethylaminobenzyl) Fork) _ 4_hydroxycyclohexanone, 4,6-dimethyl-7-ethylamino coumarin, 7-diethylamino-4-methyl Bean, 7-diethylamino-3-(1-methylbenzimidazolyl)coumarin, 3-(2-benzothiazolyl)-7-diethylamine coumarin, 2 - (p-Dimethylaminostyryl)benzoxan, 2-(p-dimethylaminostyryl)quinoline, 4-(P-dimethylaminostyryl)quinoline , 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)-3,3-dimethyl-3H-D, D, etc. . (C) a photoreaction initiator and/or a sensitizer, preferably 100 parts by weight based on 100 parts by weight of the soluble polyimide resin (A). The ratio of 1 to 50 parts by weight is present in the composition, more preferably 0. A ratio of 3 to 20 parts by weight exists. If it is off 0. In the range of 1 to 50 parts by weight, sensitization may not be obtained or may have a poor influence on development. As a sensitizer, one compound can be used, and the size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------------1---- -Book---------- (Please read the notes on the back and fill out this page) 1299043 A7 ___ B7____ V. Invention Description (??) It is also possible to mix several types for use. The above photopolymerization aid is used to improve the sensitivity of the photosensitive resin composition of the present invention. The photopolymerization aid may, for example, be exemplified by the following compounds: 4-diethylaminoethyl benzoate, 4-dimethylaminoethyl benzoate, 4-diethylamino group Propyl benzoate, 4-dimethylaminopropyl benzoate, 4-dimethylaminoisoamyl benzoate, N-phenylglycine, N-methyl-N-benzene Glycine, N-(4-cyanophenyl)glycine, 4-dimethylaminobenzonitrile, ethylene glycol dimercaptoacetate, ethylene glycol bis(3-mercaptopropionate), Trimethylolpropane decyl acetate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetradecyl acetate, pentaerythritol tris(3-mercaptopropionate), trimethylol Ethyl tridecyl acetate, trimethylolpropane tridecyl acetate, trimethylolethane tris(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate) , mercaptoacetic acid, α-mercaptopropionic acid, tert-butyl peroxybenzoate, tert-butyl peroxymethoxybenzoate, tert-butyl peroxynitrobenzoate, tert-butyl Peroxyethyl benzoate, phenyl isopropyl peroxybenzoate, double tertidine Diperoxyphthalate, tributyl butyl triperoxy trimellitate, tetrabutyl butyl tetraperoxy benzene tetracarboxylate, 2,5-dimethyl-2,5-di Phenylhydrazine peroxy)hexane, 3,3,4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(p-pentylperoxycarbonyl) Benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 2,6-bis(p-azidobenzylidene)-4-hydroxycyclohexanone, 2, 6-bis(p-azidobenzylidene)-4-carboxycyclohexanone, 2,6-bis(p-azidobenzylidene)-4-methoxycyclohexanone, 2,6-bis(p-azidobenzyl) Fork)-4-hydroxymethylcyclohexanone, 3,5-bis(p-azidobenzylidene)-1-methyl-4-piperidone, 3,5-bis (p-azide bromide 42 paper scale Applicable to China National Standard (CNS) A4 specification (210x297 mm) tI----tr--------- (Please read the note on the back and fill out this page) 1299043 A7 _B7_ V. Invention description ( f.) Fork)-4 - p hindiketone, 3,5-bis(p-azidobenzylidene)-N-ethinyl-4-pyridinone, 3,5-bis(p-azidobenzylidene) -N-methoxycarbonyl-4-piperidone, 2,6-bis(p-azidobenzylidene)-4-hydroxycyclohexanone, 2,6-double (m-azinobenzylidene)-4-carboxycyclohexanone, 2,6-bis(diazobenzyl)-4-methoxycyclohexanone, 2,6-bis(disazobenzidine)- 4-hydroxymethylcyclohexanone, 3,5-bis(disazobenzylidene)_N-methyl-4-piperidone, 3,5-bis(disazobenzylidene)_ 4 - p-propane Ketone, 3,5-bis(disazobenzylidene)-N-ethinyl-4-oxanthone, 3,5-bis(disazobenzidine)-N-methoxycarbonyl-4- Pyridone, 2,6-bis(p-azidocinnacil)-4-hydroxycyclohexanone, 2,6-bis(p-azidocinnazone)-4-carboxycyclohexanone, 2,6-double (pair Azide cinnabarin) - 4-cyclohexanone, 3,5-bis(p-azidocindol)-N-methyl-4-cyclohexanone, 4,4f-diazide chalcone, 3,3f -diazide chalcones, 3,4'-diazide chalcone, 4,3'-diazide chalcone, 1,3-diphenyl-1,2,3-propanetrione- 2-(o-ethylidene) fetus, 1,3 _diphenyl-1,2,3-propanetrione _ 2 -(o-n-propylcarbonyl), 1,3 -diphenyl-1,2 , 3 -propanetrione 2 - (o-methoxycarbonyl)fl, 1,3 - diphenyl-1,2,3-propanetrione-2-(o-ethoxycarbonyl), 1 3-diphenyl-1,2,3-propiontrione-2 -(o-benzoquinone) hydrazine, 1,3 -diphenyl- 1,2,3-propanetrione-2 -(o-phenoxycarbonyl), 1,3-bis(p-methylphenyl)- 1,2,3-propanetrione-2-(o-benzoquinone), 1,3-bis(p-methylphenyl)-1,2,3-propanetrione-2-(o-ethoxycarbonyl) Hi, 1-(p-methoxyphenyl)-3-(p-nitrophenyl)-1,2,3-propanetrione-2-(o-phenoxycarbonyl)anthracene and the like. A trialkylamine such as triethylamine, tributylamine or triethanolamine may be contained as an auxiliary agent other than the above. These photopolymerization auxiliaries can be used in one compound, 43 paper scales are applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ----IIII ^ --------- (please Read the notes on the back and fill out this page. A7 1299043 _____B7___ V. Invention Description (W) It is also possible to mix several types for use. (Please read the precautions on the back side and fill out this page.) The photopolymerization aid is preferably present in the composition in an amount of from 1 to 50 parts by weight based on 100 parts by weight of the soluble polyimide resin (A). In the middle, it is better to 0. A ratio of 3 to 20 parts by weight exists. If it is out of 0. 1 to 50 parts by weight of the formula may not provide the sensitizing effect of the purpose or may have a poor influence on the developability. The photosensitive resin composition of the present invention contains the above-mentioned soluble polyimine (oxime), polyfunctional (meth)acrylic compound (Β), and (C) photoreaction initiator, and may contain the above if necessary. Sensitizers, photopolymerization aids, and other ingredients. As the photopolymerization aid, one type of compound can be used, and a plurality of types can be used. Further, in the composition of the present invention, in addition to the above-mentioned sensitizer and photopolymerization aid, the # comonomer other than the (Β) component can be contained in order to achieve practical sensitivity. The comonomer is a compound having a carbon-carbon double bond, and photopolymerization is facilitated. Preferred as the comonomer are: divinylbenzene, 1,6-hexanediol dipropionate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane Triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetrapropionate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl Alcohol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, four Hydroxymethylpropane tetramethacrylate, tetraethylene glycol dimethacrylate, this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 ___ B7__ V. Description of invention (U) Methoxyethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, /3 _ methacryl oxime hydroxyethyl hydrogen phthalate, no - methacryl oxime hydroxyethyl hydrogenation Succinate, 3-chloro-2-hydroxypropyl Methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, fluorene-acrylonitrile hydroxyethyl hydrogenated amber Acid ester, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3 - Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3 - two Methyl propylene oxypropane, 2,2-bis[4-(methacryloxyethoxy)phenyl]propane, 2,2-bis[4-(methacryloxydiethoxy)phenyl]propane , 2,2-bis[4-(methylpropaneoxypolyethoxy)phenyl]propene, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2- Bis[4-(acryloxydiethoxy)phenyl]propane, 2,2-bis[4-(acryloxypolyethoxy)phenyl]propane, 2-hydroxy-1-propenyloxy-3- Methyl propylene oxide Propane, trimethylolpropane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, methoxydipropylene glycol methacrylate, methoxy triethylene glycol acrylic acid Ester, nonylphenoxy polyethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, 1-propenylhydroxypropyl-2-phthalate, isostearyl acrylate, polyoxygen Vinyl alkyl ether acrylate, nonylphenoxy ethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 3 _methyl-1,5-pentane Alcohol dimethacrylate, 1,6-hexane 45 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ------------------ -^-------- (Please read the notes on the back and fill out this page) 1299043 A7 ___jB7___ —__ V. Description of invention (μ) Diol dimethacrylate, 1,9-terpenediol Methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, L4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane Trimethanol diacrylate, 2,2-hydrobis[4-(acryloxypolyethoxy)phenyl]propane, 2,2-bis[4-(acryloxypolypropoxy)phenyl]propane , 2,4-Diethyl-1,5-pentanediol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, isocyanuric acid tris(ethane acrylate Ester), pentaerythritol tetraacrylate, pentoxide tetraol tetraacrylate, propoxypentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol polyacrylate, triallyluric acid triallyl, glycidylmethyl Acrylate, glycidyl allyl ether, 1,3,5-benzene carboxylate, triallylamine, triallyl citrate, triallyl phosphate, 5,5-diallyl bebabi Toluene, diallylamine, diallyldimethyl decane, diallyl disulfide, diallyl ether, diallyl cyanurate, diallyl isophthalate, Allyl terephthalate, 1,3 -dipropoxy-2-propanol, diallyl sulfide, diallyl horse. And the like, but not limited to, 4,4'-isopropylidene bisphenol dimethacrylate. In order to increase the crosslinking density, it is more preferred to use a monomer having two or more functional groups. In addition, when the coating layer obtained by using the resin composition for a photosensitive coating layer of the present invention is laminated on a flexible substrate, it is preferable to use a bisphenol F EO as a comonomer from the viewpoint of reducing sheet bending. At least one or more diacrylates of denatured diacrylate, bisphenol A EO denatured diacrylate, and bisphenol S EO denatured diacrylate. The comonomer is equivalent to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) based on 1 part by weight of the polyimine of the present invention. - Packing -------- Order --------- (Please read the notes on the back and fill out this page) 1299043 A7 ____B7____ V. Description of invention (call) It is preferably 1~200 The ratio of parts by weight is more preferably in the range of 3 to 150 parts by weight. If it is out of the range of 1 to 200 parts by weight, the sensitizing effect of the object may not be obtained, or the developability may be adversely affected. As the comonomer, one type of compound may be used, or a plurality of types may be used in combination. Examples of the other components include a resin other than the soluble polyimine (A) and the polyfunctional (meth)acrylic compound (B), an organic or inorganic pigment, a reinforcing material, a coupling agent, and various additives. Solvents and so on. The resin other than the soluble polyimine (A) or the polyfunctional (meth)acrylic compound (B) is, for example, a thermosetting resin or a thermoplastic resin. Examples of the thermosetting resin include an epoxy resin and a thermosetting acrylic resin. Examples of the thermoplastic resin include polyester, polyamide, polyurethane, polycarbonate, etc., and the above epoxy resin is used to enhance the photosensitive resin composition. Followers. The type of the epoxy resin is not particularly limited, and examples thereof include bisphenol resins such as the following compounds, Epikote 828 (manufactured by Oiled Shell Co., Ltd.), and o-cresol novolac paints such as 180S65 (manufactured by Oilseed Shell Co., Ltd.). Resin, bisphenol A phenolic enamel resin such as 157S70 (manufactured by Hosei Shell Co., Ltd.), trishydroxyphenylmethane phenolic enamel resin such as 1032H60 (manufactured by Hosei Shell Co., Ltd.), naphthyl aryl phenol oxime such as ESN375 Paint resin, tetraphenol phenolate 1031S (manufactured by Oil Chemical Shell Co., Ltd.), YGD414S (Dongdu Chemical), trihydroxyphenylmethane EPPN502H (Nippon Chemical), special bisphenol VG3101L (Mitsui Chemical), special naphthol NC7000 (曰本Chemicals), glycidylamine type resins such as TETRAD-X, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.). 47 The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------------- Order --------- ( Please read the precautions on the back and fill out this page.) 1299043 A7 _____B7_____ V. Invention Description Ur) Epoxy resin can be mixed in a molecule with a double or triple bond compound formed with an epoxy group, or other thermosetting resin. use. As such a compound, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, propargyl glycidyl ether, glycidyl propargyl ester, ethynyl glycidyl ether can be exemplified. Wait. Examples of the other thermosetting resin include bismaleimide, bisallylbisindole, phenol resin, cyanate resin and the like. When an epoxy resin is contained in the photosensitive resin composition of the present invention, if a curing agent of an epoxy resin is further contained, a cured product having good physical properties can be obtained. The curing agent is not particularly limited, and examples thereof include an amine system, an imidazole system, an acid anhydride system, and an acid curing agent. The photosensitive composition of the present invention may contain an organic solvent. As long as it is dissolved in a suitable organic solvent, it can be used in a solution state, and it becomes very convenient when the coating is dried. The solvent to be used is preferably an aprotic polar solvent from the viewpoint of solubility, and specific examples thereof include N-methyl-2-pyrrolidone, N-ethinyl-2-pyrrolidone, and N-benzyl group. -2 - pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, dimethyl amide, hexamethylphosphoniumamine, N_Ethyl-ε-, caprolactone, dimethylimidazolidinone, divinyl dimethyl ether, trivinyl dimethyl ether, r-butyrolactone, dioxane, dioxane, Tetrahydrofuran, chloroform, dichloromethane, and the like. These can be used alone or in a mixed form. The organic solvent can be used for the solvent residue used in the synthesis reaction of the soluble polyimine (A), or in the soluble polyimine after isolation. The paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) ---I----丨丨---- — III ^ · I I------ (Please read the notes on the back and fill out this page) 1299043 A7 _B7 __ V , invention description (Μ) Newly added to use. In order to improve the coating property of the resin composition solution, a solvent other than the above may be mixed in a range which does not adversely affect the solubility of the polymer, such as toluene, xylene, diethyl ketone, methoxybenzene or cyclopentanone. can. Further, in order to leave a certain amount of solvent in the film after drying, the pressure-bondable temperature can be lowered, and a low-boiling solvent and a high-boiling solvent can be mixed. Since the soluble polyimine contained in the composition of the present invention has good solubility in an organic solvent, it can be dissolved in an ether solvent such as dioxane, dioxane or tetrahydrofuran, and chloroform or dichlorochloride. A halogen-based solvent such as methane is a solvent having a boiling point of 120 ° C or lower. In particular, as a main component of acid dianhydride, 2,2'-hexafluoropropanedicarboxylic dianhydride, 2,3,3\4·-bisphenyltetracarboxylic dianhydride, and formula (VI) are used. The ester-based acid dianhydride is a diamine, and a diamine having two or more carboxyl groups in the molecule, an aromatic diamine having an amine group at the m position, a diamine having a rolling group, and a general formula are used. (3) The dioxane diamine represented by the above, the solubility of the obtained soluble polyimine (A) is extremely high. Since it can be dissolved in a solvent having a boiling point of 12 or less (TC or less), if a solution obtained by dissolving a photosensitive resin composition in the solvent is applied and dried, high temperature is not required during drying, so that it can be prevented (A) Thermal polymerization of the decenoic acid-based compound (B). The photosensitive resin composition of the present invention has a high decomposition start temperature after heat curing, and is usually 300 ° C or higher, and may be 32 (TC or more and 340 ° C or higher). 〇The curing temperature can be set below 200 ° C. The main layer of the conductor layer of FPC uses copper. If the copper is exposed to a temperature exceeding 200 ° C, the crystal structure of copper will gradually change and the strength will decrease. Inventive photosensitive resin 49 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page). ------- 1299043 A7 _B7___ V. INSTRUCTION DESCRIPTION U7) The composition can be used as a coating film for FPC. The elastic modulus of the photosensitive resin composition of the present invention after curing can be 10 to 3000 MPa. By using the elastic modulus of this range, when used for coating The stress generated by the mismatch between the modulus of elasticity and the coefficient of thermal expansion between the coating film and the base film can be alleviated. Preferably, it is 10 to 2500 MPa, more preferably 10 to 2000 MPa. The photosensitive resin composition of the present invention, after hardening The solder heat resistance (300 ° C) can be 3 or more. Therefore, the resin which is cured by lamination of copper has heat resistance, and even if it is immersed in solder at 300 ° C for 3 minutes, foaming or peeling is not observed. The solder of 200 ° C is not deteriorated even if it is immersed for 5 or more. The photosensitive resin composition of the present invention has a thermal expansion coefficient after hardening of 20 ppm to 500 ppm. When the film is laminated on the copper, the difference between the thermal expansion coefficient and the copper foil is not large, and the plate bending of the substrate can be prevented. The thermal expansion coefficient after curing is preferably 20 to 500 ppm, more preferably 20 to 400 ppm, and particularly preferably 20 ～300 ppm. As described above, the photosensitive resin composition of the present invention can be used as a photosensitive solder resist because the (A) soluble polyimine contained therein is soluble in an organic solvent. For example, as a photosensitive property Resin composition solution, It can be used as a liquid photoresist directly, and can be easily formed into a film by casting or the like to form a photosensitive film, which can be used as a photosensitive dry film resist. It is divided into two types, namely, a film-like photoresist which is to be peeled off after the role of the etchant which forms a copper circuit, and 50 sheets of insulating protective film and film-like photoresist which are accompanied by a circuit such as a printed wiring board. The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------Installation--------Set--------- ( Please read the precautions on the back and fill out this page.) 1299043 A7 ___J7___ V. Invention Description (#) Photosensitive coating for two characters. The "coated film" in the present invention is accompanied by two roles of a film-like photoresist and an insulating protective film. In the production of the photosensitive film, the photosensitive resin composition (the soluble polyimine containing the component (A) and the component (B) have one or more aromatic rings and two or more carbon-carbons. The double bond-bonded compound, the photoreaction initiator (C) of the component (C), and/or the sensitizer, and other components are all dissolved in an organic solvent. The organic solvent to be used herein may be any solvent which can dissolve the photosensitive resin composition. For example, an ether solvent such as tetrahydrofuran, dioxane or dioxin, or a ketone such as acetone or methyl ethyl ketone can be used. A solvent, an alcohol solvent such as methanol or ethanol, or the like. These solvents may be used singly or in combination of two or more. Since the solvent must be removed afterwards, it is advantageous to select a low boiling point which can dissolve the components (A), (B), and (C) as much as possible. The solution of the obtained photosensitive resin composition was uniformly applied onto a support film and dried to form a film-like photosensitive film. Use it as a coating. In this case, it can be applied to a support such as a metal or a PET film, dried, and then peeled off from the support to be treated as a film alone. Further, as shown in Fig. 1, it can be used in a form in which a film is laminated on a film 16 such as PET. It is also possible to use the protective film 16 on the surface layer of the photosensitive polyimide 14 for use. The preferred temperature range of the drying temperature of the photosensitive resin composition is such that the double bond of the polyfunctional (meth)acrylic compound (B) or the other compound contained in the composition is not caused by heat. The temperature at which the bond, the triple bond, and the epoxy group are inactivated by the reaction is specifically 180 ° C or lower, preferably 150 ° C or lower, more preferably 100 ° C or lower. Drying temperature from low temperature 51 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---------------------------- --- (Please read the note on the back and fill out this page) 1299043 A7 —_ B7___ V. Invention Description (叼) The segment can also be raised. The drying time 'as long as the solvent contained therein is mostly volatilized', and the time during which the applied enamel paint can be thinned can be specifically tens to 30 minutes, preferably several minutes to 15 minutes. The coating film of the present invention will be described. In general, the FPC process is to apply an adhesive to a long strip-shaped film, and after continuous drying, a copper foil is continuously laminated, so that productivity is good. However, as described in the prior art, it is necessary to perform drilling or windowing in accordance with the circuit terminal portion or the component joint portion on the coating film before bonding, and to form a hole of the coating film and the FPC terminal portion. Or the work of aligning the joints of the parts is almost close to the manual work, and since the batch fit is performed under a small workpiece size, workability and positional accuracy are low, and there is a problem of cost. Since the coating film of the present invention can be used in the form of a film, it can be easily bonded to the substrate conductor surface. In particular, it can be laminated at a temperature of 150 ° C or lower, and can be directly laminated on a printed substrate without passing through an adhesive. The photosensitive resin composition of the present invention is easily insolubilized in the developer by exposure, and the unexposed portion has high solubility in the developer. Therefore, a high-precision pattern can be formed. In this manner, a coated laminated substrate excellent in positional accuracy can be obtained with good work efficiency. Fig. 2 is a view showing a process of using a flexible printed substrate of the coated film of the present invention. Fig. 2 (a) and (b) show a process of bonding a copper-area laminate (CCL) to a photosensitive coating film in the form of a laminate having a PET film and a protective film of the present invention. This process is a process in which a CCL conductive surface of a circuit is formed by a conductor such as a copper foil in advance, and is protected by a photosensitive dry film (coating film). Specifically, the CCL and the photosensitive dry film (coating film) are aligned, and the heat is layered and hot pressed 52. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public) ---- -------•装--------Book--------- (Please read the notes on the back and fill out this page) 1299043 A7 _B7 _ V. Invention description (θ ) or thermal vacuum laminate for bonding. The lower the laminate temperature, the better, at 150 ° C or lower, preferably 130 ° C or lower, more preferably ll 〇 ° C or lower. The temperature condition at the time of pressure bonding of the acrylic resin photosensitive film used in the prior art is 80 to 150 ° C, and the case of the non-photosensitive film is usually 18 〇 to 200 ° C. Further, the conditions of the polyimide film used in the past are 150 to 300 °C. However, in contrast to these temperature conditions, the pressure-bonding of the coating film of the present invention can be carried out at a temperature lower than the above-described temperature, for example, a temperature in the range of 20 to 150 ° C, so that the film can be bonded in a B-stage state. A pattern with good resolution is obtained. The temperature at this time is preferably a temperature range in which no epoxy group or double bond or triple bond is opened by heat, specifically 150 ° C or lower, preferably 130 ° C or lower, more preferably l〇 Below 〇 °C. Further, in order to laminate the di(meth)acrylic compound without curing, the temperature at which the layering can be carried out is 150 t or less, preferably 130 ° C or less, more preferably 10 ° C or less. The coating film is a film which is spread at room temperature, and exhibits fluidity and adhesion upon heating at the time of lamination. In the coating film of the present invention, by bonding and developing the FPC and the coating film, the hole for joining the FPC terminal portion can be formed, and the problem of positional accuracy and workability can be improved. Specifically, by performing exposure and development, a hole or the like for bonding the terminal portions of the substrate can be carried out where necessary. The step of (c) of FIG. 2 is to irradiate light through a mask pattern of a predetermined pattern on the laminated body; the step of (d) of FIG. 2 removes the unexposed portion of the coating film by dissolution of an alkaline solution. The development process is performed to obtain the desired pattern. For the development, general positive resist development can be used. 53 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -----------Install ------ --Book --------- (Please read the note on the back and fill out this page) 1299043 B7 V. Invention Description (Magic) Device to carry out. Before exposure, a mask is placed on the coating film, which is provided with a fine parallel line, curve, and aperture X line width of the line width/line width = 100/100//m = l〇〇#mXl〇〇 A pattern formed by micro holes of equal to or smaller than m. After exposure, the pattern is developed by development. Then, it was washed with a rinsing liquid to remove the developing solvent. In this manner, the substrate on which the coating film is laminated can be obtained with high work efficiency and excellent positional accuracy. When the substrate and other parts are joined by solder, they are usually joined by exposure to a high temperature of 200 ° C or higher for several seconds. The photosensitive resin composition of the present invention has a high heat resistance temperature after heat curing, and is usually 300 ° C or higher, preferably 32 (TC or higher, more preferably 340 ° C or higher. Therefore, the cured film is not deteriorated. The coated multilayer printed circuit board can be bonded to the desired component. The coated elastic film of the present invention has a smaller elastic modulus as the individual is based on, in order to buffer the elasticity between the coated film and the base film. The stress generated by the mismatch between the modulus and the coefficient of thermal expansion. Preferably, the modulus of elasticity after hardening is from 10 MPa to 3,000 MPa, and the photosensitive resin composition of the present invention has such a property. When the number is too high, when the film and the copper-area layer (CCL) on which the circuit is formed are heated and hardened, the hardening shrinkage of the polyimide may cause curling and bending of the sample. When it is used as a coating film of a flexible printed circuit (FPC), there is a disadvantage that peeling or disconnection of a fine copper circuit is likely to occur. Therefore, '54 __ ------------- ------Book --------- (Please read the notes on the back first Write this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 ___B7 V. Invention Description (Y) The elastic modulus after hardening of the film is preferably lOOMPa~2500MPa, Preferably, it is 100 MPa to 2000 MPa, and particularly preferably 100 MPa to 1500 MPa. Next, after coating the coating film on the substrate through a mask of a predetermined pattern, the unexposed portion is dissolved and removed by using a developing solution of an alkaline solution. The development process can be carried out using a general positive-type resist development apparatus. As the developer, an alkaline aqueous solution or an organic solvent can be used. The photosensitive resin composition of the present invention can be dissolved in an organic solvent and An aqueous solution which is a soluble or testable aqueous solution or an organic solvent for alcohols such as water or methanol, and may be a solution of one compound or a solution of two or more kinds of compounds. a solution in which an alkaline compound is dissolved in an alcohol such as water or methanol. The alkali contained in the alkaline solution used as the developer is soluble in water or alcohol, and the solution is present. The compound (basic compound) is not particularly limited, and examples of such a compound include an alkali metal, a soil-measuring metal, a hydroxide of an ammonium ion, a carbonate, an amine salt, and the like. The following compounds are listed: 2-dimethylamine ethanol, 3-dimethylamine-1-propanol, 4-dimethylamine-1-butanol, 5-dimethylamine-1-pentanol, 6-dimethylamine-1 -hexanol, 2-dimethylamine-2-methyl-1-propanol, 3-dimethylamine-2,2-dimethyl-1-propanol, 2-diethylamine ethanol, 3-diethyl Amine-propanol, 2-diisopropylamineethanol, 2-bis-n-butylamineethanol, n,n"dibenzyl-2-aminoethanol, 2-(2-dimethylamine ethoxy)ethanol, 2 Mono(2-ethylamine ethoxy)ethanol, 1-dimethylamine-2-propanol, ~ethylamine-2-propanol, N-methyldiethanolamine, N-ethyldiethanolamine, N_55^ The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public meal 1 ------------ ----------- loaded -------- Order ------ 丨! § (Please read the notes on the back and fill out this page) A7 1299043 ____B7_ —_ V. Invention description (β ) (Please read the note on the back and fill out this page) n-butyl diethanolamine, N_t-butyl Diethanolamine, N-lauryldiethanolamine, 3-diethylamine-1,2-propanediol, triethanolamine, triisopropanolamine, N-methylethanolamine, N-ethylethanolamine, N-n-butylethanolamine, N-tert-butylethanolamine, diethanolamine, diisopropanolamine, 2-aminoethanol, 3-amino-1-propanol, [amino-butanol, 6-amino-p-hexanol, 1 -Amino-2-propanol, 2-amino-2,2-dimethyl plant 1-propanol, 1-aminobutanol, 2-amino-1-butanol, N-(2-amine Ethyl)ethanolamine, 2-amino-2-methyl-1,3-propane-ol, 2-month-female- 2-ethyl1,3-propanediol, 3-amino-1,2-propanediol , 2_Amino 2-hydroxymethyl-1,3-propanediol, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate , tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide Amino methanol, 2-aminoethanol, 3-aminopropanol, 2-aminopropanol, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, These compounds, such as trimethylamine, triethylamine, tripropylamine, and triisopropylamine, can be used individually or in combination of 2 or more types. The developing solution can also use an organic solvent in addition to the alkaline solution. In this case, an organic solvent may be used alone, or a mixed solvent solution which completely dissolves the photosensitive polyimine and a poor solvent having a poor solubility may be used. Specifically, in order to improve the solubility of the polyimine, it may partially contain methanol, ethanol, propanol, isopropanol, isobutanol, N-methyl-2-pyrrolidone, N,N-dimethylformamidine. A water-soluble organic solvent such as an amine or N,N-dimethylacetamide may be used by mixing two or more kinds of solvents. The concentration of the above basic compound is generally 56. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1299043 B7 5. The invention description (sand) is 0. 1 to 50% by weight, in view of the influence on the supporting substrate, etc., it is preferably 0. 1 to 30% by weight. More preferably, it is 1% to 1% by weight, particularly preferably 0. 1 to 5% by weight. The pattern formed by development is washed with a washing liquid to remove the developing solution. Examples of the rinsing liquid are methanol, ethanol, isopropyl alcohol, water, and the like which are well mixed with the developing solution. The substrate ' of the photoresist film having the pattern formed by the above treatment is subjected to heat treatment at an appropriate temperature of 20 to 200 ° C to react an unreacted group (double bond or the like) to completely cure the photoresist. When the heating temperature at this time exceeds 200 °C, the crystal structure of copper mainly used in the substrate conductor layer is changed, which causes a decrease in strength, so care must be taken. In this manner, a polyimide film having a high-resolution desired pattern can be formed as a substrate of the coating film. The film has high heat resistance and excellent mechanical properties. Since the photosensitive resin composition of the present invention is soluble, the substrate having the coating film (forming a desired pattern) can be easily prepared by using the photosensitive dry film resist of the present invention. The pattern obtained by the above treatment is subjected to heat treatment at a temperature selected in the range of 100 to 200 ° C, and a CCL having a resin pattern formed thereon can be obtained without a coating drying process. The CCL in which the coating film of the photosensitive resin composition of the present invention is laminated is formed into a flat shape without being bent or curled based on the characteristics of the photosensitive resin composition. The resin pattern obtained by the coating film of the present invention has high heat resistance, excellent mechanical properties, and particularly high resolution. In detail, the hardened modulus of elasticity is from 100 MPa to 3000 MPa and has excellent mechanical strength. 57 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — I — Aw .  I — II---t---111111 (Please read the note on the back and fill out this page) 1299043 A7 ___B7___ V. Description of invention (bamboo) Degree, resolution is line width / line spacing = 100/100// High resolution below m. Further, after curing, it has high heat resistance of solder heat resistance (300 ° C) for 3 minutes or more. The resin which has been hardened with the copper laminate has a solder bath heat resistance of 300 ° C or higher, and does not cause foaming or peeling or the like even if it is immersed in the solder at 300 ° C for 3 minutes, and does not deteriorate at all. For the solder of 200 ° C, no deterioration occurs even after immersion for 5 minutes or more. The coating film of the present invention can have a three-layer structure and is composed of a base film, a photosensitive film obtained by using the photosensitive resin composition of the present invention, and a protective film. The protective film has appropriate adhesion and peelability to the photosensitive film. Specifically, it is a three-layer structure in which (1) a base film, (2) a photosensitive film composed of the photosensitive resin composition of the present invention, and (3) a protective film are laminated in this order. The protective film is obtained by laminating a copolymer film of polyethylene and ethylene glycol resin with a stretched polyethylene film; or a copolymer film of polyethylene and ethylene vinyl alcohol resin, and stretching The polyethylene film was obtained by simultaneous extrusion method and the protective film was formed into a photosensitive adhesive sheet bonding surface. In the base film of the three-layer structure sheet of the present invention, various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide, and polyimide film can be used, particularly in terms of requirements. For the purpose of heat resistance, a polyimide film is preferably used. Regarding the photosensitive film joint surface of the base film, it is preferred to carry out a surface treatment so as not to be easily peeled off. In the photosensitive film of the present invention, the resin composition having photocurability and thermosetting property is maintained in a semi-cured state (B-stage). It is designed to have fluidity during hot pressing or lamination processing, and can follow the irregularities of the circuit on the flexible printed wiring board to form a close contact, which can be used for photocrosslinking reaction during exposure, and stamping ___ Standard (CNS) A4 specification (21G X 297 public) ~ . —装--------订--------- (Please read the notes on the back and fill out this page) 1299043 A7 ___^_____ V. Description of the invention (I) Heat during processing The heat hardening after the press working is performed to complete the hardening. Specifically, as the base polymer, a resin such as polyimide or the like is preferable from the viewpoint of heat resistance and flex resistance of the film after curing. It is also possible to use a polyimine oligomer, but it is preferably a soluble polyimine used in the present invention. Further, in order to improve the adhesion to the flexible printed wiring board, the epoxy-modified polyimine is preferred. Further, as the photocurable resin, an acrylic resin having a double bond or a triple bond, a methacrylic resin, a vinyl resin or the like can be typically used. As the thermosetting resin, an acrylic resin, an epoxy resin or the like can be typically used. The photocurable resin and the thermosetting resin may also have the same situation, and no special distinction is required. The protective film of the present invention is characterized by, typically, a "copolymer film of polyethylene and ethylene vinyl alcohol" (abbreviated as (PE+EVA) copolymer film) and "stretched polyethylene film" (abbreviated as ΟΡΕ) a film-based laminate, or a "copolymer of polyethylene and ethylene vinyl alcohol resin" and a "polyethylene" film which are simultaneously extruded (having a film of a ρΕ film surface and a film surface of a (PE+EVA) copolymer), And the (pE+EVA) copolymer film surface forms a photosensitive sheet bonding surface. There are two main methods for producing protective films. That is, a method of laminating two kinds of films, and a method of simultaneously extruding two kinds of resins. In the lamination method, a (PE+EVA) copolymer film and an ope film are bonded together. Further, the ethylene vinyl alcohol resin film and the ruthenium film may be bonded together. Typically, an adhesive is applied to the film-bonding surface. In this case, the (PE+EVA) copolymer film surface to be bonded to the 〇ρΕ film is preferably subjected to an easy-to-continue treatment such as corona treatment. 59 ^The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " ^ " --------^--------- (Please read the back of the note first) Matters fill out this page) 1299043 A7 ^_B7 ___ V. OBJECT DESCRIPTION (θ) A film made by simultaneously extruding two kinds of resins, consisting of a polyethylene resin and a copolymer of polyethylene and ethylene vinyl alcohol resin. The resin was produced by simultaneously extruding and thinning. In this method, a film having a PE film surface on one side and a (PE+EVA) copolymer surface on the other side is obtained. The (PE + EVA) copolymer film is preferably an additive which does not contain a lubricant, an antistatic agent or the like. When the (PE+EVA) copolymer film is directly in contact with the photosensitive film, when these additives are rewound from the protective film and transferred to the photosensitive film, the adhesion and adhesion of the photosensitive film and CCL may be lowered. Therefore, when additives or surface treatment are used in the photosensitive film, these points must be fully considered. The (PE+EVA) copolymer film thickness is as thin as possible, and the handleability is preferably 2 to 50/m. The (PE+EVA) copolymer film is characterized in that the adhesion to the photosensitive film is improved, the drying of the photosensitive film can be prevented, and the like, and the photosensitive film can be easily peeled off. The ruthenium film used in the protective film according to the affixing method is bonded as a reinforcing body of a (PE+EVA) copolymer film, and its thickness is preferably 10 to 50/zm. When the thickness is too thin, there is a tendency to be prone. In particular, it is preferably in the range of 10 to 30/zm. One reason for using the ruthenium film is that it has a sliding property when the sheet is formed into a wound material. In the case of the bonding method, as a method of bonding the (PE + EVA) copolymer film and the ruthenium film, various examples are generally used. Generally, an adhesive is applied to the ruthenium film, and after drying, the adhesive surface is The corona-treated surface of the (PE+EVA) copolymer film was laminated with a hot roll. The adhesive used for the bonding is not particularly limited. A commercially available adhesive can be used, especially in the use of polyurethane 60 paper scales applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---III----I Aw ·1111111 ^ · II I --- — I <Please read the notes on the back and fill out this page.) A7 1299043 _____ B7____ V. INSTRUCTIONS (β) The following agents are more effective. In the case where a protective film is produced by a simultaneous extrusion method, the amount of the resin composed of the copolymer of polyethylene and ethylene vinyl alcohol resin and the amount of the polyethylene resin are adjusted at the time of simultaneous extrusion. By this adjustment, the thickness of the (PE + EVA) copolymer film and the ruthenium film of the produced sheet can be individually controlled. At this time, the thickness of the (PE + EVA) copolymer film and the ruthenium film is preferably 2 to 50 # m, 10 to 50 # m, respectively, based on the same reason as described above. The protective film can be provided with light blocking properties. There are several methods for imparting light shielding properties to the protective film, and in the case of the present invention, it is preferred to color the ruthenium film. In particular, it is preferably colored to absorb light of a specific wavelength which is a range which the photoreaction initiator contained in the photosensitive film can absorb. In the photosensitive film of the present invention, it is preferred to blend a photoreaction initiator to draw a desired pattern by exposure and development. The photoreaction initiator is not particularly limited as long as it absorbs light of a specific wavelength to generate a radical or a base, or a reactive group having a double bond and/or a triple bond (vinyl, propylene, methacryl) The reaction ratio of the base polymer, the photocurable resin, and/or the thermosetting resin and the photoreaction initiator may be 100% by weight based on the reaction of the base, the allyl group, and the like. The portion is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight. The photosensitive film of the present invention preferably has a thickness of 10 to 75 / zm. More preferably 40 to 70//m, and most preferably 45 to 65//m. If the thickness of the photosensitive film is too small, it is not preferable from the viewpoint that the copper circuit on the flexible printed wiring board and the underlying polyimide film cannot be buried and the flatness of the surface after bonding cannot be maintained. If the thickness is too large, development based on fine patterns will be difficult. 61 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------------- ---Book--------- (Please read the note on the back and then fill out this page) 1299043 a7 _______B7___ V. Description of the invention (smart) It is not easy to produce a view of the bending of the sample. In general, the photosensitive film is formed by maintaining the above-mentioned photocurable and thermosetting adhesive composition in a semi-hardened state (B-stage), and is designed to have fluidity during hot pressing or lamination processing. The adhesion can be made to follow the irregularities of the circuit on the flexible printed wiring board, and the curing can be completed by the photocrosslinking reaction at the time of exposure, the heat during the press working, and the heat hardening performed after the press working. The photosensitive film used in the present invention contains polyimine. In particular, an aromatic ring or an alicyclic polyimine in the molecule is preferred because it has high mechanical strength such as high heat resistance and flex resistance. It is preferred to use a film composed of the above photosensitive resin composition. The method for producing the three-layered structural coating film of the present invention will be described below. After the solution-like photosensitive resin composition is uniformly applied onto a base film such as a PET film, the solvent is removed by heating and/or blowing hot air to obtain a photosensitive dry film resist. As the base film of the present invention, various commercially available various films such as polyethylene terephthalate (PET) film, polyphenylene sulfide, and polyimide film can be used. Regarding the photosensitive film joint surface of the base film, it is preferred to carry out a surface treatment to make it easy to peel off. A PET film is preferably used as the base film based on the viewpoint of having a considerable degree of heat resistance, being inexpensive and easily available. The photosensitive film of the present invention preferably has a thickness of 5 to 75 m. More preferably 10 to 70/zm, most preferably 15 to 40/zm. When the thickness of the photosensitive film is too small, the unevenness of the copper circuit based on the flexible printed wiring board and the polyimide film of the underlying layer cannot be buried, and the flatness of the surface after bonding cannot be maintained. 62 ___________ This paper size is applicable. China National Standard (CNS) A4 Specification (210 X 297 mm) -------------111111! ·11111111 (Please read the back note first and then fill out this page) 1299043 B7 V. Invention Description ( Oh.) Not good. Further, if the thickness is too large, development based on fine patterns may be difficult, and the viewpoint of bending of the sample tends to occur, which is not preferable. (Please read the precautions on the back and fill out this page.) The general photosensitive film is a semi-hardened state (Β step) in which the above-mentioned photocurable and thermosetting adhesive composition is maintained. It has fluidity during hot pressing or lamination processing, and can follow the irregularities of the circuit on the flexible printed wiring board to form a close contact, which can be carried out by the photocrosslinking reaction during exposure, the heat during press working, and the press working. The heat is hardened to complete the hardening. In the three-layer structure sheet of the present invention, the above-mentioned base film, photosensitive film, and protective film are laminated in this order, and the focus is on the protective film (PE+EVA) copolymer film surface forming the bonding film bonding surface ( Stripping surface). As a method of laminating, a photosensitive resin component is applied onto a base film, and after drying, a film of a (PE+EVA) copolymer film surface of a photosensitive adhesive film and a protective film is laminated, and can be wound into a cylindrical shape. . The photosensitive coating layer composed of the three-layer structure sheet wound in a cylindrical shape can be stored in a wound state, and when it is bonded to the CCL in which the circuit is formed, it is not necessary to use a conventional batch laminate. The continuous laminate can be used to smoothly perform the process of the flexible printed wiring board. When the ruthenium film for a flexible printed wiring board is produced by using the three-layer structure sheet of the present invention, after the protective film is removed, the flexible printed wiring board on which the circuit is formed and the photosensitive film are laminated by heating. When the temperature at the time of lamination is too high, the photosensitive portion is crosslinked to harden the film, and since it functions as a photosensitive coating layer, the temperature at the time of lamination is preferably low. Specifically, it is 60 to 150 ° C, more preferably 60 to 12 (TC. When the temperature is too low, 63 paper grades apply to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 _ B7 _ five According to the invention, (W) the fluidity of the photosensitive film is deteriorated. Therefore, it is difficult to cover the fine circuit on the flexible printed wiring board, and the adhesion tends to be deteriorated. The three-layer structure of the present invention is used. In the case of a photosensitive film composed of a sheet, in order to improve the burying property of the fine circuit, preheating of the substrate can be performed. However, if the photosensitive film is heated as described above, it is not necessary to preheat the substrate in advance. The wiring board/photosensitive film/base film is sequentially laminated. The base film can be peeled off when the laminate is completed, or peeled off after the exposure is completed. Based on the viewpoint of protecting the photosensitive film, it is preferably 'placed' After the reticle pattern is exposed, the film is peeled off. After the film is laminated on the flexible printed wiring board, the film is cured by heat curing after being irradiated with light such as ultraviolet light. Insulate the circuit The photosensitive film of the present invention is also applicable to a coating film for a circuit board of a magnetic head portion of a hard disk device of a computer. It can also be used for a suspension for a hard disk, and can also be used for a circuit of a conductor layer. Specifically, after the coating film of the present invention is laminated on a substrate for a suspension having a circuit, the mask can be easily formed by exposure and development, thereby making it possible to form a pattern for wiring. The viewpoint of the process and the cost is useful. When the photosensitive film of the present invention is used as a photosensitive coating layer for a magnetic head portion of a flexible printed wiring board or a computer hard disk device, it is attached to the circuit and then mounted. The reticle pattern can be opened at a predetermined position by exposure and development. The photoreactive initiator contained in the photosensitive film can be used as an effective radiation source because it generally absorbs light in the ultraviolet region. ------------------Book --------- (Please read the note on the back and fill out this page) This paper scale applies to the Chinese National Standard (CNS) ) A4 size (210 X 297 mm) 1299043 A7 ___- _B7____ V. Invention The developing solution at this time may be an organic solvent having an alkaline aqueous solution as described above. The solvent for dissolving the basic compound may be water or an organic solvent. It is preferred to prevent damage of the film and environmental influence. In order to improve the solubility of the polyimine, it may further contain methanol, ethanol, propanol, isopropanol, isobutanol, N-methyl-2-pyrrolidone, N,N-dimethyl A water-soluble organic solvent such as formamide or N,N-dimethylacetamide may be used by mixing two or more kinds of solvents. The concentration of the above basic compound is generally 〇·1 to 1% by weight, and is considered. The influence on the film or the like is preferably 0.1 to 5% by weight. Examples of the basic compound include hydroxides or carbonates of alkali metals, alkaline earth metals, or ammonium ions, amine compounds, and the like. After the development, the substrate is washed with distilled water or the like, and then dried and heat-cured to obtain a coating layer excellent in heat resistance and chemical resistance. The heat hardening is carried out in the range of 100 to 200 ° C for about 15 to 90 minutes. In this manner, a coating film is formed on the printed wiring board, and electronic components such as a 1C wafer can be assembled. [Examples] Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the examples. In the examples, ESDA stands for 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3f,4,4'-tetracarboxylic dianhydride, and BAPS-Μ represents bis[4- (3) -Aminophenoxy)phenyl]boron, DMF stands for hydrazine, hydrazine-dimethylformamide. (Thermal decomposition start temperature): The Chinese National Standard (CNS) A4 specification is applied from 65 paper scales by the Seiko Instruments Inc. thermal analysis and measurement device (TG/DTA220) at an air temperature increase rate of 10 ° C / min. 210 X 297 mm) -----------Install--------Book--------- (Please read the notes on the back and fill out this page) 1299043 A7 _____B7_ V. Description of the invention (") Temperature range from room temperature to 500 ° C, the temperature at which the weight is reduced by 5% is the thermal decomposition onset temperature. (Coefficient of thermal expansion) Using a precision electronic TMA device (Model 120C) in nitrogen The temperature range from room temperature to 350 ° C was measured at a temperature increase rate of 10 ° C / min. (The modulus of elasticity, tensile strength, and elongation of the film after curing) The measurement was carried out in accordance with JIS C 2318. Tensile strength and elongation were measured by a tensile tester (AutoGraph S - 100 - C) manufactured by Shimadzu Corporation as follows. First, a photosensitive composition solution (lacquer) was uniformly coated. On a copper foil, a coating of 25 cm×25 cm was prepared by drying. Full exposure was performed (exposure conditions: 10 mJ/ After cm2 was irradiated for 3 minutes with parallel light having a wavelength of 400 nm, and hardened at 180 ° C for 2 hours, the copper foil was removed by etching. The obtained film was hung on a needle holder, and dried at 100 ° C for 3 minutes, and then cut into several widths. A film strip of 0.015 m long and 0.20 m long. The portion of the film strip having a length of 0.10 m was clamped by a testing machine, and stretched at a constant speed to measure the force required for elongation of 5%. The force was removed by 0.05, and then Dividing the average modulus (m) and the bandwidth (0.015 m), the modulus of elasticity (MPa) is calculated. The film strip is stretched all the time, and the force (Pa • m2) when the film is pulled off is divided by the average thickness of the film (m). And the bandwidth obtained by the bandwidth (0.015m) is the tensile force (MPa), and the film strip is pulled to the longest elongated star' divided by the original tape length (0.10m) and multiplied by 1〇〇. Rate (%). {Elastic Modulus (MPa)} = {force required to stretch 5% (pa· m2) } /〇·〇5Χ [{Mean film thickness (m)} X {Bandwidth (〇. 〇15m)}〕 {stretching force (1^&)}={force when pulling the film strip (Pa.m2)}/[ { 66 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------------- Order --------- (Please read the notes on the back and fill in This page) 1299043 A7 ______ B7____ V. INSTRUCTION DESCRIPTION (Material) Membrane average thickness (m)} X (bandwidth (〇.〇15m)}] {elongation (%)} =1〇〇Χ {Maximum elongation zone Length {original length (m)} (glass transition temperature Tg and 5% weight loss temperature) was measured using a DSC CELL SCC-41 (differential scanning calorimeter) manufactured by Shimadzu Corporation under a nitrogen gas flow rate at a temperature increase rate of 10 ° C / min. Room temperature ~ 4 〇〇. (In the temperature range of -20%, the 5% weight loss temperature is TG/DTA (differential thermal analyzer) manufactured by Shimadzu Corporation, and the temperature is measured at a temperature increase rate of 2 (rc/min) from 20 to 600 °C. The temperature at which the sample weight was reduced by 5% was taken as the 5% weight loss temperature, and the 5% weight loss temperature was an index showing the heat resistance. (Weight average molecular weight) It was measured using GPC manufactured by Waters according to the following conditions. Column: Shodex KD-806M 2 pieces, temperature 60 ° C, detector RI, flow rate: lml / min, developing solution: DMF (lithium bromide 0.03M, phosphoric acid 0.03M), sample concentration: 〇. 2wt%, injection amount: 20/zl, reference material: polyoxyethylene) (Determination of sulfhydrylation rate) 1 Cast poly-proline solution (DMF solution) onto PET film, 10 (TC X 10 points, 130 ° C X 10 minutes) After heating, it is peeled off from the PET film, fixed on a needle frame, and heated at 15 ° C X60 minutes, 200 ° C X 60 minutes, and 250 ° C X 60 minutes to obtain a 5/zm thick polyimine film. The polyimine prepared in the examples or the comparative examples was dissolved in DMF, cast on a PET film, heated at 100 ° C for 30 minutes, and then transferred from the PET film. Next, fixed to the needle frame, at 67 paper scales applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -----------Installation--------Set- ------—(Please read the precautions on the back and fill in this page) 1299043 A7 ____ B7____ V. Invention Description) In a vacuum oven, heat and dry at 80 ° C, 660 Pa for 12 hours to obtain 5# m thick polyimine film. The IR of each film was measured to determine the ratio of ruthenium absorption/benzene ring absorption. The ruthenium absorption/benzene ring absorption obtained by 1 was 100% imidization rate. In this case, the ratio of the ruthenium absorption to the benzene ring absorption ratio of 2 is determined. The ruthenium is used as the ruthenium imidization ratio. (Method for Measuring COOH Equivalent) A 0.1 N KOH ethanol solution is used with 0.1 N oxalic acid. The aqueous solution is titrated to determine the correct concentration. The weight of the soluble polyimine is accurately determined and dissolved in dioxane to about 2%. The above KOH ethanol solution is used for titration. The titration end point is based on the phenolic peptide solution. The color change is determined. The COOH equivalent is obtained according to the following formula: COOH equivalent = (soluble ruthenium weight) + (〇Η 〇Η ethanol solution concentration) + (drop Χ1000 where the amount of the titer is the amount (ml) required for titrating the soluble quinone imine with a KOH solution. (Continuing strength) The method for measuring the peel strength (90 degrees) according to JIS C6481, measured by a width of 3 mm, and converted The thickness of the solder is 1 cm. (Characteristics of the heat resistance of the solder bath) After the laminate of the polyimide film and the copper foil is cured, it is immersed in a solder at 300 ° C for 3 minutes, and the deterioration such as foaming or peeling is visually observed. degree. Further, the three-layer structure sheet of the example, the production of the protective film, the three-layer structure sheet, and the evaluation of the photosensitive film were carried out in the following manner. 68 The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- (Please read the notes on the back and fill out this page) ^--------t--- ------ 1299043 A/ _ B7 _ V. INSTRUCTIONS (0) (1) Preparation of photosensitive resin composition Dissolve soluble polyamidene resin in an organic solvent to 30% by weight of a solid component, and then mix (B) a diacrylate compound of the component, a photoreaction initiator of the component (C), and/or a sensitizer, to prepare a uniform photosensitive resin composition. (2) Production of a three-layer structure sheet The organic solvent solution of the photosensitive resin composition prepared in (1) was applied to a PET film (thickness 25/m) so as to have a thickness of 50/m after drying. The organic solvent was removed by drying at 45 ° C for 5 minutes and then at 65 ° C for 5 minutes to bring the photosensitive film into a B-stage state. Next, a photosensitive coating layer of a three-layer structure sheet was laminated (PE+EVA (the copolymer film surface contacted the photosensitive film surface). The lamination conditions were a roll temperature of 40 ° C and a roll point pressure of 1500 Pa. (3) Production of protective film As a ruthenium film, a film having a thickness of 38 #m was used, and a polyurethane-based adhesive was applied thereto at a thickness of 0.5/zm after drying, and dried at a temperature of 120 ° C for 5 minutes. Then, the adhesive coating surface of the enamel film and the corona-treated surface of the (PE+EVA) copolymer film surface (made by Sekisui Chemical Co., Ltd., thick l〇em, single-sided corona treatment) are attached. The laminate was laminated at a roll temperature of 120 ° C and a roll point pressure of 2000 Pa · m. Further, a resin composed of a copolymer of a polyethylene resin, polyethylene, and an ethylene vinyl alcohol resin was simultaneously protected by an extrusion method. For the membrane, a PR〇TECT (#6221F) membrane (thickness 50/zm) made of Sekisui Chemical Co., Ltd. was used. (4) Evaluation of three-layer construction sheet 69 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X). 297 mm) -----------•装--------Book---------^9, (Please read the notes on the back and fill out this page. 1299043 B7 V. DESCRIPTION OF THE INVENTION (W) The obtained three-layer structure sheet and photosensitive film ' were evaluated for each characteristic according to the following method. <Protective film peeling property> A strip-shaped three-layer structure sheet cut into a width of 30 mm was attached to an aluminum plate (thickness: 3 mm) with a double-sided tape, and then measured by a stretching apparatus which stretched the protective film at 90 degrees. The peeling property of the protective film is preferably from 3·3 to 13.3 Pa·m in practice, and the range is acceptable. When it is 33.3 Ρ α · m or more, it is judged as unqualified because it is too difficult to peel off. <Developability of Photosensitive Film> After the protective film of the three-layer structure sheet was peeled off, the photosensitive film area layer was laminated on the shiny surface of the electrolytic copper foil under conditions of 100 ° C and 20000 Pa · m. A mask pattern was placed on the base film of the laminate, and exposed to light having a wavelength of 400 nm, and subjected to heat treatment at 10 ° C for 2 minutes, and development was carried out under any of the following conditions. 1% potassium hydroxide aqueous solution (liquid temperature 4 〇 ° C) X2 concentration of 1% tetramethylammonium isopropyl alcohol solution (liquid temperature 40 ° C) X5 points, placed on the coating film during exposure The mask pattern is a microporous hole of 200//mX200//m and 100/zm×100/zm. The pattern formed by the development was washed with water, and the developing solvent was removed, and dried at 90 ° C for 15 minutes. As long as at least 20〇emX200 //m pores can be imaged, it is judged as pass. <Solid heat resistance of photosensitive film> After peeling off the protective film of the three-layer structure sheet, the photosensitive film area layer is layered on the shiny side of the electrolytic copper foil 35 m, at 10 ° C, 20000 Pa · m Condition 70 The paper size applies to the Chinese National Standard (CNS) A4 specification (210x297 mm) " (Please read the note on the back and fill out this page) i------ --- 1299043 A7 : ___ — B7 _ V. Description of invention (W) Implementation of the layer. The photosensitive film of the laminate was exposed to light having a wavelength of 400 nm through the base film, and the base film was peeled off and then heat-treated at 180 ° C for 2 hours. The laminated sample was cut into 25 mm squares, subjected to humidity conditioning treatment at 20 ° C / humidity of 65% for 24 hours, and then immersed in molten solder at 300 ° C for 1 minute. At this time, it is observed whether the sample has an abnormality such as swelling or peeling. If there is no abnormality, it is judged as qualified. <Fold-resistant strength of photosensitive film> Photosensitive property after laminating the protective film on a pattern of a copper-area laminate (CCL) forming a reverse pattern of a line width/line spacing = l〇0/100#m The film was laminated at 100 ° C and 20000 Pa · m. After exposing the photosensitive film and peeling off the base film, the laminated sample was heat-treated at 18 ° C for 2 hours. The sample was placed in an MIT tester, and a flexural test was carried out under the conditions of a deflection radius of 1 mm, a deflection angle of 270°, and a tensile load of 4.9 N, and the number of times the pattern was turned on was measured. It was judged to be qualified after 500 times or more. The measurement of the folding strength is one of the indexes for observing the mechanical strength of the film. The soft film has a higher number of conduction times, and the hard and brittle film has a lower number of conduction times. <Line-to-line insulation resistance of photosensitive film> Photosensitive property after lamination of the protective film on a comb-shaped pattern of a copper area laminate (CCL) forming a comb pattern of a line width/line pitch=100/100 The film was laminated at 100 ° C and 20000 Pa · m. The resistance between the wires is measured according to the standard of IPC -4.8.10.2.1. The higher the resistance, the better, and it is judged to be acceptable by 1·0Χ1013Ω or more. [Example 1] 71 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------------------^----- --- (Please read the note on the back and fill out this page) 1299043 A/ _ ___B7_____ V. Description of invention (0) In a 2000ml separate reactor equipped with a stirrer, under vigorous stirring, BAPS - M 43.05 g (0.10 mol), DMF 300 g, and ESDA 57.65 g (0.10 mol) were added together, and stirring was continued for 30 minutes to prepare a polyaminic acid solution. The polyamine has a weight average molecular weight (Mw) of 62,000. The polyamic acid solution was poured into a tray coated with a Teflon film, and heated in a vacuum oven at 20 (TC, 660 Pa for 2 hours under reduced pressure. It was taken out from the vacuum oven to obtain 96 g of thermoplastic polymer. The imine has a Mw of 68,000, a Tg of 200 ° C, and a ruthenium iodide ratio of 1% by weight. 30 g of soluble polyimine is dissolved in 70 g of dioxane. Sc=30% enamel paint. In 18.3g of enamel paint, add 4.5g of isocyanuric acid EO modified triacrylate (A-9300) manufactured by Shin-Nakamura Chemical Industry Co., Ltd., photo-reactive initiator Ig 819 O .lg, a polymerization inhibitor of 4-methoxyphenol (MEHQ) O.Olg to prepare a solution, which is defoamed and coated on a PET film at 45 ° C, X5, 65 ° C, X5, 80 ° After C X5 was dried, a 50/zm thick film of photosensitive polyimide was obtained, which was superposed in the order of copper foil/polyimine film/PET film (release paper) at 120 ° C, 1000 Pa The conditions of m were laminated, and after lamination, the mask pattern was attached for 3 minutes exposure (exposure conditions: 400 nm parallel light was irradiated at 10 mJ/cm 2 ), the PET film was peeled off, and heat treatment was performed at 100 ° C for 3 minutes, using 1%. It The tetramethyl isopropanol solution (liquid temperature: 40 ° C) was developed for 5 minutes, and then cured at 100 ° C for X 2 hours, 120 ° C for X 2 hours, and 140 ° C for 2 hours. The Tg after curing was At 290 ° C, the thermal expansion coefficient after hardening is 55 ppm from room temperature to 100 ° C. In addition, the copper foil of the soft copper panel is etched away, leaving the hardened 72 paper size applicable to the Chinese National Standard (CNS) A4 specification. (210 X 297 mm) ------------Package---------Book--------- (Please read the notes on the back and fill in the form) Page) 1299043 A7 _______B7 V. Inventive Note (7°) The photosensitive polyimide film has an elastic modulus of 400 MPa, an elongation of 2.8%, and a tensile strength of 12 MPa. [Example 2] In a 2000 ml separate reactor equipped with a stirrer, BAPS-M 68.88 g (0.16 mol), DMF 320 g, and ESDA 138.4 g (0·24 mol) were added together under vigorous stirring, and stirring was continued for 3 minutes. The reaction was carried out by cooling with ice water, and then, 1218 g of diaminobenzoic acid was dissolved in 120 g of DMF, and stirred for 30 minutes to obtain a polyaminic acid solution. The weight average molecular weight (Mw) was 58,000. The polyfluorene acid solution was poured into a tray coated with a Teflon film, and heated under reduced pressure at 200 ° C and 660 Pa for 2 hours in a vacuum oven. It was taken out from the vacuum oven to obtain 98 g of a thermoplastic polyimine. The polyamidimide had a Mw of 65,000 and a Tg of 190. (:, the imidization ratio of hydrazine is 100%. (Synthesis of epoxy-modified polyimine) 48.4 g (56 mmol) of the soluble polyimine after synthesis is dissolved in dioxane ll 〇 g MEHQ O.lg was added and dissolved by heating in an oil bath of 50 to 60 ° C. 1.42 g (10 mmol) of glycidyl methacrylate was dissolved in 5 g of dioxane and added to the above solution. The mixture was heated and stirred at 60 ° C for 6 hours. Then, 3-80 g (10 mmol) of epoxy 828 resin manufactured by Olefin Shell Co., Ltd. was dissolved in 14 g of dioxane, and then added to the above solution at 60 ° C. Epoxy-denatured polyimine was synthesized by heating and stirring for 6 hours.

在該環氧變性聚醯亞胺溶液18.3g中，添加多官能丙 烯酸酯A- 9300 2.0g、東亞合成阿羅尼克斯製雙酚F EO 73 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------^—------ (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _________B7_ 五、發明說明（7丨） (請先閱讀背面之注意事項再填寫本頁) 變性(n与2)二丙烯酸酯(M_ 208)2.5g、伊格膠819 O.lg、 4,4’ 一二胺基二苯甲烷(DDM)O.lg、MEHQ O.Olg 後，使其 混合並脫泡。將該溶液塗佈在PET膜上，經45°C X5分、 65°C X5分、8〇t χ5分之乾燥後，製得感光性聚醯亞胺之 50/zm厚的薄膜。 以銅箱/聚醯亞胺膜/PET膜（剝離紙）的順序重疊，以 120°C：、lOOGGPa · m的條件實施積層。積層後，裝上光罩 圖案實施3分鐘曝光(曝光條件：以10mJ/cm2照射400nm 的平行光），剝去PET膜後於l〇〇°C進行3分鐘熱處理，用 1%之氫氧化四甲基的異丙醇溶液(液溫40。〇實施顯影後， 以 100°C X2 小時、120°C X2 小時、140°c X2 小時、160°C X3小時的條件進行硬化。硬化後的Tg爲12(rc，硬化後 的熱膨脹係數於室溫〜l〇〇°C爲65ppm。 又，將軟性銅面板之銅箔予以蝕刻除去，留下的硬化 後之感光性聚醯亞胺膜之彈性模數爲2800MPa、伸長率爲 5.0%，拉伸強度爲103MPa。 〔實施例3〕 在實施例2所合成之環氧變性聚醯亞胺溶液20.0g中 ，添加 A- 9300 1.3g、Μ - 208 2.7g、伊格膠 819 (Ug、 DDM O.lg、MEHQ O.Olg，使其混合並脫泡。將該瑢液塗 佈在PET膜上，經45°C X5分乾燥後，製得感光性聚醯亞 胺之50#m厚的薄膜。 以銅箔/聚醯亞胺膜/PET膜（剝離紙）的順序重疊’以 120°C、l〇〇〇〇Pa · m的條件實施積層。積層後，裝上光罩 74 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 B7 五、發明說明（p ) 圖案實施3分鐘曝光(曝光條件：以l〇mJ/Cm2照射400nm 的平行光），於100°C進行3分鐘熱處理，用1%之氫氧化 四甲基的異丙醇溶液(液溫40°C)實施顯影後，以l〇〇°C X2 小時、120°C X2小時、140°C X2小時、160°C X3小時的條 件進行硬化。硬化後的Tg爲187°C，硬化後的熱膨脹係數 於室溫〜100°C爲350ppm。 又，將軟性銅面板之銅箔予以蝕刻除去，留下的硬化 後之感光性聚醯亞胺膜之彈性模數爲400MPa、伸長率爲 5.0%，拉伸強度爲83MPa。 〔實施例4〕 在設有攪拌器之2000ml分離式反應器中，於激烈攪 拌下，將 BAPS - M 68.88g(0.16 莫耳）、DMF320g、ESDA 184.5g(0.32莫耳)一起加入，持續攪拌30分後，用冰水冷 卻再進行反應。接著，加入將二胺基苯甲酸24.34g(0.16莫 耳)溶於DMF120g而成者，攪拌30分，製得聚醯胺酸溶液 。該聚醯胺酸之重量平均分子量(Mw)爲5.8萬。將該聚醯 胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空烘箱內，以 200°C、660Pa的壓力實施2小時減壓加熱。 從真空烘箱中取出，獲得260g的具有羧酸之熱可塑 性聚醯亞胺。該聚醯亞胺之Mw爲6.5萬，Tg爲190°C、 醯亞胺化率爲100%。 (環氧變性聚醯亞胺的合成） 將合成後的可溶性聚醯亞胺l〇〇g(12〇毫莫耳)溶解於 二惡茂院300g中’添加MEHQ 0.2g，用60°C的油浴邊加 75 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） ' '~: -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 p ---—^_B7 ___ 五、發明說明（7》） °將縮水甘油甲基丙讎酯4.26g(30毫莫耳) 溶解於一惡茂燒後加入前述溶液中，於6(TC進行6小 時加熱擾泮/接著，將油化殼牌公司製環氧828樹脂 12.92g(34\笔奠耳)溶解於二惡茂烷3〇g後加入前述溶液中 ’於60°C5t^ 6小時加熱攪拌，合成出環氧變性聚醯亞胺 〇 在該環氧變性聚醯亞胺溶液26.0g中，添加多官能丙 烯酸酯 A- 9300 l.Og、M - 208 2.5g、伊格膠 819 O.lg、 DDM (Ug ' MEHQ 〇.〇ig後，使其混合並脫泡。將該溶液 塗佈在PET膜上，經45°C X5分乾燥後，製得感光性聚醯 亞胺之50# m厚的薄膜。 以銅箱/聚醯亞胺膜/PET膜(剝離紙）的順序重疊，以 100°C、lOOOPa · m的條件實施積層。積層後，經3分鐘曝 光(曝光條件：以l〇mj/cm2照射400nm的平行光)後，經 100°C X3分之後烘烤，用1%之氫氧化四甲基的異丙醇溶 液(液溫40°C )實施顯影後，以1〇〇。(： χ2小時、120°C X2 小時、140C X2小時、160°C X3小時的條件進行硬化。硬 化後的Tg爲170°C，硬化後的熱膨脹係數於室溫〜100°C爲 135ppm 〇 又，將軟性銅面板之銅箔予以蝕刻除去，留下的硬化 後之感光性聚醯亞胺膜之彈性模數爲3100MPa、伸長率爲 1.0%，拉伸強度爲26MPa。 〔實施例5〕 在設有攪拌器之2000ml分離式反應器中，於激烈攪 76 --------------------^---------^9. <請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 ----------------------------[____ 五、發明說明（―） 拌下，將 BAPS - M 64.57g(0.15 莫耳）、DMF335g、ESDA 115.3g(0.20莫耳)一起加入，持續攪拌30分後，用冰水冷 卻再進行反應。接著，加入將二胺基苯甲酸7.61g(0.050莫 耳)溶於DMF70g而成者，攪拌30分’製得聚醯胺酸溶液 。該聚醯胺酸之重量平均分子量(Mw)爲5.8萬。將該聚醯 胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空烘箱內’以 200°C、660Pa的壓力實施2小時減壓加熱。 從真空烘箱中取出，獲得260g的具有羧酸之熱可塑 性聚醯亞胺。該聚醯亞胺之Mw爲6.5萬，Tg爲190°C、 醯亞胺化率爲100% 〇 (環氧變性聚醯亞胺的合成） 將合成後的可溶性聚醯亞胺50g(55.5毫莫耳)溶解於 二惡茂烷130g中，添加MEHQ O.lg，用60°C的油浴邊加 熱邊使其溶解。將油化殼牌公司製環氧828樹脂5.7g(15 毫莫耳)溶解於二惡茂烷l〇g後加入前述瑢液中，於60°C 進行8小時加熱攪拌，合成出環氧變性聚醯亞胺。 在該環氧變性聚醯亞胺溶液26.0g中’添加三官能丙 烯酸酯 A - 9300 l.Og、Μ - 208 2.5g、伊格膠 819 O.lg、 DDM O.lg、MEHQ O.Olg後，使其混合並脫泡。將該溶液 塗佈在PET膜上，經45°C X 5分乾燥後，製得感光性聚醯 亞胺之50/zm厚的薄膜。 以銅箔/聚醯亞胺膜/PET膜（剝離紙）的順序重疊，以 l〇〇°C、1000Pa · m的條件實施積層。積層後，裝上光罩圖 案經3分鐘曝光(曝光條件··以i〇mj/cm2照射400nm的平 77 _ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----------.—裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ____B7 _ 五、發明說明（ 行光)後，經i〇0°C X3分之後烘烤’用1%之氫氧化四甲基 的異丙醇溶液(液溫40°C)實施顯影後，以l〇〇°C X2小時、 120°C X 2小時、140°C X 2小時、160°C X 3小時的條件進行 硬化。硬化後的Tg爲180°C，硬化後的熱膨脹係數於室溫 〜100°C 爲 260ppm。 又，將軟性銅面板之銅箔予以蝕刻除去，留下的硬化 後之感光性聚醯亞胺膜之彈性模數爲2790MPa、伸長率爲 3.6%，拉伸強度爲92MPa 〇 〔比較例1〕 在實施例2所合成出之環氧變性聚醯亞胺溶液36.6g 中，不添加(B)成份之二（甲基)丙烯酸系化合物，而添加伊 格膠 819 O.lg、DDM O.lg、MEHQ O.Olg 後，使其混合並 脫泡，和實施例同樣地製得感光性聚醯亞胺之50//m厚的 薄膜。 以銅箔/聚醯亞胺膜/PET膜的順序重疊，以lOOOPa· m的條件實施積層時，必須在190°C以上才能進行積層。 積層後，裝上光罩圖案經3分鐘曝光（曝光條件：以 10mJ/cm2照射400nm的平行光)後，經100°C X3分之後烘 烤，用1%之氫氧化四甲基的異丙醇溶液(液溫40°C)實施顯 影，但幾乎無法顯示出圖案。之後，以l〇〇°C X2小時、 120°C X2小時、140°C X2小時、160°C X3小時的條件進行 硬化。硬化後的Tg爲280°C，硬化後的熱膨脹係數於室溫 〜l〇〇°C 爲 300ppm。 如此般，在環氧變性聚醯亞胺中，未添加(B)成份而僅 78 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱" ' (請先閱讀背面之注意事項再填寫本頁) 一裝 -----訂--------- 1299043 B7 五、發明說明（W) 混合光反應起始劑、環氧硬化劑、聚合起始劑所得之被覆 膜’雖S旨耐筒溫，但低溫下的積層有困難，必須在高溫下 才能積層，故解析度變差。 〔實施例6〕 在設有攪拌器之2000ml分離式反應器中，於激烈擾 拌下，將BAPS - M 8.60g(0.02莫耳）、矽氧烷二胺之信越 化學製 KF8010(通式(3)中，x=3、y=i〇、R=CH3)33.2g(〇.〇4 莫耳）、DMF200g、ESDA 57.65g(〇.l〇 莫耳)—起加入，持 續攪拌30分。接著，加入將二胺基苯甲酸6.1g(〇.〇4莫耳) 溶於DMF75g而成者，攪拌30分，製得聚醯胺酸溶液。 該聚醯胺酸之重量平均分子量(Mw)爲6萬。 將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空 烘箱內，以 150°C X 10 分、160°C X 1〇 分、170°C X 10 分、 180°C X 10 分、190°C X 10 分、21〇°C X 30 分、660Pa 的壓 力實施減壓加熱。 從真空烘箱中取出，獲得l〇〇g的具有羧酸之熱可塑 性聚醯亞胺。該聚醯亞胺之Mw爲6.5萬，醯亞胺化率爲 100% 〇 (環氧變性聚醯亞胺的合成） 將合成後的可溶性聚醯亞胺33g溶解於二惡茂烷63g 中，添加三乙胺O.lg、甲氧基乙醇50mg後，加入縮水甘 油甲基丙烯酸酯〇.85g(6毫莫耳)。於7〇°c攪拌1〇小時後 ，加入油化殻牌公司製環氧828樹脂3.0g(8毫莫耳），攪拌 5小時而合成出環氧變性聚醯亞胺。 79 本紙張尺玉適用中國國家標準（CNS)A4規格（210 X 297公~ -- (請先閱讀背面之注意事項再填寫本頁) -裝--------訂--------- 1299043 A7 _____B7____ 五、發明說明（77 ) 在該環氧變性聚醯亞胺溶液100g中，添加4,4f -二胺 基二苯礪(DDS)0.5g、光反應起始劑之雙(2,4,6 -三甲基苯 醯）-苯基氧化膦〇.5g(1.2毫莫耳）、東亞合成製阿羅尼克 斯M - 208(雙酚F EO變性(n^2)二丙烯酸酯25g，將所得 溶液塗佈於25/zm厚的PET膜上，經45°C X 5分乾燥後， 剝去PET膜後固定在針框，經65°C X5分乾燥，製得感光 性聚醯亞胺之60/zm厚/PET膜25# m厚的2層薄膜。 以銅箔/感光性聚醯亞胺膜60#m/PET膜25/zm厚的 順序重疊，以100°C、l〇〇〇〇Pa · m的條件實施積層。積層 後’裝上光罩圖案經3分鐘曝光(曝光條件：以l〇nJ/cm2 照射400nm的平行光)後，剝去PET膜進行l〇〇°C X3分之 後烘烤，於180°C X2小時的條件下硬化。 該軟性銅面板的剝離接著強度爲9800Pa · m，可形成 100/zm線寬/線距的圖案，且浸在260°C的焊料浴1分並未 發現脹起等的缺陷。將軟性銅面板之銅箔予以蝕刻除去， 留下的硬化後之被覆膜之彈性模數爲lOOOMPa、伸長率爲 25%，熱分解開始溫度爲370°C。 以銅箔/感光性聚醯亞胺膜60/zm/PET膜25/zm厚的 順序重疊，以l〇〇°C、lOOOOPa · m的條件實施積靥。積層 後，裝上線寬/線距= 100/100//m的光罩，經3分鐘曝光(曝 光條件：以lOmJ/cm2照射4〇Onm的平行光)後，剝去pET 膜進行100°C X3分之後烘烤，用0.5%之氫氧化四甲基之 異丙醇/水=50/50重量比的溶液(液溫40°C)顯影後，於18〇 °C X2小時的條件下硬化。用顯微鏡觀察感光性被覆膜的 80 參紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) ---- ---------------I I---訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 a7 ______B7 _ 五、發明說明（W) 圖案發現，可形成線寬/線距=100/100#m2圖案。 接著，在軟性印刷基板上，使用本發明的被覆層作爲 被覆層時，測定其板彎。在鐘淵化學工業製聚醯亞胺膜之 阿匹卡魯NPI(25/zm厚)上，將杜邦製膜狀接著劑派拉利仕 (LF100)的接著面貼合，於180°C進行積層。剝去剝離紙， 於180°C積層三井金屬製電解銅箔3EC-VLP(1盎司），以 180°C進行硬化，製得底膜(聚醯亞胺)/接著劑/銅箔之3層 構造。藉由蝕刻而製作出單面形成有線寬/線距=200 # m/200/zm圖案之FPC(圖3)。以感光性聚醯亞胺層和銅箔 貼合的方式將該FPC和前述感光性聚醯亞胺60/zm厚/PET 膜25/zm厚的2層膜於100°C進行積層，經3分鐘曝光(曝 光條件：以l〇mJ/cm2照射4〇Onm的光)後，剝去PET膜， 於180°C硬化2小時，製作出包覆著被覆層之FPC。將該 FPC切成l〇cm見方來觀察其板彎，發現並沒有板彎的產 生。 〔實施例7〕 將實施例6所合成的具有羧酸之熱可塑性聚醯亞胺 33g、二惡茂烷 66g、4,4·-二胺基二苯硼(DDS)0.5g、雙 (2,4,6-三甲基苯醯）_苯基氧化膦〇.5g(1.2毫莫耳）、東亞 合成製阿羅尼克斯M- 208(雙酚F E0變性(Π4 2)二丙烯酸 酯25g，將所得溶液塗佈於25 /z m厚的PET膜上，經45°C X5分乾燥後，剝去PET膜後固定在針框，經65°C X5分 乾燥，製得感光性聚醯亞胺之60/zm厚/PET膜25//m厚 的2層薄膜。 81 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂---------^9. (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 p------ -B7___ 五、發明說明（^ ) 和實施例6同樣地，該軟性銅面板的剝離接著強度爲 1080Pa · m，可形成1〇〇//ιη線寬/線距的圖案，且浸在260 °C的焊料浴1分並未發現脹起等的缺陷。將軟性銅面板之 銅予以蝕刻除去，留下的硬化後之感光性聚醯亞胺之彈 性模數爲1500MPa、伸長率爲20%，熱分解開始溫度爲 375〇C 〇 接著，在軟性印刷基板上，使用本發明的被覆層作爲 被覆層時，測定其板彎。並無板彎的產生。 〔實施例8〕 <具有經基之聚醯亞瞭的合成> 在設有攪拌器之2000ml分離式反應器中，於激烈攪 拌下，將 BAPS - M 12.91g(0.03 莫耳）、DMF260g、ESDA 57_65g(0.10莫耳)一起加入，持續攪拌3〇分。接著，加入 2J -雙(3 -胺基-4 -羥基苯基）六氟丙烷14.65g(0.04莫 耳），攪拌30分後，加入砂氧院二胺（信越化學製 KF8010)2.49g(0.03莫耳），攪拌30分，製得聚醯胺酸溶液 。該聚醯胺酸之重量平均分子量(Mw)爲5.5萬。這時用冰 水冷卻使反應進行。將該聚醯胺酸溶液倒在被覆鐵氟龍膜 之盤中，於真空烘箱內，以150°C X 10分、160°C X 10分 、170°C X 10 分、180°C X 10 分、190°C X 10 分、210°C X30 分、660Pa的壓力實施減壓加熱。從真空烘箱中取出，獲 得105g的具有羥基之熱可塑性聚醯亞胺。該聚醯亞胺之 Mw爲6.0萬，醯亞胺化率爲1〇〇%。 <環氧變性聚醯亞胺之合成> 82 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂--------- 1 1299043 A7 _____ B7_____ 五、發明說明（粆） 將合成出之具有羥基的聚醯亞胺33g溶解於二惡茂烷 66g中，將三乙胺〇.lg與縮水甘油甲基丙烯酸酯1.42g(10 毫莫耳)溶解於二惡茂烷25g後加入前述溶液中，於60°C 進行5小時加熱攪拌。接著，將油化殼牌公司製HP4032 4.08g(環氧當量136)加入，於60°C進行5小時反應，合成 出環氧變性聚醯亞胺。 在該環氧變性聚醯亞胺溶液l〇〇g中，添加DDS 0.5g 、3,3’-羰基雙〔7-(二甲基胺基)香豆素〕〇.3g、二苯甲酮 lg、三丁胺〇.5g、東亞合成製阿羅尼克斯M- 208(雙酚F EO變性(n^2)二丙烯酸酯25g、異氰尿酸三（乙烷丙烯酸酯 )3g，調製成感光性組成物。將該溶液塗佈在25^m厚之 PET膜上，經45艽\5分乾燥後，剝去？£1[膜，固定在針 框上，經65°C X5分乾燥，製得感光性聚醯亞胺60/zm厚 /PET膜25 厚之2層膜。 和實施例6同樣地，該軟性銅面板的剝離接著強度爲 lOOOPa · m，可形成100/zm線寬/線距的圖案，且浸在260 °C的焊料浴1分並未發現脹起等的缺陷。將軟性銅面板之 銅箔予以蝕刻除去，留下的硬化後之感光性聚醯亞胺之彈 性模數爲1250MPa、伸長率爲25%，熱分解開始溫度爲 380〇C ° 接著，在軟性印刷基板上，使用本發明的感光性被覆 層作爲被覆層時，和實施例6同樣地測定其板彎，發現並 無板彎的產生。 〔比較例2〕 83 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） ^------—^--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _______B7_ 五、發明說明（W ) (請先閱讀背面之注意事項再填寫本頁) 在設有攪拌器之2000ml分離式反應器中，於激烈攪 拌下，將 BAPS - M 43.05g(0.1 莫耳）、DMF200g、ESDA 57.65g(0.10莫耳卜起加入，持續攪拌30分，製得聚醯胺 酸溶液。該聚醯胺酸之重量平均分子量(Mw)爲6.2萬。 將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空 烘箱內，以 15〇°C X 10 分、160°C X 10 分、170°C X 10 分、 180°C X10 分、19〇°C X10 分、2HTC X30 分、660Pa 的壓 力實施減壓加熱。從真空烘箱中取出，獲得95g的熱可塑 性聚醯亞胺。該聚醯亞胺之Mw爲6.4萬，醯亞胺化率爲 100% 〇 將該可溶性聚醯亞胺30g、油化殼牌製環氧828 3g溶 解於二惡茂烷67g所得的溶液塗佈在25# m厚之PET膜上 ，經45°C X 5分乾燥後，剝去PET膜，固定在針框上，經 65°C X5分乾燥，剝去PET膜再經l〇〇°C X5分乾燥，製得 感光性聚醯亞胺6〇/zm厚膜。該膜的彈性模數爲32〇〇MPa 〇 在實施例6所製成之—面描繪著線寬/線距=200 // m/200/zm的線之FPC上，放置該可溶性聚醯亞胺60/zm 膜，將剝離紙之鐵氟龍片擺在上下二面，以250°C、3MPa 的壓力壓合，製作出覆蓋著被覆層之FPC。和實施例6同 樣地切成l〇cm見方而測定板彎時，發現是呈半徑i〇cm的 筒狀。 〔實施例9〕 在設有攪拌器之2000ml分離式反應器中，於激烈攪 84 本紙張尺度適用中闕家標準（CNS)A4規格(210x297公爱） ~" 1299043 A7 B7 " ' ---- --- 五、發明說明（P ) 拌下，將ESDA 57.7g((U0莫耳）、DMF2〇〇g攪拌而使其 溶解後，將矽氧烷二胺KF8010(信越矽酮製)315g(〇 〇35莫 耳）、DMFlOg —起加入，持續攪拌3〇分。接著，加入將 —^月女基本甲酸吴耳)溶於DMFlOg而成者，擾 拌30分。接著，在用冰水冷卻反應容器下，於激烈攪拌下 ，將BAPS - M 17.22g(0.040莫耳）—口氣加入，再加入 DMF 24g持續攪拌1小時，製得聚醯胺酸溶液。該聚醯胺 酸之重量平均分子量(Mw)爲6.2萬。 將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空 烘箱內，以200°C、660Pa的壓力實施減壓加熱2小時。從 真空烘箱中取出，獲得85g的熱可塑性聚醯亞胺。該聚醯 亞胺之Mw爲6.8萬，Tg爲54°C，醯亞胺化率爲100%。 (環氧變性聚醯亞胺之合成） 將合成後的可溶性聚醯亞胺44.1g溶解於二惡茂烷 l〇〇g中，添加MEHQ O.lg，於60°C的攪拌下使其溶解。 溶解後，將油化殼牌公司製環氧828樹脂4.50g溶解於二 惡茂烷13g後添加三乙胺〇.〇5g，於60°C進行8小時加熱 攪拌，如此般製得Sc=30%之環氧變性聚醯亞胺的淸漆。 (被覆膜之製作） 在該淸漆16.7g中，添加異氰尿酸EO變性三丙烯酸 酯(新中村化學工業製A- 9300)0.5g、東亞合成阿羅尼克斯 製雙酚F EO變性(η与2)二丙烯酸酯(M- 208)4.5g、光反應 起始劑之汽巴特用化學製伊格膠819 O.lg、4,4’ -二胺基二 苯甲烷(DDM)O.lg、MEHQ O.Olg後，使其混合並脫泡。將 85 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） — II-------- (請先閱讀背面之注意事項再填寫本頁) 5-0·- 1299043 A7 ________B7_______ 五、發明說明（θ ) 該溶液塗佈在PET膜上，經45°C X5分、65°C X5分乾燥 後’製得感光性聚醯亞胺之50//m厚的被覆膜。 以銅箔/聚醯亞胺膜(被覆膜)/PET膜(剝離紙)的順序重 疊，以80°C、9200Pa · m的條件實施積層。積層後，裝上 光罩圖案實施3分鐘曝光（曝光條件：以i〇mJ/cm2照射 400nm的平行光），剝去PET膜後於10(TC進行2分鐘後烘 烤處理，用1%之氫氧化四甲基(TMAH)的異丙醇溶液(液溫 45°C)實施5分鐘顯影後，以1〇〇。〇 X2小時、120°C X2小 時、14〇°C X2小時、180°C X2小時的條件進行硬化。 其對軟性銅面板的銅箔無光澤面之接著強度爲1300Pa • m，可形成loo/iooem之線寬/線距的直線和100/ζιηχ 100/zm之孔圖案。 將被覆膜與銅箔、被覆膜與其他聚醯亞胺膜(彈性模數 4000MPa ’厚25/zm)貼合，經曝光、熱硬化而成之樣本， 兩者均未產生彎曲或捲曲而呈平坦狀。 將銅箔和被覆膜之積層體所硬化成之樣本，浸漬於 300°C的焊料3分後，完全沒有發泡和剝離，並未產生劣化 〇 又’將銅箔和被覆膜的積層體於180°C 2小時的條件 加熱硬化後，將該樣本的銅箔蝕刻除去，所得硬化後的感 光性聚醯亞胺膜之5%重量損失溫度爲363°C。關於其機械 特性，彈性模數爲1600MPa，伸長率34.0%，拉伸強度 22MPa 〇 〔實施例10〕 86 本紙張尺度適用中.國國家標準（CNS)A4規格（210 X 297公釐） Μ--------tr---------Ίιρ- (請先閱讀背面之注意事項再填寫本頁) A7 1299043 B7__ 五、發明說明（料） 在設有攪拌器之2000ml分離式反應器中，於激烈攪 拌下’將ESDA 57.6g(0.10莫耳）、DMF2〇〇g攪拌而使其 溶解後’將砂氧院二胺KF8010(信越砍酮製)25.〇g(〇.〇3〇莫 耳）、DMFlOg —起加入，持續攪拌3()分。接著，加入將 二胺基苯甲酸5.33g(0.035莫耳)溶於DMFlOg而成者，攪 拌30分。接著，在用冰水冷卻反應容器下，於激烈攪拌下 ，將BAPS- M 15.1g(0.35莫耳)一口氣加入，持續攪拌i 小時’製得聚醯胺酸溶液。該聚醯胺酸之重量平均分子量 (Mw)爲5.8萬。將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤 中，於真空烘箱內，以2〇〇°C、660Pa的壓力實施減壓加熱 2小時。從真空烘箱中取出，獲得94g的具有羧基之熱可 塑性聚釀亞肢。該聚釀亞fee之Mw爲6·5萬’Tg爲6〇。〇， 醯亞胺化率爲100%。 (瓌氧變性聚醯亞胺之合成） 將合成後的可溶性聚醯亞胺84.〇§(〇·〇8莫耳)溶解於二 惡茂烷2〇扣中，添加MEHQ O.lg，於5〇〜6(TC下便其溶解 。溶解後，將縮水甘油基甲基丙烯酸酯L42g(〇.〇l莫耳)溶 解於二惡茂烷4g後加入，於60°C進行2小時加熱攪样。 接著，將油化殼牌公司製環氧828樹脂3.80g(〇.〇1奠耳)溶 解於二惡茂烷bg後加入，於6〇°C進行6小時加熱搜梓♦ 如此般製得Sc=30%之環氧變性聚醯亞胺。 (被覆膜之製作） 在該環氧變性聚醯亞胺溶液(淸漆）19.8g中，添加雙官 能丙烯酸酯208 4.0g、伊格膠819 O.lg、DDM 、 87 (請先閱讀背面之注意事項再填寫本頁) -·1111111 « — I — — — — — —* 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） A7 1299043 _______B7 ___ 五、發明說明（A) MEHQ O.Olg後，使其混合並脫泡。將該溶液塗佈在PET 膜上’經45°CX5分、65CX5分乾燥後’製得約50/zni 厚的感光性聚醯亞胺膜。 以銅箔/聚醯亞胺膜/PET膜（剝離紙）的順序重疊’以 loot：、9200Pa · m的條件實施積層。積層後，裝上光罩圖 案實施3分鐘曝光(曝光條件··以10mJ/cm2照射400nm的 平行光)後，於100°C進行3分鐘後烘烤處理，用1%之氫 氧化四甲基的異丙醇溶液(液溫40°C)實施5分鐘顯影後， 以 100°C X2 小時、120°c X2 小時、140°C X2 小時、180°c X 2小時的條件進行硬化。 其對軟性銅面板的銅箔無光澤面之接著強度爲 •m，可形成l〇〇/l〇〇#m之線寬/線距的直線和100/zmX 100 /z m之孔圖案。 將被覆膜與銅箔、被覆膜與其他聚醯亞胺膜(彈性模數 4000MPa，厚25/zm)貼合，經曝光、熱硬化而成之樣本， 兩者均未產生彎曲或捲曲而呈平坦狀。 將銅箔和被覆膜之積層體所硬化成之樣本，浸漬於 300°C的焊料3分後，完全沒有發泡和剝離，並未產生劣化 〇 又，將銅箔和被覆膜的積層體於180°C 2小時的條件 加熱硬化後’將該樣本的銅箔蝕刻除去，所得硬化後的感 光性聚醯亞胺膜之5%重量損失溫度爲356°C。關於其機械 特性，彈性模數爲900MPa，伸長率25.6%，拉伸強度 21MPa 〇 88 本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐） ·£--------tr--------- (請先閱讀背面之注意事項再填寫本頁) A7 1299043 ___B7_____ 五、發明說明（以） 〔實施例11〕 在實施例9所合成出之環氧變性聚醯亞胺溶液16.7g 中，添加 A - 9300 0.3g、Μ - 208 4.7g、伊格膠 819 O.lg、 DDM O.lg、MEHQ O.Olg後，使其混合並脫泡。將該溶液 塗佈在PET膜上，經45°C X5分、65°C X5分乾燥後，製 得約50//m厚的感光性聚醯亞胺膜。 以銅箔/聚醯亞胺膜/PET膜（剝離紙）的順序重疊，以 120°C、9200Pa · m的條件實施積層。積層後，裝上光罩圖 案實施3分鐘曝光(曝光條件：以10mJ/cm2照射400nm的 平行光)後，於l〇〇°C進行3分鐘後烘烤處理，用1%之氫 氧化四甲基的異丙醇溶液(液溫40°C)實施顯影後，以100 °C X2 小時、120°C X2 小時、140°C X2 小時、180°C X2 小 時的條件進行硬化。 其對軟性銅面板的銅箔無光澤面之接著強度爲lOOOPa • m，可形成70/70#m之線寬/線距的直線和70/zmX70/z m之孔圖案。 將被覆膜與銅箔、被覆膜與其他聚醯亞胺膜(彈性模數 4000MPa，厚25/zm)貼合，經曝光、熱硬化而成之樣本， 兩者均未產生彎曲或捲曲而呈平坦狀。 將銅箔和被覆膜之積層體所硬化成之樣本，浸漬於 300°C的焊料3分後，完全沒有發泡和剝離，並未產生劣化 〇 又，將銅箔和被覆膜的積層體於180°C2小時的條件 加熱硬化後，將該樣本的銅箔蝕刻除去，所得硬化後的感 89 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------*t--------IT--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ____ Β7 _ 五、發明說明U7 ) 光性聚醯亞胺膜之彈性模數爲630MPa，伸長率32.0%，拉 伸強度12MPa，5%重量損失溫度爲370°C。 〔實施例12〕 在實施例9所合成出之環氧變性聚醯亞胺溶液20.0g 中，添力口 A - 9300 0.3g、Μ - 208 3.7g、伊格膠 819 O.lg、 DDM O.lg、MEHQ O.Olg後，使其混合並脫泡。將該溶液 塗佈在PET膜上，經45°C X5分、65t X5分乾燥後，製 得約50# m厚的感光性聚醯亞胺膜。 以銅箔/聚醯亞胺膜/PET膜的順序重疊，以120°C、 9200Pa · m的條件實施積層。積層後，裝上光罩圖案實施 3分鐘曝光(曝光條件：以10mJ/cm2照射400nm的平行光) 後，於l〇〇°C進行3分鐘後烘烤處理，用1%之氫氧化四甲 基的異丙醇溶液(液溫40°C)實施5分鐘顯影後，以100°C X2 小時、120°C X2 小時、140t X2 小時、180°C X2 小時 的條件進行硬化。 其對軟性銅面板的銅箔無光澤面之接著強度爲1000Pa • m，可形成50/50 /zm之線寬/線距的直線和50/zmX50/z m之孔圖案。 將被覆膜與銅箔、被覆膜與其他聚醯亞胺膜(彈性模數 4000MPa，厚25/z m)貼合，經曝光、熱硬化而成之樣本， 兩者均未產生彎曲或捲曲而呈平坦狀。 將銅箔和被覆膜之積層體所硬化成之樣本，浸漬於 300°C的焊料3分後，完全沒有發泡和剝離，並未產生劣化 〇 90 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂---------^^^^1 1299043 B7 五、發明說明（糾） 又，將銅箔和被覆膜的積層體於180°C2小時的條件 加熱硬化後，將該樣本的銅箔蝕刻除去，所得硬化後的感 光性聚醯亞胺膜之彈性模數爲630MPa，伸長率32.0%，拉 伸強度12MPa，5%重量損失溫度爲370°C。 〔實施例13〕 將實施例9所合成出的可溶性聚醯亞胺26.4g溶解於 二惡茂烷60g中，添加MEHQ 0.05g，用60°C的油浴邊加 熱邊使其溶解。將環氧HP - 4032(大日本油墨製 )1.75g(0.007莫耳)溶解於二惡茂烷6g後加入前述溶液中， 並添加三乙胺0.03g，於60°C進行6小時加熱攪拌，合成 出環氧變性聚醯亞胺。 在該環氧變性聚醯亞胺溶液(淸漆）17.9g中，添加Μ -208 5.0g、伊格膠 819 0」g、DDM O.lg、MEHQ O.Olg 後， 使其混合並脫泡。將該溶液塗佈在PET膜上，經45°C X5 分、65°C X5分乾燥後，製得約50/zm厚的感光性聚醯亞 胺膜。 以銅箔/聚醯亞胺膜/PET膜（剝離紙）的順序重疊，以 60°C、9200Pa · m的條件實施積層。積層後，裝上光罩圖 案實施3分鐘曝光(曝光條件：以l〇mjr/cm2照射4〇〇nm的 平行光)後，於l〇〇°C進行3分鐘後烘烤處理，用〇·5%之氫 氧化四甲基的異丙醇溶液(液溫40。〇實施10分鐘顯影後， 以 100°C Χ2 小時、120°c Χ2 小時、140°c Χ2 小時、18(rc X 2小時的條件進行硬化。 其對軟性銅面板的銅箔無光澤面之接著強度爲 91 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ______B7_________ 五、發明說明（Θ ) • m，可形成100/100# m之線寬/線距的直線和100//mx 100# m之孔圖案。 Γ清先閱讀背面之注音？事項再填寫本頁} 將被覆膜與銅箔、被覆膜與其他聚醯亞胺膜(彈性楔數 4000MPa，厚25//m)貼合，經曝光、熱硬化而成之樣本， 兩者均未產生彎曲或捲曲而呈平坦狀。 將銅箔和被覆膜之積層體所硬化成之樣本，浸漬於 300°C的焊料3分後，完全沒有發泡和剝離，並未產生劣化 〇 又，將銅箔和被覆膜的積層體於180°C2小時的條件 加熱硬化後，將該樣本的銅箔蝕刻除去，所得硬化後的感 光性聚醯亞胺膜之彈性模數爲520MPa，伸長率15.0%，拉 伸強度6.0MPa。 〔實施例14〕 在設有攪拌器之2〇〇〇ml分離式反應器中，於激烈攪 拌下，將ESDA 23.lg(0.〇4莫耳）、DMF5〇g攪拌而使其溶 解後，將矽氧烷二胺KF801〇(信越矽酮製）16 6g(〇 〇2〇莫耳 )、DMF5g —起加入，持續攪拌3〇分。接著，加入將二胺 基苯甲酸1.52g(0.010莫耳)溶解於DMFlOg而成者，攪拌 30分。接著，在用冰水冷卻反應容器下，於激烈攪拌下， 將BAPS - M 8.61g(0.020莫耳）一口氣加入，再添加 DMFlOg並持續攪拌30分。最後加入將偏苯三甲酸酐 3.84g(0_02莫耳)溶解於DMF 5g而成者，持續攪拌丨小時 ，製得聚醯胺酸彳谷液。該聚醯胺酸之重量平均分子量(Mw) 爲 5500 。 92 尺度適用中國國家標準（CNS)A4規格（210 x 297公爱1--*- A7 1299043 _ ____B7___ 五、發明說明（） 將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空 烘箱內，以200°C、660Pa的壓力實施減壓加熱1小時。從 真空烘箱中取出，獲得45g的熱可塑性聚醯亞胺。該聚醯 亞胺之Mw爲6000，Tg爲80°C，醯亞胺化率爲100%。 (環氧變性聚醯亞胺的合成） 將合成出的可溶性聚醯亞胺36g溶解於二惡茂烷36g 中，添加MEHQ O.lg，用6(TC的油浴邊加熱邊使其溶解。 將油化殻牌製環氧828樹脂7.6溶解於二惡茂烷8g後加入 前述溶液中，於60 °C進行8小時加熱攪拌，合成出 Sc=50%之環氧變性聚醯亞胺。 在該環氧變性聚醯亞胺溶液12.0g中，添加雙官能丙 烯酸酯 Μ - 208 2.0g、伊格膠 819 O.lg、DDM O.lg、 MEHQ O.Olg後，使其混合並脫泡。將該溶液塗佈在PET 膜上，經45°C X5分、65°C X5分、80°C X5分乾燥後，製 得約50/zm厚的感光性聚醯亞胺膜。 以銅箔/聚醯亞胺膜/PET膜的順序重疊，以l〇〇°C、 9200Pa · m的條件實施積層。積層後，實施3分鐘曝光(曝 光條件：以lOmJ/cm2照射400nm的平行光)後，於l〇〇t 進行3分鐘後烘烤處理，用1%之氫氧化四甲基的異丙醇溶 液(液溫40°C)實施5分鐘顯影後，以l〇〇°C X2小時、120 °C X2小時、140°C X2小時、160°C X3小時的條件進行硬 化。In the epoxy resin-denatured polyimine solution 18.3g, add polyfunctional acrylate A-9300 2.0g, East Asia synthetic arlenol bisphenol F EO 73 This paper scale is applicable to China National Standard (CNS) A4 specification ( 210 X 297 mm) --------------------^—------ (Please read the notes on the back and fill out this page) 1299043 A7 _________B7_ V. Description of the invention (7丨) (Please read the note on the back and fill out this page) Denatured (n and 2) diacrylate (M_ 208) 2.5g, Igge 819 O.lg, 4,4' After diaminodiphenylmethane (DDM) O.lg, MEHQ O.Olg, it is mixed and defoamed. This solution was coated on a PET film, and dried at 45 ° C for 5 minutes, 65 ° C for 5 minutes, and 8 〇t χ for 5 minutes to obtain a film of 50 μm thick photosensitive polyimide. The laminate was superposed in the order of a copper box/polyimine film/PET film (release paper), and laminated at 120 ° C:100 MPaPa. After lamination, the mask pattern was attached for 3 minutes exposure (exposure conditions: 400 nm parallel light was irradiated at 10 mJ/cm 2 ), the PET film was peeled off, and heat treatment was performed at 1 ° C for 3 minutes, using 1% hydrogen hydroxide. a methyl isopropanol solution (liquid temperature 40. After developing, the film is cured at 100 ° C for X 2 hours, 120 ° C for X 2 hours, 140 ° C for X 2 hours, and 160 ° C for 3 hours. It is 12 (rc, the thermal expansion coefficient after hardening is 65 ppm at room temperature ~ l 〇〇 ° C. Further, the copper foil of the soft copper panel is etched away, leaving the elasticity of the cured photosensitive polyimide film The modulus was 2800 MPa, the elongation was 5.0%, and the tensile strength was 103 MPa. [Example 3] In 20.0 g of the epoxy-modified polyimine solution synthesized in Example 2, A- 9300 1.3 g, Μ - 208 2.7 g, Ig Glue 819 (Ug, DDM O.lg, MEHQ O.Olg, mixed and defoamed. The mash was coated on a PET film and dried at 45 ° C for 5 minutes. 50#m thick film of photosensitive polyimide. Overlap in the order of copper foil/polyimine film/PET film (release paper) at 120 ° C, l〇〇〇〇Pa · m Conditioning is carried out. After lamination, the mask is attached 74. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1299043 B7 V. Invention Description (p) Pattern implementation for 3 minutes exposure (exposure conditions: l〇mJ/Cm2 was irradiated with 400 nm of parallel light), heat-treated at 100 ° C for 3 minutes, and developed with 1% tetramethylammonium hydroxide in isopropanol solution (liquid temperature 40 ° C), followed by l〇〇 Hardening at °C for X2 hours, 120°C for X2 hours, 140°C for X2 hours, and 160°C for X3 hours. The Tg after hardening is 187 °C, and the coefficient of thermal expansion after hardening is 350 ppm at room temperature to 100 °C. Further, the copper foil of the soft copper panel was removed by etching, and the cured photosensitive polyimide film having a modulus of elasticity of 400 MPa, an elongation of 5.0%, and a tensile strength of 83 MPa. [Example 4 ] In a 2000 ml separate reactor equipped with a stirrer, BAPS-M 68.88 g (0.16 mol), DMF 320 g, ESDA 184.5 g (0.32 mol) were added together with vigorous stirring, and stirring was continued for 30 minutes. The reaction was carried out by cooling with ice water. Then, 24.34 g of diaminobenzoic acid (0.16 mol) was added. Dissolved in 120 g of DMF, stirred for 30 minutes to obtain a polyaminic acid solution. The weight average molecular weight (Mw) of the polylysine was 58,000. The polyproline solution was poured on the coated Teflon film. In the tray, the pressure was reduced under reduced pressure at 200 ° C and 660 Pa for 2 hours in a vacuum oven. It was taken out from the vacuum oven to obtain 260 g of a thermoplastic polyimide having a carboxylic acid. The polyamidimide had a Mw of 65,000, a Tg of 190 ° C, and a hydrazine imidation ratio of 100%. (Synthesis of epoxy-modified polyimine) The synthesized soluble polyimine l〇〇g (12 〇 millimolar) was dissolved in 300 g of Dioxin Institute, adding MEGQ 0.2 g, using 60 ° C Oil bath plus 75 paper scales applicable to China National Standard (CNS) A4 specification (210 x 297 mm) ' '~: -----------装--------Set- -------- (Please read the notes on the back and fill in this page) 1299043 A7 p ----^_B7 ___ V. Description of invention (7)) °Glycidylmethylpropionate 4.26g (30 mmol) dissolved in a moxacin, added to the above solution, heated at 6 (TC for 6 hours) / then, oiled Shell epoxide 828 resin 12.92 g (34 liters) After being dissolved in 3 〇g of dioxane, the solution was added to the above solution and heated and stirred at 60 ° C for 5 hours for 6 hours to synthesize epoxy-modified polyimine oxime in 26.0 g of the epoxy-modified polyimine solution. Polyfunctional acrylate A-9300 l.Og, M-208 2.5 g, Igge 819 O.lg, DDM (Ug ' MEHQ 〇.〇ig, mixed and defoamed. The solution was coated on PET On the film, after drying at 45 ° C X5, the photosensitive polyimine is prepared. 50# m thick film. The copper box/polyimine film/PET film (release paper) was superposed in the order, and the layer was laminated at 100 ° C, lOOOPa · m. After lamination, exposure was performed for 3 minutes (exposure conditions) : After irradiating 400 nm parallel light with l〇mj/cm 2 , baking after 100 ° C X 3 minutes, and developing with 1% tetramethylammonium hydroxide in isopropanol solution (liquid temperature 40 ° C), (1: χ 2 hours, 120 ° C X 2 hours, 140 ° X 2 hours, 160 ° C X 3 hours of hardening. The Tg after hardening is 170 ° C, the thermal expansion coefficient after hardening is from room temperature to 100 ° C is 135 ppm. Further, the copper foil of the soft copper panel is removed by etching, and the cured photosensitive polyimide film has a modulus of elasticity of 3,100 MPa, an elongation of 1.0%, and a tensile strength of 26 MPa. Example 5] In a 2000 ml separate reactor equipped with a stirrer, stir vigorously 76 --------------------^-------- -^9. <Please read the notes on the back and fill out this page.) This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 --------------- ------------- [____ V. Inventive Note (―) Add BAPS-M 64.57g (0.15 Moule), DMF335g, ESDA 115.3g (0.20 Moule) together. After continuously stirring for 30 minutes, the reaction was carried out by cooling with ice water. Next, 7.61 g (0.050 mol) of diaminobenzoic acid was dissolved in 70 g of DMF, and stirred for 30 minutes to obtain a polyaminic acid solution. The polyamine has a weight average molecular weight (Mw) of 58,000. The polyamic acid solution was poured into a tray coated with a Teflon film, and heated under reduced pressure at 200 ° C and 660 Pa for 2 hours in a vacuum oven. It was taken out from the vacuum oven to obtain 260 g of a thermoplastic polyimide having a carboxylic acid. The polyetherimine has a Mw of 65,000, a Tg of 190 ° C, and a hydrazine imidation ratio of 100% 〇 (synthesis of epoxy-modified polyimine) 50 g of soluble polyimine after synthesis (55.5 m Mol) was dissolved in 130 g of dioxane, and MEHQ O.lg was added thereto, and dissolved in an oil bath of 60 ° C while heating. 5.7g (15 millimolar) of epoxy 828 resin made by Petrified Shell Co., Ltd. was dissolved in dioxin, and then added to the mash, and heated and stirred at 60 ° C for 8 hours to synthesize epoxy denatured poly Yttrium. Adding trifunctional acrylate A - 9300 l.Og, Μ - 208 2.5 g, Igge 819 O.lg, DDM O.lg, MEHQ O.Olg in 26.0 g of the epoxy-modified polyimine solution , to mix and defoam. This solution was coated on a PET film and dried at 45 ° C for 5 minutes to obtain a film of 50 μm thick photosensitive polyimide. The laminate was laminated in the order of copper foil/polyimine film/PET film (release paper), and laminated at a temperature of 1000 ° C and 1000 Pa·m. After lamination, the reticle pattern is exposed for 3 minutes (exposure conditions · illuminate 400 nm at i〇mj/cm2 _ This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -- --------.—装--------订--------- (Please read the notes on the back and fill out this page) 1299043 A7 ____B7 _ V. Invention Description After (lighting), after i〇0°C X3 minutes, bake 'developing with 1% tetramethylammonium hydroxide in isopropanol (liquid temperature 40 ° C), then l〇〇°C X2 Hardening was carried out under the conditions of hours, 120 ° C X 2 hours, 140 ° C X 2 hours, and 160 ° C X 3 hours. The Tg after hardening was 180 ° C, and the coefficient of thermal expansion after hardening was 260 ppm at room temperature to 100 ° C. The copper foil of the soft copper panel was removed by etching, and the cured photosensitive polyimide film having a modulus of elasticity of 2790 MPa, an elongation of 3.6%, and a tensile strength of 92 MPa [Comparative Example 1] were carried out. In the 36.6 g of the epoxy-modified polyimine solution synthesized in Example 2, the (meth)acrylic compound of the component (B) was not added, and the Igge 819 O.lg, DDM O.lg, MEHQ was added. After O.Olg, make The film was mixed and defoamed, and a 50/m thick film of photosensitive polyimide was obtained in the same manner as in the examples. The copper foil/polyimine film/PET film was superposed in the order of 100 OPa·m. When laminating, it is necessary to laminate at 190 ° C. After lamination, the mask pattern is exposed for 3 minutes (exposure conditions: 400 nm parallel light is irradiated at 10 mJ/cm 2 ), and then dried at 100 ° C for X 3 minutes. Bake, and develop with a 1% solution of tetramethylammonium hydroxide in isopropyl alcohol (liquid temperature: 40 ° C), but the pattern is hardly displayed. Thereafter, it is X 2 hours, 120 ° C X 2 hours, Hardening at 140 ° C for X 2 hours and 160 ° C for 3 hours. The Tg after hardening is 280 ° C, and the coefficient of thermal expansion after hardening is 300 ppm at room temperature ~ l ° ° C. Thus, in epoxy denaturation polymerization In the imine, no (B) component is added and only 78 paper grades are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love " ' (please read the back note and fill out this page) -----Order--------- 1299043 B7 V. Description of invention (W) Mixed photoreaction initiator, epoxy hardener, polymerization initiator The obtained coating film is resistant to the cylinder temperature, but it is difficult to laminate at a low temperature, and it is necessary to laminate at a high temperature, so that the resolution is deteriorated. [Example 6] A 2000 ml separation reactor equipped with a stirrer In the case of severe scrambling, BAPS-M 8.60g (0.02 mol), 矽 烷 diamine of Shin-Etsu Chemical KF8010 (in general formula (3), x=3, y=i〇, R=CH3 33.2g (〇.〇4 Moer), DMF200g, ESDA 57.65g (〇.l〇莫耳) - added, stirring for 30 minutes. Next, 6.1 g of diaminobenzoic acid was dissolved in 75 g of DMF, and the mixture was stirred for 30 minutes to prepare a polyaminic acid solution. The polyamine has a weight average molecular weight (Mw) of 60,000. Pour the polyamic acid solution into a tray coated with Teflon film in a vacuum oven at 150 ° C X 10 min, 160 ° C X 1 〇 min, 170 ° C X 10 min, 180 ° C X 10 min, 190 The pressure was reduced by a pressure of °CX 10 minutes, 21 ° C C 30 minutes, and 660 Pa. It was taken out from the vacuum oven to obtain 10 g of a thermoplastic polyimide having a carboxylic acid. The polyetherimine has a Mw of 65,000, and the oxime imidization ratio is 100% 〇 (synthesis of epoxy-denatured polyimine). 33 g of the synthesized soluble polyimine is dissolved in 63 g of dioxane. After adding 50 mg of triethylamine O.lg and methoxyethanol, glycidyl methacrylate 〇.85 g (6 mmol) was added. After stirring at 7 ° C for 1 hour, 3.0 g (8 mmol) of an epoxy 828 resin manufactured by Olefin Shell Co., Ltd. was added, and stirred for 5 hours to synthesize an epoxy-modified polyimine. 79 This paper ruler is applicable to China National Standard (CNS) A4 specification (210 X 297 gong~ -- -- (Please read the note on the back and fill in this page) - Pack-------- ----- 1299043 A7 _____B7____ V. Inventive Note (77) Into 100 g of the epoxy-denatured polyimine solution, add 4,4f-diaminodiphenyl hydrazine (DDS) 0.5 g, photoreaction initiator Double (2,4,6-trimethylphenylhydrazine)-phenylphosphine oxide ruthenium.5g (1.2 millimolar), East Asian synthetic Aronix M-208 (bisphenol F EO denaturation (n^2 25 g of diacrylate, the obtained solution was coated on a 25/zm thick PET film, dried at 45 ° C for 5 minutes, peeled off the PET film, fixed in a needle frame, and dried at 65 ° C X 5 to obtain Photosensitive polyimine 60/zm thick / PET film 25 # m thick two-layer film. The copper foil / photosensitive polyimide film 60 #m / PET film 25 / zm thick overlap, to 100 The conditions of °C and l〇〇〇〇Pa · m were carried out. After lamination, the mask pattern was attached and exposed for 3 minutes (exposure conditions: 400 nm parallel light was irradiated at 10 μN/cm 2 ), and the PET film was peeled off. After l°°C X3 minutes, it is baked and hardened at 180 ° C for 2 hours. The peeling strength of the copper panel was 9800 Pa·m, and a pattern of 100/zm line width/line spacing was formed, and the solder bath immersed at 260 ° C showed no defects such as swelling. The copper of the soft copper panel was formed. The foil was etched away, and the cured film after curing had a modulus of elasticity of 100 MPa, an elongation of 25%, and a thermal decomposition initiation temperature of 370 ° C. Copper foil/photosensitive polyimide film 60/zm The thickness of the /PET film 25/zm overlaps, and the accumulation is carried out under the conditions of l〇〇°C and 1000oPa·m. After lamination, the mask with line width/line spacing = 100/100//m is mounted for 3 minutes. Exposure (exposure conditions: 4 〇 Onm parallel light was irradiated at 10 μM/cm 2 ), and then the pET film was peeled off and baked at 100 ° C for X 3 minutes, and 0.5% of tetramethylammonium hydroxide/water = 50 was used. /50 weight ratio solution (liquid temperature 40 ° C) developed, hardened under conditions of 18 ° C for 2 hours. The 80-parameter paper size of the photosensitive coating film observed with a microscope is applicable to the Chinese National Standard (CNS) A4 specification. (210 X 297 mm) ---- ---------------I I---book--------- (please read the notes on the back first) Fill in this page) 1299043 a7 ______B7 _ V. Invention Description (W) Pattern discovery, line width/line spacing = 100/100 #m2 pattern can be formed. Next, when the coating layer of the present invention is used as a coating layer on a flexible printed circuit board, the plate bending is measured. On the Apicarpus NPI (25/zm thick) of the polyimide film made by Zhongyuan Chemical Industry, the adhesive surface of DuPont film-forming adhesive Paraseli (LF100) was bonded and processed at 180 °C. Laminated. Strip the release paper, laminate 3C-VLP (1 oz) of Mitsui Metal Electrolytic Copper Foil at 180 ° C, and harden at 180 ° C to obtain 3 layers of base film (polyimine) / adhesive / copper foil structure. An FPC (Fig. 3) having a line width/line pitch = 200 # m/200/zm pattern was formed by etching. The FPC and the photosensitive polyimide polyimide 60/zm thick/PET film 25/zm thick two-layer film were laminated at 100 ° C for 3 minutes by laminating the photosensitive polyimide layer and the copper foil. After exposure (exposure conditions: 4 〇 Onm light was irradiated at 10 μM/cm 2 ), the PET film was peeled off and cured at 180 ° C for 2 hours to prepare an FPC coated with a coating layer. The FPC was cut into l〇cm squares to observe the plate bend, and it was found that no plate bend was produced. [Example 7] 33 g of a thermoplastic carboxylic acid polyimide having a carboxylic acid synthesized in Example 6, a dioxane 66 g, a 4,4·-diaminodiphenylboron (DDS) 0.5 g, and a double (2) , 4,6-trimethylphenylhydrazine)-phenylphosphine oxide ruthenium.5g (1.2 millimolar), East Asian synthesis of Aronics M-208 (bisphenol F E0 denatured (Π4 2) diacrylate 25g The obtained solution was coated on a 25/zm thick PET film, dried at 45 ° C for 5 minutes, and then the PET film was peeled off, fixed in a needle frame, and dried at 65 ° C for 5 minutes to obtain a photosensitive polyimide. A 60-zm thick amine/PET film 25//m thick 2-layer film. 81 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -----------装--------Book---------^9. (Please read the notes on the back and fill out this page) 1299043 A7 p------ -B7___ V. Invention Description (^) In the same manner as in the sixth embodiment, the flexible copper panel has a peeling strength of 1080 Pa·m, and can form a pattern of 1 line/line width/line spacing, and is immersed in a solder bath at 260 ° C for 1 minute. No defects such as swelling were observed. The copper of the soft copper panel was etched away, leaving the cured photosensitive polyimide. The modulus of elasticity was 1500 MPa, the elongation was 20%, and the thermal decomposition initiation temperature was 375 ° C. Then, when the coating layer of the present invention was used as a coating layer on a flexible printed circuit board, the plate bending was measured. [Embodiment 8] <Synthesis with a group of agglomerates> In a 2000 ml separation reactor equipped with a stirrer, BAPS-M 12.91 g (0.03 mol), DMF260 g, ESDA 57_65 g (0.10) under vigorous stirring. Moer) join together and continue to stir for 3 minutes. Next, 14.65 g (0.04 mol) of 2J-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added, and after stirring for 30 minutes, the oxadiamine diamine (KF8010 manufactured by Shin-Etsu Chemical Co., Ltd.) was added. 2.49 g (0.03) Mohr), stirring for 30 minutes, to obtain a polyaminic acid solution. The polyamine has a weight average molecular weight (Mw) of 55,000. At this time, the reaction was carried out by cooling with ice water. Pour the polyamic acid solution into a tray coated with Teflon film, in a vacuum oven at 150 ° C X 10 minutes, 160 ° C X 10 minutes, 170 ° C X 10 minutes, 180 ° C X 10 minutes, 190 ° CX 10 minutes, 210 ° C X 30 minutes, and a pressure of 660 Pa were subjected to reduced pressure heating. It was taken out from the vacuum oven to obtain 105 g of a thermoplastic polyimine having a hydroxyl group. The polyamidomine had a Mw of 60,000 and a hydrazine imidation ratio of 1%. <Synthesis of Epoxy-denatured Polyimine> 82 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) ---- ----订--------- 1 1299043 A7 _____ B7_____ V. Description of the invention (粆) 33g of polyethylenimine having a hydroxyl group synthesized is dissolved in 66g of dioxane, which will be triethyl Acridine.lg and glycidyl methacrylate 1.42 g (10 mmol) were dissolved in 25 g of dioxane, and added to the above solution, followed by heating and stirring at 60 ° C for 5 hours. Subsequently, 4.03 g (epoxy equivalent weight 136) of HP4032 manufactured by Olefin Shell Co., Ltd. was added, and the reaction was carried out at 60 ° C for 5 hours to synthesize an epoxy-modified polyimine. Add DDS 0.5g, 3,3'-carbonyl bis[7-(dimethylamino)coumarin] 〇.3g, benzophenone to the epoxy-modified polyimine solution l〇〇g Lg, tributylamine 〇.5g, East Asian synthesis of Aronics M-208 (bisphenol F EO denatured (n^2) diacrylate 25g, isocyanuric acid tris (ethane acrylate) 3g, prepared into a photosensitive The composition was coated on a 25 μm thick PET film, dried after 45 艽 5 minutes, and peeled off [1] [film, fixed on a needle frame, dried at 65 ° C X 5 minutes, A two-layer film of a photosensitive polyimide polyimide having a thickness of 60/zm thick and a thickness of the PET film 25 was obtained. Similarly to Example 6, the peeling strength of the soft copper panel was 100 OPa·m, and a line width of 100/zm was formed. The pattern of the line pitch and the solder bath immersed in the solder bath at 260 °C did not reveal defects such as swelling. The copper foil of the soft copper panel was etched away, leaving the elasticity of the photosensitive polyimide after curing. The modulus is 1250 MPa, the elongation is 25%, and the thermal decomposition initiation temperature is 380 〇C. Next, when the photosensitive coating layer of the present invention is used as a coating layer on a flexible printed circuit board, the sheet is measured in the same manner as in Example 6. Bend, it was found that there was no plate bend. [Comparative Example 2] 83 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) ^------—^------ --- (Please read the note on the back and fill out this page) 1299043 A7 _______B7_ V. Invention Description (W) (Please read the note on the back and fill out this page) 2000ml Separate Reactor with Mixer In the middle, under vigorous stirring, BAPS-M 43.05g (0.1 mole), DMF200g, ESDA 57.65g (0.10 moles) were added, and stirring was continued for 30 minutes to prepare a polyaminic acid solution. The weight average molecular weight (Mw) is 62,000. The polyamic acid solution is poured into a tray coated with a Teflon film, in a vacuum oven at 15 ° C 10 10 minutes, 160 ° C X 10 minutes, 170 ° CX 10 minutes, 180 ° C X 10 minutes, 19 ° ° C X 10 minutes, 2HTC X30 minutes, 660 Pa pressure was applied to reduce the pressure. Take out from the vacuum oven to obtain 95 g of thermoplastic polyimine. The Mw is 64,000, and the oxime imidization rate is 100%. 可溶性 The soluble polyimine 30g and the oiled shell epoxy 828 3g are dissolved in dioxins. The solution obtained by 67 g of alkane was coated on a 25# m thick PET film, and after drying at 45 ° C for 5 minutes, the PET film was peeled off, fixed on a needle frame, dried at 65 ° C for 5 minutes, and the PET film was peeled off. The photosensitive polyimine 6 〇/zm thick film was obtained by drying at 10 ° C for 5 minutes. The film has a modulus of elasticity of 32 MPa. 〇 On the FPC of the line prepared by the method of Example 6, which has a line width/line distance=200 // m/200/zm, the soluble polyphthaladium is placed. In the amine 60/zm film, the Teflon sheet of the release paper was placed on the upper and lower sides, and pressed at 250 ° C and 3 MPa to produce an FPC covering the coating layer. When the plate was bent in the same manner as in Example 6, the plate was bent and found to have a cylindrical shape with a radius of i〇cm. [Example 9] In a 2000 ml separate reactor equipped with a stirrer, the standard of the paper (CNS) A4 specification (210x297 public) was applied to the vigorously smashed the paper size of the paper. [" 1299043 A7 B7 " ' - --- --- V. Description of the invention (P) Mixing, after dissolving ESDA 57.7g ((U0 Moer), DMF2〇〇g, and dissolving it, then preparing the oxime diamine KF8010 (manufactured by Shine 315g (〇〇35mol), DMFlOg was added, and stirring was continued for 3 minutes. Then, the addition of -^month female basic formic acid Wuer was dissolved in DMFlOg, and 30 minutes were disturbed. Next, under cooling of the reaction vessel with ice water, BAPS-M 17.22 g (0.040 mol) was added under vigorous stirring, and then DMF 24 g was added thereto, and stirring was continued for 1 hour to obtain a polyaminic acid solution. The polyamine has a weight average molecular weight (Mw) of 62,000. The polyamic acid solution was poured into a tray coated with a Teflon film, and heated under reduced pressure at 200 ° C and 660 Pa for 2 hours in a vacuum oven. It was taken out from the vacuum oven to obtain 85 g of a thermoplastic polyimine. The polyamidimide had a Mw of 68,000, a Tg of 54 ° C, and a hydrazine imidation ratio of 100%. (Synthesis of epoxy-denatured polyimine) 44.1 g of the synthesized soluble polyimine was dissolved in dioxanol l〇〇g, and MEHQ O.lg was added thereto, and dissolved at 60 ° C with stirring. . After dissolving, 4.50 g of epoxy 828 resin manufactured by Olefin Shell Co., Ltd. was dissolved in 13 g of dioxane, and then added with 3 g of triethylamine hydrazine. 5 g was heated and stirred at 60 ° C for 8 hours, so that Sc = 30% was obtained. A enamel paint of an epoxy-modified polyimine. (Preparation of a coating film) 0.5 g of isocyanuric acid EO-modified triacrylate (A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) and bisphenol F EO denatured by East Asian synthetic Aronix were added to 16.7 g of the enamel paint. η and 2) diacrylate (M-208) 4.5g, photoreaction starter of the steam batter with chemical Ig Gum 819 O.lg, 4,4'-diaminodiphenylmethane (DDM) O. After lg, MEHQ O.Olg, it is mixed and defoamed. Apply 85 paper sizes to Chinese National Standard (CNS) A4 specifications (21〇X 297 mm) — II-------- (Please read the notes on the back and fill out this page) 5-0·- 1299043 A7 ________B7_______ V. INSTRUCTIONS (θ) This solution is coated on a PET film and dried at 45 ° C for 5 minutes and at 65 ° C for 5 minutes to produce a 50/m thick photosensitive polyimide. Laminating. The copper foil/polyimine film (coated film)/PET film (release paper) was stacked in this order, and laminated at 80 ° C and 9200 Pa · m. After lamination, the mask pattern was attached and exposed for 3 minutes (exposure conditions: 400 nm parallel light was irradiated at i〇mJ/cm2), and the PET film was peeled off and then baked at 10 (TC for 2 minutes, 1%). After tetramethylammonium hydroxide (TMAH) in isopropanol solution (liquid temperature: 45 ° C) was developed for 5 minutes, 1 〇〇 X 2 hours, 120 ° C X 2 hours, 14 ° ° C X 2 hours, 180 ° C X2 hours of hardening. The bonding strength of the matte side of the copper foil of the soft copper panel is 1300 Pa • m, which can form the line width/line distance of the loo/iooem and the hole pattern of 100/ζιηχ 100/zm. The film and the copper foil, the coating film and other polyimide film (the modulus of elasticity 4000 MPa 'thickness 25/zm) are bonded together, and the exposed and heat-hardened samples are not bent or both. The sample which is cured by the laminate of the copper foil and the coating film is immersed in the solder at 300 ° C for 3 minutes, and there is no foaming or peeling at all, and no deterioration occurs. After the laminate with the coating film is heat-hardened at 180 ° C for 2 hours, the copper foil of the sample is removed by etching to obtain a cured photosensitive film. The 5% weight loss temperature of the polyimide film is 363 ° C. Regarding its mechanical properties, the modulus of elasticity is 1600 MPa, the elongation is 34.0%, and the tensile strength is 22 MPa 实施 [Example 10] 86 This paper scale is suitable. National Standard (CNS) A4 Specification (210 X 297 mm) Μ--------tr---------Ίιρ- (Please read the notes on the back and fill out this page) A7 1299043 B7__ V. INSTRUCTION DESCRIPTION (Material) In a 2000 ml separate reactor equipped with a stirrer, stir the ESDA 57.6 g (0.10 mol) and DMF 2 g after stirring to dissolve the sand. Oxygen diamine KF8010 (manufactured by Shin-Etsu ketone) 25. 〇g (〇.〇3〇莫耳), DMFlOg is added together, stirring is continued for 3 () points. Then, 5.33 g (0.035) of diaminobenzoic acid is added. Mol) is dissolved in DMFlOg and stirred for 30 minutes. Then, under the cooling reaction vessel with ice water, BAPS-M 15.1g (0.35 mol) is added in one breath and stirring is continued for 1 hour. The polyaminic acid solution was prepared, and the weight average molecular weight (Mw) of the polyamic acid was 58,000. The polyamic acid solution was poured into a tray coated with a Teflon film. The vacuum oven was heated under reduced pressure at a pressure of 2 ° C and 660 Pa for 2 hours, and taken out from the vacuum oven to obtain 94 g of a thermoplastic polyhydric limb having a carboxyl group. The Mw of the poly-feet was 6 50,000 'Tg is 6 〇. 〇, 醯 imidization rate is 100%. (Synthesis of oxime-denatured polyimine) Synthetic soluble polyimine 84. 〇§(〇·〇8莫耳Dissolved in dioxane 2 oxime, added MEHQ O.lg, dissolved at 5 〇~6 (TC). After the dissolution, glycidyl methacrylate L42g (〇.〇l Moer) was dissolved in 4 g of dioxane, and the mixture was heated and stirred at 60 ° C for 2 hours. Next, 3.80g of epoxy 828 resin made by Oilified Shell Co., Ltd. was dissolved in dioxane bg, and then heated at 6 ° C for 6 hours. ♦ So S = 30% epoxy modified polyimine. (Production of coating film) In 19.8 g of the epoxy-modified polyimine solution (淸 lacquer), a bifunctional acrylate 208 4.0 g, Igge 819 O.lg, DDM, 87 was added (please read the back first) Note: Please fill out this page) -·1111111 « — I — — — — — —* The paper size applies to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) A7 1299043 _______B7 ___ V. Description of invention (A After MEHQ O.Olg, mix and defoam. The solution was coated on a PET film to dry at 45 ° C for 5 minutes and dried at 65 ° C for 5 minutes to obtain a photosensitive polyimide film having a thickness of about 50 / zni. The laminate was carried out in the order of copper foil/polyimine film/PET film (release paper) in the condition of loot: 9200 Pa·m. After lamination, the mask pattern was attached and exposed for 3 minutes (exposure conditions: 400 nm parallel light was irradiated at 10 mJ/cm 2 ), and then post-baked at 100 ° C for 3 minutes, using 1% tetramethylammonium hydroxide. The isopropyl alcohol solution (liquid temperature: 40 ° C) was developed for 5 minutes, and then cured under the conditions of 100 ° C for X 2 hours, 120 ° C for X 2 hours, 140 ° C for X 2 hours, and 180 ° C for 2 hours. The matte strength of the copper foil matte side of the soft copper panel is • m, which can form a line width/line distance of l〇〇/l〇〇#m and a hole pattern of 100/zmX 100 /z m. The coating film and the copper foil, the coating film and another polyimide film (elastic modulus: 4000 MPa, thickness: 25/zm) are bonded together, and the exposed and heat-hardened samples are neither bent or curled. It is flat. A sample obtained by curing a laminate of a copper foil and a coating film, immersed in a solder at 300 ° C for 3 minutes, completely without foaming and peeling, and without deterioration, and laminating the copper foil and the coating film After the body was heat-hardened at 180 ° C for 2 hours, the copper foil of the sample was removed by etching, and the resulting 5% weight loss temperature of the cured photosensitive polyimide film was 356 ° C. Regarding its mechanical properties, the modulus of elasticity is 900 MPa, the elongation is 25.6%, and the tensile strength is 21 MPa. 本88 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). £------- -tr--------- (Please read the precautions on the back and fill out this page) A7 1299043 ___B7_____ V. Description of Invention (Example 11) Epoxidation denature synthesized in Example 9 In 16.7 g of a polyimine solution, 0.3 g of A-9300, 4.7 g of Μ-208, 819 O.lg of Dage, DDM O.lg, and MEHQ O.Olg were added, and then mixed and defoamed. This solution was applied onto a PET film, and dried at 45 ° C for 5 minutes and at 65 ° C for 5 minutes to obtain a photosensitive polyimide film having a thickness of about 50 / / m. The copper foil/polyimine film/PET film (release paper) was superposed in this order, and laminated at 120 ° C and 9200 Pa · m. After lamination, the mask pattern was attached for 3 minutes exposure (exposure conditions: 400 nm parallel light was irradiated at 10 mJ/cm 2 ), and then baked at 3 ° C for 3 minutes, using 1% of tetramethyl hydroxide. After the development of the isopropyl alcohol solution (liquid temperature: 40 ° C), the substrate was cured at 100 ° C for X 2 hours, 120 ° C for X 2 hours, 140 ° C for X 2 hours, and 180 ° C for 2 hours. The matte strength of the copper foil matte side of the soft copper panel is 100 OOPa m, which can form a line width/line distance of 70/70 #m and a hole pattern of 70/zmX70/z m. The coating film and the copper foil, the coating film and another polyimide film (elastic modulus: 4000 MPa, thickness: 25/zm) are bonded together, and the exposed and heat-hardened samples are neither bent or curled. It is flat. A sample obtained by curing a laminate of a copper foil and a coating film, immersed in a solder at 300 ° C for 3 minutes, completely without foaming and peeling, and without deterioration, and laminating the copper foil and the coating film After heat-hardening at 180 ° C for 2 hours, the copper foil of the sample was etched away, and the resulting cured paper was applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). -------*t--------IT--------- (Please read the notes on the back and fill out this page) 1299043 A7 ____ Β7 _ V. Invention description U7 The optical polyimide film has an elastic modulus of 630 MPa, an elongation of 32.0%, a tensile strength of 12 MPa, and a 5% weight loss temperature of 370 °C. [Example 12] In 20.0 g of the epoxy-modified polyimine solution synthesized in Example 9, Adding a mouth A - 9300 0.3 g, Μ - 208 3.7 g, Igge 819 O.lg, DDM O After .lg and MEHQ O.Olg, they are mixed and defoamed. This solution was coated on a PET film, and dried at 45 ° C for 5 minutes and 65 t X 5 to obtain a photosensitive polyimide film having a thickness of about 50 # m. The copper foil/polyimine film/PET film was superposed in this order, and the laminate was carried out under the conditions of 120 ° C and 9200 Pa·m. After lamination, the mask pattern was attached for 3 minutes exposure (exposure conditions: 400 nm parallel light was irradiated at 10 mJ/cm 2 ), and then baked at 1 ° C for 3 minutes, using 1% of tetramethyl hydroxide. After the base isopropyl alcohol solution (liquid temperature: 40 ° C) was developed for 5 minutes, it was cured at 100 ° C for X 2 hours, 120 ° C for X 2 hours, 140 ° X 2 hours, and 180 ° C for 2 hours. The matte strength of the copper foil matte side of the soft copper panel is 1000 Pa·m, which can form a line width/line distance of 50/50 /zm and a hole pattern of 50/zmX50/z m. The coating film and the copper foil, the coating film and another polyimide film (elastic modulus: 4000 MPa, thickness: 25/zm) are bonded together, and the exposed and heat-hardened samples are neither bent or curled. It is flat. A sample obtained by hardening a laminate of copper foil and coated film, immersed in solder at 300 ° C for 3 minutes, no foaming and peeling at all, no deterioration 〇 90 This paper scale applies to China National Standard (CNS) A4 size (210 X 297 mm) (Please read the notes on the back and fill out this page) --------Book ---------^^^^1 1299043 B7 V. Invention Description (correction) Further, after the laminate of the copper foil and the coating film was heat-cured at 180 ° C for 2 hours, the copper foil of the sample was removed by etching, and the elastic modulus of the cured photosensitive polyimide film was obtained. The number was 630 MPa, the elongation was 32.0%, the tensile strength was 12 MPa, and the 5% weight loss temperature was 370 °C. [Example 13] 26.4 g of the soluble polyamidene synthesized in Example 9 was dissolved in 60 g of dioxane, and 0.05 g of MEHQ was added thereto, and the mixture was dissolved while heating in an oil bath of 60 °C. 1.75 g (0.007 mol) of epoxy HP-4032 (manufactured by Dainippon Ink) was dissolved in 6 g of dioxane, and then added to the above solution, and 0.03 g of triethylamine was added thereto, and the mixture was stirred and heated at 60 ° C for 6 hours. An epoxy-modified polyimine is synthesized. In 17.9 g of the epoxy-modified polyimine solution (淸 paint), Μ-208 5.0 g, Igge 819 0"g, DDM O.lg, MEHQ O.Olg were added, and then mixed and defoamed. . This solution was coated on a PET film, and dried at 45 ° C for 5 minutes and at 65 ° C for 5 minutes to obtain a photosensitive polyimide film having a thickness of about 50 / zm. The copper foil/polyimine film/PET film (release paper) was superposed in this order, and the laminate was applied at 60 ° C and 9200 Pa·m. After laminating, the mask pattern was attached for 3 minutes exposure (exposure conditions: 4 〇〇 nm parallel light was irradiated at 10 μmjr/cm 2 ), and then baked at 3 ° C for 3 minutes, using 〇· 5% solution of tetramethylammonium hydroxide in isopropanol (liquid temperature 40. After 10 minutes of development, at 100 ° C for 2 hours, 120 ° c for 2 hours, 140 ° c for 2 hours, 18 (rc X 2 hours) The conditions are hardened. The matte strength of the copper foil matte side of the soft copper panel is 91. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------- - Packing -------- Order --------- (Please read the notes on the back and fill out this page) 1299043 A7 ______B7_________ V. Invention Description (Θ ) • m, can form 100/ 100# m line width/line distance line and 100//mx 100# m hole pattern. ΓQing first read the back of the phonetic? Please fill out this page} Will be covered with copper foil, coated film and other A polyimide film (elastic wedge number 4000 MPa, thickness 25/m) is attached, and the sample is exposed and heat-hardened, and both are not bent or curled to be flat. The copper foil and the film are coated. Laminated body The sample which was hardened was immersed in solder at 300 ° C for 3 minutes, and there was no foaming or peeling at all, and no deterioration occurred. The laminate of the copper foil and the coating film was heat-hardened at 180 ° C for 2 hours. Thereafter, the copper foil of the sample was removed by etching, and the obtained photosensitive polyimide film had a modulus of elasticity of 520 MPa, an elongation of 15.0%, and a tensile strength of 6.0 MPa. [Example 14] A stirrer was provided. In a 2 〇〇〇 ml separate reactor, ESDA 23.lg (0. 〇4 mol) and DMF 5 〇g were stirred and dissolved under vigorous stirring, and then the oxirane diamine KF801 〇 ( 16 6g (〇〇2〇莫耳), DMF5g was added, and stirring was continued for 3 minutes. Then, 1.52 g (0.010 mol) of diaminobenzoic acid was added to dissolve in DMF10 g. Stir for 30 minutes. Then, under cooling reaction vessel with ice water, add BAPS-M 8.61g (0.020 mol) in one breath, add DMF10g and continue stirring for 30 minutes. Finally add parabens. The acid anhydride 3.84g (0_02 mol) was dissolved in 5 g of DMF, and stirring was continued for a few hours to obtain a polyphosphonium phthalate. The weight average molecular weight (Mw) of the polyamic acid is 5500. 92 The scale applies to the Chinese National Standard (CNS) A4 specification (210 x 297 public love 1--*- A7 1299043 _ ____B7___ V. Invention description () The polyamic acid solution was poured into a tray coated with a Teflon film, and heated under reduced pressure at 200 ° C and 660 Pa for 1 hour in a vacuum oven. It was taken out from the vacuum oven to obtain 45 g of thermoplastic polyimine. The polyamidimide had a Mw of 6,000, a Tg of 80 ° C, and a hydrazine imidation ratio of 100%. (Synthesis of Epoxy-denatured Polyimine) 36 g of the synthesized soluble polyimine was dissolved in 36 g of dioxane, and MEHQ O.lg was added thereto, and dissolved in 6 (TC oil bath) while heating. The oiled shell epoxy 828 resin 7.6 was dissolved in 8 g of dioxane, and then added to the above solution, and heated and stirred at 60 ° C for 8 hours to synthesize an epoxy-denatured polyimine of Sc = 50%. 12.0 g of the epoxy-modified polyimine solution was added with a difunctional acrylate Μ-208 2.0 g, an yoghurt 819 O.lg, DDM O.lg, and MEHQ O.Olg, and then mixed and defoamed. The solution was coated on a PET film, and dried at 45 ° C, X5 minutes, 65 ° C, X5 minutes, and 80 ° C, X5 minutes to obtain a photosensitive polyimide film having a thickness of about 50 / zm. The order of the polyimide/polyimide film/PET film was superimposed, and lamination was carried out under conditions of 10° C. and 9200 Pa·m. After lamination, exposure was carried out for 3 minutes (exposure conditions: 400 nm parallel light was irradiated at 10 μM/cm 2 ) After baking for 3 minutes at l〇〇t, it was developed with 1% tetramethylammonium hydroxide in isopropanol solution (liquid temperature 40 ° C) for 5 minutes, then at 10 ° C for 2 hours. 120 °C X2 small , 140 ° C X2 hour, 160 ° C X3 hours hardened condition.

其對軟性銅面板的銅箔無光澤面之接著強度爲l〇〇〇Pa •m，可形成100/100//m之線寬/線距的直線和100/zmX 93 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝Its matte strength to the matte side of the copper foil of the soft copper panel is l〇〇〇Pa • m, which can form a line width/line distance of 100/100//m and 100/zmX. 93 The paper scale is applicable to the Chinese country. Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back and fill out this page)

n I i n 一so, I n n I in n n In I 1299043 A7 ____B7__ 五、發明說明（，/ ) 100 // m之孔圖案。 將被覆膜與銅箔、被覆膜與其他聚醯亞胺膜(彈性模數 4000MPa，厚25//m)貼合，經曝光、熱硬化而成之樣本， 兩者均未產生彎曲或捲曲而呈平坦狀。 將銅箔和被覆膜之積層體所硬化成之樣本，浸漬於 300°C的焊料3分後，完全沒有發泡和剝離，並未產生劣化 〇 又，將銅箔和被覆膜的積層體於180°C2小時的條件 加熱硬化後，將該樣本的銅箔蝕刻除去，所得硬化後的感 光性聚醯亞胺膜之彈性模數爲1120MPa，伸長率3.5%，拉 伸強度20MPa。 〔比較例3〕 在設有攪拌器之2000ml分離式反應器中，於激烈攪 拌下，將 BAPS - M 68.88g(0.16 莫耳）、DMF 320g、ESDA 138.4g(0.24莫耳)加入，持續攪拌30分。這時用冰水冷卻 使反應進行。接著，加入將二胺基苯甲酸12.18g(0.08莫耳 )溶解於DMF120g而成者，攪拌30分，製得聚醯胺酸溶液 。將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空烘 箱內，以200°C、660Pa的壓力實施減壓乾燥2小時。從真 空供箱中取出，獲得98g的具有羧基之熱可塑性聚醯亞胺 。該聚醯亞胺之Mw爲65000，Tg爲190°C，醯亞胺化率 爲 100% 〇 將合成出的可溶性聚醯亞胺48.4g(56毫莫耳)溶解於 二惡茂烷110g中，添加MEHQ O.lg，用50〜60°C的油浴邊 94 參紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) "" — -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 ____一 —_B7 五、發明說明（P ) 加熱邊使其溶解。將縮水甘油基甲基丙烯酸酯1.42g(10毫 莫耳)溶解於二惡茂烷14g後加入前述溶液中，於60°C進 行1小時加熱攪拌。接著，將油化殻牌製環氧828樹脂 3.80g(10毫莫耳)溶解於二惡茂烷14g後加入前述溶液中， 於60°C進行8小時加熱攪拌，合成出環氧變性聚醯亞胺。 使用該聚醯亞胺之淸漆，以和實施例14同樣的條件 製作出被覆層，以銅箔/聚醯亞胺膜/PET膜(剝離紙)的順序 重疊，以120°C、9200Pa · m的條件實施積層。積層後， 裝上光罩實施3分鐘曝光（曝光條件：以i〇mj/cm2照射 400nm的平行光)後，於i〇〇°c進行3分鐘後烘烤處理，用 1%之氫氧化四甲基的異丙醇溶液(液溫40。〇實施顯影後， 以 100°C X2 小時、120°C X2 小時、140°c X2 小時、160°c X3小時的條件進行硬化。 顯像後的圖案雖能描繪出線寬/線距=200 // m/200 /z m 的直線，但無法形成更精細的圖案。 將該被覆膜和銅箔貼合，經曝光、熱硬化而成之樣本 ’因聚醯亞胺的收縮而在聚醯亞胺側產生捲曲。其對軟性 銅面板的銅箔無光澤面之接著強度小於l〇〇Pa · m。 又，將銅箔和被覆膜的積層體於180°C2小時的條件 加熱硬化後，將該樣本的銅箔蝕刻除去，所得硬化後的感 光性聚醯亞胺膜之彈性模數爲5000MPa，伸長率2.0%，拉 伸強度16MPa。硬化後的Tg爲290°C，熱膨脹係數在室溫 〜l〇〇°C 爲 200ppm。 如此般可知，原料中未使用矽氧烷二胺之聚醯亞胺所 95 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 一 · _1 n n ·ϋ ϋ n —ϋ 訂--------- %, 1299043 A7 ---- -B7______ 五、發明說明（p ) 製成的膜，其機械強度差。原料中未使用矽氧烷二胺之聚 醯亞胺，由於硬化後的彈性模數高，若和其他膜貼合後實 施熱硬化，因底膜和被覆膜間的彈性模數不同，所得樣本 會捲曲。而可知，當其應用於軟性印刷基板(FPC)的被覆膜 時，將使微細的銅電路剝落或斷線等，而使FPC的性能變 差。 〔實施例15〕 在設有攪拌器之2000ml分離式反應器中，將BAPS -M 8.60g(0.02莫耳）、矽氧烷二胺（信越化學製KF8010; 通式（3)中 x=3、y=10、1^=(：113)16.6§(0.020 莫耳）、 DMF200g —起加入，於激烈攪拌下將ESDA 57.65g(0.1〇 莫耳)一次就加入，持續攪拌30分。接著，加入將雙(4〜 胺基-3 -羧基-苯基）甲烷l7.2g(0.06莫耳）溶解於 DMF75g而成者，攪拌30分，製得聚醯胺酸溶液。該聚醯 胺酸之重量平均分子量(Mw)爲6萬。 將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空 烘箱內，以 150°C X10 分、160°C X10 分、170°C X10 分、 180°C X 10 分、190°C X 10 分、210°C X30 分、660Pa 的壓 力實施減壓加熱。從真空洪箱中取出，獲得96g的具有羧 基之熱可塑性聚醯亞胺。該聚醯亞胺之Mw爲9.2萬，醯 亞胺化率爲1〇〇%(COOH當量=804)。 將合成後的可溶性聚醯亞胺溶解於二惡茂烷而作成30 重量％的溶液，在所得之30重量％可溶性聚醯亞胺溶液 l〇〇g中，添加光反應起始劑之雙(2,4,6 -三甲基苯醯卜苯 96 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公ϋ {請先閱讀背面之注音？事項再填寫本頁}n I i n a so, I n n I in n n In I 1299043 A7 ____B7__ V. Description of the invention (, / ) 100 // m hole pattern. The coating film and the copper foil, the coating film and another polyimide film (the modulus of elasticity 4000 MPa, thickness 25 / / m) are bonded together, and the sample which is exposed and heat-hardened does not cause bending or both. Curl and flat. A sample obtained by curing a laminate of a copper foil and a coating film, immersed in a solder at 300 ° C for 3 minutes, completely without foaming and peeling, and without deterioration, and laminating the copper foil and the coating film After the body was heat-hardened at 180 ° C for 2 hours, the copper foil of the sample was removed by etching, and the obtained photosensitive polyimide film had a modulus of elasticity of 1,120 MPa, an elongation of 3.5%, and a tensile strength of 20 MPa. [Comparative Example 3] In a 2000 ml separate reactor equipped with a stirrer, BAPS-M 68.88 g (0.16 mol), DMF 320 g, ESDA 138.4 g (0.24 mol) were added under vigorous stirring, and stirring was continued. 30 points. At this time, the reaction was carried out by cooling with ice water. Next, 12.18 g (0.08 mol) of diaminobenzoic acid was dissolved in 120 g of DMF, and the mixture was stirred for 30 minutes to obtain a polyaminic acid solution. The polyamic acid solution was poured into a tray coated with a Teflon film, and dried under reduced pressure at 200 ° C and 660 Pa for 2 hours in a vacuum oven. It was taken out from the vacuum supply tank to obtain 98 g of a thermoplastic polyimine having a carboxyl group. The polyamidomine has a Mw of 65,000, a Tg of 190 ° C, and a ruthenium iodide ratio of 100%. The synthesized soluble polyamidiamine 48.4 g (56 mmol) is dissolved in 110 g of dioxane. , add MEHQ O.lg, use oil bath edge of 50~60 °C 94 纸张 paper scale applicable Chinese National Standard (CNS) A4 specification (210 X 297 mm) "" — -------- ---装--------Book--------- (Please read the note on the back and fill out this page) 1299043 A7 ____一—_B7 V. Invention Description (P) Heating Let it dissolve. After dissolving 1.42 g (10 mmol) of glycidyl methacrylate in 14 g of dioxane, the solution was added to the above solution, and the mixture was stirred under heating at 60 ° C for 1 hour. Next, 3.80 g (10 mmol) of the oil-resistant shell epoxy 828 resin was dissolved in 14 g of dioxane, and then added to the above solution, and heated and stirred at 60 ° C for 8 hours to synthesize an epoxy-denatured polyfluorene. Imine. Using the enamel paint of the polyimide, the coating layer was produced under the same conditions as in Example 14 and superposed in the order of copper foil/polyimine film/PET film (release paper) at 120 ° C and 9200 Pa. The condition of m is layered. After laminating, a photomask was attached for 3 minutes exposure (exposure conditions: 400 nm parallel light was irradiated at i〇mj/cm2), and then baked at i〇〇°c for 3 minutes, using 1% of NaOH. Methyl isopropanol solution (liquid temperature 40. After development, the film is cured at 100 ° C for X 2 hours, 120 ° C for X 2 hours, 140 ° C for X 2 hours, and 160 ° C for 3 hours. Although the pattern can draw a line with a line width/line distance = 200 // m/200 /zm, it cannot form a finer pattern. The film and the copper foil are bonded together and exposed to heat and hardened. The curling occurs on the polyimine side due to the shrinkage of the polyimide. The bonding strength to the matte side of the copper foil of the soft copper panel is less than 10 ÅPa · m. Further, the copper foil and the coating are laminated. After the body was heat-hardened at 180 ° C for 2 hours, the copper foil of the sample was removed by etching, and the obtained photosensitive polyimide film having a modulus of elasticity of 5000 MPa, an elongation of 2.0%, and a tensile strength of 16 MPa. The latter Tg is 290 ° C, and the coefficient of thermal expansion is 200 ppm at room temperature ~ l 〇〇 ° C. As can be seen, the raw materials are not made.矽 醯 二 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 95 ϋ n —ϋ ---------- %, 1299043 A7 ---- -B7______ V. INSTRUCTIONS (p) The film produced has poor mechanical strength. No oxyalkylene diamine is used in the raw material. The polyimine has a high modulus of elasticity after hardening, and if it is bonded to another film and then thermally cured, the obtained sample may be curled due to the difference in elastic modulus between the base film and the coating film, and it is known that When applied to a coating film of a flexible printed circuit board (FPC), the fine copper circuit is peeled off or broken, and the performance of the FPC is deteriorated. [Example 15] A 2000 ml separation reactor equipped with a stirrer Among them, BAPS-M 8.60g (0.02 mole), alkoxydiamine (KF8010 manufactured by Shin-Etsu Chemical; x=3, y=10, 1^=(:113)16.6§(0.020) Mol), DMF200g - Add, ESDA 57.65g (0.1〇mol) is added once under vigorous stirring, stirring for 30 minutes. Then, adding bis (4~ Amino-3 - The base-phenyl)methane (17.2 g (0.06 mol) was dissolved in 75 g of DMF, and stirred for 30 minutes to obtain a polyaminic acid solution. The weight average molecular weight (Mw) of the polylysine was 60,000. The polyamic acid solution is poured into a tray coated with a Teflon film in a vacuum oven at 150 ° C X 10 minutes, 160 ° C X 10 minutes, 170 ° C X 10 minutes, 180 ° C X 10 minutes, 190 ° C X Decompression heating was carried out at a pressure of 10 minutes, 210 ° C X 30 minutes, and 660 Pa. It was taken out from the vacuum chamber to obtain 96 g of a thermoplastic polyimine having a carboxyl group. The polyamidimide had a Mw of 92,000 and a hydrazine imidation ratio of 1% by weight (COOH equivalent = 804). The synthesized soluble polyimine is dissolved in dioxane to form a 30% by weight solution, and in the obtained 30% by weight soluble polyimine solution, a double of the photoreaction initiator is added ( 2,4,6-Trimethylbenzoquinone 96 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 ϋ {Please read the phonetic on the back first? Please fill out this page again}

A7 1299043 五、發明說明（Μ ) 基氧化膦0.5g(1.2毫莫耳）、雙酚A EO變性(η与30)二丙烯 酸酯(新中村化學工業製ABE- 30)25g、聚合抑制劑之甲氧 苯酌10mg。將該溶液塗佈在25 // m厚PET膜上，經45°C X5分、65°C X5分乾燥後，製得感光性聚醯亞胺膜(38/zm 厚)/PET膜(25 μ m厚)的2層膜。 以銅箔/感光性聚醯亞胺膜(38/zm厚)/PET膜(25/zm) 的順序重疊，以iOVC、lOOOOPa · m的條件實施積層。積 層後，從PET膜側表面實施3分鐘曝光（曝光條件：以 10mJ/cm2照射400nm的平行光），剝去PET膜後於100它 進行3分鐘後烘烤處理，以180°C X2小時的條件進行硬化 〇 所得聚醯亞胺膜/銅箔(軟性銅面板)之剝離接著強度爲 1180Pa · m，且於260°C的焊料浴中浸漬丨分鐘未觀察到脹 起等的缺陷。 將軟性銅面板的銅箔鈾刻除去，所留下的硬化後被覆 膜之彈性模數爲l〇〇〇MPa，伸長率爲25%，熱分解開始溫 度爲370°C。 另外，在上述感光性聚醯亞胺膜(38# m厚)/ρΕτ膜(25 /zm厚)的2層膜上，以銅箔/感光性聚醯亞胺膜/ρΕΤ膜的 順序重疊，以l〇〇°C、10〇〇〇pa · m的條件實施積層。積層 後，裝上線寬/線距= 100/1 〇〇# m之光罩，從PET膜側實施 3分鐘曝光(曝光條件··以i〇mj/cm2照射4〇〇nm的平行光） ，剝去PET膜後於l〇(rc進行3分鐘後烘烤處理，經 1%ΚΟΗ水溶液(液溫4〇°C)顯影後，以18(rc χ2小時的條 97 I紙張尺度適用中國國家標準（CNS)A4規7格（210 X 297公釐Γ ' ~ (請先閱讀背面之注意事項再填寫本頁) 一 --------訂--------- 1299043 A7 ____B7__·_ 五、發明說明（7tr) 件進行硬化。用顯微鏡觀察該被覆膜的圖案時，係確認可 繪出線寬/線距= 100/100//m的圖案。 〔實施例16〕 在實施例15所得之30重量％可溶性聚醯亞胺溶液 l〇〇g中，添加雙（2,4,6 -三甲基苯醯苯基氧化膦 〇.5g(1.2毫莫耳）、雙酚F EO變性(11与2)二丙烯酸酯(東亞 合成製阿羅尼克斯M- 208)5g、雙酚A EO變性(n^30)二 丙烯酸酯(新中村化學工業製ABE- 30)25g、聚合抑制劑之 甲氧苯酚l〇mg。將該溶液塗佈在25/z m厚PET膜上，經 45°C X5分、65°C X5分乾燥後，製得感光性聚醯亞胺膜 (38 /z m 厚)/PET 膜(25 # m 厚)的 2 層膜。 和實施例1同樣地，在該2層膜上貼合銅箔，製得軟 性銅面板。該軟性銅面板之剝離接著強度爲l〇80Pa · m， 且於260°C的焊料浴中浸漬1分鐘未觀察到脹起等的缺陷 。將軟性銅面板的銅涪蝕刻除去，所留下的硬化後被覆膜 之彈性模數爲1500MPa，伸長率爲20%，熱分解開始溫度 爲 375°C 〇 另外，在上述感光性聚醯亞胺膜(38# m厚)/PET膜(25 μ m厚)的2層膜上，以銅箔/感光性聚醯亞胺膜/PET膜的 順序重疊，以100°C、lOOOOPa · m的條件實施積層。積層 後’裝上線寬/線距= 100/100 # m之光罩，從PET膜側實施 3分鐘曝光(曝光條件：以l〇mj/cm2照射400nm的平行光） ，剝去PET膜後於i〇(TC進行3分鐘後烘烤處理，經 1%ΚΟΗ水溶液(液溫40。〇顯影後，以180。。X2小時的條 98 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂--------- 1299043 A7 ____B7_ 五、發明說明（炒） 件進行硬化。用顯微鏡觀察該被覆膜的圖案時，係確認可 繪出線寬/線距= 100/100//m的圖案。 〔實施例17〕 在設有攪拌器之2000ml分離式反應器中，將BAPS -M 8.61g(0.02莫耳）、MDF 260g加入，於激烈攪拌下將 ESDA 57.65g(0.10莫耳)一次就加入，持續攪拌30分。接 著加入矽氧烷二胺（信越化學製KF8010)24.9g(0.03莫耳) ，攪拌30分後，加入2,5 -二胺基對苯二甲酸9.81g(0.05 莫耳），邊用冰水冷卻邊攪拌，製得聚醯胺酸溶液。該聚醯 胺酸之重量平均分子量(Mw)爲5.3萬。 將該聚醯胺酸溶液倒在被覆鐵氟龍膜之盤中，於真空 烘箱內，以 150°C X 10 分、160°C X 10 分、170°C X 10 分、 180°C X 1〇 分、190°C X 10 分、210°C X30 分、660Pa 的壓 力實施減壓加熱。從真空烘箱中取出，獲得具有羧基之熱 可塑性聚醯亞胺。該聚醯亞胺之Mw爲6.0萬，醯亞胺化 率爲 1〇〇%(COOH 當量=974)。 將該可溶性聚醯亞胺溶解於二惡茂烷而作成30重量％ 的溶液，在所得之30重量％可溶性聚醯亞胺溶液100g中 ，添加4,4’ -雙（二乙胺）二苯甲酮〇.3g、日本油脂製 BTTB(25%甲苯溶液）1.0g、雙酚A EO變性(n*30)二丙烯 酸酯(新中村化學工業製ABE - 30)20g、雙酚A EO變性(n 与10)二丙烯酸酯(新中村化學工業製ABE _ 10)5g、聚合抑 制劑之甲氧苯酚l〇mg，製得感光性樹脂組成物溶液。將該 溶液塗佈在25#m厚PET膜上，經45°C X5分、65°C X5 99 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) _ · -1 n ϋ n 1 n n · n n n I» ϋ I . 1299043 A7 ___B7_____ 五、發明說明（？7 ) 分乾燥後，製得感光性聚醯亞胺膜(38//m厚)/PET膜(25# m厚）的2層膜。 和實施例15同樣地，在該2層膜上貼合銅箔，製得 軟性銅面板。該軟性銅面板之剝離接著強度爲lOOOPa · m ，且於260°C的焊料浴中浸漬1分鐘未觀察到脹起等的缺 陷。 將軟性銅面板的銅箔蝕刻除去，所留下的硬化後被覆 膜之彈性模數爲1250MPa，伸長率爲25%，熱分解開始溫 度爲380°C。 另外’在上述感光性聚醯亞胺膜(38/zm厚)/PET膜(25 /z m厚)的2層膜上，以銅箔/感光性聚醯亞胺膜/pET膜的 順序重疊，以l〇〇°C、lOOOOPa · m的條件實施積層。積層 後，裝上線寬/線距= 100/100//m之光罩，從PET膜側實施 3分鐘曝光(曝光條件：以l〇mJ/cm2照射400nm的平行光） ，剝去PET膜後於l〇〇°c進行3分鐘後烘烤處理，經 1%ΚΟΗ水溶液(液溫40。(：顯影後，以l8(TC X2小時的條 件進行硬化。用顯微鏡觀察該被覆膜的圖案時，係確認可 繪出線寬/線距= 100/100# m的圖案。 〔實施例18〕 除將實施例15的可溶性聚醯亞胺之原料構成比改成 如下外，係進行同樣的操作。BAPS - M 17.20g(〇.〇4莫耳） 、矽氧烷二胺（信越化學製KF8010 ;通式（3冲χ=3、尸ι〇 、1^=<：113)24々(0.030 莫耳）、ESDA 57.65g((X10 莫耳）、雙 (4-胺基-3-羧基-苯基）甲烷8·6§(0·03莫耳）。所得聚 100 本紙張尺度適用中國國家標準（CNS)A4規格（_21〇 X 297公釐） ' -----— <請先閱讀背面之注意事項再填寫本頁)A7 1299043 V. INSTRUCTIONS (Μ) Radical phosphine oxide 0.5g (1.2 millimolar), bisphenol A EO denatured (η and 30) diacrylate (ABE-30, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 25g, polymerization inhibitor 10 mg of methoxybenzene. The solution was coated on a 25 // m thick PET film, and dried at 45 ° C, X 5 min, 65 ° C, and X 5 to obtain a photosensitive polyimide film (38/zm thick) / PET film (25). 2 m film of μ m thick). The copper foil/photosensitive polyimide film (38/zm thick)/PET film (25/zm) was superposed in this order, and lamination was carried out under the conditions of iOVC and 1000 Pa·m. After lamination, the surface of the PET film was exposed for 3 minutes (exposure conditions: 400 nm of parallel light was irradiated at 10 mJ/cm 2 ), the PET film was peeled off, and after 100 minutes, it was baked for 3 minutes at 180 ° C for 2 hours. The peeling strength of the obtained polyimide film/copper foil (soft copper panel) obtained by hardening was 1180 Pa·m, and immersion in a solder bath of 260 ° C for a minute did not observe defects such as swelling. The copper foil of the soft copper panel was removed by uranium, and the cured mold film after leaving the film had an elastic modulus of 10 MPa, an elongation of 25%, and a thermal decomposition starting temperature of 370 °C. Further, on the two-layer film of the photosensitive polyimide film (38# m thick)/ρΕτ film (25/zm thick), the copper foil/photosensitive polyimide film/ρΕΤ film was superposed in the order of The laminate was carried out under the conditions of l〇〇°C and 10〇〇〇pa·m. After laminating, attach a mask with line width/line spacing = 100/1 〇〇# m, and expose for 3 minutes from the side of the PET film (exposure conditions · illuminate 4 〇〇 nm of parallel light with i〇mj/cm2), After peeling off the PET film, it was baked at 3 rpm (rc for 3 minutes, and after 1% hydrazine aqueous solution (liquid temperature 4 〇 °C), it was applied to 18 (rc χ 2 hours strip 97 I paper scale for Chinese national standard). (CNS) A4 gauge 7 grid (210 X 297 mm Γ ' ~ (Please read the back of the note and then fill out this page) One -------- Order --------- 1299043 A7 ____B7__·_ V. Inventive Note (7tr) The material was hardened. When the pattern of the coating film was observed with a microscope, it was confirmed that a pattern having a line width/line pitch = 100/100//m could be drawn. [Example 16] In the 30 wt% soluble polyimine solution obtained in Example 15, 100 g of bis(2,4,6-trimethylphenylhydrazine phenylphosphine oxide ruthenium. 5 g (1.2 mmol), double Phenol F EO denatured (11 and 2) diacrylate (Alonix M-208, East Asia Synthetic) 5 g, bisphenol A EO denatured (n^30) diacrylate (ABE-30, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 25 g , a polymerization inhibitor of methoxyphenol l〇mg. The solution is coated On a 25/zm thick PET film, after drying at 45 ° C X 5 minutes and 65 ° C X 5 minutes, a photosensitive polyimide film (38 / zm thick) / PET film (25 # m thick) of 2 layers was obtained. In the same manner as in Example 1, a copper foil was bonded to the two-layer film to obtain a soft copper panel. The flexible copper panel was peeled off at a strength of 10 Å to 80 Pa·m and was placed in a solder bath at 260 ° C. No defects such as swelling were observed after immersion for 1 minute. The copper ruthenium of the soft copper panel was removed by etching, and the cured film after curing had an elastic modulus of 1500 MPa, an elongation of 20%, and a thermal decomposition initiation temperature of 375. °C 〇 In addition, on the two-layer film of the above-mentioned photosensitive polyimide film (38 # m thick) / PET film (25 μm thick), copper foil / photosensitive polyimide film / PET film The layers were overlapped and laminated at 100 ° C and 1000 Pa · m. After lamination, the mask with line width/line spacing = 100/100 # m was attached, and exposure was performed for 3 minutes from the PET film side (exposure conditions: 1) Mj/cm2 was irradiated with parallel light of 400 nm), and the PET film was peeled off and then baked at TC (TC for 3 minutes, and then treated with 1% hydrazine aqueous solution (liquid temperature 40. After sputum development, 180 °. X 2 hours strip) 98 paper The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) --------Book --------- 1299043 A7 ____B7_ V. Invention description (fried) pieces are hardened. When the pattern of the coating film was observed with a microscope, it was confirmed that a pattern having a line width/line pitch = 100/100//m can be drawn. [Example 17] In a 2000 ml separate reactor equipped with a stirrer, BAPS-M 8.61 g (0.02 mol) and MDF 260 g were added, and ESDA 57.65 g (0.10 mol) was added once under vigorous stirring. , continue to stir for 30 minutes. Then, 24.9 g (0.03 mol) of a nonyloxane diamine (KF8010 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and after stirring for 30 minutes, 9.81 g (0.05 m) of 2,5-diaminoterephthalic acid was added thereto, and ice water was used. The mixture was stirred while cooling to prepare a polyaminic acid solution. The polyamine has a weight average molecular weight (Mw) of 53,000. Pour the polyamic acid solution into a tray coated with Teflon film in a vacuum oven at 150 ° C X 10 min, 160 ° C X 10 min, 170 ° C X 10 min, 180 ° C X 1 〇 min, 190 The pressure was reduced by a pressure of °CX 10 minutes, 210 ° C X 30 minutes, and 660 Pa. It was taken out from the vacuum oven to obtain a thermoplastic polyimine having a carboxyl group. The polyamidomine had a Mw of 60,000 and a hydrazine imidization ratio of 1% by weight (COOH equivalent = 974). The soluble polyamidiamine was dissolved in dioxane to prepare a 30% by weight solution, and in the obtained 30% by weight soluble polyimide solvent solution, 4,4'-bis(diethylamine) diphenyl was added. Ketone ketone.3g, BTTB (25% toluene solution) made from Japanese fats and oils, 1.0g, bisphenol A EO denatured (n*30) diacrylate (ABE-30, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 20g, bisphenol A EO denaturation n and 10) diacrylate (ABE _ 10, manufactured by Shin-Nakamura Chemical Co., Ltd.) 5 g of methoxy phenol of a polymerization inhibitor, and a photosensitive resin composition solution. The solution was coated on a 25#m thick PET film at 45°C, X5 minutes, 65°C, X5 99. The paper size was applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back first) Note: Please fill in this page) _ · -1 n ϋ n 1 nn · nnn I» ϋ I . 1299043 A7 ___B7_____ V. Description of invention (?7) After drying, a photosensitive polyimide film is produced (38) //m thick)/PET film (25# m thick) 2-layer film. In the same manner as in Example 15, a copper foil was bonded to the two-layer film to obtain a flexible copper panel. The peeling strength of the soft copper panel was 100 OPa·m, and no defects such as swelling were observed when immersed in a solder bath at 260 ° C for 1 minute. The copper foil of the soft copper panel was removed by etching, and the cured film after leaving the film had an elastic modulus of 1,250 MPa, an elongation of 25%, and a thermal decomposition starting temperature of 380 °C. Further, 'on the two-layer film of the above-mentioned photosensitive polyimide film (38/zm thick) / PET film (25 / zm thick), the copper foil / photosensitive polyimide film / pET film overlaps in order. The layering was carried out under the conditions of l〇〇°C and 1000oPa·m. After lamination, a mask with a line width/space distance = 100/100//m was attached, and exposure was performed for 3 minutes from the PET film side (exposure condition: 400 nm parallel light was irradiated at 10 μM/cm 2 ), and the PET film was peeled off. The mixture was baked at 3 ° C for 3 minutes, and passed through a 1% aqueous solution of hydrazine (liquid temperature 40. (: After development, it was hardened by l8 (TC X 2 hours). When the pattern of the coating film was observed with a microscope It was confirmed that the pattern of the line width/line distance = 100/100 #m can be drawn. [Example 18] The same operation was carried out except that the raw material composition ratio of the soluble polyimine of Example 15 was changed as follows. BAPS-M 17.20g (〇.〇4mol), alkoxydiamine (KF8010 by Shin-Etsu Chemical; general formula (3 χ=3, 尸〇, 1^=<:113) 24々( 0.030 Mohr), ESDA 57.65g ((X10 Mo), Bis(4-Amino-3-carboxy-phenyl)methane 8.6§ (0·03 Moh). The resulting 100-sheet paper scale is applicable to China. National Standard (CNS) A4 Specification (_21〇X 297 mm) ' ------ <Please read the notes on the back and fill out this page)

-· I----I--^ -----I A7 1299043 ______B7__ 五、發明說明（，） 醯胺酸的分子量爲5.9萬。進行和實施例15同樣的醯亞胺 化，製得可溶性聚醯亞胺104g(COOH當量1746)。 和實施例15同樣地製作出感光性聚醯亞胺/PET膜之 2層膜，接著，和實施例15同樣地，在該2層膜上貼合銅 箔，製得軟性銅面板。該軟性銅面板之剝離接著強度爲 1200Pa · m，且於260°C的焊料浴中浸漬1分鐘未觀察到脹 起等的缺陷。將軟性銅面板的銅箔鈾刻除去，所留下的硬 化後被覆膜之彈性模數爲lOOOMPa，伸長率爲25%，熱分 解開始溫度爲370°C。 另外，在上述感光性聚醯亞胺膜(38/zm厚)/PET膜(25 厚)的2層膜上，以銅箔/感光性聚醯亞胺膜/PET膜的 順序重疊，以l〇〇°C、lOOOOPa · m的條件實施積層。積層 後，裝上線寬/線距= 100/100//m之光罩，從PET膜側實施 3分鐘曝光(曝光條件：以10mJ/cm2照射400nm的平行光) ，剝去PET膜後於l〇〇°C進行3分鐘後烘烤處理，經 l%KOH 7JC溶液(液溫40。〇顯影後，以180。。X 2小時的條 件進行硬化。用顯微鏡觀察該被覆膜的圖案時，係確認可 繪出線寬/線距=100/100/zm的圖案。 〔比較例4〕 除將實施例15的可溶性聚醯亞胺之原料構成比改成 如下外，係進行同樣的操作。BAPS - M 17.22g(0.04莫耳) 、矽氧烷二胺（信越化學製KF8010 ;通式(3)中x=3、y=10 、Ι^=(：Η3)24·98(0·030 莫耳）、ESDA 57.65g(0.10 莫耳）、 3,5-二胺基苯甲酸4.56g(〇.〇3莫耳）。所得聚醯胺酸的分 101 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公ϋ " (請先閱讀背面之注意事項再填寫本頁) _ · I I I 1 1 I 1 訂----— II--. A7 1299043 ___ B7___ 五、發明說明（W ) 子量爲5·9萬。進行和實施例15同樣的醯亞胺化，製得可 溶性聚醯亞胺99g(COOH當量3358)。 和實施例15同樣地製作出感光性聚醯亞胺/pet膜之 2層膜，接著，和實施例15同樣地，在該2層膜上貼合銅 箔，製得軟性銅面板。該軟性銅面板之剝離接著強度爲 1200Pa · m，且於260°C的焊料浴中浸漬1分鐘未觀察到脹 起等的缺陷。將軟性銅面板的銅箔触刻除去，所留下的硬 化後被覆膜之彈性模數爲lOOOMPa，伸長率爲25%，熱分 解開始溫度爲370°C。 另外，在上述感光性聚醯亞胺膜(38/zm厚)/PET膜(25 # m厚)的2層膜上，以銅箔/感光性聚醯亞胺膜/ΡΕτ膜的 順序重疊，以l〇〇°C、lOOOOPa · m的條件實施積層。積層 後，裝上線寬/線距= 100/100//m之光罩，從PET膜側實施 3分鐘曝光(曝光條件：以l〇mJ/cm2照射400nm的平行光） ，剝去PET膜後於l〇〇°C進行3分鐘後烘烤處理，雖嘗試 用1%ΚΟΗ水溶液(液溫40。〇實施顯影，但因未曝光部不 溶解故無法描繪出圖案。 〔實施例19〕 作爲聚醯亞胺的原料，係使用雙〔4 - (3 -胺基苯氧基 )苯基〕碾(BAPS - M)，（2,2,-雙(4 -羥基苯基)丙烷二苯甲 酸酯-3,3^4,41 -四羧酸二酐(ESDA)，二胺基苯甲酸。 (聚醯亞胺樹脂的合成） 在設有攪拌器之20〇〇ml分離式反應器中，將BAPS-M 68.88g(0.16莫耳）、Dmf 320g加入，於激烈攪拌下將 __ 102 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂--------- 1299043 A7 ____ Β7 _ 五、發明說明（ί σ ) ESDA 138.4g(0.24莫耳卜次就加入，持續攪拌30分。此 時用冰水冷卻並使反應進行。接著，加入將二胺基苯甲酸 12.18g(0.08莫耳)溶解於DMF 120g而成者，攪拌30分， 製得聚醯胺酸溶液。將該聚醯胺酸溶液倒在被覆氟樹脂之 盤中，於真空烘箱內，以200°C、660Pa的壓力實施減壓乾 燥2小時，獲得96g之聚醯亞胺。 (變性聚醯亞胺的合成） 將所合成出的聚醯亞胺48.4g(56毫莫耳)溶解於二惡 茂烷ll〇g，添加4_甲氧基苯酚〇.ig，用50〜60°C的油浴 邊加熱邊使其溶解。將縮水甘油甲基丙烯酸酯1.42g(10毫 莫耳)溶解於二惡茂烷5g後加入前述溶液中，於60°C進行 6小時加熱攪拌。接著，將油化殼牌公司製環氧828樹脂 3.80g(10毫莫耳)溶解於二惡茂烷14g後加入前述溶液中， 於60°C進行6小時加熱攪拌，合成出GMA變性聚醯亞胺 〇 (感光性膜之製作） 混合以下(a)〜(d)成份調整成感光性樹脂組成物，依(2) 的方法在PET膜上製作B階的感光性膜。 (a) 以上方法所合成出之變性聚醯亞胺樹脂 65重量份 (b) 異氰尿酸EO變性三丙烯酸酯(新中村化學工業(股) 製 A - 9300) 5重量份 (c) 雙酚F EO變性(11=2)二丙烯酸酯(東亞合成(股)製阿 103 $氏張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐〉 " " <請先閱讀背面之注意事項再填寫本頁) --------訂---------· A7 1299043 B7___ 五、發明說明（W ) 羅尼克斯Μ- 208) 30重量份 (d)雙酚(2,4,6 -三甲基苯醯)苯基氧化膦(汽巴特用化學 (股)製伊格膠819) 1重量份 在該具有PET膜之感光性膜面上，積層(3)所作成之 (PE+EVA)共聚物膜/ΟΡΕ膜之貼合品所構成之保護膜，製 作出三層構造片。 該三層構造片之保護膜剝離性爲3.3Pa · m。以曝光條 件：1800mJ/cm2強度之波長400nm光，顯影液：1%氫氧 化鉀水溶液進行感光性膜的顯影性測試時，可顯像出200 /zm見方及100/zm見方之微細孔。又，調濕後的焊料耐 熱性試驗下，在300°C的熔融焊料中浸漬1分鐘並未發現 膜從銅箔上剝離或脹起。耐折強度爲可導通1800次，線間 之絕緣電阻値爲5.ΟΧΙΟ15Ω。 〔實施例20〕 (聚醯亞胺樹脂的合成） 在設有攪拌器之500ml分離式反應器中，將ESDA 17.3g(0.030莫耳）、DMF 30g加入，在攪拌機的攪拌下使 其溶解。接著，將和歌山精化製之二胺MBAA 5.15g(0.〇i8 莫耳)溶解於DMF 9g後加入，激烈攪拌1小時。接著，加 入矽氧烷二胺之KF-8010(信越矽酮製)7.47g(0.009莫耳) ，攪拌1小時左右。最後，加入BAPS - M 1.29g(0.003莫 耳），激烈攪拌1小時。將所得聚醯胺酸溶液倒在被覆氟樹 104 (請先閱讀背面之注意事項再填寫本頁) ----11 I I 訂-------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 1299043 ______B7___ 五、發明說明ο 脂之盤中，於真空烘箱內’以200°c、660Pa的壓力實施減 壓乾燥2小時’獲得26.40g之可溶性聚醯亞胺。 (變性聚醯亞胺的合成） 將所合成出的聚醯亞胺2(h8g(0.020莫耳)溶解於二惡 茂烷80g，添加4-甲氧基苯酚0.030g，用60°C的油浴邊 加熱邊使其溶解。將縮水甘油甲基丙烯酸酯3.75g(0.0264 莫耳)溶解於二惡茂烷5g後加入前述溶液中，再加入解媒 之三乙胺O.Olg後於60°C進行6小時加熱攪拌。如此般合 成出變性聚醯亞胺。 (感光性膜之製作） 混合以下(e)〜(g)、（d)成份調整成感光性樹脂組成物， 依(2)的方法在PET膜上製作B階的感光性乾膜光阻。 (e)以上方法所合成出之變性聚醯亞胺樹脂 60重量份 ⑴雙酚A E0變性(m+n^30)二丙烯酸酯(新中村化學 工業(股)製NK酯A - ΒΡΕ - 30) 2〇重量份 (g)雙酚A Ε0變性(m+n与10)二丙烯酸酯(新中村化學 工業(股)製NK酯A - ΒΡΕ - 10) 2〇重量份 (d)汽巴特用化學(股)製伊格膠819 1重量份 在該具有PET膜之感光性膜面上，積層保護膜之積水 化學(股)製Protect(#6221F)膜(厚50^111)，製作出三層構造 105 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) - — — — — III ·1!11111<* 1299043 A7 ___B7- ------ 五、發明說明 片。 該三層構造片之保護膜剝離性爲3.3Pa · m。以曝光條 件：1800mJ/cm2強度之波長400nm光，顯影液：1%氫氧 化鉀水溶液進行感光性膜的顯影性測試時，可顯像出2GG 見方及100//m見方之微細孔。又，調濕後的焊料耐 熱性試驗下，在300°C的熔融焊料中浸漬1分鐘並未發現 膜從銅箔上剝離或脹起。耐折強度爲可導通1200次，線間 之絕緣電阻値爲7·0Χ1015Ω。 〔實施例21〕 在實施例20之感光性膜的製作中，使用不同的色素 作爲感光色素而製作出感光性膜。 混合以下的(e)〜⑴成份而調整成感光性樹脂組成物， 依(2)的方法在PET膜上製作出B階的感光性乾膜光阻。 (e) 上述方法所合成出之聚醯亞胺樹脂 60重量份 (f) 雙酚A EO變性(m+n#30)二丙烯酸酯(新中村化學 工業(股)製NK酯A _ ΒΡΕ - 30) 20重量份 (g) 雙酚A ΕΟ變性(m+n与10)二丙烯酸酯(新中村化學 工業(股)製NK酯A - ΒΡΕ - 10) 20重量份 (h) 4,4’ -雙(二乙胺)二苯甲酮(矽酮技硏(股)製s - 112) 1重量份 (i) 3,3，，4,4,-四（特丁基過氧羰基）二苯甲酮（曰本油月旨（ 106 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） -----------_裝—— (請先閱讀背面之注意事項再填寫本頁) · 1299043 A7 ____B7_ —_ 五、發明說明（〆） 股)製 BTTB - 25) 1重量份 在該具有PET膜之感光性膜面上，積層保護膜之積水 化學(股)製Protect(#6221F)膜(厚50/zm)，製作出三層構造 片。 該三層構造片之保護膜剝離性爲3.5Pa · m。以曝光條 件：600mJ/cm2強度之波長4〇Onm光，顯影液：1%氫氧化 鉀水溶液進行感光性膜的顯影性測試時，可顯像出200/zm 見方及l〇〇em見方之微細孔。又，調濕後的焊料耐熱性 試驗下，在300°C的熔融焊料中浸漬1分鐘並未發現膜從 銅箔上剝離或脹起。耐折強度爲可導通800次，線間之絕 緣電阻値爲1·6Χ1014Ω。 〔實施例22〕 混合以下各成份而調整成感光性樹脂組成物，依(2)的 方法在PET膜上製作出Β階的感光性乾膜光阻。 (e) 實施例20所合成出之聚醯亞胺樹脂 50重量份 (c)雙酚F EO變性(n=2)二丙烯酸酯(東亞合成(股)製阿 羅尼克斯M- 208) 40重量份 (f) 雙酸A EO變性(m+n与30)二丙稀酸酯(新中村化學 工業(股)製NK酯A - ΒΡΕ - 30) 10重量份 (h)4,-雙(二乙胺)二苯甲酮(矽酮技硏(股)製s — 112) 107 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---- (請先閱讀背面之注意事項再填寫本頁) - — — III — — ·111111--· A7 1299043 ___B7 _ ^ --- 五、發明說明（〆） 0.5重量份 (i)3,3f，4,4’ -四（特丁基過氧羰基）二苯甲酮（臼本油脂( 股)製 BTTB - 25) 2重量份 在該具有PET膜之感光性膜面上，積層(3)所作成之 (PE+EVA)共聚物膜/ΟΡΕ膜的貼合品所構成之保護膜，製 作出三層構造片。 該三層構造片之保護膜剝離性爲3.5Pa · m。以曝光條 件：600mJ/cm2強度之波長400nm光，顯影液·· 1%氫氧化 鉀水溶液進行感光性膜的顯影性測試時，可顯像出200//m 見方及l〇〇//m見方之微細孔。又，調濕後的焊料耐熱性 試驗下，在300°C的熔融焊料中浸漬1分鐘並未發現膜從 銅箔上剝離或脹起。耐折強度爲可導通750次，線間之絕 緣電阻値爲5.5 X 1013Ω。 〔實施例23〕 混合以下各成份而調整成感光性樹脂組成物，依(2)的 方法在PET膜上製作出β階的感光性膜。 (e)實施例20所合成出之聚醯亞胺樹脂 50重量份 ⑷雙酚F EO變性(n=2)二丙烯酸酯(東亞合成(股)製阿 羅尼克斯Μ - 208) 2〇重量份 (0雙酚A ΕΟ變性(m+n4 30)二丙烯酸酯(新中村化學 工業(股)製NK酯A - ΒΡΕ - 30) _ 108 本^氏張尺度適用中國國家標準（CNS)A4規格（210 χ 297公~~ (請先閱讀背面之注意事項再填寫本頁) ^ · 1 n n H II n n^OJ« n ϋ I n I ϋ 1« I · A7 1299043 __B7 _ ___-· I----I--^ ----- I A7 1299043 ______B7__ V. Description of the invention (,) The molecular weight of proline is 59,000. The same ruthenium imidization as in Example 15 was carried out to obtain 104 g of soluble polyimine (COOH equivalent 1746). A two-layer film of a photosensitive polyimide/PET film was produced in the same manner as in Example 15. Then, in the same manner as in Example 15, a copper foil was bonded to the two films to obtain a flexible copper panel. The peeling strength of the soft copper panel was 1200 Pa·m, and no defects such as swelling were observed when immersed in a solder bath at 260 °C for 1 minute. The copper foil of the soft copper panel was removed by uranium, and the hardened coating film left had a modulus of elasticity of 100 MPa, an elongation of 25%, and a heat decomposition starting temperature of 370 °C. Further, on the two-layer film of the above-mentioned photosensitive polyimide film (38/zm thick)/PET film (25 thick), the copper foil/photosensitive polyimide film/PET film was superposed in the order of l The conditions of 〇〇°C and lOOOOPa·m are layered. After lamination, a mask with a line width/space distance = 100/100//m was attached, and exposure was performed for 3 minutes from the PET film side (exposure condition: 400 nm parallel light was irradiated at 10 mJ/cm 2 ), and the PET film was peeled off. After 3°C, the post-baking treatment was carried out for 3 minutes, and the solution was cured by a solution of 1% KOH 7JC (liquid temperature 40. 〇 after development, at 180 ° C for 2 hours). When the pattern of the coating film was observed with a microscope, It was confirmed that a pattern having a line width/line distance = 100/100/zm can be drawn. [Comparative Example 4] The same operation was carried out except that the raw material composition ratio of the soluble polyimine of Example 15 was changed as follows. BAPS-M 17.22g (0.04 mole), alkoxydiamine (KF8010 manufactured by Shin-Etsu Chemical Co., Ltd.; x=3, y=10, Ι^=(:Η3)24·98(0·030) in the general formula (3) Moer), ESDA 57.65g (0.10 mole), 3,5-diaminobenzoic acid 4.56g (〇.〇3 mole). The obtained polylysine is divided into 101 paper standards for Chinese national standards (CNS) ) A4 size (210 X 297 ϋ " (Please read the back note first and then fill out this page) _ · III 1 1 I 1 order----- II--. A7 1299043 ___ B7___ V. Description of invention ( W) The amount is 590,000. Example 15 was similarly imidized to obtain 99 g of soluble polyimine (COOH equivalent: 3358). A two-layer film of a photosensitive polyimide/pet film was produced in the same manner as in Example 15, and then, and In the same manner as in Example 15, a copper foil was bonded to the two-layer film to obtain a soft copper panel. The peeling strength of the soft copper panel was 1200 Pa·m, and it was not observed in a solder bath of 260 ° C for 1 minute. Defects such as swelling. The copper foil of the soft copper panel is removed by contact, and the cured film after curing has a modulus of elasticity of 1000 MPa, an elongation of 25%, and a thermal decomposition onset temperature of 370 ° C. On the two-layer film of the above-mentioned photosensitive polyimide film (38/zm thick)/PET film (25 #m thick), the copper foil/photosensitive polyimide film/ΡΕτ film was superposed in the order of l积°C, lOOOOPa · m conditions are laminated. After lamination, a mask with line width/line spacing = 100/100//m is mounted, and exposure is performed for 3 minutes from the PET film side (exposure conditions: l〇mJ/ Cm2 was irradiated with 400 nm of parallel light), peeled off the PET film, and then baked at 1 ° C for 3 minutes, although attempting to develop with a 1% aqueous solution of hydrazine (liquid temperature 40 〇) However, since the unexposed portion was not dissolved, the pattern could not be drawn. [Example 19] As a raw material of polyimine, bis[4-(3-aminophenoxy)phenyl] mill (BAPS-M) was used. ), (2,2,-bis(4-hydroxyphenyl)propane dibenzoate-3,3^4,41-tetracarboxylic dianhydride (ESDA), diaminobenzoic acid. (Synthesis of Polyimine Resin) In a 20 〇〇 ml separate reactor equipped with a stirrer, BAPS-M 68.88 g (0.16 mol) and Dmf 320 g were added, and __ 102 was added under vigorous stirring. The paper scale applies to the Chinese National Standard (CNS) A4 specification (21〇X 297 mm) (please read the notes on the back and fill out this page) --------Book --------- 1299043 A7 ____ Β7 _ V. Inventive Note (ί σ ) ESDA 138.4g (0.24 Mob is added, stirring is continued for 30 minutes. At this time, it is cooled with ice water and the reaction is carried out. Then, diaminobenzoic acid is added. 12.18g (0.08 mol) dissolved in 120 g of DMF, stirred for 30 minutes to prepare a polyaminic acid solution. The polyamic acid solution was poured into a disk coated with fluororesin, in a vacuum oven, to 200 The pressure of 660 Pa was dried under reduced pressure for 2 hours to obtain 96 g of polyimine. (Synthesis of denatured polyimine) 48.4 g (56 mmol) of the synthesized polyimine was dissolved in two. Oxaloline ll 〇g, 4_methoxyphenol 〇.ig was added, and it was dissolved by heating with an oil bath of 50 to 60 ° C. The glycidyl methacrylate was 1.42 g (10 mmol) After dissolving in 5 g of dioxane, it was added to the above solution, and it was heated and stirred at 60 ° C for 6 hours. Then, 3.80 g (10 mmol) of epoxy 828 resin manufactured by Olefin Shell Co., Ltd. was dissolved in dioxane. After 14 g, the solution was added to the solution, and heated and stirred at 60 ° C for 6 hours to synthesize GMA-denatured polyimine oxime (manufactured by a photosensitive film). The following components (a) to (d) were mixed to adjust the photosensitive resin composition. A B-stage photosensitive film is formed on the PET film according to the method of (2). (a) 65 parts by weight of the denatured polyimine resin synthesized by the above method (b) isocyanuric acid EO modified triacrylate (new Nakamura Chemical Industry Co., Ltd. A - 9300) 5 parts by weight (c) Bisphenol F EO denatured (11 = 2) diacrylate (East Asia Synthetic (Shares) system A 103 $ Zhang Zhang scale applicable Chinese National Standard (CNS) A4 size (210 x 297 mm) ""<Please read the notes on the back and fill out this page) --------Book---------· A7 1299043 B7___ , invention description (W) Ronix Μ - 208) 30 parts by weight (d) bisphenol (2,4,6-trimethylphenylhydrazine) phenyl phosphine oxide (Cart Bart chemical (share) made of Ig glue 819) 1 part by weight On the photosensitive film surface of the PET film, a protective film composed of a laminate of (PE+EVA) copolymer film/ruthenium film (3) was laminated to prepare a three-layer structure sheet. The protective film peelability of the three-layer structure sheet was 3.3 Pa·m. The exposure conditions: 1800 mJ/cm2 intensity 400 nm light, developer: 1% potassium hydroxide aqueous solution for the developability test of the photosensitive film, the 200/zm square and the 100/zm square micropores were visualized. Further, under the solder heat resistance test after the humidity control, the film was immersed in molten solder at 300 ° C for 1 minute, and no peeling or swelling of the film from the copper foil was observed. The folding strength is 1800 times, and the insulation resistance 线 between the wires is 5.ΟΧΙΟ15Ω. [Example 20] (Synthesis of Polyimine Resin) In a 500 ml separation reactor equipped with a stirrer, 17.3 g (0.030 mol) of ESDA and 30 g of DMF were added, and the mixture was dissolved under stirring with a stirrer. Next, the diamine MBAA 5.15 g (0. 〇i8 Mo) prepared by Wakayama Refined was dissolved in 9 g of DMF, and stirred vigorously for 1 hour. Next, 7.47 g (0.009 mol) of KF-8010 (manufactured by Shin-Etsurone) of a nonanediamine diamine was added, and the mixture was stirred for about 1 hour. Finally, BAPS-M 1.29 g (0.003 mol) was added and vigorously stirred for 1 hour. Pour the obtained polyaminic acid solution onto the coated fluorinated tree 104 (please read the note on the back and fill out this page) ----11 II-------- This paper scale applies to the Chinese National Standard (CNS) A4 size (210 X 297 mm) A7 1299043 ______B7___ V. Description of invention ο In a vacuum pan, dry-drying at 200 ° C and 660 Pa for 2 hours in a vacuum oven to obtain 26.40 g of soluble polyfluorene. Imine. (Synthesis of Denatured Polyimine) The synthesized polyimine 2 (h8g (0.020 mol) was dissolved in 80 g of dioxane, and 0.030 g of 4-methoxyphenol was added thereto, and oil at 60 ° C was used. The bath was dissolved while heating. 3.75 g (0.0264 mol) of glycidyl methacrylate was dissolved in 5 g of dioxane, and then added to the above solution, followed by addition of triethylamine O.Olg at 60 °. C is heated and stirred for 6 hours. The denatured polyimine is synthesized in this way. (Production of photosensitive film) The following components (e) to (g) and (d) are mixed to form a photosensitive resin composition, and (2) Method for producing B-stage photosensitive dry film photoresist on PET film. (e) 60 parts by weight of denatured polyimine resin synthesized by the above method (1) bisphenol A E0 denatured (m+n^30) diacrylic acid Ester (Nippon Nakamura Chemical Industry Co., Ltd. NK ester A - ΒΡΕ - 30) 2 parts by weight (g) bisphenol A Ε 0 denatured (m + n and 10) diacrylate (Xin Nakamura Chemical Industry Co., Ltd. NK) Ester A - ΒΡΕ - 10) 2 parts by weight (d) steam bat using chemical (strand) yoghurt 819 1 part by weight on the photosensitive film surface of the PET film, the accumulation of protective film of water chemistry (shares) System Protect(#6221F ) Film (thickness 50^111), making a three-layer structure 105 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note before filling this page) - — — III ·1!11111<* 1299043 A7 ___B7- ------ V. Invention sheet. The protective film peelability of the three-layer structure sheet is 3.3 Pa·m. Exposure conditions: 1800 mJ/cm2 strength At a wavelength of 400 nm, a developing solution: a 1% potassium hydroxide aqueous solution is used to test the developability of a photosensitive film, and a micropore of 2 GG square and 100//m square can be visualized. Further, under the test of heat resistance of the solder after humidity control The film was immersed in molten solder at 300 ° C for 1 minute, and the film was not peeled or swelled from the copper foil. The folding strength was 1200 times, and the insulation resistance 线 between the wires was 7·0 Χ 1015 Ω. [Example 21] In the production of the photosensitive film of Example 20, a photosensitive film was produced by using a different dye as a photosensitive dye. The following components (e) to (1) were mixed and adjusted to a photosensitive resin composition, and the method according to (2) A B-order photosensitive dry film photoresist was produced on the PET film. (e) The above method was combined. 60 parts by weight of polyimine resin (f) bisphenol A EO denatured (m+n#30) diacrylate (NK ester A _ ΒΡΕ - 30, manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts by weight (g) Bisphenol A ΕΟ denaturing (m+n and 10) diacrylate (NK ester A - ΒΡΕ - 10 manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts by weight (h) 4,4'-bis(diethylamine) Benzophenone (s-112) s - 112) 1 part by weight (i) 3,3,,4,4,-tetra(tert-butylperoxycarbonyl)benzophenone (曰本油The purpose of the month (106 paper scale applies to China National Standard (CNS) A4 specification (210 x 297 mm) -----------_Installation - (Please read the notes on the back and fill out this page ) 1299043 A7 ____B7_ —_ V. OBJECTIVES (〆) BTTB - 25) 1 part by weight of the water-based chemical (strand) made of the protective film on the photosensitive film surface of the PET film (#6221F) The film (thickness 50/zm) was used to produce a three-layer structure sheet. The protective film peelability of the three-layer structure sheet was 3.5 Pa·m. Exposure conditions: 600mJ/cm2 intensity of 4〇Onm light, developer: 1% potassium hydroxide aqueous solution for the developability test of the photosensitive film, can show 200/zm square and l〇〇em square hole. Further, under the solder heat resistance test after the humidity control, the film was immersed in the molten solder at 300 ° C for 1 minute, and the film was not peeled off or swollen from the copper foil. The folding strength is 800 times, and the insulation resistance between wires is 1.6 Χ 1014 Ω. [Example 22] The following components were mixed to adjust a photosensitive resin composition, and a photosensitive dry film resist of a ruthenium step was produced on the PET film according to the method (2). (e) 50 parts by weight of the polyimine resin synthesized in Example 20 (c) bisphenol F EO denatured (n=2) diacrylate (Aronix M-208 manufactured by Toagos Co., Ltd.) 40 Parts by weight (f) Diacid A EO denatured (m+n and 30) diacrylate (Nan Nakamura Chemical Industry Co., Ltd. NK ester A - ΒΡΕ - 30) 10 parts by weight (h) 4,-double ( Diethylamine) benzophenone (矽 硏 硏 制 112 — 112) 107 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ---- (Please read the back first Note: Please fill in this page) - — — III — — 111111--· A7 1299043 ___B7 _ ^ --- V. Description of invention (〆) 0.5 parts by weight (i) 3, 3f, 4, 4' - four (Tetrabutyl peroxycarbonyl) benzophenone (BTTB-25, manufactured by Emu Oil Co., Ltd.) 2 parts by weight on the photosensitive film surface of the PET film, laminated (3) (PE+EVA) A protective film composed of a laminate of a copolymer film and a ruthenium film, and a three-layer structure sheet was produced. The protective film peelability of the three-layer structure sheet was 3.5 Pa·m. When the exposure condition: 600 mJ/cm2 intensity 400 nm light, developer solution · 1% potassium hydroxide aqueous solution for the developability test of the photosensitive film, 200//m square and l〇〇//m square can be visualized. Micropores. Further, under the solder heat resistance test after the humidity control, the film was immersed in the molten solder at 300 ° C for 1 minute, and the film was not peeled off or swollen from the copper foil. The folding strength is 750 times, and the insulation resistance between the wires is 5.5 X 1013 Ω. [Example 23] A photosensitive resin composition was prepared by mixing the following components, and a photosensitive film of a β-stage was produced on the PET film according to the method (2). (e) 50 parts by weight of the polyimine resin synthesized in Example 20 (4) bisphenol F EO denatured (n=2) diacrylate (Alonix® - 208 manufactured by Toagosei Co., Ltd.) 2 〇 weight (0 bisphenol A ΕΟ denatured (m+n4 30) diacrylate (Nippon Nakamura Chemical Industry Co., Ltd. NK ester A - ΒΡΕ - 30) _ 108 This standard is applicable to China National Standard (CNS) A4 specifications (210 χ 297 gong~~ (Please read the notes on the back and fill out this page) ^ · 1 nn H II nn^OJ« n ϋ I n I ϋ 1« I · A7 1299043 __B7 _ ___

五、發明說明（fO 20重量份 (g)雙酚A EO變性(m+n^io)二丙烯酸酯(新中村化學 工業(股)製NK酯A _ ΒΡΕ - 10) 20重量份 (i) 3,3，，4,4’ -四（特丁基過氧羰基）二苯甲酮（曰本油脂（ 股)製 BTTB - 25) 2重量份 (j) 3,3,-羧基-雙〔7 -（二乙胺)香豆素〕（日本感光色 素硏究所(股)製NKX- 653) 1重量份 在該具有PET膜之感光性膜面上，積層(3)所作成之 (PE+EVA)共聚物膜/ΟΡΕ膜的貼合品所構成之保護膜，製 作出三層構造片。 該三層構造片之保護膜剝離性爲3.5Pa · m。以曝光條 件：600mJ/cm2強度之波長400nm光，顯影液：1°/。氫氧化 鉀水溶液進行感光性膜的顯影性測試時，可顯像出200//m 見方及100//m見方之微細孔。又，調濕後的焊料耐熱性 試驗下，在300°C的熔融焊料中浸漬1分鐘並未發現膜從 銅箔上剝離或脹起。耐折強度爲可導通750次，線間之絕 緣電阻値爲8·0Χ1013Ω。 〔比較例5〕 完全不使用醯亞胺，混合以下成份而調整成感光性樹 脂組成物。依(2)的方法在PET膜上製作Β階的感光性膜 〇 109 (請先閱讀背面之注意事項再填寫本頁) ’裝 0 n I— an n I fBi n 訂---------· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 ________B7_ 五、發明說明（r7) ⑷雙酚F E〇變性(n=2)二丙烯酸酯(東亞合成(股)製阿 羅尼克斯Μ - 208) 50重量份 ⑴雙酚A ΕΟ變性(m+n与30)二丙烯酸酯(新中村化學 工業(股)製NK酯A - ΒΡΕ - 30) 5〇重量份 (d)雙酚(2,4,6-三甲基苯醯)苯基氧化膦(汽巴特用化學 (股)製伊格膠819) 1重量份 在該具備PET膜之感光性膜面上，使用保護膜之ΟΡΕ 膜(厚30/zm)製作出三層構造片。保護片無法密合於感光 膜，保護膜剝離性爲1.6Pa · m以下，就算不刻意進行剝離 ，保護膜和感光性膜也會馬上產生橫向滑動，而無法密合 〇 如此般，若使用不具備(PE+EVA)共聚物膜面者來作爲 保護膜，其對感光性膜的密合性不佳。 〔比較例6〕 在比較例5所製作之具備PET膜之感光性膜面上，積 層(3)所作成之(PE+EVA)共聚物膜/ΟΡΕ膜的貼合品所構成 之保護膜，製作出三層構造片。 該三層構造片之保護膜剝離性爲4.0Pa · m。以曝光條 件：1800mJ/cm2強度之波長400nm光，顯影液：1%氫氧 化鉀水溶液進行感光性膜的顯影性測試時，可顯像出200 //m見方及100/zm見方之微細孔。又’調濕後的焊料耐 110 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) _ --------訂---------· A7 1299043 __B7__ 五、發明說明（〆） 熱性試驗下，在300°C的熔融焊料中浸漬1分鐘發現膜有 脹起產生。耐折強度僅可導通35次，線間之絕緣電阻値爲 1·3 X 1〇12Ω 〇 如此般，若不使用醯亞胺而僅用丙烯酸系樹脂來製作 感光性膜，保護膜在剝離性及顯影性上雖沒有問題，但膜 會變硬且脆而使耐折強度變差，且電氣特性的表現不佳。 〔比較例7〕 使用不具備芳香環之丙烯酸系樹脂，混合以下成份調 整成感光性樹脂組成物，依(2)的方法在PET膜上製作出Β 階的感光性膜。 (e)實施例20所合成之樹脂 60重量份 (k)聚乙二醇二丙烯酸酯(η与4)(東亞合成（股)製阿羅尼 克斯Μ - 240) 40重量份 (i) 3,3，，4,4’ -四（特丁基過氧羰基）二苯甲酮（曰本油脂（ 股)製 BTTB - 25) 2重量份 (j) 3,3、羧基-雙〔7 -(二乙胺）香豆素〕（曰本感光色 素硏究所(股)製NKX- 653) 1重量份 在該具有PET膜之感光性膜面上，積層保護膜之積水 化學(股)製Protect(#6221F)膜(厚50/zm)，製作出三層構造 111 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " (請先閱讀背面之注意事項再填寫本頁) -裝 I «I I n^OJI n n ϋ n ϋ . 1299043 ^__B7___‘ 五、發明說明（（”） 該三層構造片之保護膜剝離性爲3.〇Pa · m。以曝光條 件：600mJ/cm2強度之波長400nm光，顯影液：1%氫氧化 鉀水溶液進行感光性膜的顯影性測試時，由於被覆膜部分 不管在曝光部或未曝光部均產生溶解，故無法形成微細的 孔。又，調濕後的焊料耐熱性試驗下，在300°C的熔融焊 料中浸漬1分鐘時，發現膜從銅箔上剝離。耐折強度僅可 導通60次，線間之絕緣電阻値爲2·7Χ1013Ω。 如此般，若使用不具芳香環之丙烯酸系樹脂來製作感 光性膜，其顯影性不良，且焊料耐熱性及耐折強度均降低 〇 〔比較例8〕 混合以下成份而調整成感光性樹脂組成物。依(2)的方 法在PET膜上製作Β階的感光性乾膜光阻。 (e)上述方法所合成之聚醯亞胺樹脂 60重量份 ⑷雙酚F EO變性(11=2)二丙烯酸酯(東亞合成(股)製阿 羅尼克斯M- 208) 20重量份 ⑴雙酚A EO變性(m+n与30)二丙烯酸酯(新中村化學 工業(股)製NK酯A - ΒΡΕ - 30) 20重量份 (d)雙酚(2,4,6-三甲基苯醯)苯基氧化膦(汽巴特用化學 (股)製伊格膠819) 1重量份 112 本紙張尺度適用中國國家樣準（CNS)A4規格（210 X 297公釐） -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 A7 _____B7__ 五、發明說明（ 在該具備PET膜之感光性膜面上，使用保護膜之ΟΡΕ 膜(厚30#m)製作出三層構造片。保護片無法密合於感光 膜，保護膜剝離性爲1.6Pa · m以下，就算不刻意進行剝離 ，保護膜和感光性膜也會馬上產生橫向滑動，而無法密合 〇 如此般，若使用不具備(PE+EVA)共聚物膜面者來作爲 保護膜，其對感光性膜的密合性不佳。 〔產業上之可利用性〕 本發明之感光性樹脂組成物，能提供一防焊劑，其具 有可溶性，能在150°C以下的溫度實施積層，且能不透過 接著劑直接積層在FPC上。又，可提供一被覆層，其耐熱 性等各種特性優異，積層於FPC時能減少板彎的產生。本 發明之被覆膜，由於屬乾膜型故處理容易。亦即，在形成 有電路之基板上積層感光性被覆層後，進行所望圖案之曝 光，使曝光部硬化而形成硬化膜後，經顯影除去未曝光部 ，藉由在硬化膜不分解但有機溶劑會蒸發的溫度下進行熱 處理，即形成所望的圖案。 因此，由於僅實施積層即可形成被覆層，故以往之使 用液狀樹脂來製作感光性被覆層時所必經之乾燥過程不再 需要。又，由於積層溫度較低，不致弄傷基板而能形成耐 熱性、機械性均優異之被覆層。使用本發明的感光性樹脂 組成物之被覆層，係適用於軟性基板等的電路用保護膜。 如上述般，本發明之被覆膜，由於硬化後之彈性模數 爲100〜2500MPa，可形成微細的圖案，又因具有耐熱性、 113 張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱1 " -----------裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 1299043 B7 五、發明說明（ί/f ) 機械特性，故能提供出一感光性被覆膜，其適用於作爲膜 狀的光罩及絕緣保護膜。 (請先閱讀背面之注意事項再填寫本頁) 使用本發明的感光性樹脂組成物之被覆膜，由於凰乾 膜型故處理容易，可節省PFC製程中之乾燥時間。亦即， 在形成有電路之基板上積層感光性被覆層後，進行所望圖 案之曝光，使曝光部硬化而形成硬化膜後，經顯影除去未 曝光部，藉由在硬化膜不分解但有機溶劑會蒸發的溫度下 進行熱處理，即形成所望的圖案。 因此，由於僅實施積層即可形成被覆層，故以往之使 用液狀樹脂來製作感光性被覆層時所必經之乾燥過程不再 需要。又，由於積層溫度較低，不致弄傷基板而能形成耐 熱性、機械性均優異之被覆層。使用本發明的感光性樹脂 組成物之被覆層，係適用於軟性基板等的電路用保護膜。 又，本發明之感光性樹脂組成物所構成之防焊劑、被 覆膜，經曝光後，使用鹼性溶液即可容易地進行顯影，例 如，在簡單操作下能效果良好地製得具有高精度的既定圖 案之被覆膜積層基板。若將本發明的組成物當作感光性被 覆膜來使用，以往所需之基板上的對準等操作將不再需要 〇 硬化後之本發明的組成物，具有充分的機械強度且耐 熱性優異。因此，本發明之組成物及乾膜光阻，能效果良 好的應用於特別是電子材料領域所使用之印刷基板的保護 用、或是硬碟用懸吊具。本發明之防焊劑，可作成三層構 造片，該保護膜，對於感光性接著片(作爲軟性印刷配線板 114 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1299043 A7 B7 五、發明說明（ Π: 用的被覆層來使用）具有適度的密合性與易剝離性，由於不 使用脫模劑故因保存所造成之被覆層特性的經時變化減少 。又，使保護膜具備遮光性的情形，將感光性接著片積層 在形成有電路之軟性銅面積層板時，所具備的好處有：其 表裏容易分辨，且能避免感光性接著片的變質。 115 (請先閱讀背面之注意事項再填寫本頁) ^ · 1 n n n ϋ ·1 n^OJ* I · I I I 1 I 垂▲ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）5. Description of the invention (fO 20 parts by weight (g) bisphenol A EO denatured (m+n^io) diacrylate (NK ester A _ ΒΡΕ - 10 manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts by weight (i) 3,3,,4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB-25, manufactured by Sakamoto Oil Co., Ltd.) 2 parts by weight (j) 3,3,-carboxy-double [ 7-(diethylamine) coumarin] (Nippon Photosensitive Pigment Research Institute, NKX-653) 1 part by weight of the photosensitive film surface having the PET film, laminated (3) (PE) +EVA) A protective film composed of a copolymer film/ruthenium film laminate to produce a three-layer structure sheet. The three-layer structure sheet has a protective film peelability of 3.5 Pa·m. Exposure conditions: 600 mJ/cm2 strength The wavelength of 400 nm light, the developing solution: 1 ° /. When the potassium hydroxide aqueous solution is tested for the developability of the photosensitive film, the micropores of 200 / / m square and 100 / / m square can be visualized. Under the solder heat resistance test, the film was immersed in molten solder at 300 ° C for 1 minute, and the film was not peeled or swelled from the copper foil. The folding strength was 750 times, and the insulation resistance 线 between the wires was 8·0 Χ 1013 Ω. [Comparative Example 5] Finished The bismuth imine is not used, and the following components are mixed to adjust the photosensitive resin composition. According to the method of (2), a photosensitive film 〇109 is formed on the PET film (please read the back note first and then fill in this page). ) '装0 n I— an n I fBi n 订---------· This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 ________B7_ V. Description of invention ( R7) (4) bisphenol FE deuterium (n=2) diacrylate (Alonix® - 208 manufactured by East Asia Synthetic Co., Ltd.) 50 parts by weight (1) bisphenol A deuterated (m+n and 30) diacrylate (Xinzhongcun Chemical Industry Co., Ltd. NK ester A - ΒΡΕ - 30) 5 〇 parts by weight (d) bisphenol (2,4,6-trimethylphenylhydrazine) phenyl phosphine oxide (steam bat chemical) Igomer 819) 1 part by weight A three-layer structure sheet was produced on the surface of the photosensitive film having the PET film by using a film of a protective film (thickness: 30/zm). The protective sheet could not be adhered to the photosensitive film. The peeling property of the protective film is 1.6 Pa·m or less, and even if the peeling is not intentionally performed, the protective film and the photosensitive film immediately slide laterally, and cannot be adhered to each other, and if it is not used (P The E+EVA) copolymer film was used as a protective film, and its adhesion to the photosensitive film was not good. [Comparative Example 6] The surface of the photosensitive film having the PET film produced in Comparative Example 5 was laminated ( 3) A protective film composed of a bonded product of (PE+EVA) copolymer film/ruthenium film, and a three-layer structure sheet was produced. The protective film peelability of the three-layer structure sheet was 4.0 Pa·m. The exposure conditions: 1800 mJ/cm2 intensity 400 nm light, developer: 1% potassium hydroxide aqueous solution for the developability test of the photosensitive film, the micropores of 200 // m square and 100/zm square can be visualized. Also 'solder resistance after soldering 110 This paper scale applies to China National Standard (CNS) A4 specifications (210 X 297 public) (Please read the back of the precautions and then fill out this page) _ -------- Order ---------· A7 1299043 __B7__ V. Description of the invention (〆) Under the thermal test, the film was immersed in molten solder at 300 ° C for 1 minute to find that the film was swollen. The folding strength can only be turned on 35 times, and the insulation resistance 线 between the wires is 1.3 X 1 〇 12 Ω. Thus, if the bismuthimide is not used, only the acrylic resin is used to form the photosensitive film, and the protective film is peelable. There is no problem in the developability, but the film is hard and brittle, and the folding strength is deteriorated, and the electrical characteristics are not well expressed. [Comparative Example 7] An acrylic resin having no aromatic ring was used, and the following components were mixed to prepare a photosensitive resin composition, and a photosensitive film of a gradation was produced on the PET film according to the method (2). (e) 60 parts by weight of the resin synthesized in Example 20 (k) polyethylene glycol diacrylate (η and 4) (Alonix® 240 manufactured by Toagosei Co., Ltd.) 40 parts by weight (i) 3 ,3,,4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB-25, manufactured by Sakamoto Oil Co., Ltd.) 2 parts by weight (j) 3,3, carboxy-double [7 - (Diethylamine) Coumarin] (Nippon Photosensitive Pigment Research Institute, NKX-653) 1 part by weight of the water-based chemical film on the photosensitive film surface of the PET film Protect(#6221F) film (thickness 50/zm), made of three-layer structure 111 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) " (Please read the notes on the back and fill in This page) - I «II n^OJI nn ϋ n ϋ . 1299043 ^__B7___' V. Description of invention ((") The peeling property of the protective film of the three-layer structure sheet is 3. 〇Pa · m. With exposure conditions: 600 mJ/cm2 intensity 400 nm light, developer: 1% potassium hydroxide aqueous solution, when the developability test of the photosensitive film is performed, the coating film portion cannot be formed regardless of whether it is dissolved in the exposed portion or the unexposed portion. Fine pores. Further, under the solder heat resistance test after humidity control, when immersed in molten solder at 300 ° C for 1 minute, it was found that the film was peeled off from the copper foil. The folding strength was only turned on 60 times, and insulation between wires was performed. In the same manner, when a photosensitive film is produced by using an acrylic resin having no aromatic ring, the developability is poor, and the solder heat resistance and the folding strength are lowered. [Comparative Example 8] The following components are mixed. Adjusted to a photosensitive resin composition. According to the method of (2), a photosensitive dry film resist of a gradation is prepared on the PET film. (e) 60 parts by weight of the polyimine resin synthesized by the above method (4) bisphenol F EO Denatured (11=2) diacrylate (Alonix M-208 manufactured by East Asia Synthetic Co., Ltd.) 20 parts by weight (1) bisphenol A EO denatured (m+n and 30) diacrylate (Xinzhongcun Chemical Industry Co., Ltd.) Manufacture of NK ester A - ΒΡΕ - 30) 20 parts by weight of (d) bisphenol (2,4,6-trimethylphenylhydrazine) phenylphosphine oxide (Isolator 819 by steam bat) Parts by weight 112 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -----------Package--------Book ------ --- (Please read the back first Note: Please fill out this page again. 1299043 A7 _____B7__ V. Inventive Note (On the photosensitive film surface provided with the PET film, a three-layer structure sheet was produced using a film of a protective film (thickness 30#m). The protective sheet cannot be adhered to the photosensitive film, and the peeling property of the protective film is 1.6 Pa·m or less. Even if the peeling is not intentionally performed, the protective film and the photosensitive film immediately slide laterally, and cannot be adhered to each other. A (PE+EVA) copolymer film surface is used as a protective film, and the adhesion to the photosensitive film is not good. [Industrial Applicability] The photosensitive resin composition of the present invention can provide a solder resist which is soluble, can be laminated at a temperature of 150 ° C or lower, and can be directly laminated on the FPC without passing through the subsequent agent. Further, it is possible to provide a coating layer which is excellent in various properties such as heat resistance, and can reduce the occurrence of plate bending when laminated in FPC. The coating film of the present invention is easy to handle because it is a dry film type. That is, after the photosensitive coating layer is laminated on the substrate on which the circuit is formed, exposure of the desired pattern is performed, and the exposed portion is cured to form a cured film, and then the unexposed portion is removed by development, and the organic solvent is not decomposed in the cured film. The heat treatment is carried out at a temperature at which evaporation occurs, i.e., the desired pattern is formed. Therefore, since the coating layer can be formed only by laminating, the drying process which is conventionally required to produce a photosensitive coating layer using a liquid resin is no longer required. Further, since the laminate temperature is low, the coating layer excellent in heat resistance and mechanical properties can be formed without causing damage to the substrate. The coating layer of the photosensitive resin composition of the present invention is applied to a protective film for a circuit such as a flexible substrate. As described above, the coating film of the present invention can form a fine pattern due to the elastic modulus after hardening of 100 to 2500 MPa, and has a heat resistance and a 113-sheet scale applicable to the Chinese National Standard (CNS) A4 specification (210 X). 297 公爱1 " -----------装--------Book--------- (Please read the notes on the back and fill out this page) 1299043 B7 V. INSTRUCTIONS (ί/f ) Mechanical characteristics, so that a photosensitive coating film can be provided, which is suitable for use as a film-like mask and an insulating protective film. (Please read the back note and then fill out this page. The coating film using the photosensitive resin composition of the present invention is easy to handle due to the diatom film type, and the drying time in the PFC process can be saved. That is, after the photosensitive coating layer is laminated on the substrate on which the circuit is formed, After exposing the desired pattern, the exposed portion is cured to form a cured film, and then the unexposed portion is removed by development, and heat treatment is performed at a temperature at which the cured film is not decomposed but the organic solvent evaporates, thereby forming a desired pattern. The coating layer can be formed only by laminating, so the conventional use liquid The drying process which is necessary for the production of the photosensitive coating layer by the resin is no longer necessary. Moreover, since the deposition temperature is low, the coating layer which is excellent in heat resistance and mechanical properties can be formed without causing damage to the substrate. The photosensitivity of the present invention is used. The coating layer of the resin composition is applied to a protective film for a circuit such as a flexible substrate. Further, the solder resist or the coating film composed of the photosensitive resin composition of the present invention can be easily dried using an alkaline solution. Development is carried out, for example, a coated film substrate having a predetermined pattern with high precision can be obtained with good results in a simple operation. When the composition of the present invention is used as a photosensitive coating film, it is conventionally required. The alignment or the like on the substrate eliminates the need for the composition of the present invention after the hardening, and has sufficient mechanical strength and excellent heat resistance. Therefore, the composition of the present invention and the dry film resist can be applied to a good effect. In particular, it is used for the protection of a printed circuit board used in the field of electronic materials, or a suspension for a hard disk. The solder resist of the present invention can be formed into a three-layer structure sheet, and the protective film is For the photosensitive adhesive sheet (as the flexible printed wiring board 114, the paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A7 B7 5. The invention description (Π: used for the coating layer) is moderate The adhesion and the peelability are reduced, and the change in the characteristics of the coating layer due to storage is reduced without using a release agent. Further, when the protective film is provided with a light-shielding property, the photosensitive layer is formed in the laminated layer. The soft copper area of the circuit has the following advantages: it is easy to distinguish in the surface, and can avoid the deterioration of the photosensitive film. 115 (Please read the back note and then fill out this page) ^ · 1 nnn ϋ · 1 n^OJ* I · III 1 I ▲ This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

1299043 A8 B8 C8 D81299043 A8 B8 C8 D8 六 、申請專利範圍 m 讀 4 I 明 :索 # 1、一種感光性樹脂組成物，其必須成份爲（A)沸點 120°C以下的溶劑中可溶之可溶性聚醯亞胺，（B)l分子中 具有1個以上芳香環、2個以上雙鍵之化合物； 該(A)成分之可溶性聚醯亞胺，至少是使用具有1〜6個 芳香環之酸酐或脂環式酸二酐、及/或具有1〜6個二胺而製 得；且包含通式（1) Ν——R1 ASixth, the scope of application for patents m Read 4 I Ming: Suo #1, a photosensitive resin composition, the necessary components are (A) soluble soluble polyimine in a solvent having a boiling point of 120 ° C or less, (B) l a compound having one or more aromatic rings and two or more double bonds in the molecule; the soluble polyimine of the component (A), at least an acid anhydride having an aromatic ring of 1 to 6 or an alicyclic acid dianhydride, and / or having 1 to 6 diamines; and comprising the formula (1) Ν - R1 A η 式⑴ c請先閲讀背面之注意事項再塡寫本頁) k f % (式中R2爲4價有機基，R3爲2價有機基，R1爲3價有機 基，R4爲擇自羧基、羥基或群(I) 一C 一 II 0 °Τη R5 〇η (1) c Please read the notes on the back and write this page again) kf % (wherein R2 is a tetravalent organic group, R3 is a divalent organic group, R1 is a trivalent organic group, and R4 is a carboxyl group or a hydroxyl group. Or group (I)-C-II 0 °Τη R5 〇 Η R5 一0—C—R5 、π: 一 9一 0Η R5 - 0 - C - R5, π: a 9 - 0 R5 η2οη 0R5 η2οη 0 Η R5 國國家標準(CNS)Α4規格(210 X 297公釐) 1 之聚醯亞胺； 2 3 (式中R5爲具有擇自環氧基、碳-碳三鍵、碳-碳雙鍵所 構成群中之至少一種以上之1價有機基)之有機基)所代表 4 又該組成物係含有（A)成分1〇〇重量份、（B)成分 5 1〜200重量份。 1299043 A8 B8 C8 D8 *申請專利挑圍 2、一種感光性樹脂組成物，其必須成份爲（A)沸點 120°C以下的溶劑中可溶之可溶性聚醯亞胺，（B)l分子中 具有1個以上芳香環、2個以上雙鍵之化合物，（C)光反應 起始劑及/或增感劑； 該(A)成分之可ί谷性聚釀亞胺，至少是使用具有1〜6個 芳香環之酸酐或脂環式酸二酐、及/或具有丨〜6個二胺而製 得；且包含通式（1) ΝΗ R5 National Standard (CNS) Α 4 specification (210 X 297 mm) 1 Polyimine; 2 3 (wherein R5 is selected from the group consisting of an epoxy group, a carbon-carbon triple bond, and a carbon-carbon double bond. The organic group represented by at least one or more monovalent organic groups in the group is represented by 4 parts by weight of the component (A) and 5 to 200 parts by weight of the component (B). 1299043 A8 B8 C8 D8 * Patent application 2, a photosensitive resin composition, which must have a composition of (A) a soluble polyimine soluble in a solvent having a boiling point of 120 ° C or less, and (B) 1 molecule a compound having one or more aromatic rings, two or more double bonds, (C) a photoreaction initiator and/or a sensitizer; and the (A) component of the gluten-based styrene, having at least 1 to 6 An aromatic ring anhydride or an alicyclic acid dianhydride, and/or having 丨~6 diamines; and comprising the general formula (1) Ν Rc π 式Ο (式中R1爲4價有機基，R2爲2價有機基，R3爲3價有機 基，R4爲擇自羧基、羥基或群(I) Ϊ〇"ΪΗ R5 ΟRc π Formula Ο (wherein R1 is a tetravalent organic group, R2 is a divalent organic group, R3 is a trivalent organic group, and R4 is a carboxyl group, a hydroxyl group or a group (I) Ϊ〇"ΪΗ R5 Ο Η R5 Ο 一 C一 FT (請先閲讀背面之注意事項再填寫本頁) 、1Tr ·1 -C一 〇 II ΟΗ R5 Ο A C-FT (please read the notes on the back and fill out this page), 1Tr ·1 -C一 〇 II Ο R5 η2οη οR5 η2οη ο Η R5 (I ) (式中R5爲具有擇自環氧基、碳—碳三鍵、碳-碳雙鍵所 構成群中之至少一種以上之1價有機基)之有機基)所代表 之聚醯亞胺； 又該組成物係含有（Α)成分1〇〇重量份、（Β)成分 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1299043 B8 C8 D8 六、申請專利範圍 1〜200重量份、（c)成分0.1〜50重量份。 3、如申請專利範圍第1或第2項之感光性樹脂組成物 ’其中前述(A)成份，係包含通式（1)Η R5 (I ) (wherein R 5 is an organic group having at least one or more monovalent organic groups selected from the group consisting of an epoxy group, a carbon-carbon triple bond, and a carbon-carbon double bond)醯 imine; this composition contains (Α) component 1 〇〇 by weight, (Β) component of this paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 B8 C8 D8 VI. Application The patent range is 1 to 200 parts by weight, and the component (c) is 0.1 to 50 parts by weight. 3. The photosensitive resin composition of claim 1 or 2 wherein the component (A) comprises the formula (1) (式中R1爲4價有機基，R2爲2價有機基，R3爲3價有機 基，R4爲羧基或羥基)所代表之聚醯亞胺。 4、 如申請專利範圍第3項之感光性樹脂組成物，其中 前述通式（1)所代表之聚醯亞胺，係包含COOH當量 200〜3000之可溶性聚醯亞胺。 5、 如申請專利範圍第1或第2項之感光性樹脂組成 物，其中前述通式（1)所代表之聚醯亞胺，係使用二胺（包 含分子內具有2個以上COOH基之二胺)而製得。 6、 如申請專利範圍第1或第2項之感光性樹脂組成物 ，其中前述(A)成份，係使用具有矽氧烷鍵之二胺而得之聚 醯亞胺。 7、如申請專利範圍第6項之感光性樹脂組成物，其中 前述可溶性聚醯亞胺，係包含通式(2) (請先閲讀背面之注意事項再填寫本頁) 訂：(wherein R1 is a tetravalent organic group, R2 is a divalent organic group, R3 is a trivalent organic group, and R4 is a carboxyl group or a hydroxyl group). 4. The photosensitive resin composition of claim 3, wherein the polyimine represented by the above formula (1) is a soluble polyimine having a COOH equivalent of 200 to 3,000. 5. The photosensitive resin composition of claim 1 or 2, wherein the polyimine represented by the above formula (1) is a diamine (including two or more COOH groups in the molecule) Made with amines). 6. The photosensitive resin composition according to claim 1 or 2, wherein the component (A) is a polyimine obtained by using a diamine having a siloxane coupling. 7. The photosensitive resin composition of claim 6, wherein the soluble polyimine comprises a formula (2) (please read the back of the back sheet and fill out this page). 式（2) L本紙張尺度適用中國國冢標準(CNS)A4規格(210 X 297公釐) 1299043 A8B8C8D8 申請專利範圍 (式中R6爲4價有機基，R7爲2價有機基，R8爲1價有機 基，X爲1以上的整數，y爲1以上的整數，z爲1〜40的 整數，11爲1〜5的整數）。 8、如申請專利範圍第7項之感光性樹脂組成物，其中 前述可溶性聚醯亞胺，係包含在全部二胺中，使用5〜95莫 耳％之擇自通式(3) / (CH2) ^Si -μ —Si 4〇 —^2)—NH2nR8A H "Formula (2) L This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 A8B8C8D8 Patent application range (where R6 is a tetravalent organic group, R7 is a divalent organic group, and R8 is 1 The valence organic group, X is an integer of 1 or more, y is an integer of 1 or more, z is an integer of 1 to 40, and 11 is an integer of 1 to 5). 8. The photosensitive resin composition of claim 7, wherein the soluble polyimine is contained in all diamines, and 5 to 95 mol% is selected from the formula (3) / (CH2) ) ^Si -μ -Si 4〇—^2)—NH2nR8A H " ΊΠ 式（3) (式中R8爲碳數1〜12之烷基、苯基、甲氧基，z爲1〜40之 整數，η分別爲獨立的1〜20之整數)之矽氧烷二胺而得之 聚醯亞胺。 9、如申請專利範圍第1或第2項之感光性樹脂組成物 ，其中前述可溶性聚醯亞胺，係包含在全部二胺中，使用 5〜99莫耳％之擇自通式(4)(R1〇)mΊΠ Formula (3) wherein R8 is an alkyl group having 1 to 12 carbon atoms, a phenyl group, a methoxy group, z is an integer of 1 to 40, and η is an independent integer of 1 to 20, respectively. A polyimine obtained from an amine. 9. The photosensitive resin composition according to claim 1 or 2, wherein the soluble polyimine is contained in all diamines, and 5 to 99 mol% is selected from the general formula (4). (R1〇)m nh2 (R1〇)m 式（4) (請先閲讀背面之注意事項再塡寫本頁) (式中R9爲-0 -CH〗-、 CO -C(CF3)2- C(CH3)2 coo S02-，Rl()爲氫、鹵素、甲 氧基 OH、- COOH、Cl - C5 之烷基，I 爲 0 2、3 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1299043 申請專利範圍 A8 B8 C8 D8 、4，m爲0、1、2、3)之二胺而得之聚醯亞胺。 10、如申請專利範圍第1項或第2項之感光性樹脂組 成物，其中前述可溶性聚醯亞胺，係包含在全部酸二酐中 ，使用10〜100莫耳％之擇自通式(5)、通式(6) 〇 Ο V II ORNh2 (R1〇)m Equation (4) (Please read the note on the back and write this page first) (where R9 is -0 -CH) -, CO -C(CF3)2- C(CH3)2 coo S02-, Rl() is hydrogen, halogen, methoxy OH, -COOH, Cl - C5 alkyl, I is 0 2,3 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 Patented A8 B8 C8 D8, 4, m is a polyamine of 0, 1, 2, 3) diamine. 10. The photosensitive resin composition according to claim 1 or 2, wherein the soluble polyimine is contained in all acid dianhydrides, and 10 to 100 mol% is selected from the formula ( 5), general formula (6) 〇Ο V II OR -S〇2 _ (V) (式中R11爲-、-CO (VI) ο -、- c(cf3)2 (請先閲讀背面之注意事項再填寫本頁)-S〇2 _ (V) (where R11 is -, -CO (VI) ο -, - c(cf3)2 (please read the notes on the back and fill out this page) C(CH3)2-，R12爲2價有機基)之酸二酐而得之聚醯亞 胺 -ία 11、如申請專利範圍第10項之感光性樹脂組成物， 其中前述可溶性聚醯亞胺，係包含在全部酸二酐中，使用 5〜95莫耳％之通式(6)中R12爲擇自群(II) % 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐) A8 B8 C8 D8 1299043 申請專利範圍 A ί^ϊΐ )5)〇, -〇-，〇-卜 〇τ ’ CF3 ◦-〇-，^〇’ Ό™Γ TAnd a photosensitive resin composition of the invention, wherein the soluble polyimine is as described in claim 10, wherein the photosensitive polyacetal is obtained from the acid dianhydride of the divalent organic group. It is contained in all acid dianhydrides, using 5~95 mol% of formula (6), R12 is selected from group (II) %. This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 PCT) A8 B8 C8 D8 1299043 Patent Application A ί^ϊΐ ) 5) 〇, -〇-,〇-卜〇τ 'CF3 ◦-〇-,^〇' ΌTMΓ T TT (請先閲讀背面之注意事項再填寫本頁) -c- Τ -〇-? 〒Η3Χ[(Please read the notes on the back and fill out this page) -c- Τ -〇-? 〒Η3Χ[ rs-0 ν°Οΐί(^°〇· ^ -〇-〇， ▲ ▲ Ί Ί 阼〇2 CPH2p 八- 八 0 八 (P爲1〜20之整數)Rs-0 ν°Οΐί(^°〇· ^ -〇-〇, ▲ ▲ Ί Ί 阼〇2 CPH2p 八-八八八 (P is an integer from 1 to 20) 群（II)Group (II) (Τ代表H、F、Q、Br、I、MeO-、碳數1〜20之烷基) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1299043 截 C8 D8 六、申請專利範圍 之酸二酐而得之聚醯亞胺。 12、 如申請專利範圍第1〇項之感光性樹脂組成物， 其中前述酸二酐，係通式(7)(Τ represents H, F, Q, Br, I, MeO-, alkyl with 1 to 20 carbon atoms) This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1299043 Cut C8 D8 VI. Polyimine obtained from the patented range of acid dianhydride. 12. The photosensitive resin composition of claim 1, wherein the acid dianhydride is a formula (7) (請先閱讀背面之注意事項再填寫本頁) oW： (VII) (式中，R13 爲―〇 —、— co -、-、- c(cf3)2 -、-C(CH3)2 -、- coo -、- S〇2 -）。 13、 如申請專利範圍第1或第2項之感光性樹脂組成 物，其中前述(A)可溶性聚醯亞胺之Tg爲100〜300°C。 14、 如申請專利範圍第1或第2項之感光性樹脂組成 物，其硬化後的彈性模數爲1〇〇〜3000MPa。 15、 如申請專利範圍第1或第2項之感光性樹脂組成 物，其硬化後的熱分解開始溫度爲300°C以上。 16、 如申請專利範圍第1或第2項之感光性樹脂組成 物，其硬化溫度爲200°C以下。 17 '如申請專利範圍第1或第2項之感光性樹脂組成 物，其硬化後之焊接耐熱性(3〇〇°C)爲3分以上。 18、 如申請專利範圍第1或第2項之感光性樹脂組成 物，其硬化後之熱膨脹係數爲20ppm〜500ppm。 19、 如申請專利範圍第2項之感光性樹脂組成物，其 中前述光反應起始劑，係藉由g線或i線之至少一方來產 生游離基。 20、 如申請專利範圍第1或第2項之感光性樹脂組成 7 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1299043 C8 D8 六、申請專利範圍 物，其硬化後的Tg爲50°c〜30(TC。 21、 如申請專利範圍第1或第2項之感光性樹脂組成 物，其中前述(B)成份爲具有碳-碳雙鍵之共聚單體。 22、 如申請專利範圍21項之感光性樹脂組成物，其 中前述(B)成份，係多官能（甲基)丙烯酸系化合物及/或其類 似體之多官能（甲基)丙烯酸系化合物類。 23、 如申請專利範圍第22項之感光性樹脂組成物， 其中前述多官能（甲基)丙烯酸系化合物類，係2官能，且 具有（-Ο - CH2CH2 -)的反覆單位。 24、 如申請專利範圍第23項之感光性樹脂組成物， 其中前述(B)成份，係擇自雙酚F EO變性二丙烯酸酯、雙 酚A EO變性二丙烯酸酯、雙酚S EO變性二丙烯酸酯中之 至少一種二丙烯酸酯。 25、 一種感光性膜，係由申請專利範圍第1或第2項 之感光性樹脂組成物所構成，且能在150°C以下的溫度下 進行積層。 26、 如申請專利範圍第25項之感光性膜，其B階狀 態的膜之可壓接溫度爲20°C〜150°C。 27、 一種感光性膜之製造方法，係包含，將申請專利 範圍第1或第2項之感光性樹脂組成物的有機溶劑溶液塗 佈於底膜上並進行乾燥之製程。 28、 一種防焊劑，係至少由申請專利範圍第1或第2 項之感光性樹脂組成物所構成。 8 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)(Please read the notes on the back and fill out this page) oW: (VII) (where R13 is 〇—, — co —, —, — c(cf3)2 -, -C(CH3)2 -, - coo -, - S〇2 -). 13. The photosensitive resin composition according to claim 1 or 2, wherein the (A) soluble polyimine has a Tg of from 100 to 300 °C. 14. The photosensitive resin composition of claim 1 or 2, wherein the elastic modulus after curing is from 1 3000 to 3,000 MPa. 15. The photosensitive resin composition of claim 1 or 2, wherein the thermal decomposition starting temperature after curing is 300 ° C or higher. 16. A photosensitive resin composition according to claim 1 or 2, wherein the curing temperature is 200 ° C or lower. 17 ' As in the photosensitive resin composition of the first or second aspect of the patent application, the solder heat resistance (3 ° C) after curing is 3 minutes or more. 18. The photosensitive resin composition of claim 1 or 2, which has a thermal expansion coefficient after hardening of 20 ppm to 500 ppm. 19. The photosensitive resin composition of claim 2, wherein the photoreaction initiator produces a radical by at least one of a g-line or an i-line. 20. If the photosensitive resin composition of the patent scope 1 or 2 is applied, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1299043 C8 D8 VI. Application for patent scope, after hardening The photosensitive resin composition of the first or second aspect of the invention, wherein the component (B) is a comonomer having a carbon-carbon double bond. The photosensitive resin composition of claim 21, wherein the component (B) is a polyfunctional (meth)acrylic compound of a polyfunctional (meth)acrylic compound and/or the like. The photosensitive resin composition of claim 22, wherein the polyfunctional (meth)acrylic compound is bifunctional and has a repeating unit of (-Ο-CH2CH2-). The photosensitive resin composition according to Item 23, wherein the component (B) is at least one selected from the group consisting of bisphenol F EO modified diacrylate, bisphenol A EO modified diacrylate, and bisphenol S EO modified diacrylate. Diacrylate. 25, a kind The photosensitive film is composed of the photosensitive resin composition of the first or second aspect of the patent application, and can be laminated at a temperature of 150 ° C or lower. 26. The photosensitive film of claim 25 The pressure-bondable temperature of the film in the B-stage state is 20 ° C to 150 ° C. 27. A method for producing a photosensitive film, comprising the photosensitive resin composition of claim 1 or 2 The organic solvent solution is coated on the base film and dried. 28. A solder resist consisting of at least the photosensitive resin composition of claim 1 or 2. 8 This paper size applies to China Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back and fill out this page) 1299043 I D8 六、申請專利範園 ........................…… (請先閱讀背面之注意事項再填寫本頁) 29、 一種防焊劑，係至少由申請專利範圍第1或第2 項之感光性樹脂組成物所構成，在未曝光時爲可溶，曝光 後因產生聚合反應而變得不溶於鹼性水溶液中。 30、 一種被覆膜，係至少由申請專利範圍第1或第2 項之感光性樹脂組成物所構成，其可壓接溫度爲20°C〜150 V。 31、 一種被覆膜，係由申請專利範圍第1或第2項之 感光性樹脂組成物所構成，在未曝光時爲可溶，曝光後因 產生聚合反應而變得不溶於鹼性水溶液中。 32、 如申請專利範圍第30或31項之被覆膜，其具有 線寬/線距寬= 100/100//m以下之解析度。 33、 一種被覆膜，係將底膜、申請專利範圍第29項 之感光性膜、保護膜依序積層而成之三層構造片； 該保護膜係由（a)聚乙烯和乙烯-乙烯醇樹脂的共聚物 膜、及(b)聚乙烯膜之積層膜所組成，且（a)共聚物膜側係形 成該感光性膜接合面。 34、 如申請專利範圍第33項之被覆膜，其中前述感 光性膜厚爲5〜75//m。 35、 如申請專利範圍第33項之被覆膜，其中，構成 保護膜之⑻共聚物膜厚爲2〜50//m，（b)聚乙烯膜厚爲 10〜50"m〇 36、 如申請專利範圍第33項之被覆膜，其中前述底 膜爲聚對苯二甲酸乙二醇酯膜。 37、 如申請專利範圍第30:或33項之被覆膜，係用於 9 本紙張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) 1299043 A8 B8 C8 D8 六、申請專利範圍 軟性印刷配線板。 38、 如申請專利範圍第30或33項之被覆膜，係用於 硬碟用懸吊具。 39、 如申請專利範圍第30或33項之被覆膜，係用於 硬碟記憶裝置之磁頭部分。 40、 一種印刷配線板，係積層申請專利範圍第30或 33項之被覆膜而構成。 (請先閱讀背面之注意事項再塡寫本頁) 、?Tr 缘屬 10 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)1299043 I D8 VI. Applying for a patent garden........................ (Please read the notes on the back and fill out this page) 29. A solder resist is composed of at least a photosensitive resin composition of the first or second aspect of the patent application, is soluble when not exposed, and is insoluble in an alkaline aqueous solution due to a polymerization reaction after exposure. A coating film comprising at least a photosensitive resin composition according to the first or second aspect of the patent application, wherein the pressure-bondable temperature is from 20 ° C to 150 V. 31. A coating film comprising the photosensitive resin composition of claim 1 or 2, which is soluble when not exposed, and which is insoluble in an alkaline aqueous solution due to polymerization reaction after exposure. . 32. The coated film of claim 30 or 31, which has a line width/line width = 100/100//m or less. 33. A coated film comprising a base film, a photosensitive film of claim 29, and a protective film sequentially laminated; the protective film is composed of (a) polyethylene and ethylene-ethylene The copolymer film of the alcohol resin and (b) the laminated film of the polyethylene film are formed, and (a) the copolymer film side forms the photosensitive film joint surface. 34. The coated film of claim 33, wherein the photosensitive film thickness is 5 to 75/m. 35. The coating film of claim 33, wherein the (8) copolymer film forming the protective film has a thickness of 2 to 50/m, and (b) the polyethylene film has a thickness of 10 to 50 " m〇36, such as The coating film of claim 33, wherein the base film is a polyethylene terephthalate film. 37. If the coating film of patent application No. 30: or 33 is applied to 9 paper scales, the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 1299043 A8 B8 C8 D8 is applied. Flexible printed wiring board. 38. The coated film of claim 30 or 33 is used for a suspension for hard discs. 39. The coated film of claim 30 or 33 is used for the magnetic head portion of a hard disk memory device. 40. A printed wiring board comprising a coating film of claim 30 or 33. (Please read the precautions on the back and write this page first), Tr Dependence 10 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)
TW090125377A 2000-10-16 2001-10-15 TWI299043B (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2000315946A JP2002121207A (en) 2000-10-16 2000-10-16 Composition, photosensitive composition using the same, and cover lay
JP2000356492A JP2002162740A (en) 2000-11-22 2000-11-22 Composition for photosensitive cover lay film and photosensitive cover lay film
JP2000360199A JP2002164642A (en) 2000-11-27 2000-11-27 Photosensitive cover lay film
JP2000400072 2000-12-28
JP2001078201A JP4981215B2 (en) 2001-03-19 2001-03-19 Photosensitive resin composition and photosensitive dry film resist using the same
JP2001163470A JP2002258474A (en) 2000-12-28 2001-05-30 Photosensitive dry film resist

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WO2004092838A1 (en) * 2003-04-15 2004-10-28 Kaneka Corporation Photosensitive resin composition capable of being developed with aqueous developer and photosensitive dry film resist, and use thereof
WO2004109403A1 (en) * 2003-06-02 2004-12-16 Toray Industries, Inc. Photosensitive resin composition, and electronic component and display using same
KR101139091B1 (en) * 2004-09-30 2012-05-02 신에쓰 가가꾸 고교 가부시끼가이샤 Polyimide having alcoholic hydroxyl group and process for preparing the same
CN101831174B (en) 2009-03-10 2014-04-09 三星电子株式会社 Cross-linked material of metal containing polyamic acid, cross-linked material of metal containing polyimide, manufacturing method thereof, and polyimide film using same
KR102258263B1 (en) * 2019-05-16 2021-05-28 마이크로코즘 테크놀리지(수 조우) 씨오., 엘티디 Photosensitive soluble polyimide resin composition and protective film using the same

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JPH05339373A (en) * 1992-06-11 1993-12-21 Hitachi Chem Co Ltd Heat-resistant photosensitive material
JP3721768B2 (en) * 1997-01-24 2005-11-30 宇部興産株式会社 Photosensitive polyimide siloxane composition and insulating film
JPH1152572A (en) * 1997-08-08 1999-02-26 Fujitsu Ltd Photosensitive resin composition and pattern forming method by using the same
JP2002003516A (en) * 2000-06-26 2002-01-09 Kanegafuchi Chem Ind Co Ltd Composition and photosensitive composition as well as cover layer film using the same
JP2002003715A (en) * 2000-06-26 2002-01-09 Kanegafuchi Chem Ind Co Ltd Composition, photosensitive composition and cover lay film using the same

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