TW201006867A - Polyimide precursor, photosensitive polyimide precursor composition, photosensitive dry film, and flexible printed circuit board using those materials - Google Patents

Polyimide precursor, photosensitive polyimide precursor composition, photosensitive dry film, and flexible printed circuit board using those materials Download PDF

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TW201006867A
TW201006867A TW98113793A TW98113793A TW201006867A TW 201006867 A TW201006867 A TW 201006867A TW 98113793 A TW98113793 A TW 98113793A TW 98113793 A TW98113793 A TW 98113793A TW 201006867 A TW201006867 A TW 201006867A
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photosensitive
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polyimine precursor
precursor
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TWI384015B (en
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Kuon Miyazaki
Takashi Hayakawa
Akihiro Kato
Hideaki Takahashi
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Asahi Kasei E Materials Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046Polyimides containing oxygen in the form of ether bonds in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16Polyester-imides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions 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
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/022Quinonediazides
    • G03F7/023Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0393Flexible materials
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/28Applying non-metallic protective coatings
    • H05K3/285Permanent coating compositions
    • H05K3/287Photosensitive compositions

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  • Chemical & Material Sciences (AREA)
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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)
  • Engineering & Computer Science (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)

Abstract

Disclosed is a polyimide precursor: which enables the production of such a photosensitive dry film that has no tackiness, causes no cracking in a photosensitive layer thereof when folded after removal of a solvent therefrom, and can achieve good lithography thereon; which can be applied to a FPC that causes less warpage after baking; and which can exhibit flame retardancy without the need of adding any halogen compound thereto. Also disclosed is a photosensitive polyimide precursor composition. Further disclosed is a photosensitive dry film. Still further disclosed is a flexible printed circuit board produced by using any one of the aforementioned materials. The polyimide precursor is characterized by comprising an acid dianhydride represented by general formula (1) [wherein X represents a bivalent organic group having a C3-30 alkylene group; and R1 represents a hydrogen atom, a C1-10 univalent alkyl group, an alkoxy group or a halogen group].

Description

201006867 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種聚醯亞胺前驅體、感光性聚醯亞胺前 驅體組合物、感光性乾式膜及使用其等之撓性印刷電路基 板。 【先前技術】 近年來,稱為撓性印刷基板(以下,亦稱為「FPC (Flexible201006867 VI. Description of the Invention: The present invention relates to a polyimide precursor, a photosensitive polyimide precursor composition, a photosensitive dry film, and a flexible printed circuit board using the same . [Prior Art] In recent years, it has been called a flexible printed circuit board (hereinafter, also referred to as "FPC (Flexible)

Printed Circuit,撓性印刷電路).」)之膜狀印刷基板趨於繁 β 榮。該基板形成於經配線加工之FCCL(Flexible CupperPrinted Circuit (Flexible Printed Circuit).") The film-shaped printed substrate tends to be versatile. The substrate is formed in a wire-processed FCCL (Flexible Cupper)

Clad Laminate,撓性覆銅板)上具備由聚醯亞胺膜等構成 之覆蓋層之結構,主要用於行動電話、筆記型電腦、數位 攝影機等設備。FPC即便彎折亦維持功能,因此成為對於 設備之小型化、輕量化而言必不可少之材料。尤其近年 來,由筆記型電腦所代表之電子設備向小型化、輕量化發 展,此種產品中採用FPC,藉此對相關設備之尺寸及重量 減少、產品成本之降低以及設計單純化等作出貢獻。Clad Laminate (flexible copper clad laminate) has a structure composed of a polyimide film or the like, and is mainly used for a mobile phone, a notebook computer, a digital camera, and the like. FPC maintains its function even when it is bent, so it is an indispensable material for miniaturization and weight reduction of equipment. In particular, in recent years, electronic devices represented by notebook computers have been developed to be smaller and lighter, and FPCs have been used in such products to contribute to reduction in size and weight of related devices, reduction in product cost, and design simplification. .

A 該FPC中具備之覆蓋層主要係藉由使用具備黏著劑之聚 醯亞胺膜等,加以貼合而形成。然而,由於FPC之微細 _ 化、薄膜化,而使貼合之位置精度產生問題。因此,開始 對可藉由照射紫外線等活性光線而僅對必需之部分進行高 精度微細加工之感光性覆蓋層進行開發。其中,乾式膜型 感光性覆蓋層呈現優異之尺寸精度,亦無需溶劑之乾燥步 驟,因此製造FPC時,可簡化製程,期待作為環境負荷低 之材料。 139901.doc 201006867 感光性覆蓋層材料之中’使用聚酿亞胺前驅體之感光性 盍層’自源自聚酿亞胺之耐f折性、耐熱性、電絕緣性 之觀點考慮,期待作為優異之覆蓋層。例如,於專利文獻 1中揭示有使用四艘酸二針及二胺之耐熱性黏著劑。又, j彳文獻2中揭不有使用聚酿亞胺前驅體之膜形成性感 先性耐熱樹脂組合物,於專利文獻3中揭示有包含聚酿胺 ,之感光性面塗材料。χ,於專利文獻4中揭示有包含特 定酸項之黏著膜。然而,於使用㈣亞胺前驅體之感光 性覆蓋層之情形時’會產生感光性乾式膜之黏性之問題, 或由於感光性乾式膜之形成所伴隨之去溶劑而使聚酿亞胺 前驅體之分子量下降’所獲得之感光性乾式膜弯折時導致 感光層破裂之問題。進而,由於聚醯亞胺前驅體之分子量 下降’故利用微影形成圖案時,於使用驗性水溶液之顯影 中產生顯影時間不穩定,圖案之膜厚變薄,圖案形狀變形 等問題。X,自聚醯亞胺前驅體轉換成聚醯亞胺之步驟 中,由於去溶劑、或聚醯亞胺前驅體之醯亞胺化所伴隨之 閉環反應引起的應力,會於FPC中產生翹曲。若Fpc中產 生翹曲,則產生FCCL與覆蓋層之黏著性不良、或具備Fpc 之電子設備之驅動功率變高等問題。因此,尋求改善於銅 配線上具備覆蓋層之FPC之勉曲。 此外,尋求覆蓋層在由UL規格之VTM試驗所代表之阻 燃性試驗中呈現阻燃性。以呈現阻燃性為目的而於原來之 覆蓋層中調配鹵素化合物。然而,自環境保護之觀點戈生 物毒性之觀點考慮,希望以非函素呈現阻燃性。 139901.doc 201006867 [專利文獻i]日本專利特開2004_269622號公報 [專利文獻2]曰本專利特開平〇4_1845〇號公報 [專利文獻3]曰本專利特開平〇5 158237號公報 [專利文獻4]曰本專利特開平ι〇_33〇723號公報 【發明内容】 [發明所欲解決之問題] 本發明係鑒於上述方面開發而成者,其目的在於提供一 種在用於FPC之情形時’烘烤後之Fpc之麵曲少且變折性 優異之聚醯亞胺前驅體、感光性聚醯亞胺前驅體組合物、 感光性乾式膜及使用其等之撓性印刷電路基板。 [解決問題之技術手段] 本發明之聚醯亞胺前驅體之特徵在於,包含由下述通式 (1)所表示之酸二酐。 [化1]A The coating layer provided in the FPC is mainly formed by bonding using a polyimide film having an adhesive or the like. However, due to the fineness and thinning of the FPC, the positional accuracy of the bonding is problematic. Therefore, development of a photosensitive coating layer capable of performing high-precision microfabrication only on a necessary portion by irradiation with active light such as ultraviolet rays has begun. Among them, the dry film type photosensitive cover layer exhibits excellent dimensional accuracy and does not require a solvent drying step. Therefore, when manufacturing an FPC, the process can be simplified, and it is expected to be a material having a low environmental load. 139901.doc 201006867 Among the photosensitive coating materials, 'the photosensitive ruthenium layer using the polyimide intermediate precursor' is expected to be derived from the viewpoint of resistance to f-resistance, heat resistance and electrical insulation of the styrene. Excellent cover. For example, Patent Document 1 discloses a heat-resistant adhesive using four acid two needles and a diamine. Further, JP 2 discloses that a film of a thermoplastic precursor resin is formed by using a film of a polyimide intermediate precursor, and Patent Document 3 discloses a photosensitive top coat material comprising polyamine.专利, Patent Document 4 discloses an adhesive film containing a specific acid term. However, in the case of using the photosensitive coating of the (iv) imine precursor, the problem of the stickiness of the photosensitive dry film may occur, or the solvent may be used due to the solvent removal accompanying the formation of the photosensitive dry film. The decrease in the molecular weight of the body is caused by the problem that the photosensitive dry film obtained is bent when the photosensitive dry film is bent. Further, since the molecular weight of the polyimide precursor is lowered, when the pattern is formed by the lithography, the development time is unstable in the development using the aqueous test solution, the film thickness of the pattern is reduced, and the pattern shape is deformed. X, in the step of converting the polyimine precursor to polyimine, the stress caused by the ring closure reaction accompanying the desolvation or the sulfhydryl imidization of the polyimide precursor will cause warping in the FPC. song. If warpage occurs in the Fpc, there is a problem that the adhesion between the FCCL and the cover layer is poor, or the driving power of the electronic device having the Fpc is high. Therefore, it is sought to improve the distortion of the FPC having a cover layer on the copper wiring. In addition, the cover layer was sought to exhibit flame retardancy in the flame retardancy test represented by the UL specification VTM test. The halogen compound is formulated in the original cover layer for the purpose of exhibiting flame retardancy. However, from the viewpoint of environmental protection, it is desirable to exhibit flame retardancy by an element. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The present invention has been developed in view of the above aspects, and an object thereof is to provide a case for use in an FPC. A polyimide polyimide precursor, a photosensitive polyimide precursor precursor composition, a photosensitive dry film, and a flexible printed circuit board using the same, which have a small surface curvature and excellent folding property after FPC. [Technical means for solving the problem] The polyimine precursor of the present invention is characterized by comprising an acid dianhydride represented by the following formula (1). [Chemical 1]

(X係具有碳數為3至30之伸烷基之2價有機基.心表示氫原 子、碳數為1至10之1價烷基、烷氧基、或鹵基) 本發明之聚醯亞胺前驅體中,較好的是包含由下述通式 (2)所表示之二胺。 139901.doc 201006867 [化2](X is a divalent organic group having an alkylene group having a carbon number of 3 to 30. The core represents a hydrogen atom, a monovalent alkyl group having a carbon number of 1 to 10, an alkoxy group, or a halogen group) Among the imine precursors, a diamine represented by the following formula (2) is preferred. 139901.doc 201006867 [Chemical 2]

(Y係具有碳數為2至20之伸烷基之2價有機基。R2表示氫原 子、碳數為1至10之1價烷基、烷氧基、或鹵基) 本發明之聚醯亞胺前驅體中,較好的是包含由下述通式 (3)所表示之酸二酐。 [化3](Y is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. R2 represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a halogen group) Among the imine precursors, it is preferred to contain an acid dianhydride represented by the following formula (3). [Chemical 3]

(a表示1至20之整數。b表示3至30之整數。R3表示氫原子 或碳數為1至10之1價烷基) 本發明之聚醯亞胺前驅體_,較好的是包含由下述通式 (4)所表示之二胺。 [化4](a represents an integer of 1 to 20. b represents an integer of 3 to 30. R3 represents a hydrogen atom or a monovalent alkyl group having a carbon number of 1 to 10) The polyimine precursor of the present invention _, preferably contains A diamine represented by the following formula (4). [Chemical 4]

(4) (Z係碳數為2至20之伸烷基。R4表示氫原子、碳數為1至1〇 139901.doc 201006867 之1價烧基、院氧基、或鹵基。c表示2至3〇之整數) 本發明之聚醯亞胺前驅體中’較好的是包含由下述通式 (3)所表示之酸二酐。 [化5](4) (Z series is a 2 to 20 alkylene group. R4 represents a hydrogen atom, a carbon number of 1 to 1 〇 139901.doc 201006867 of a monovalent alkyl group, a hospitaloxy group, or a halogen group. c represents 2 In the polyimine precursor of the present invention, it is preferred to include an acid dianhydride represented by the following formula (3). [Chemical 5]

L。細 HiL. Fine Hi

(a表示1至15之整數。b表示5至20之整數。&表示氫原子 或碳數為1至10之1價烷基) 本發明之聚醯亞胺前驅體中,較好的是由上述通式(4) 所表示之二胺在所有二胺成分中為25莫耳%至75莫耳%。 本發明之感光性聚醯亞胺前驅體組合物之特徵在於,含 有1〇〇質量份之上述聚醯亞胺前驅體、及5〜3〇質量份之感 光劑。 本發明之感光性聚醯亞胺前驅體組合物中,較好的是上 述感光劑包含醒二疊氮結構。 本發明之感光性聚醯亞胺前驅體組合物中,較好的是包 含具有盼性經基之化合物作為溶解抑制劑。 本發明之感光性乾式膜之特徵在於,將如上述感光性聚 醯亞胺前驅體組合物塗佈於支持膜上,進行去溶劑,繼而 積層覆蓋膜。 本發明之撓性印刷電路基板之特徵在於,其係使用上述 139901.doc 201006867 感光性乾式膜而形成。 本發明之聚醯亞胺前驅體之特徵在於,清漆之重量平均 分子量(Mwl)與120°C以下之去溶劑後之重量平均分子量 (Mw2)之間的比(Mw2/Mwl)為0.7以上。 [發明之效果](a represents an integer of 1 to 15. b represents an integer of 5 to 20. & represents a hydrogen atom or a monovalent alkyl group having a carbon number of 1 to 10) Among the polyamidene precursors of the present invention, preferably The diamine represented by the above formula (4) is from 25 mol% to 75 mol% in all the diamine components. The photosensitive polyimide intermediate composition of the present invention is characterized in that it contains 1 part by mass of the above polyimine precursor and 5 to 3 parts by mass of a light-sensitive agent. In the photosensitive polyimine precursor composition of the present invention, it is preferred that the sensitizer contains a awake azide structure. In the photosensitive polyimine precursor composition of the present invention, a compound having a desired trans group is preferably used as a dissolution inhibitor. The photosensitive dry film of the present invention is characterized in that the photosensitive polyimide precursor composition is applied onto a support film, and a solvent is removed, followed by lamination of the film. The flexible printed circuit board of the present invention is characterized in that it is formed using the above-mentioned 139901.doc 201006867 photosensitive dry film. The polyimine precursor of the present invention is characterized in that the ratio (Mw2/Mwl) between the weight average molecular weight (Mwl) of the varnish and the weight average molecular weight (Mw2) after desolvation of 120 ° C or less is 0.7 or more. [Effects of the Invention]

本發明之感光性聚醯亞胺前驅體組合物係藉由使用由具 有特定結構之酸二酐獲得之聚醯亞胺前驅體,而實現用於 FPC時,烘烤後之FPC之翹曲少且彎折性優異之效果。 【實施方式】 以下,對本發明加以具體之說明。 (A)聚醯亞胺前驅體 聚酿亞胺前驅體之單體係使用酸二肝、二胺。已知聚 亞胺前驅體由於伴隨加熱之去溶劑*分子量下降,自減 分子量之下降之觀點考慮,用於聚醯亞胺前驅體之酸二 係使用由下述通式(1) .执 1 )所表不之酸二酐。若為由該結構所 不之酸一酐,則可|The photosensitive polyimide intermediate precursor composition of the present invention achieves a low warpage of FPC after baking by using a polyimide intermediate precursor obtained from an acid dianhydride having a specific structure. And the effect of excellent bending property. [Embodiment] Hereinafter, the present invention will be specifically described. (A) Polyimine precursor The single system of the polyamidene precursor uses acid dihepatic and diamine. It is known that the polyimine precursor is reduced in molecular weight due to the decrease in the molecular weight of the desolvent* accompanying heating, and the acid secondary system used for the polyimide precursor is used by the following formula (1). ) is not the acid dianhydride. If it is not the acid anhydride of the structure, then |

^ 獨使用’亦可將2種以上组合使用 精由抑制去溶劑步驟 使用 中之为子量下降,可防止製成咸伞 乾式膜時之彎折時的 I成4先 的斷裂,可提高彎折性。 [化6]^Individual use' can also be used in combination with two or more types. The use of the anti-solvent step in the use of the anti-solvent step can reduce the amount of I to 4 in the bending of the dry film of the salted umbrella, and can improve the bending. Folding. [Chemical 6]

139901.doc (1) 201006867 (X係具有碳數為3至30之伸烷基之2價有機基。心表示氫原 子、碳數為1至10之1價烷基、烷氧基、或鹵基) 該等之中’自抑制去溶劑步驟中之分子量下降之觀點考 慮,較好的是使用由下述通式(3)所表示之酸二酐。 [化7]139901.doc (1) 201006867 (X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms. The core represents a hydrogen atom, a monovalent alkyl group having a carbon number of 1 to 10, an alkoxy group, or a halogen group. In the above, from the viewpoint of the decrease in the molecular weight in the self-inhibiting solvent removal step, it is preferred to use an acid dianhydride represented by the following formula (3). [Chemistry 7]

❹ ❿ P (3) j 0 (a表7F1至20之整數。b表示3至3〇之整數。&表示氮原子 或碳數為1至10之1價烧基) 由上述通式(3)所表示之駿二肝中,a較好的是 較㈣是5Λ20。具體而言可列舉:丁二醇-雙偏苯三甲酸 =一酵-雙偏笨三甲酸酐酯、庚二醇·雙偏苯三曱酸 =肝Γ醇雙偏苯三甲酸㈣、二代二醇·雙偏苯三 雔偏t丙—醇·雙偏笨三甲酸酐醋、聚1,4· 丁二醇· 曼酐S曰專。該等化合物可單獨使 種以上組合使用。 』J將2 本發月之聚醯亞胺前驅體中 使用其他酸二針。星_而^ 江曼—軒之外,亦可 舉:均苯… 作為芳香族四竣酸,可列 I I、3,3,,4,4,·聯苯四甲酸二肝、 2,3,3,4'-聯苯四甲酸-w m 酸一酐、2,2,,3,3,·聯苯四甲酸-肝 3,3,,4,4、二笨曱綱 甲酸一酐、 四甲酸-野、2,2,,3,3、二笨 139901.doc 201006867 二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧 基苯基)丙烷二酐、1,1_雙(3,4-二羧基苯基)乙烷二酐、1,1-雙(2,3-二羧基笨基)乙烷二酐、雙(3,4-二羧基苯基)甲烷二 酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4_二羧基苯基)颯 二針、3,3·-氧雙鄰苯二甲酸二酐、4,4,_氧雙鄰苯二甲酸二 針、2,2-雙(4-(4-胺基苯氧基)苯基)丙烷、13-二氩-i,3-二 氧-5_異苯并呋喃曱酸-1,4-苯二酯、4-(2,5-二氧四氫呋喃-3_基)_1,2,3,4-四氫化萘_1,2-二甲酸酐、1,2,5,6-萘四曱酸二 針、2,3,6,7-萘四甲酸二酐、2,3,5,6_吡啶四甲酸二酐、 3,4,9,1〇-茈四甲酸二酐、2,2_雙(3,4_二羧基苯基)六氟丙烷 針2,2-雙(4-(3,4-一缓基苯氧基)苯基)六氟丙烧二肝、 2’2-雙(4-(3,4-二羧基苯甲醯氧基)苯基)六氟丙烷二酐、 2,2-雙(三氟甲基)_4,4,_雙(3,4_二羧基苯氧基)聯苯二酐、 乙二醇-雙偏苯三甲酸酐酯等。 作為脂肪族四羧酸二酐,可列舉:環丁烷四甲酸二酐、 環戊烷四曱酸二酐、2,3,5,6環己烷四甲酸二酐、 5_(2,5_二氧四氫呋喃基)-3-曱基-3-環己烯-1,2-二甲酸二 肝、雙環[:糾辛^稀-如細甲酸二針〜从丁: 四甲酸二酐。自降低烘烤後之翹曲之觀點考慮,該等酸: =目對於聚醯亞胺前驅體之酸二酐總量,較好的是 耳至5〇莫耳%之範圍内使用。 、 之:=於聚醯亞胺前驅體之二胺,自抑制去溶劑步驟中 刀ΐ下降之觀點、及去溶劑後製成感 高黏性之太;I , 祀式膜時提 考慮,較好的是使用由下述通式(2)所表示之 139901.doc 201006867 二胺。若為由該結構所表示之二胺,可單獨使用,亦可將 2種以上組合使用。下述通式(2)中,r2較好的是氫原子或 碳數為1至10之1價烷基。 [化8]❹ ❿ P (3) j 0 (a is an integer of Tables 7F1 to 20. b represents an integer of 3 to 3 。. & represents a nitrogen atom or a monovalent alkyl group having a carbon number of 1 to 10) by the above formula (3) In the Junji liver expressed by a, a is better than (4) is 5Λ20. Specifically, it can be mentioned: butanediol-meta-trimellitic acid=one fermentation-bi-p-trimellitic anhydride, heptanediol·bis-p-trimellitic acid=hepatic sterol trimellitic acid (four), second generation two Alcohol·bis-p-trimethylene benzoate-t-propanol-bis-p-stacked tris-acetic anhydride vinegar, poly 1,4·butanediol·manic anhydride S曰 special. These compounds may be used alone or in combination. 』J will use 2 other needles in the polyimide precursor of 2 months. Star _ and ^ Jiangman - Xuan, can also be cited: homobenzene... As aromatic tetradecanoic acid, can be listed II, 3,3,,4,4, · biphenyltetracarboxylic acid, liver, 2,3, 3,4'-biphenyltetracarboxylic acid-wm acid anhydride, 2,2,3,3,-biphenyltetracarboxylic acid-liver 3,3,,4,4, dimethane-formic acid anhydride, tetracarboxylic acid - wild, 2, 2, 3, 3, 2 stupid 139901.doc 201006867 dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2,3- Dicarboxyphenyl)propane dianhydride, 1,1 bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, double (3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl) fluorene, 3,3·-oxygen Diphthalic dianhydride, 4,4,_oxydiphthalic acid two-needle, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 13-di-argon-i ,3-dioxy-5-isobenzofurandecanoic acid-1,4-phenylenedicarboxylate, 4-(2,5-dioxotetrahydrofuran-3-yl)_1,2,3,4-tetrahydronaphthalene _ 1,2-Dicarboxylic anhydride, 1,2,5,6-naphthalene tetracarboxylic acid two-needle, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine tetra Diacetate, 3,4,9,1〇-indole tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane needle 2,2-bis(4-(3,4- Iso-phenoxy)phenyl)hexafluoropropanil-dissolved liver, 2'2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane dianhydride, 2,2 - bis(trifluoromethyl)_4,4,_bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, ethylene glycol-trimellitic anhydride, and the like. Examples of the aliphatic tetracarboxylic dianhydride include cyclobutane tetracarboxylic dianhydride, cyclopentane tetraphthalic acid dianhydride, 2,3,5,6 cyclohexanetetracarboxylic dianhydride, and 5_(2,5_ Dioxotetrahydrofuranyl-3-indolyl-3-cyclohexene-1,2-dicarboxylic acid di-hepatic, bicyclo[: 纠 ^ 稀 - - such as fine formic acid two needle ~ from butyl: tetracarboxylic dianhydride. From the viewpoint of lowering the warpage after baking, the acid: = is used in the range of the total amount of the acid dianhydride of the polyimide precursor, preferably from the ear to 5 〇 mol%. And: = the diamine of the polyimide precursor, the viewpoint of the reduction of the knives in the step of suppressing the solvent removal, and the high viscosity of the solvent after the solvent removal; I, the ruthenium film is considered, compared It is preferred to use 139901.doc 201006867 diamine represented by the following formula (2). The diamines represented by the above structures may be used singly or in combination of two or more. In the following formula (2), r2 is preferably a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms. [化8]

(Y係具有碳數為2至20之伸烷基之2價有機基。&表示氫原 子、碳數為1至10之1價烷基、烷氧基、或齒基) 具體而§可列舉.雙(2-胺基苯甲酸)乙二g旨、雙(3_胺基 苯甲酸)乙二酯、雙(4-胺基笨甲酸)乙二酯、雙(2_胺基苯甲 酸)1,3_丙二酯、雙(3-胺基笨甲酸}1,3_丙二酯、雙(4_胺基 苯曱酸)1,3-丙二酯、雙(2-胺基苯曱酸}1,4_丁二酯、雙(3_ 胺基苯甲酸)1,4-丁二酯、雙(4_胺基笨甲酸)•丁二酯、 雙(2-胺基苯甲酸)3-甲基_ι,4-丁二醋 雙(3-胺基苯甲酸)3_ 甲基-1,4-丁二酯、雙(4-胺基苯甲酸)3_甲基“,牡丁二酯、 雙(2-胺基苯甲酸)1,5-戊二酿、雙(3_胺基苯甲酸:二 酯、雙(4-胺基苯曱酸)1,5-戊二酯、雙(2_胺基笨甲酸儿1〇 癸二酯、雙(3-胺基苯甲酸)1,1〇_癸二醋、 酸)1,10-癸二酯等。該等二胺可單獨使用, 種以上。 雙(4-胺基苯甲 亦可同時使用2 進而,兵 / τ ,〜刀卞量下降之觀 、及去溶劑後製成感光性乾式膜時提高黏性之方面考 139901.doc 201006867 慮,較好的是使用由下述通式(4)所表示之化合物。 [化9](Y is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. & represents a hydrogen atom, a monovalent alkyl group having a carbon number of 1 to 10, an alkoxy group, or a dentate group) Illustrative. Bis(2-aminobenzoic acid) Ethylenedihydrate, bis(3-aminobenzoic acid) ethylene diester, bis(4-aminobenzoic acid) ethylene diester, bis(2-aminobenzoic acid) ) 1,3_propylene diester, bis(3-aminobenzoic acid} 1,3_propylene diester, bis(4-aminobenzoic acid) 1,3-propane diester, bis(2-amino group) Benzoic acid}1,4-butane diester, bis(3-aminobenzoic acid) 1,4-butane diester, bis(4-aminobenzoic acid)•butylate, bis(2-aminobenzoic acid) 3-methyl-I,4-butanediacetate bis(3-aminobenzoic acid) 3-methyl-1,4-butanediester, bis(4-aminobenzoic acid) 3-methyl", oyster Butane diester, bis(2-aminobenzoic acid) 1,5-pentane, bis (3-aminobenzoic acid: diester, bis(4-aminophenylphthalic acid) 1,5-pentane diester , bis (2_amino-based acid formic acid 1 〇癸 diester, bis(3-aminobenzoic acid) 1,1 〇 癸 癸 vinegar, acid) 1,10-decane diester, etc. Used alone, more than one species. Bis(4-aminobenzamide) Can be used at the same time 2, further, soldiers / τ, ~ the amount of knives decreased, and the solvent to improve the viscosity of the photosensitive dry film test 139901.doc 201006867 care, it is better to use a compound represented by the formula (4).

(Z係碳數為2至20之伸烷基。I表示氫原子、碳數為1至1〇 之1價烧基、烧氧基、或鹵基。c表示2至3〇之整數) 具體而言可列舉:聚氧化二亞甲基_二_鄰胺基苯甲酸 酯、聚氧化二亞甲基-二-間胺基苯甲酸酯、聚氧化二亞甲 基-二-對胺基苯甲酸酯、聚氧化三亞曱基_二_鄰胺基苯曱 酸8曰、聚氧化三亞甲基·二·間胺基苯曱酸酯、聚氧化三亞 甲基-二·對胺基苯甲酸酯、聚氧化四亞甲基-二-鄰胺基苯 甲酸酯、聚氧化四亞甲基_二_間胺基苯曱酸酯、聚氧化四 亞甲基-一-對胺基苯甲酸酯、聚氧化3 -曱基四亞曱基-二_ 鄰胺基苯甲酸酯、聚氧化3_甲基四亞甲基_二_間胺基苯甲 酸酯、聚氧化3-曱基四亞曱基_二_對胺基苯甲酸酯、聚氧 化五亞甲基-二-鄰胺基苯甲酸酯、聚氧化五亞甲基-二-間 月女基笨甲酸酯、聚氧化五亞甲基_二_對胺基苯曱酸酯、聚 氧化十亞曱基_二-鄰胺基苯甲酸酯、聚氧化十亞甲基-二_ 間胺基苯甲酸酯、聚氧化十亞甲基_二-對胺基苯曱酸酯、 聚(四亞曱基/3-甲基四亞甲基醚)二醇雙(4_胺基苯甲酸酯) 等。該等二胺可單獨使用,亦可同時使用2種以上。 進而’自降低烘烤後之翹曲之觀點考慮,該等二胺之調 139901.doc -12· 201006867 分中為25莫:至由二二:。(4)所表示之二胺於所有二胺成 特別好的是,將由上述通式 α. ϋ -ν (αλ^· ± )斤表示之化合物與由上 达通式(4)所表示之化合物同 ^ ^ A 卞使用。於將由上述通式(2) 所表不之化合物與由上述通 ^ (Μ, D± ^ 、式(4)所表示之化合物同時使用 之If开> k ’自降低勉曲、去滚 ^ ω 紊,合劑後提高製成感光性乾式膜 時之黏性、及良好之微影特性 一 點考慮,由上述通式(4)(Z is an alkylene group having 2 to 20 carbon atoms. I represents a hydrogen atom, a monovalent alkyl group having a carbon number of 1 to 1 Torr, an alkoxy group, or a halogen group. c represents an integer of 2 to 3 Å) For example, polyoxymethylene_di-o-amino benzoate, polyoxymethylene-di-m-amino benzoate, polyoxymethylene-di-p-amine Benzobenzoate, polyoxytriazinyl-bis-o-aminobenzoic acid 8曰, polyoxymethylene-di-m-aminophenylphthalate, polyoxymethylene-di-p-amino group Benzoate, polyoxytetramethylene-di-o-amino benzoate, polyoxytetramethylene-di-m-aminophenyl phthalate, polyoxytetramethylene-mono-p-amine Benzoate, polyoxy-3-indolyltetradecylene-di-o-aminobenzoate, polyoxy-3-methyltetramethylene-di-amino-m-phenyl benzoate, polyoxidation 3-mercaptotetrakisinyl-di-p-aminobenzoic acid ester, polyoxypentaethylene-di-o-amino benzoate, polyoxypentaethylene-di-m-moon female Formate, polyoxypentamethyl_di-p-aminobenzoate, polyoxydecainyl-di-o-aminobenzamide Ester, polyoxymethylene-di-m-amino benzoate, polyoxymethylene-di-p-aminobenzoate, poly(tetradecyl/3-methyltetramethylene) Ethyl ether) diol bis(4-aminobenzoate) and the like. These diamines may be used singly or in combination of two or more kinds. Further, from the viewpoint of reducing the warpage after baking, the diamines are adjusted to 139901.doc -12· 201006867 by 25 mo: to 22:. (4) The diamine represented by all the diamines is particularly preferably a compound represented by the above formula α. ϋ -ν (αλ^· ± ) kg and a compound represented by the above formula (4) Use with ^ ^ A 。. The compound represented by the above formula (2) and the If opened by the above-mentioned compound (Μ, D±^, and the formula (4) are used to reduce the distortion and de-rolling ^ Omega turbulence, the viscosity of the photosensitive dry film after the mixture is improved, and good lithographic properties are considered by the above formula (4)

所表示之化合物之調配量較 夏杈好的疋,相對於二胺總量而為 25莫耳%至75莫耳%。 又’可將上述二胺與其以外之二胺同時使用。具體而言 可列舉:1,4-二胺基苯、i,3_二胺基苯、2,4_二胺基甲苯、 4’4’-二胺基二苯基甲烷、M、二胺基二苯醚、二胺基 二笨醚、 3,3^二甲基 _4,4,_ 二胺基聯苯、2,2,_二甲基 _4,4,· 二胺基聯苯、2’2,-雙(三氟甲基)_4,4._二胺基聯苯、3,7_二 胺基-二曱基苯并噻吩_5,5_二氧化物、4,4,_二胺基二苯甲 酮、3,3'-二胺基二苯甲酮、4,4,_雙(4_胺基苯基)硫化物、 4,4'-二胺基二苯基砜、4,4,_二胺基苯曱醯苯胺、in-雙(4_ 胺基苯氧基)烷烴、1,3-雙(4·胺基苯氧基)_2,2-二甲基丙 烷、1,2-雙[2-(4-胺基苯氧基)乙氧基]乙烷、9,9_雙(4_胺基 苯基)苐、5(6)-胺基·1_(4-胺基曱基)-1,3,3-三甲基茚滿、 1,4-雙(4-胺基苯氧基)苯、ϋ —雙(4·胺基苯氧基)苯、ϋ —雙 (3_胺基苯氧基)苯、4,4,_雙(4_胺基苯氧基)聯苯、44,_雙(3_ 胺基苯氧基)聯苯、2,2-雙(4-胺基苯氧基苯基)丙烷、雙[4-(4-胺基苯氧基)苯基]颯、雙[4_(3_胺基苯氧基)苯基]颯、 139901.doc •13- 201006867 2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、3,3,-二緩基_4,4,_ 二胺基二苯基甲烧、4,6-二經基-1,3 -苯二胺、3,3,-二經基_ 4,4’-二胺基聯苯、1,4_雙(4_胺基苯氧基)戊烷、15雙(4,_ 胺基苯氧基)戊烧、雙(γ-胺基丙基)四甲基二矽氧燒、14_ 雙(γ-胺基丙基二甲基矽烷基)苯、雙(4-胺基丁基)四曱基二 矽氧烷、雙(γ-胺基丙基)四苯基二矽氧烷、由下述通式 所表示之二胺基矽氧烧化合物等。該等可單獨使用,亦可 將2種以上組合使用。自降低烘烤後之翹曲之觀點考慮, 該等二胺較好的是相對於二胺之總莫耳數,調配〇莫耳% 至50莫耳〇/〇。 [化 10]The compounding amount of the compound represented is better than that of the summer, and is 25 mol% to 75 mol% with respect to the total amount of the diamine. Further, the above diamine can be used together with a diamine other than the above. Specific examples thereof include 1,4-diaminobenzene, i,3-diaminobenzene, 2,4-diaminotoluene, 4'4'-diaminodiphenylmethane, M, and diamine. Diphenyl ether, diaminodiphenyl ether, 3,3^ dimethyl-4,4,-diaminobiphenyl, 2,2,-dimethyl-4,4,diaminobiphenyl , 2'2,-bis(trifluoromethyl)_4,4.diaminobiphenyl, 3,7-diamino-dimercaptothiophene_5,5-dioxide, 4,4 , _diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4,_bis(4-aminophenyl) sulfide, 4,4'-diaminodiphenyl Sulfone, 4,4,-diaminobenzidine, in-bis(4-aminophenoxy)alkane, 1,3-bis(4.aminophenoxy)_2,2-dimethyl Propane, 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 9,9-bis(4-aminophenyl)anthracene, 5(6)-amino group·1_ (4-aminomercapto)-1,3,3-trimethylindan, 1,4-bis(4-aminophenoxy)benzene, anthracene-bis(4.aminophenoxy)benzene , bis-(3-aminophenoxy)benzene, 4,4,_bis(4-aminophenoxy)biphenyl, 44,_bis(3-aminophenoxy)biphenyl, 2, 2-bis(4-aminophenoxyl) Phenyl)propane, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 139901.doc •13- 201006867 2,2 - bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3,3,-disulfoyl-4,4,-diaminodiphenylcarbamate, 4,6-di 1,3-phenylenediamine, 3,3,-di-diyl-4,4'-diaminobiphenyl, 1,4-bis(4-aminophenoxy)pentane, 15 pairs ( 4,_Aminophenoxy)pentane, bis(γ-aminopropyl)tetramethyldioxanthene, 14_bis(γ-aminopropyldimethylmethylalkyl)benzene, bis(4- Aminobutyl) tetradecyldioxane, bis(γ-aminopropyl)tetraphenyldioxane, a diamine oxime compound represented by the following formula, and the like. These may be used alone or in combination of two or more. From the standpoint of lowering the warpage after baking, it is preferred that the diamines are blended with % to 50 moles per mole relative to the total moles of diamine. [化10]

α成5^酿亞胺刖驅體時’視需要可使用單官能酸酐、單 官能羧酸、單官能胺對聚醯胺前驅體進行封端。 又’亦可使用醇化合物等眾所周知之化合物、及方法, 將本發明之聚醯亞胺前驅體之羧基之一部分醋化。 本發明之聚醯亞胺前驅體可藉由調配感光劑及有 機溶劑’而製成感光性聚醯亞胺前驅體組合物。 (B)感光劑 本發明之感光性聚醯亞胺前驅體組合物係調配藉由照射 活性光線而產生酸之化合物作為感光劑。該感光劑若藉由 /舌性光線之照射而產生酸,則無特別限定,其辛較好的是 139901.doc -14- 201006867 笨醌二疊氮化合物、萘酿二疊氮化合物等包含酿二疊氮結 構之化口物例如可使用§己載於美國專利第⑺m 3號說 明書、美國專利第3669658號說明書中者。其中,較好的 是盼化合物與ls2-萘酿_2·二疊氮績酸或1>2蔡酿_2_二疊 氣-5-«之醋化合物。該等可單獨使用,,亦可將2種以上 組合使用。When α is 5 olefinized oxime, the polyamine precursor can be blocked by using a monofunctional acid anhydride, a monofunctional carboxylic acid or a monofunctional amine as needed. Further, a part of the carboxyl group of the polyimide precursor of the present invention may be partially acetified by using a well-known compound such as an alcohol compound and a method. The polyimide precursor of the present invention can be prepared into a photosensitive polyimide intermediate composition by blending a sensitizer and an organic solvent. (B) Photosensitive agent The photosensitive polyimine precursor composition of the present invention is formulated as a sensitizer by compounding an acid by irradiation with active light. The sensitizer is not particularly limited as long as it generates an acid by irradiation with lingual light, and the sensitizer is preferably 139901.doc -14-201006867. The awkward diazide compound or the naphthalene-containing diazide compound contains The hydration of the diazide structure can be used, for example, in the specification of U.S. Patent No. (7) m 3 and U.S. Patent No. 3,669,658. Among them, it is preferred to use a compound of sulphuric acid with ls2-naphthalene-2·diazide acid or 1>2 broccoli-2_disodium-5-«. These may be used alone or in combination of two or more.

本發明之感光劑之調配量相對於聚醯亞胺前驅體1〇〇質 量份,較好的是5質量份至35質量份,進而好的是1〇質量 份至30質量份。感光劑之調配量自呈現感光性、及抑制於 包含鹼性水溶液之顯影液中之溶解的觀點考慮較好的是 5質量份以上,自靈敏度及呈現覆蓋層之㈣之觀點考 慮’較好的是35質量份以下。 (C)有機溶劑 ’例如可列舉:N_甲基 、Ν,Ν·二甲基乙醢胺、γ 本發明中所使用之有機溶劑中 2-«比洛啶_、N,N_二甲基甲醯胺 丁内醋、二甲基亞礙。χ,視需要可調配彿點低於該等溶 劑之溶劑。可藉由調配低沸點溶劑,而抑制乾燥時之發 泡。作為低沸點溶劑,具體而言可列舉:丙酮、甲基乙美 酮、甲基異丁基酮等酮類,乙醇、異丙醇、正丁醇、乙 醇、一乙二醇、三乙二酵、丙二醇或己二醇等醇類,I〆 二噁烷、三噁烷、二乙基縮醛、1,2-二氧戊環、二乙二醇 二曱醚、四氫呋喃、苯曱醚、三乙二醇二甲醚等醚類,乙 酸乙酯、苯甲酸甲酯、乙二醇單甲醚乙酸酯、乙二醇單乙 醚乙酸S曰、乙二醇單丙醚乙酸酯、乙二醇二乙酸酯、丙二 139901.doc •15- 201006867 酵單曱醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙 酸酯、丙一醇單丁醚乙酸酯、丙二醇二乙酸酯、二乙二醇 單曱醚乙酸酯、一乙二醇單乙醚乙酸酯、二乙二醇二乙酸 酯等酯類,正庚烷、正辛烷、環己烷、苯、曱苯、二甲 苯、乙苯及二乙苯等煙類。有機溶劑之調配量相對於聚醯 亞胺别驅體100質量份,較好的是25質量份至900質量份, 進而好的是100質量份至400質量份。若調配量多於9〇〇質 量份,則塗敷後難以保持膜厚,若少於25質量份,則聚酸 亞胺前驅體未完全溶解。 (D)溶解抑制劑 本發明之感光性聚醯亞胺前驅體組合物中可視需要而調 配溶解抑制劑。可藉由調配溶解抑制劑,而抑制於包含聚 醯亞胺前驅體之鹼性水溶液之顯影液中的溶解。本發明之 溶解抑制劑係指與聚醯亞胺前驅體之羧基或酚性羥基進行 氫鍵結之化合物。藉由聚醯亞胺前驅體之羧基或酚性羥基 與溶解抑制劑進行氫鍵結,而與顯影液阻斷,又,與該化 合物之疏水性相結合,可抑制聚醯亞胺前驅體之溶解。 作為具有與羧基或酚性羥基進行氫鍵結之基之化合物, T列舉.綾酸化合物、叛酸酯化合物、醯胺化合物、腺化 合物等。自於包含鹼性水溶液之顯影液中之溶解抑制效果 及保存穩定性的觀點考慮,較好的是由下述通式(6)所表示 之化合物’進而好的是醯胺化合物、脲化合物。 139901.doc 201006867 [化 11]The amount of the sensitizer to be used in the present invention is preferably from 5 parts by mass to 35 parts by mass, more preferably from 1 part by mass to 30 parts by mass, per part by mass of the ruthenium imine precursor. The amount of the sensitizer is preferably 5 parts by mass or more from the viewpoint of exhibiting photosensitivity and inhibiting dissolution in a developing solution containing an alkaline aqueous solution, and is considered to be good from the viewpoint of sensitivity and presentation of the coating layer (IV). It is 35 parts by mass or less. (C) The organic solvent 'for example, N-methyl, hydrazine, hydrazine dimethyl acetamide, γ 2-«pilotidine _, N, N dimethyl in the organic solvent used in the invention Carbamide butyl vinegar, dimethyl sulphate. χ, if necessary, the solvent can be adjusted to be lower than the solvents of the solvents. The foaming during drying can be suppressed by blending a low boiling point solvent. Specific examples of the low boiling point solvent include ketones such as acetone, methylethethenone, and methyl isobutyl ketone, and ethanol, isopropanol, n-butanol, ethanol, monoethylene glycol, and triethylene glycol. An alcohol such as propylene glycol or hexanediol, I〆dioxane, trioxane, diethyl acetal, 1,2-dioxolane, diethylene glycol dioxime ether, tetrahydrofuran, benzoin ether, three Ethers such as ethylene glycol dimethyl ether, ethyl acetate, methyl benzoate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate S曰, ethylene glycol monopropyl ether acetate, ethylene Alcohol diacetate, propylene II 139901.doc •15- 201006867 Fermented monoterpene ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propanol monobutyl ether acetate, propylene glycol II Esters such as acetate, diethylene glycol monoterpene ether acetate, monoethylene glycol monoethyl ether acetate, diethylene glycol diacetate, n-heptane, n-octane, cyclohexane, benzene , such as toluene, xylene, ethylbenzene and diethylbenzene. The amount of the organic solvent to be added is preferably from 25 parts by mass to 900 parts by mass, more preferably from 100 parts by mass to 400 parts by mass, per 100 parts by mass of the polyimine. If the amount is more than 9 parts by mass, it is difficult to maintain the film thickness after coating, and if it is less than 25 parts by mass, the polyimide precursor is not completely dissolved. (D) Dissolution inhibitor The dissolution inhibitor can be optionally provided in the photosensitive polyimide intermediate composition of the present invention. The dissolution in the developer containing the alkaline aqueous solution of the polyimide precursor can be inhibited by formulating the dissolution inhibitor. The dissolution inhibitor of the present invention means a compound which is hydrogen-bonded to a carboxyl group or a phenolic hydroxyl group of a polyimide precursor. By hydrogen bonding of a carboxyl group or a phenolic hydroxyl group of the polyimide precursor to the dissolution inhibitor, blocking with the developer, and in combination with the hydrophobicity of the compound, the polyimine precursor can be inhibited. Dissolved. As a compound having a group which hydrogen-bonds to a carboxyl group or a phenolic hydroxyl group, T is a decanoic acid compound, a tarenic acid ester compound, a guanamine compound, an adenoid compound, and the like. The compound represented by the following general formula (6) is more preferably a guanamine compound or a urea compound from the viewpoint of the dissolution inhibiting effect and the storage stability in the developer containing the aqueous alkaline solution. 139901.doc 201006867 [Chem. 11]

(6) (m表示包含碳原子、氮原子、氡原子、硫原子之全 部或一部分之有機基。尺5及&可相同亦可不同) ❿ 作為醯胺化合物,例如可列舉:Ν,Ν^乙基乙_ > Ν,Ν-二異丙基曱醯胺、Ν,Ν·二曱基丁基醯胺、Ν,Ν_二丁基 乙酿胺、Ν,Ν_二丙基乙酿胺、__二丁基甲醯胺、Ν,Ν= 乙基丙醯胺、Ν,Ν·二甲基丙酿胺、Ν,Ν,•二甲氧基_ν,ν,_二 甲基草醢胺、Ν.甲基_ε.己内醯胺、4_經基苯基笨甲酿胺、 水楊醢胺、水楊醯替笨胗、7 ^ 臂本胺、乙醯苯胺、2,-羥基乙醯苯胺、 3·-經基乙酿苯胺、4,_羥基乙酿苯胺。 其中’自W層及藉由烘烤該感光層而獲得之膜之低玻 璃轉移點化、㈣於包切性水溶液之顯㈣中之溶解 性、高殘媒率化之觀點考慮,較好的是具有龄性經基之化 合物’更好的是具有酚性羥基之醯胺化合物。具體而言可 =舉· 4·㈣本基苯酿胺、2’·經基乙酿苯胺、3,_經基乙酿 本胺、4 4基乙酿笨胺。該等可單獨使用,亦可將2種以 上組合使用。 作為脲化合物,, 物例如可列舉·· 二甲基脲、四甲基 脲、四乙基脲、13 ’ 一本基脲、3-羥基苯基脲。其中,自 控制於包含鹼性水& /合液之顯影液中之溶解性、高殘膜率 化、感光層及藉由板& # β , '、烤該感光層而獲得之膜之低玻璃轉移 139901.doc •17· 201006867 點化的觀點考慮,更好的是含有酚性羥基之脲化合物。具 體而s可列舉3-羥基苯基脲。該等可單獨使用,亦可將2 種以上組合使用。 本發明之溶解抑制劑於使用醯胺化合物之情形時,自呈 現溶解抑制效果之觀點考慮,相對於聚醯亞胺前驅體之羧 基及酚性羥基1 mol,較好的是調配〇丨^^丨至〕〇 m〇i,更 好的是調配0.15 mol至1.5 mol。 本發明之溶解抑制劑於使用脲化合物之情形時,自呈現 溶解抑制效果之觀點考慮,相對於聚醯亞胺前驅體之羧基 及酚性羥基1 mol,較好的是〇.!瓜〇1至2 〇 m〇h自呈現溶 解抑制效果及呈現藉由烘烤而獲得之樹脂之韌性的觀點考 慮’更好的是調配0.15 mol至1.5 mol。 又,於使用醯胺化合物與脲化合物兩者之情形時,自溶 解抑制效果之觀點考慮,醯胺化合物與脲化合物之總量相 對於聚醯亞胺前驅體之羧基及酚性羥基i m〇1,較好的是 0.1 mol至 1.5 mol之範圍。 (E)酌·化合物 本發明之感光性聚醯亞胺前驅體組合物中可視需要而調 配酚化合物。自降低包含烘烤後之膜及基板之片材的翹 曲、及控制於鹼性水溶液中之溶解性之觀點考慮,酚化合 物係包含由下述通式(7)所表示之化合物及下述通式之 結構之酚化合物(作為並不相當於本申請案之溶解抑制劑 的成分)。 139901.doc •18- 201006867 [化 12](6) (m represents an organic group containing all or a part of a carbon atom, a nitrogen atom, a halogen atom, or a sulfur atom. The rule 5 and & may be the same or different) ❿ As the guanamine compound, for example, Ν, Ν ^Ethylethyl _ > Ν, Ν-diisopropyl decylamine, hydrazine, hydrazine dimethyl decyl decylamine, hydrazine, hydrazine _ dibutyl ethanoamine, hydrazine, hydrazine _ dipropyl propyl Amine, __dibutylformamide, hydrazine, hydrazine = ethyl propyl amide, hydrazine, hydrazine dimethyl propylamine, hydrazine, hydrazine, • dimethoxy _ν, ν, _ dimethyl grass Indoleamine, hydrazine. methyl _ ε. caprolactam, 4 _ phenyl phenyl stearamine, salicylamine, salicylate, alum, 7 ^ armamine, acetophenone, 2, - hydroxyethyl anilide, 3 ·- phenyl aniline, 4, hydroxy phenyl aniline. Preferably, it is preferred from the viewpoint of the low glass transition point of the film obtained by baking the photosensitive layer, (4) the solubility in the coating (4) of the inclusive aqueous solution, and the high residual rate. It is a compound having an aging base, and more preferably a guanamine compound having a phenolic hydroxyl group. Specifically, it can be as follows: 4. 4 (4) benzyl phenylamine, 2'. phenyl aniline, 3, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ These may be used singly or in combination of two or more. Examples of the urea compound include dimethyl urea, tetramethyl urea, tetraethyl urea, 13'-based urea, and 3-hydroxyphenyl urea. Wherein, the solubility in the developing solution containing the alkaline water & /liquid mixture, the high residual film rate, the photosensitive layer, and the film obtained by baking the photosensitive layer by the plate &#β, ' Low glass transfer 139901.doc •17· 201006867 Point of view, better is a urea compound containing a phenolic hydroxyl group. Specifically, s can be exemplified by 3-hydroxyphenylurea. These may be used alone or in combination of two or more. In the case of using a guanamine compound, the dissolution inhibitor of the present invention is preferably formulated with respect to the carboxyl group of the polyimide precursor and the phenolic hydroxyl group of 1 mol from the viewpoint of exhibiting a dissolution inhibiting effect.丨 to 〇m〇i, it is better to mix 0.15 mol to 1.5 mol. In the case of using a urea compound, the dissolution inhibitor of the present invention is preferably a ruthenium of a polyethylenimine precursor and a phenolic hydroxyl group of 1 mol from the viewpoint of exhibiting a dissolution inhibiting effect. From 2 〇m〇h, from the viewpoint of exhibiting dissolution inhibition effect and exhibiting the toughness of the resin obtained by baking, it is preferable to formulate 0.15 mol to 1.5 mol. Further, in the case of using both the guanamine compound and the urea compound, the total amount of the guanamine compound and the urea compound is relative to the carboxyl group and the phenolic hydroxy group of the polyimide precursor, from the viewpoint of the dissolution inhibiting effect. It is preferably in the range of 0.1 mol to 1.5 mol. (E) Discrete compound The photosensitive polyamidiamine precursor composition of the present invention may optionally contain a phenol compound. The phenol compound contains a compound represented by the following general formula (7) and the following from the viewpoint of reducing the warpage of the film including the baked film and the substrate, and controlling the solubility in the alkaline aqueous solution. A phenolic compound of the general structure (as a component which is not equivalent to the dissolution inhibitor of the present application). 139901.doc •18- 201006867 [Chem. 12]

YY

⑺ (R7及Rs分別獨立表示氫原子或者包含碳原子i至5〇及氧原 ❹ 子〇至1()之有機基。X分別獨立表示氫原子或經基或碳數為 1至20之有機基) [化 13] ,R9—R!(7) (R7 and Rs each independently represent a hydrogen atom or an organic group containing a carbon atom of i to 5 Å and an oxo sulfonium to 1 (). X independently represents a hydrogen atom or an organic group having a base or a carbon number of 1 to 20. Base) [Chem. 13], R9-R!

R 11 (8) (R9及Rn分別獨立表示碳數為丨至6之有機基,Riq表示鍵結 基或碳數為1至20之有機基) 具體而言可列舉:二羥基二苯基曱烷、4,4,_氧基二笨 ® 酚、丨,4-雙羥基苯氧基)笨、1,3_雙(4-羥基苯氧基)苯、 1,5_雙(鄰羥基苯氧基)_3_氧雜戊烷、〇1,〇1,_雙(4_羥基苯基)_ 1,4-二異丙基苯等2核體,三(羥基苯基)甲烷、三(羥基苯 基)乙烷、4-{4-[1,1_雙(4_羥基苯基)乙基]_α,α_二曱基苄基} 苯盼等3核體’由下述結構式(a)至結構式(h)所表示之多核 體等。该等酚化合物可單獨使用,亦可將2種以上組合使 用0 139901.doc -19- 201006867 [化 14]R 11 (8) (R9 and Rn each independently represent an organic group having a carbon number of 丨 to 6, and Riq represents a bonding group or an organic group having 1 to 20 carbon atoms) Specifically, dihydroxydiphenyl fluorene is exemplified. Alkane, 4,4,-oxydiphenyl phenol, anthracene, 4-bishydroxyphenoxy), 1,3-bis(4-hydroxyphenoxy)benzene, 1,5-bis(o-hydroxybenzene) 2 nucleus such as oxy)_3_oxapentane, hydrazine 1, hydrazine 1, bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, tris(hydroxyphenyl)methane, tri Hydroxyphenyl)ethane, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]_α, α-didecylbenzyl} phenanthene and the like 3 nucleus 'from the following structural formula (a) to a polynuclear body represented by the structural formula (h). These phenol compounds may be used singly or in combination of two or more. 0 139901.doc -19- 201006867 [Chem. 14]

本發明之盼化合物之調配量相對於聚醯亞胺前驅體1〇〇 質量份,較好的是1質量份至30質量份,進而好的是5質量 伤至20質量份。若調配量少於i質量份,則難以抑制於包 3鹼陡水,谷液之顯影液中之溶解性若多於3 〇質量份,則 去溶劑步驟後所獲得之感光性乾式膜之感光層變脆。 (F)塑化劑 本發明之感光性聚醯亞胺前驅體組合物令,亦 <適赏使 用由下述通式(9)所表示之化合物作為塑化劑。 13990l.doc -20- (9) 201006867 [化 15]The compounding amount of the desired compound of the present invention is preferably from 1 part by mass to 30 parts by mass, more preferably from 5 parts by mass to 20 parts by mass, per part by mass of the polyimine precursor. If the amount is less than i part by mass, it is difficult to suppress the sensitization of the photosensitive dry film obtained after the solvent removal step if the solubility in the solution of the solution is more than 3 parts by mass. The layer becomes brittle. (F) Plasticizer The photosensitive polyimine precursor composition of the present invention is also used as a plasticizer by using a compound represented by the following formula (9). 13990l.doc -20- (9) 201006867 [Chem. 15]

Rl3Rl3

(尺12至1114係包含乙二醇鏈及/或丙二醇鏈之有機基,可分 別相同亦可不同) 具體而言,可列舉由下述結構式(i)、(j)所表示之化合 物,但並不限定於此。又,該等化合物可單獨使用,亦可 將2種以上組合使用。 [化 16](Foot 12 to 1114 is an organic group containing an ethylene glycol chain and/or a propylene glycol chain, and may be the same or different) Specific examples thereof include compounds represented by the following structural formulae (i) and (j). However, it is not limited to this. Further, these compounds may be used singly or in combination of two or more. [Chemistry 16]

(d為0以上之整數,e為0以上之整數) 本發明之塑化劑之調配量相對於聚醯亞胺前驅體100質 139901.doc -21 - 201006867 量份,較好的是1質量份至30質量份,進而好的是i質量份 至1〇質量份。若調配量為i質量份以上,則£現降低麵曲 之效果,若為30質量份以下,則不會對顯影性造成不良影 響而獲得所需圖案。 (G)交聯劑 本發明中,以提高烘烤後之膜之韌性為目的,可調配交 聯劑。作為交聯劑,較好的是由下述通式(1〇)所表示之四 羧酸化合物或四羧酸酯化合物、由下述通式(ιι)所表示之 聚醯亞胺前驅體或含羧基之聚醯亞胺前驅體酯化合物。 [化 17] °(d is an integer of 0 or more, and e is an integer of 0 or more) The amount of the plasticizer of the present invention is preferably 1 part by mass relative to the mass of the polyamidene precursor 100 139901.doc -21 - 201006867 The amount is preferably 30 parts by mass, and further preferably i parts by mass to 1 part by mass. When the amount is more than i part by mass, the effect of the surface curvature is reduced, and if it is 30 parts by mass or less, the desired pattern is obtained without adversely affecting the developability. (G) Crosslinking agent In the present invention, a crosslinking agent can be blended for the purpose of improving the toughness of the film after baking. The crosslinking agent is preferably a tetracarboxylic acid compound or a tetracarboxylic acid ester compound represented by the following formula (1), a polyfluorene imine precursor represented by the following formula (1) or A carboxyl group-containing polyimine precursor ester compound. [化17] °

Ri6〇〇C\ /COOR19Ri6〇〇C\ /COOR19

/R1S r17ooc 、coor18 (10) 係4價有機基,心6至心9係氫或碳數為1至2〇之1價有機 基,可分別相同亦可不同) [化 18] 0 0 o o R25〇OC\ / yRa>/ \ λ RmOOC coor27 \//R1S r17ooc, coor18 (10) is a tetravalent organic group, a core 6 to a heart 9 series hydrogen or a monovalent organic group having a carbon number of 1 to 2, which may be the same or different) [Chemical 18] 0 0 oo R25 〇OC\ / yRa>/ \ λ RmOOC coor27 \/

HH

HH

N«23—N R28〇〇C coor, g fC〇〇Rj /R24 D / \ R30OOC COOR5 (11) (ho、R22 ' R24係4價有機基,可分別相同亦可不同。 hi、R23係2價有機基,可分別相同亦可不同。尺25至尺32係 氫或碳數為1至20之i價有機基,可分別相同亦可不同。g 係0至100之整數) 自呈現交聯效果之觀點考慮, 本發明之交聯劑之調配量 139901.doc • 22- 201006867 相對於聚醯亞胺前驅體之殘留胺基的莫耳數,較好的是 0.1 mol至1.5 mol,更好的是〇·5 moli i丨m〇1。殘留胺基 量可使用高效液相層析法算出。 (H)熱驗產生劑 本發明之感光性聚醯亞胺前驅體組合物中可視需要而包 含熱驗產生劑。熱鹼產生劑係指藉由加熱而產生鹼之化合 物。例如,係藉由以胺等鹼化合物之胺基與磺酸等酸製作 鹽結構,由二碳酸酯化合物保護,且由醯氣化合物保護而 獲得。藉此’於室溫下不呈現鹼性而穩定,可利用加熱進 行去保護,製成產生驗之熱驗產生劑。又,亦可藉由調配 該熱驗產生劑,而使聚醯亞胺前驅體之烘烤溫度為比較低 之溫度。 作為熱鹼產生劑’具體而言可列舉:U-CAT(註冊商 標)SA810、U-CAT SA831、U-CAT SA841、U-CAT SA851 (以上為商品名,San-Apro公司製造)、N-(異丙氧基羰基)_ 2,6-二甲基哌啶、N_(第三丁氧基羰基)_2,6·二甲基哌咬、 N·(苄氧基羰基)·2,6-二曱基哌啶、芳香族二胺之胺基由二 碳酸二丁酯保護的化合物等。該等之中,自感光性聚醯亞 胺前驅體組合物之保存穩定性、去溶劑之分子量穩定性、 驗溶解性、離子遷移性之觀點考慮,較好的是Ν_(異丙氧 基羰基)-2,6-二甲基哌啶、Ν-(第三丁氧基羰基)_2,6_二甲基 哌啶、Ν-(苄氧基羰基)-2,6-二曱基哌啶、4,4_二胺基二苯 醚之胺基由二碳酸二丁酯保護之化合物、3,4,_二胺基二苯 醚之胺基由二碳酸二丁酯保護之化合物、^夂雙^ —胺基苯 139901.doc -23- 201006867 氧基)本之胺基由二碳_酸二丁醋保護之化合物、1,3_雙(4-胺基苯氧基)苯之胺基由二碳酸二丁酯保護之化合物、雙 (4-胺基本甲酸)ι,3 -丙二S旨之胺基由二碳酸二丁 g旨保護之 化合物、1,4-雙(4-胺基苯氧基)戊烷之胺基由二碳酸二丁 醋保護之化合物。該化合物例如可利用Chmistry Letters Vol· 34, No, 10 (2005)中記載之眾所周知之方法合成。 自醯亞胺化之促進及顯影性能之觀點考慮,本發明之熱 驗產生劑之調配量相對於聚醯亞胺前驅體1〇〇質量份,較 好的是0.5質量份至30質量份,更好的是〇5質量份至2〇質 ® 量份。 (I)磷酸酯化合物 本發明之感光性聚酿亞胺前驅體組合物中可視需要而調 配磷酸酯化合物。該等化合物對於感光性聚醯亞胺前驅體 組合物發揮阻燃劑、溶解助劑或塑化劑之作用。 作為磷酸酯化合物,係使用選自由下述通式(丨2)、下述 通式(13)或下述通式(14)所表示之化合物所組成之群中的 至少一種化合物。 [化 19] R33——Ο ——P——〇—R35 I (12) Ο (R33至R”表不碳數為1以上之有機基,可分別相同亦可不 同) 139901.doc -24· (13) 201006867 [化 20]N«23—N R28〇〇C coor, g fC〇〇Rj /R24 D / \ R30OOC COOR5 (11) (ho, R22 ' R24 is a tetravalent organic group, which can be the same or different. hi, R23 2 The valence organic group may be the same or different. The 25-foot 32 hydrogen or the 1-valent organic polymer having a carbon number of 1 to 20 may be the same or different. g is an integer from 0 to 100. From the viewpoint of the effect, the amount of the crosslinking agent of the present invention is 139901.doc • 22-201006867 The molar number of the residual amine group relative to the polyimide precursor is preferably 0.1 mol to 1.5 mol, more preferably It is 〇·5 moli i丨m〇1. The residual amine amount can be calculated by high performance liquid chromatography. (H) Thermal test agent The photosensitive polyimine precursor composition of the present invention may contain a thermal test agent as needed. The hot base generator refers to a compound which generates a base by heating. For example, it is obtained by making a salt structure with an amine group such as an amine compound such as an amine and a salt such as a sulfonic acid, protecting it with a dicarbonate compound, and protecting it with a helium compound. Therefore, it is stable without being alkaline at room temperature, and can be deprotected by heating to prepare a thermal test agent for producing the test. Further, the baking temperature of the polyimide precursor can be set to a relatively low temperature by blending the thermal generator. Specific examples of the hot base generator include U-CAT (registered trademark) SA810, U-CAT SA831, U-CAT SA841, U-CAT SA851 (above, trade name, manufactured by San-Apro Co., Ltd.), N- (isopropoxycarbonyl)_ 2,6-dimethylpiperidine, N-(t-butoxycarbonyl)_2,6·dimethylpiperidine, N·(benzyloxycarbonyl)·2,6- A compound in which dimercaptopiperidine or an amine group of an aromatic diamine is protected by dibutyl dicarbonate or the like. Among these, from the viewpoints of storage stability of the photosensitive polyimide intermediate composition, molecular weight stability of the solvent, solubility, and ion mobility, Ν_(isopropoxycarbonyl group is preferred. -2,6-Dimethylpiperidine, Ν-(t-butoxycarbonyl)_2,6-dimethylpiperidine, Ν-(benzyloxycarbonyl)-2,6-dimercaptopiperidine a compound in which the amine group of 4,4-diaminodiphenyl ether is protected by dibutyl dicarbonate, and the amine group of 3,4,-diaminodiphenyl ether is protected by dibutyl dicarbonate, Bis-aminobenzene 139901.doc -23- 201006867 oxy) a compound of the present invention protected by dicarbo-dibutyl acetonate, an amine of 1,3-bis(4-aminophenoxy)benzene a compound protected by dibutyl dicarbonate, a compound of bis(4-amine basic formic acid), i.e., 3-aminodiamine, which is protected by dibutyl glycolate, 1,4-bis(4-amino group) A compound in which the amine group of phenoxy)pentane is protected by dibutyl phthalate. This compound can be synthesized, for example, by a well-known method described in Chmistry Letters Vol. 34, No, 10 (2005). The amount of the thermal test agent of the present invention is preferably from 0.5 part by mass to 30 parts by mass based on 1 part by mass of the polyamidene precursor, from the viewpoint of the promotion of the imidization and the development performance. More preferably, 〇 5 parts by mass to 2 〇 ®® parts. (I) Phosphate ester compound The phosphoric acid ester compound may be optionally added to the photosensitive polyimide intermediate precursor composition of the present invention. These compounds function as a flame retardant, a dissolution aid or a plasticizer for the photosensitive polyimide intermediate composition. As the phosphate compound, at least one compound selected from the group consisting of compounds represented by the following formula (丨2), the following formula (13) or the following formula (14) is used. R33——Ο——P——〇—R35 I (12) Ο (R33 to R) indicates an organic group having a carbon number of 1 or more, which may be the same or different) 139901.doc -24· (13) 201006867 [Chem. 20]

可分別相同亦可不 (R36至R39表示碳數為1以上之有機基 同) [化 21]They may be the same or not (R36 to R39 represent an organic group having a carbon number of 1 or more) [Chem. 21]

(式中Rm為氫或1價有機基) 若考慮改善感光性聚醯亞胺前驅體組合物之阻燃性戋塑 化性,則上述通式(12)中之尺”至尺35或上述通式(13)中之 R36至較好的是選自甲基、乙基、丁基、2_乙基己基、 丁氧基乙基、苯基、甲苯基、二甲笨基、胺基苯基中之有 機基。 又,同樣若考慮熱穩定性、及感光性乾式膜之翹曲改善 效果則上述通式(14)中之較好的是選自氫、二羥基笨 基、二丁基經基f基、含有(甲基)丙稀酸醋基之有機基令 之有機基。進而,若考慮與樹脂清漆之相容性或感光性乾 式膜化時之翹曲改善效果,則較好的是氫。 139901.doc -25- 201006867 該等碟酸自旨化合物可單獨調配,亦可將兩種以上組合調 配。該等磷酸酯化合物之調配量較好的是!質量份至別質 量份,進而好的是i質量份至2〇質量份。若調配量為i質量 份以上,則呈現塑化性,若為3〇質量份以下,則感光性聚 醯亞胺前驅體組合物之未照射活性光線之部分於包含驗性 水溶液之顯影液中難以被侵蚀’可獲得良好之放射線像。 (J)有機磷化合物 本發明之感光性聚醯亞胺前驅體組合物中可調配由下述 通式(15)所表有機磷化合物。可藉由調配該有機填化 合物,而對利用烘烤所獲得之樹脂圖案賦予阻燃性。 [化 22] -R 41(wherein Rm is hydrogen or a monovalent organic group), in consideration of improving the flame retardancy and plasticity of the photosensitive polyimideimine precursor composition, the ruler to the ruler 35 of the above formula (12) or the above R36 in the formula (13) is preferably selected from the group consisting of methyl, ethyl, butyl, 2-ethylhexyl, butoxyethyl, phenyl, tolyl, dimethylphenyl, aminobenzene Further, in the case of considering the thermal stability and the warpage improving effect of the photosensitive dry film, it is preferable that the above formula (14) is selected from the group consisting of hydrogen, dihydroxy stupyl and dibutyl. An organic group having a base group and an organic group containing a (meth)acrylic acid vine group. Further, it is preferable to consider the compatibility with the resin varnish or the warpage improving effect at the time of photosensitive dry film formation. Hydrogen. 139901.doc -25- 201006867 These disc acid compounds can be formulated individually or in combination of two or more. The ratio of the phosphate compounds is better than that of the mass parts. Further, i parts by mass to 2 parts by mass. If the amount is more than i parts by mass, plasticizing property is exhibited, and if it is 3 〇 mass In the following, the portion of the photosensitive polyimide intermediate composition that is not irradiated with the active light is hardly eroded in the developer containing the aqueous test solution. A good radiation image can be obtained. (J) Organic phosphorus compound The photosensitive light of the present invention The organophosphorus compound represented by the following formula (15) can be blended in the polyimine precursor composition, and the resin pattern obtained by baking can be imparted with flame retardancy by blending the organic filler compound. [化22] -R 41

(15) ι \(15) ι \

I N «41 (R/n表示有機基。h表示1至50之整數) 該等有機磷化合物之調配量較好的是1質量份至SO質量 份,進而好的是3質量份至25質量份。若調配量為】質量份 以上,則呈現阻燃性,若為3〇質量份以下則烘烤後所獲 得之樹脂圖案變得強韌。 (K)其他成分 本發明之感光性聚醯亞胺前驅體組合物中可視需要而調 配米生化合物、三唾化合物、四唾化合物、硫_化合物。 可藉由調配該等化合物,而改善與銅基板之黏著性。 139901.doc 201006867 該等化合物之調配量較好的是0.1質量份至10質量份, 進而好的是0.1質量份至5質量份。若調配量為〇.丨質量份以 上’則呈現黏著性之改善效果,若為1 〇質量份以下,則不 會對顯影性造成不良影響而可獲得良好之放射線像。 本發明之感光性聚醯亞胺前驅體組合物中,以提高與支 持膜之潤濕性為目的,可視需要而調配乙醇、2_丙醇、乙 二醇等酵類,乳酸乙酯、苯甲酸甲酯、乙二醇單丙醚乙酸 • 醋等酯類’曱基乙基酮、曱基異丁基酮等酮類,正丁醚、 四氫呋喃、二噁烷等醚類,乙二醇單乙醚、丙二酵單乙鱗 等二醇醚類。 本發明之感光性聚酿亞胺前驅體組合物可用作覆蓋層。 覆蓋層係指保護矽晶圓、銅箔積層板、FPC等上所形成之 配線的保護膜。 (感光性聚醯亞胺前驅體組合物之調合) 本發明之感光性聚醯亞胺前驅體組合物係藉由於適當之 φ 容器内調配上述聚醯亞胺前驅體及各種化合物,利用旋轉 混合器、非起泡捏合機、具備攪拌葉片之三一馬達等進行 攪拌直至完全溶解為止而獲得。 (樹脂圖案之製造) 本發明中,可使用感光性聚醯亞胺前驅體組合物製作咸 光性乾式膜,形成樹脂圖案。該樹脂圖案可利用以下步驟 形成。 11 (1)將感光性聚醯亞胺前驅體組合物塗佈於膜基材上,繼 而進行去溶劑,製作感光性乾式膜之步驟 139901.doc •27- 201006867 感光性乾式膜係藉由將感光性聚醯亞胺前驅體組合物塗 佈於支持膜(膜基材)上,使溶劑乾燥,形成感光層而獲 侍。作為支持膜,可使用低密度聚乙烯、高密度聚乙烯、 聚丙烯、聚酯、聚碳酸酯、聚芳酯、聚丙烯腈、乙烯/環 :烯共聚物等。該等支持膜中,以控制感光性聚醯亞胺前 驅體組合物之潤濕性’或由該感光性聚酿亞胺前驅體組合 物獲得之感光層之剝離性為目的,可進行表面處理。作為 表面處理方法,可列舉:電暈處理、框處理、電漿處理、 使用聚石夕氧或醇酸樹脂或烯煙樹脂等之表面改質等。又, 若考慮塗敷性、附著性、輥性、強㈣、成本等,則載體 膜之厚度通常為15 μη^ 1〇〇 _,較好的是Η哗至乃 μπι。IN «41 (R/n represents an organic group. h represents an integer of 1 to 50) The amount of the organophosphorus compound is preferably from 1 part by mass to SO part by mass, and more preferably from 3 parts by mass to 25 parts by mass. . When the blending amount is 5% by mass or more, the flame retardancy is exhibited, and if it is 3 parts by mass or less, the resin pattern obtained after baking becomes tough. (K) Other components The photosensitive polyimine precursor composition of the present invention may be formulated with a rice compound, a tris-salt compound, a tetra-salt compound, or a sulfur-compound as needed. The adhesion to the copper substrate can be improved by blending the compounds. 139901.doc 201006867 The compounding amount of the compound is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 5 parts by mass. When the amount is 〇. 丨 by mass or more, the adhesiveness is improved. When the amount is less than 1 part by mass, a good radiation image can be obtained without adversely affecting developability. In the photosensitive polyimine precursor composition of the present invention, for the purpose of improving the wettability with the support film, a yeast such as ethanol, 2-propanol or ethylene glycol, ethyl lactate or benzene may be blended as needed. Ethyl formate, ethylene glycol monopropyl ether acetate, vinegar and other esters such as ketones such as mercaptoethyl ketone and decyl isobutyl ketone; ethers such as n-butyl ether, tetrahydrofuran and dioxane; Ether ethers such as diethyl ether and propylene glycol. The photosensitive polyimide intermediate precursor composition of the present invention can be used as a cover layer. The cover layer refers to a protective film that protects wiring formed on a silicon wafer, a copper foil laminate, an FPC or the like. (Polymerization of Photosensitive Polyimine Precursor Composition) The photosensitive polyimide intermediate precursor composition of the present invention utilizes spin-mixing by blending the above-mentioned polyimine precursor and various compounds in a suitable φ container The device, the non-foaming kneader, the tri-motor equipped with the stirring blade, and the like are stirred until completely dissolved. (Production of Resin Pattern) In the present invention, a photosensitive dry film can be produced using a photosensitive polyimide intermediate composition to form a resin pattern. This resin pattern can be formed by the following steps. 11 (1) A method in which a photosensitive polyimide film precursor composition is applied onto a film substrate, followed by solvent removal to prepare a photosensitive dry film 139901.doc • 27-201006867 Photosensitive dry film system The photosensitive polyimide precursor composition is applied onto a support film (film substrate), and the solvent is dried to form a photosensitive layer. As the support film, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene/ring:ene copolymer, or the like can be used. The support film may be subjected to surface treatment for the purpose of controlling the wettability of the photosensitive polyimide precursor composition or the peeling property of the photosensitive layer obtained from the photosensitive polyimide intermediate composition. . Examples of the surface treatment method include corona treatment, frame treatment, plasma treatment, surface modification using polyoxin or an alkyd resin or an enone resin, and the like. Further, in consideration of coatability, adhesion, rollability, strength (four), cost, and the like, the thickness of the carrier film is usually 15 μη ^ 1 〇〇 _, preferably Η哗 to μ μιη.

②光!±聚醯亞胺前驅體組合物之塗佈可於上述支持膜 t涂Γ用痛式塗佈機或凹版輥式塗佈機、刮刀(c〇_) ::機、模唇塗佈機、狹縫擠壓式塗佈機 方法來進行。 4 < 去溶劑可藉由溶劑 劑之乾煉(使用熱風乾燥或遠紅外線、 近紅外線之乾燥機& A, ' 乾燥機)而進行。乾燥溫度自抑制分子量下降 之觀點考慮,較好的是溫度抓Μ 下降 定性之觀點者虐、社 c至20C自感光劑之穩 ”考慮’進而好的是5〇。〇至i 1〇。 得之感光層之膜厚#“ ^ c °由去溶劑獲 ε _Λ 、較好的是5 μηι至100 μπι,更好的β 至5 0 μπι。自絕续的疋5 μηι 自絕緣可靠性之觀點考慮 以上,自獲得良好 权㈣疋5 μΓη 1〇π 放射線像之觀點考慮,膜厚較妊μ θ 100 μηι以下。此廬 狀序較好的是 右聚醯亞胺前驅體清漆之重量平均分 139901.doc -28- 201006867 子量(Mwl)與於120乞以下去溶劑後之重量平均分子量 (Mw2)之間的比(河评2/]^你1)為〇 7以上,則實現如下效果: 即便去溶劑後之感光性乾式膜彎折,亦無感光層之斷裂。 又,可於感光性乾式膜上積層覆蓋膜而製成感光性積層 • 膜。可藉由積層覆蓋膜,而防止感光層對支持膜之黏著。 作為覆蓋臈,可使用低密度聚乙烯、高密度聚乙烯、聚丙 烯、聚酯、聚碳酸酯、聚芳酯、聚丙烯腈、乙烯/環癸烯 共聚物。 ' ^ (2)將感光性乾式膜壓接於配置有圖案之基板上而形成感 光層之步驟 使感光性乾式膜重疊於FPC等之形成有電路之面(配置有 圖案之基板上),利用平面層壓或輥層壓、真空壓製等幕 所周知之方法,一面自4(TC加熱至130它,較好的是自6〇t: 加熱至120 C,一面利用0.2 MPa至5 MPa之壓力進行層壓 (壓接),藉此可積層感光層。 φ 此時’於感光性乾式膜為積層覆蓋膜之感光性積層膜之 情形時,於層壓前剝離覆蓋膜。藉由使可層壓溫度為4(rc 以上,則於層壓前之位置對準時不會由於黏著而費事,藉 由使可層壓溫度為13(TC以下,則不會進行感光劑之分解 而可層壓。再者,可層壓溫度係指無氣泡殘留等問題,可 充分埋入至圖案中,同時可將感光層控制為感光性聚醯亞 胺前驅體組合物不會過分流動而流出至圖案外之黏度。 又精由使感光層之玻璃轉移點(以下為Tg)低於層壓溫 度’可適宜進行感光性乾式膜之層壓。感光層之層壓後, 139901.doc •29· 201006867 支持膜可剝離亦可x卑丨丨触 a 』不剝離。於層壓後未剝離支持膜之情形 時,於曝光步驟後剝離。 (3)對感光層照射活性光線之步驟 為了形成微細孔或微細寬度線,感光層通過描繪有任意 圖案之光罩進行曝光。曝光量根據感光性聚醯亞胺前驅體 口物H成而不同’通常為1〇〇 ,剛^^2。 作為此時所使用之活性光線,例如可列舉n線、電子 束兔外,線彳見光線等。作為活性光線之光源,可使用 低壓水銀燈、高壓水銀燈、超高壓水銀燈、i素燈等。本 發明中’較好的是使用水銀燈之i射線(365㈣、h射線 ⑽nm)、g射線(436 nm)。作為照射活性光線之方法可 為密著曝光、投影曝光中之任一種方法。 (4)利用鹼性水溶液進行顯影之步驟 曝光後’使用顯影液,利用浸潰法、噴霧法等眾所周知 之方法進行_,可獲得放射線像。作為顯影液,可使用 氫氧化納水溶液、氫氧化_水溶液、碳_水溶液、碳酸 钟水溶液、四甲基氫氧化録水溶液等驗性水溶液。又本 步驟中,較好的是—面對顯影液進行加熱—面進行顯影。 藉由管理顯影溫度,可控制顯影時間,從而可保持所獲得 之放射線像之形狀。由該等觀點考慮,顯影液之溫度較好 的是20C〜60°C,進而好的是25。〇〜5〇。〇。 (5)利用選自由水及酸性水溶液所組成之群中之至少—種 溶劑進行沖洗之步驟 顯影後利用浸潰法、 噴霧法等眾所周知之方法進行清 139901.doc •30- 201006867 t =為沖洗液,可使用水或在水中添加有機溶劑者。本 步驟中’較好的是將沖洗液保持成適當之溫度。藉此可於 顯影後除去基板或樹脂上之殘潰。作為沖洗液之溫度,自 除〇去殘渣之觀點考慮,較好的是15t〜6(rc好的是 中洗液進行清洗後,可❹無機酸水溶 液或有機酸水溶液進行清洗。作為無㈣㈣液,具體而2 light! The coating of the polyimide polyimide precursor composition can be applied to the above-mentioned support film t-coating gravure coater or gravure roll coater, doctor blade (c〇_) :: machine, lip coater, The slit extrusion coater method is carried out. 4 < Desolvation can be carried out by solvent drying (using a hot air drying or a far infrared ray, a near infrared ray dryer & A, 'dryer). From the viewpoint of the decrease in the molecular weight of the drying temperature, it is preferable that the temperature is scratched and the qualitative property is lowered. The social stability of C to 20C from the sensitizer is considered to be 5 〇. 〇 to i 1 〇. The film thickness of the photosensitive layer #" ^ c ° is obtained by removing the solvent from ε _ 、 , preferably from 5 μηι to 100 μπι, more preferably from β to 50 μπι. From the viewpoint of the insulation reliability of the above-mentioned 疋5 μηι, the film thickness is lower than the pregnancy μ θ 100 μηι from the viewpoint of obtaining a good weight (4) 疋 5 μΓη 1〇π radiation image. The preferred order of the ruthenium is between the weight average of the 139901.doc -28-201006867 sub-quantity (Mwl) and the weight average molecular weight (Mw2) after desolvation below 120 的. When the ratio (River 2/]^1) is 〇7 or more, the following effects are achieved: Even if the photosensitive dry film is bent after solvent removal, there is no breakage of the photosensitive layer. Further, a cover film can be laminated on a photosensitive dry film to form a photosensitive build-up film. The adhesion of the photosensitive layer to the support film can be prevented by laminating the film. As the covering crucible, low density polyethylene, high density polyethylene, polypropylene, polyester, polycarbonate, polyarylate, polyacrylonitrile, ethylene/cyclodecene copolymer can be used. ' ^ (2) A step of forming a photosensitive layer by pressure-bonding a photosensitive dry film on a substrate on which a pattern is placed, and superimposing the photosensitive dry film on a surface on which a circuit such as an FPC is formed (a substrate on which a pattern is arranged) is used. A method known in the art for flat lamination or roll lamination, vacuum pressing, etc., from 4 (TC heating to 130, preferably from 6 〇 t: heating to 120 C, using a pressure of 0.2 MPa to 5 MPa on one side) Lamination (pressure bonding) is carried out, whereby the photosensitive layer can be laminated. φ At this time, when the photosensitive dry film is a photosensitive laminated film of a laminated cover film, the cover film is peeled off before lamination. When the pressing temperature is 4 (rc or more, it does not cause trouble due to adhesion when the position is aligned before lamination, and by laminating the laminating temperature to 13 (TC or less, laminating without sensitizing agent can be laminated) Furthermore, the laminable temperature means that there is no problem such as residual bubbles, and the film can be sufficiently embedded in the pattern, and the photosensitive layer can be controlled so that the photosensitive polyimide precursor composition does not flow excessively and flows out of the pattern. The viscosity of the glass is transferred to the photosensitive layer (hereinafter T g) laminating temperature may be suitable for lamination of photosensitive dry film. After lamination of photosensitive layer, 139901.doc •29· 201006867 support film peelable or x touchless a ” no peeling. When the support film is not peeled off after lamination, it is peeled off after the exposure step. (3) Step of irradiating the photosensitive layer with active light In order to form fine pores or fine width lines, the photosensitive layer is exposed by a mask having an arbitrary pattern. The amount of exposure varies depending on the photosensitive polyimide precursor precursor H. 'It is usually 1 〇〇, just ^^2. As the active light used at this time, for example, an n-line or an electron beam rabbit can be cited. As the light source of the active light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an i-lamp, etc. can be used. In the present invention, it is preferable to use an i-ray of a mercury lamp (365 (four), h-ray (10) nm), g Radiation (436 nm). The method of irradiating the active light may be either a close exposure or a projection exposure. (4) A step of developing with an aqueous alkaline solution, after exposure, using a developing solution, using a dipping method, a spray A radiation image can be obtained by a well-known method, and as the developer, an aqueous solution of an aqueous solution of sodium hydroxide, a water-based solution, a carbon-water solution, a carbonated carbon solution, or a tetramethylammonium hydroxide aqueous solution can be used. In the step, it is preferred to carry out the heating-surface development on the surface of the developer. By managing the development temperature, the development time can be controlled so that the shape of the obtained radiation image can be maintained. From such viewpoints, the developer The temperature is preferably from 20 ° C to 60 ° C, and further preferably from 25. 〇 〜 5 〇. 〇. (5) rinsing step using at least one solvent selected from the group consisting of water and an acidic aqueous solution. Use well-known methods such as dipping method, spray method, etc. 139901.doc • 30- 201006867 t = for the rinsing liquid, water or organic solvent can be added to the water. It is preferred in this step to maintain the rinsing liquid at a suitable temperature. Thereby, the residue on the substrate or the resin can be removed after development. As the temperature of the rinsing liquid, from the viewpoint of removing the residue, it is preferably 15t to 6 (the rc is preferably the intermediate washing liquid after washing, and the inorganic acid aqueous solution or the organic acid aqueous solution can be washed. As the no (four) (four) liquid Specific

5可列舉1酸水減、⑽水μ、伽水溶液、賴 水溶液。作為有機酸水溶液,具體而言可列舉:甲酸水溶 液、乙酸水溶液、捧檬酸水溶液、乳酸水溶 機酸水溶液或有機酸水溶液之清洗時間’自清洗效率之觀 點考慮,較好的是5秒至12G秒,進而好的是Μ秒至6〇秒。 於利用酸性水溶液進行沖洗之情形時,較好的是其後利用 水來沖洗酸性水溶液。 (6)對感光層之整體照射活性光線之步驟 沖洗步驟後’可對所獲得之放射線像之整個面照射活性 光線。可藉由利本步職感光劑分解,而縮短其後之固 化步驟之時間。進而,可提高固化步驟後所獲得之樹脂圖 案之光線透射率。 又,利用本步驟,可降低源自感光劑之對基板與感光層 ]所施加之殘留應力,降低樹脂圖案製造步驟中獲得之 或多層印刷電路板之曲,提高耐折性。本步驟中照 射之曝光量根據所使用之感光劑之種_或感光層之膜厚而 不同,通常為100 mJ/cm2至3 〇〇〇 mJ/cm2。例如於感光劑 使用萘醌二疊氮化合物且感光層之膜厚為25 μηι之情形 139901.doc -31 - 201006867 時,自感光劑之光分解之觀點考慮,較好的是 mj/em2 以上。作為此時所使用之活性光線,例如可列舉:χ射 線、電子束、紫外線、可見夯蟪望 兄尤線等。作為活性光線之光 源’可使用低壓水銀燈、高壓欢镅捭 & 旷, 不銀燈、超尚壓水銀燈、鹵 素燈等。該等之中,較好的县“Μ 平乂对的疋使用水銀燈之i射線(365 nm)、h射線(405 nm)、g射線(436 nm)。又,視需要可一面 加熱-面照射活性光線。自作業性之觀點考慮,加熱溫度 較好的是30°(:至130。〇,進而好的是仆它至丨⑽它。 (7)於100至40(TC下進行烘烤之步驟 對上述步驟中所獲得之放射線像進行烘烤,藉此形成樹 脂圖案。烘烤係於1〇(TC至40(rc之溫度下連續或階段性地 進行5分鐘至5小時。然後,可製成加工品。於Fpc之情形 日守’自防止配線之氧化之觀點考慮,較好的是於i 〇〇。〇至 2〇〇°C之溫度範圍進行固化。作為以如此方式獲得之加工 品’可列舉FPC、多層印刷電路板等。 [實施例] 以下,利用實施例對本發明加以更具體之說明,但並不 受該等例之任何限定。 (聚醯亞胺前驅體之合成) 合成例1聚醯亞胺前驅體(i)之合成 向二口可分離式燒瓶中加入6.4 g之l,3-雙(3-胺基苯氧 基)苯、62 g之γ-丁内酯,進行攪拌直至成為均勻溶液。繼 而,添加10 g之戊二醇-雙偏苯三甲酸酐酯,一面冰浴冷卻 一面攪拌1小時,其後於室溫下攪拌6小時。繼而,藉由將 139901.doc -32- 201006867 產物利用5 μιη之過慮器進行加壓過滤而獲得聚酿亞胺前驅 體(i)。將所獲得之聚醯亞胺前驅體⑴之酸二酐與二胺之莫 耳比、聚醯亞胺前驅體(i)溶液之固形分及重量平均分子量 示於表1中。 合成例2聚醯亞胺前驅體(Π)之合成 向三口可分離式燒瓶中加入4.8 g之1,3-雙(3-胺基苯氧 基)苯、6.8 g之聚氧化四亞曱基-二-對胺基苯甲酸酯、82 g 之γ- 丁内酯,進行攪拌直至成為均勻溶液。繼而,添加i 〇 攀 g之戊二醇·雙偏苯三甲酸針g旨,一面冰浴冷卻一面攪拌1 小時’其後於室溫下攪拌6小時。繼而,藉由將產物利用5 μηι之過濾器進行加壓過濾而獲得聚醯亞胺前驅體(丨丨)。將 所獲得之聚醯亞胺前驅體(ii)之酸二酐與二胺之莫耳比、 聚酿亞胺前驅體(ii)溶液之固形分、及重量平均分子量示 於表1中。 合成例3聚醯亞胺前驅體(iii)之合成 參 向二口可分離式燒瓶中加入9.7 g之1,3-雙(3-胺基苯氧 基)苯、13.7 g之聚氧化四亞曱基-二-對胺基苯甲酸酯、 168.8 g之γ-丁内酯’進行攪拌直至成為均勻溶液。繼而, 添加10 g之戊二醇-雙偏苯三曱酸酐酯、115 g之癸二醇_雙 偏苯三曱酸酐酯,一面冰浴冷卻一面攪拌丨小時,其後於 至溫下攪拌6小時。繼而,藉由將產物利用5 之過濾器 進行加壓過濾而獲得聚醯亞胺前驅體(iii)。將所獲得之聚 醯亞胺前驅體(iii)之酸二酐與二胺之莫耳比、聚醯亞胺前 驅體(iii)溶液之固形分、及重量平均分子量示於表i中。 139901.doc •33- 201006867 合成例4聚醯亞胺前驅體(iv)之合成 向三口可分離式燒瓶中加入8.8 雙(3_胺基苯氧 基)苯、i2.4 §之聚氧化四亞甲基-二-對胺基苯甲酸醋、 99.7代丫-丁㈣,進行攪拌直至成為均勾溶液。繼而, 添加ίο g之戊二醇-雙偏苯三甲酸酐酯、115 g之癸二醇-雙 偏苯三甲酸酐酯,一面冰浴冷卻一面攪拌丨小時,其後於 室溫下攪拌6小時。繼而,藉由將產物利用5 μιη之過濾器 進行加壓過濾而獲得聚醯亞胺前驅體(iv)。將所獲得之聚 醯亞胺前驅體㈣之酸二酐與二胺之莫耳比、聚:亞胺前 驅體(iv)溶液之固形分、及重量平均分子量示於表1中。 合成例5聚醯亞胺前驅體(v)之合成 向三口可分離式燒瓶中加入1〇·〇 g之雙(4胺基苯甲 酸)1,3-丙二酯、13.1 g之聚氧化四亞甲基,二-對胺基苯曱 酸酯、104.1 g之γ-丁内酯,進行攪拌直至成為均勻溶液。 繼而,添加ίο g之戊二醇-雙偏苯三甲酸酐酯、ii5 g之癸 二醇-雙偏苯三甲酸_旨’―面冰浴冷卻—面攪拌i小時, 其後於室溫下授拌6小時。繼而,藉由將產物利用5叫之 過滤器進行加壓_而獲得㈣亞胺前驅體⑺。將所獲得 之聚醯亞胺前驅體⑺之酸二酐與二胺之莫耳比、聚醯亞胺 前驅體⑺溶液之固形分、及重量平均分子量示於表i中。 合成例6聚醯亞胺前驅體(vi)之合成 向三口可分離式燒瓶中加入9.8 g之雙(4_胺基苯曱 酸),3丙Sa 12·9 S之聚氧化四亞甲基_二_對胺基苯曱 魷西曰103.1 g之γ_丁内酯,進行攪拌直至成為均勻溶液。 I39901.doc 201006867 繼而’添加10 g之戊二酵-雙偏苯三曱酸針酯、Π.5 g之癸 二醇-雙偏苯三甲酸酐酯,一面冰洛冷卻一面授拌1小時, 其後於室溫下攪拌6小時。繼而,藉由將產物利用5 μΓη之 過濾'器進行加壓過濾而獲得聚醯亞胺前驅體(vi)。將所獲 得之聚醯亞胺前驅體(vi)之酸二肝與二胺之莫耳比、聚醯 亞胺前驅體(vi)溶液之固形分、及重量平均分子量示於表丄 中。 合成例7聚醯亞胺前驅體(vii)之合成 向三口可分離式燒瓶中加入9.5 g之雙(4-胺基苯甲 酸)1,3-丙二酯、12_4 g之聚氧化四亞曱基-二-對胺基苯甲 酸酯、101.0 g之γ-丁内酯,進行攪拌直至成為均勻溶液。 繼而’加入ίο g之戊二醇-雙偏笨三甲酸酐酯、115 g之癸 二醇-雙偏苯三曱酸酐酯,一面冰浴冷卻一面授拌丨小時, 其後於室溫下攪拌6小時。繼而,藉由將產物利用5 μιη2 過濾、器進行加壓過濾而獲得聚醯亞胺前驅體(vii) ^將所獲 得之聚醯亞胺前驅體(vii)之酸二酐與二胺之莫耳比、聚醯 亞胺前驅體(vii)溶液之固形分、及重量平均分子量示於表 1中。 合成例8聚醯亞胺前驅體(viii)之合成 向二口可分離式燒瓶中加入9.1 g之雙(4-胺基苯曱 酸)1,3-丙二酯、154 g之聚氧化四亞曱基二-對胺基苯曱 酸酯、107.3 g之丁内酯,進行攪拌直至成為均勻溶液。 繼而’添加ίο g之戊二醇_雙偏苯三甲酸酐酯、115 g之癸 一醇-雙偏苯三甲酸酐酯,一面冰浴冷卻一面攪拌丨小時, 139901.doc -35- 201006867 其後於室溫下攪拌6小時。繼而,藉由將產物利用5 μηι之 過濾器進行加壓過濾而獲得聚醯亞胺前驅體(viii)。將所獲 得之聚醯亞胺前驅體(viii)之酸二酐與二胺之莫耳比、聚醯 亞胺前驅體(viii)溶液之固形分、及重量平均分子量示於表 1中。 合成例9聚醯亞胺前驅體(ix)之合成 向三口可分離式燒瓶中加入9.8 g雙(3-胺基笨曱酸)1,3-丙二酯、12.9 g之聚氧化四亞甲基-二-對胺基苯甲酸酯、5 can be exemplified by 1 acid water reduction, (10) water μ, glycerin aqueous solution, and aqueous solution. Specific examples of the organic acid aqueous solution include a formic acid aqueous solution, an acetic acid aqueous solution, an aqueous citric acid solution, a lactic acid aqueous solution acid aqueous solution, or an organic acid aqueous solution. The cleaning time is preferably from 5 seconds to 12 G from the viewpoint of self-cleaning efficiency. Seconds, and thus better, leap seconds to 6 seconds. In the case of rinsing with an acidic aqueous solution, it is preferred to rinse the acidic aqueous solution with water thereafter. (6) Step of irradiating the entire photosensitive layer with the active light After the rinsing step, the entire surface of the obtained radiation image is irradiated with the active light. The time of the subsequent curing step can be shortened by the decomposition of the sensitizer. Further, the light transmittance of the resin pattern obtained after the curing step can be improved. Further, with this step, the residual stress applied to the substrate and the photosensitive layer derived from the photosensitive agent can be reduced, and the curvature of the multilayer printed circuit board obtained in the resin pattern forming step can be reduced, and the folding endurance can be improved. The amount of exposure to be irradiated in this step varies depending on the type of the sensitizer used or the thickness of the photosensitive layer, and is usually from 100 mJ/cm 2 to 3 〇〇〇 mJ/cm 2 . For example, when the sensitizer is a naphthoquinone diazide compound and the film thickness of the photosensitive layer is 25 μηι 139901.doc -31 - 201006867, it is preferably mj/em2 or more from the viewpoint of photolysis of the sensitizer. Examples of the active light rays used at this time include a ray line, an electron beam, an ultraviolet ray, and a visible gaze. As the light source of the active light, a low-pressure mercury lamp, a high-pressure mercury lamp, a silver lamp, a super-pressure mercury lamp, a halogen lamp, or the like can be used. Among these, the better county “Μ 乂 乂 疋 疋 疋 疋 疋 疋 疋 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Active light. From the viewpoint of workability, the heating temperature is preferably 30° (: to 130 〇, and it is good to serv it to 丨 (10). (7) Baking at 100 to 40 (TC) The step of baking the radiation image obtained in the above step, thereby forming a resin pattern. The baking is performed at 1 Torr (TC to 40 (continuous or staged at a temperature of rc for 5 minutes to 5 hours. Then, It is made into a processed product. In the case of Fpc, it is preferable to cure it from the viewpoint of preventing oxidation of wiring, and it is preferable to cure it in a temperature range of 2 〇〇 ° C. The product 'is an FPC, a multilayer printed circuit board, etc. [Examples] Hereinafter, the present invention will be more specifically described by way of Examples, but it is not limited to these examples. (Synthesis of Polyimine Precursor) Synthesis Example 1 Synthesis of Polyimine Precursor (i) Addition to a two-neck separable flask 6.4 g of l,3-bis(3-aminophenoxy)benzene, 62 g of γ-butyrolactone, stirred until a homogeneous solution was obtained. Then, 10 g of pentanediol-bis-trimellitic anhydride was added. The ester was stirred while being cooled in an ice bath for 1 hour, and then stirred at room temperature for 6 hours. Then, the 139901.doc -32-201006867 product was subjected to pressure filtration through a 5 μηη filter to obtain a poly-imine. Precursor (i). The molar ratio of the acid dianhydride to the diamine, the solid content and the weight average molecular weight of the polyimine precursor (i) solution of the obtained polyimine precursor (1) are shown in Table 1. Synthesis Example 2 Synthesis of Polyimine Precursor (Π) To a three-neck separable flask, 4.8 g of 1,3-bis(3-aminophenoxy)benzene and 6.8 g of polyoxytetrazide were added.曱-di-p-amino benzoate and 82 g of γ-butyrolactone are stirred until they become a homogeneous solution. Then, i 二醇 g 之 二醇 二醇 双 双 双 双 双 , Stir for 1 hour while cooling in an ice bath. Then, stir at room temperature for 6 hours. Then, pressurize the product with a filter of 5 μηι. And obtaining a polyimine precursor (丨丨). The molar ratio of the acid dianhydride to the diamine of the obtained polyimide precursor (ii), and the solid solution of the polyimide precursor (ii) solution The fractions and the weight average molecular weights are shown in Table 1. Synthesis Example 3 Polyimine imine precursor (iii) Synthetic reaction Two-neck separable flask was charged with 9.7 g of 1,3-bis(3-aminobenzene). Oxy)benzene, 13.7 g of polyoxytetradecylidene-di-p-aminobenzoate, 168.8 g of γ-butyrolactone' was stirred until it became a homogeneous solution. Then, 10 g of pentanediol was added. - Bis-trimellitic anhydride ester, 115 g of decanediol_bis-p-trimellitic anhydride ester, stirred while cooling on an ice bath for an hour, and then stirred at room temperature for 6 hours. Then, the polyimine precursor (iii) was obtained by pressure filtration of the product using a filter of 5. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (iii) solution, and the weight average molecular weight of the obtained polyamidene precursor (iii) are shown in Table i. 139901.doc •33- 201006867 Synthesis Example 4 Synthesis of Polyimine Precursor (iv) To a three-neck separable flask was added 8.8 bis(3-aminophenoxy)benzene, i2.4 § polyoxidized four Methylene-di-p-aminobenzoic acid vinegar, 99.7 hydrazine-butyl (tetra), was stirred until it became a homogenate solution. Then, ίο g pentanediol-trimellitic anhydride ester and 115 g of decanediol-bistrimellitic anhydride were added, and the mixture was stirred for an hour while cooling in an ice bath, followed by stirring at room temperature for 6 hours. Then, the polyimine precursor (iv) was obtained by pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the poly(imine precursor) (iv) solution, and the weight average molecular weight of the obtained polyimine precursor (4) are shown in Table 1. Synthesis Example 5 Synthesis of Polyimine Precursor (v) To a three-neck separable flask was added 1 〇·〇g of bis(4-aminobenzoic acid) 1,3-propanediester and 13.1 g of polyoxygenated four. Methylene, di-p-aminobenzoic acid ester, 104.1 g of γ-butyrolactone was stirred until it became a homogeneous solution. Then, adding ίο g pentanediol-bis-p-trimellitic anhydride ester, ii5 g of decanediol-meta-trimellitic acid _-----ice-bath cooling-surface stirring for 1 hour, and then at room temperature Mix for 6 hours. Then, the (iv) imine precursor (7) is obtained by pressurizing the product with a filter called 5 Å. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (7) solution, and the weight average molecular weight of the obtained polyimine precursor (7) are shown in Table i. Synthesis Example 6 Synthesis of Polyimine Precursor (vi) To a three-neck separable flask was charged 9.8 g of bis(4-aminobenzoic acid), 3 propane Sa 12·9 S polyoxytetramethylene. _Di-p-aminobenzoquinone 103.1 g of γ-butyrolactone was stirred until it became a homogeneous solution. I39901.doc 201006867 Then add '10 g of glutaraldehyde-bis-p-trimellitic acid acate, Π.5 g of decanediol-bis-p-trimellitic anhydride, and let it stand for 1 hour while cooling. It was then stirred at room temperature for 6 hours. Then, the polyimide precursor (vi) was obtained by pressure filtration using a 5 μΓ filter. The molar ratio of the diuret and diamine of the obtained polyimine precursor (vi), the solid content of the solution of the polyimine precursor (vi), and the weight average molecular weight are shown in the Table. Synthesis Example 7 Synthesis of Polyimine Precursor (vii) To a three-neck separable flask, 9.5 g of bis(4-aminobenzoic acid) 1,3-propanedicarboxylate and 12-4 g of polyoxytetramine were added. The bis-di-amino benzoate, 101.0 g of γ-butyrolactone, was stirred until it became a homogeneous solution. Then 'add ίο g pentanediol-bis-p-trimellitic anhydride ester, 115 g of decanediol-bis-p-trimellitic anhydride ester, stir it on ice for one hour, then stir at room temperature 6 hour. Then, the polyimine precursor (vii) is obtained by subjecting the product to a pressure filtration using a 5 μηη2 filter, and the obtained acid dianhydride precursor (vii) and the diamine are obtained. The ear ratio, the solid content of the polyimide intermediate (vii) solution, and the weight average molecular weight are shown in Table 1. Synthesis Example 8 Synthesis of Polyimine Precursor (viii) To a two-neck separable flask was charged 9.1 g of bis(4-aminophenylphthalic acid) 1,3-propanedicarboxylate and 154 g of polyoxygenated four. The fluorenylene di-p-aminophenyl phthalate and 107.3 g of butyrolactone were stirred until they became a homogeneous solution. Then 'add ίο g pentanediol _ bis-p-trimellitic anhydride ester, 115 g of decyl alcohol-bis-p-trimellitic anhydride ester, and stir for one hour while cooling in an ice bath, 139901.doc -35- 201006867 Stir at room temperature for 6 hours. Then, the polyimine precursor (viii) was obtained by pressure filtration using a filter of 5 μηι. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (viii) solution, and the weight average molecular weight of the obtained polyimine precursor (viii) are shown in Table 1. Synthesis Example 9 Synthesis of Polyimine Precursor (ix) To a three-neck separable flask was charged 9.8 g of bis(3-aminoformic acid) 1,3-propanediester and 12.9 g of polyoxytetramethylene. Base-di-p-aminobenzoic acid ester,

103 · 1 g之γ- 丁内酯’進行授拌直至成為均勻溶液。繼而, 添加10 g之戊二醇-雙偏苯三曱酸酐酯、U.5 g之癸二醇_雙 偏本二甲酸肝g旨,一面冰浴冷卻一面授拌1小時,其後於 室溫下攪拌6小時。繼而,藉由將產物利用5 μιη之過渡器 進行加壓過濾而獲得聚醯亞胺前驅體(ix)。將所獲得之聚 酿亞胺前驅體(ix)之酸二針與二胺之莫耳比、聚醯亞胺前 驅體(ix)溶液之固形分、及重量平均分子量示於表丨中。 合成例10聚醯亞胺前驅體(X)之合成103 · 1 g of γ-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of pentanediol-bis-p-trimellitic anhydride ester, U.5 g of decanediol-bis-dimerized dicarboxylic acid liver g were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and thereafter in the chamber. Stir for 6 hours at room temperature. Then, the polyimine precursor (ix) was obtained by pressure filtration of the product using a 5 μηη transition. The molar ratio of the acid two needles to the diamine, the solid content of the polyimine precursor (ix) solution, and the weight average molecular weight of the obtained polyimine precursor (ix) are shown in the Table. Synthesis Example 10 Synthesis of Polyimine Precursor (X)

向二口可分離式燒瓶中加入9.8 g之雙(4_胺基苯甲 酸)1,3-丙二酯、l2.9g 之聚(1,4-丁二醇/3-甲基 q,4· 丁二醇) 醚雙(4-胺基苯甲酸酯)、丨们‘丨§之7_丁内酯,進行攪拌直 至成為均勻溶液。繼而,添加10 g之戊二醇_雙偏苯三曱酸 酐醋、11_5 g之癸二醇-雙偏苯三甲酸酐酯 一面冰浴冷卻 一面攪拌1小時,其後於室溫下攪拌6小時。繼而,藉由將 產物利用5 μΐη之過滤器進行加壓過濾而獲得聚醯亞胺前驅 體00。將所獲得之聚醯亞胺前驅體(χ)之酸二酐與二胺之 139901.doc -36- 201006867 莫耳比、聚醯亞胺前驅體(x)溶液之固形分、及重量平均分 子量示於表1中。 合成例11聚醯亞胺前驅體(xi)之合成 向二口可分離式燒瓶中加入iO.l g之雙(4-胺基苯甲酸 酯)1,3-丙二酯、133 g之聚氧化四亞曱基_二_對胺基苯曱 酸酯、105.7 g之γ_丁内酯,進行攪拌直至成為均勻溶液。 繼而,添加10 g之丁二醇_雙偏笨三甲酸酐酯、u.9 g之癸 二醇-雙偏苯三甲酸酐酯,一面冰浴冷卻一面攪拌〖小時, 其後於室溫下攪拌6小時。繼而,藉由將產物利用5 μιη之 過滤器進行加壓過濾而獲得聚醯亞胺前驅體(xi)。將所獲 得之聚醯亞胺前驅體(Xi)之酸二酐與二胺之莫耳比、聚醯 亞胺刖驅體(xi)溶液之固形分、及重量平均分子量示於表1 中。 合成例12聚醯亞胺前驅體(χϋ)之合成 向二_口可分離式燒瓶中加入9.8 g之雙(4-胺基苯甲 酸)1,3-丙二酯、12.9 g之聚氧化四亞曱基-二-對胺基苯甲 酸酯、110.4 g之γ-丁内酯,進行攪拌直至成為均勻溶液。 繼而,添加10 g之戊二醇-雙偏苯三甲酸酐酯、14.6 g之二 十烧二醇-雙偏苯三曱酸針酯,一面冰浴冷卻一面攪拌1小 時,其後於室温下授拌6小時。繼而,藉由將產物利用5 μιη之過濾器進行加壓過濾而獲得聚醯亞胺前驅體(χΗ)。將 所獲得之聚醯亞胺前驅體(xii)之酸二針與二胺之莫耳比、 聚醯亞胺前驅體(xii)溶液之固形分、及重量平均分子量示 於表1中。 139901.doc •37- 201006867 合成例13聚醯亞胺前驅體(xiii)之合成 向三口可分離式燒瓶中加入98 g之雙(4_胺基苯甲 酸)1,3-丙二酯、12.9 g之聚氡化四亞甲基·二_對胺基苯曱 酸酯、123.9 g之γ-丁内酯,進行攪拌直至成為均勻溶液。 繼而,添加10 g之戊二醇·雙偏苯三甲酸酐酯、2〇 4 g之聚 丙二醇-雙偏苯三甲酸酐酯,一面冰浴冷卻一面攪拌i小 時’其後於室溫下授拌6小時。繼而’藉由將產物利用5 μιη之過渡器進行加壓過慮而獲得聚醯亞胺前驅體。 將所獲得之聚酿亞胺前驅體(xiii)之酸二軒與二胺之莫耳 比、聚醯亞胺前驅體(xiii)溶液之固形分、及重量平均分子 量示於表1中。 合成例14聚醯亞胺前驅體(xiv)之合成 向二口可分離式燒瓶中加入9.4 g之1,3_雙(3-胺基苯氧 基)本、73 g之γ-丁内S旨,進行授拌直至成為均勻溶液。繼 而’添加10 g之4,4,-氧雙鄰苯二甲酸二酐,一面冰浴冷卻 一面攪拌1小時,其後於室溫下攪拌6小時。繼而,藉由將 產物利用5 μ m之過濾器進行加壓過濾而獲得聚醯亞胺前驅 體(xiv)。將所獲得之聚醯亞胺前驅體(xiv)之酸二酐與二胺 之莫耳比、聚醢亞胺前驅體(xiv)溶液之固形分、及重量平 均分子量示於表1中。 合成例15聚醯亞胺前驅體(χν)之合成 向三口可分離式燒瓶中加入7.1 g之1,3_雙(3_胺基苯敦 基)笨、64.3 g之γ-丁内酯,進行攪拌直至成為均勻溶液。 繼而,添加10 g之乙二醇-雙偏苯三甲酸酯,一面冰浴冷卻 139901.doc _狀_ . 201006867 一面搜拌1小時,其後於室溫下攪拌6小時。繼而,藉由將 產物利用5 μη!之過濾器進行加壓過濾而獲得聚醯亞胺前驅 體(XV) °將所獲得之聚醯亞胺前驅體(χν)之酸二酐與二胺 之莫耳比、聚醯亞胺前驅體(xv)溶液之固形分、及重量平 均为子量示於表1中。 合成例16聚醯亞胺前驅體(Xvi)之合成 向二口可分離式燒瓶中加入2·7 g之1,3-雙(3-胺基笨氧 基)苯、26.3 g之聚氧化四亞曱基-二-對胺基苯甲酸酯、 91·〇 g之γ-丁内酯,進行擾拌直至成為均勻溶液。繼而, 添加10 g之4,4,-氧雙鄰苯二甲酸二酐,一面冰浴冷卻一面 擾拌1小時,其後於室溫下攪拌6小時。繼而,藉由將產物 利用5 μπι之過濾器進行加壓過濾而獲得聚醯亞胺前驅體 (xvi) 。將所獲得之聚醯亞胺前驅體(χνί)之酸二酐與二胺之 莫耳比、聚醯亞胺前驅體(xvi)溶液之固形分、及重量平均 分子量示於表1中。 合成例17聚醯亞胺前驅體(χνπ)之合成 向三口可分離式燒瓶中加入2 〇 §之丨,3_雙(3_胺基苯氧 基)苯、19.9 g之聚氧化四亞甲基-二-對胺基苯甲酸酯、 74.4 g之γ-丁内酯,進行攪拌直至成為均勻溶液。繼而’ 添加10 g之乙二醇-雙偏笨三甲酸酯,一面冰浴冷卻一面攪 拌1小時’其後於室溫下攪拌6小時。繼而,藉由將產物利 用5 μιη之過濾器進行加壓過濾而獲得聚醯亞胺前驅體 (xvii) 。將所獲得之聚醯亞胺前驅體(xvii)之酸二酐與二胺 之莫耳比、聚醯亞胺前驅體(xvii)溶液之固形分、及重量 139901.doc •39· 201006867 平均分子量示於表1中。 (感光性聚醯亞胺前驅體組合物之調合) 首先將特定量之聚醯亞胺前驅體分成小份而置於玻璃瓶 等容器中。繼而,調配特定量之感光劑或溶解抑制劑等添 加劑,利用旋轉混合器等進行攪拌直至均勻。利用該等操 作可獲得感光性聚醯亞胺前驅體組合物。 (重量平均分子量之測定) 1 :聚醯亞胺前驅體之分子量測定 利用精密天平測量所合成之聚酿亞胺前驅體〇 〇丨g,溶 解於10 g之二甲基曱醯胺(和光純藥工業公司製造)中。將 該溶液通過10 μιη之過渡器進行過渡,利用具備tsk-GEL SUPER ΗΜ-Η(商品名,Tosoh公司製造)之凝膠滲透層析儀 (曰本分光公司製造)測定分子量。 2 .感光性聚酿亞胺A驅體組合物之重量平均分子量測定 塗敷:藉由於可真空吸附及加熱之塗敷台(松木科學公 司製造)上放置聚S曰膜(Unitika公司製造),進行真空吸附而 貼附該聚酯膜。於該聚酯膜上,使用間隙為67 5 μιη之敷 料器(松木科學公司製造)來塗佈感光性聚醯亞胺前驅體組 合物。 去溶劑:使用乾燥機(SPH-201,愛斯佩克(ESpec)公司製 造)’以95°C下30分鐘之條件進行去溶劑。 分子量測定:利用精密天平測量去溶劑後所獲得之感光 性聚醯亞胺别驅體組合物0.01 g,溶解於10 g之二甲基甲 醯胺(和光純藥工業公司製造)中。將該溶液通過10 μπ1之 139901.doc -40· 201006867 過遽器進行過濾,利用具備TSIC_GEL SUPER HM-H(商品 名’ T〇s〇h公司製造)之凝膠滲透層析儀(曰本分光公司製 造)測定分子量。 分子量比之算出:將感光性聚醯亞胺前驅體組合物清漆 之重量平均分子量設為Ml,且將去溶劑後之該感光性聚 it亞胺前驅體組合物之重量平均分子量設為M2時,利用 以下式1算出分子量比。 分子量比=M2/M1 m _ (彎折試驗) 塗敷:藉由於可真空吸附及加熱之塗敷台(松木科學公 司製造)上放置聚酯膜(Unitika&司製造),進行真空吸附而 貼附該聚酯膜。於該聚酯膜上,使用間隙為1〇〇 μιη之敷料 器(松木科學公司製造)來塗佈感光性聚醯亞胺前驅體組合 物。 去溶劑:利用乾燥機(SPH-201,愛斯佩克公司製造), φ 以95°c下30分鐘之條件進行去溶劑。 彎折試驗:將去溶劑後所獲得之膜彎折1 8〇度(捲邊摺 疊)’以目視觀察感光層之破裂、剝離。將無破裂、剝離 之情形記為〇’將有破裂、剝離之情形記為X。 (翹曲評價) 塗敷:藉由於可真空吸附及加熱之塗敷台(松木科學公 司製造)上放置聚酯膜(Unitika公司製造)’進行真空吸附而 貼附該聚醋膜。於該聚酯膜上,使用間隙為67.5 μπι之敷 料器(松木科學公司製造)來塗佈感光性聚醯亞胺前驅體組 139901.doc -41 - 201006867 合物。 去溶劑:利用乾燥機(SPH-2〇l,愛斯佩克公司製造), 以95°C下30分鐘之條件進行去溶劑。 真空壓製:基材使用聚醯亞胺膜(Kapt〇n EN_l〇〇,商品 名,T〇ray-DUpont公司製造),利用真空壓製機(sa_5〇i, Tester產業公司製造),將去溶劑步驟中獲得之感光性乾式 膜,以壓製溫度為l〇(TC、壓製壓力為〇5 Mpa、真空度為 15 kPa、壓製時間為i分鐘之條件進行真空壓製。 烘烤:使用乾燥機(8ΡΗ-2(Η ’愛斯佩克公司製造),以 表5所示之條件進行固化。 翹曲之測定:將烘烤後所獲得之膜切取長5 cm、寬5 cm,除去靜電後,使用尺測定臈之翹曲。 (實施例1) 包含聚酿亞胺前驅體與感光劑之感光性聚醯亞胺前驅體 組合物之評價 將〇成例1至3中獲得之聚醯亞胺前驅體溶液丨〇 g、作為 感光劑之相對於聚醯亞胺前驅體固形分而為2〇質量份之酿 二疊氮化合物(式16)0·42 g,以表2所示之比例加以混合, 放入至2〇 "^玻璃瓶中,利用旋轉混合器(MR-5,As One公 司製造)進行授拌直至均勻,獲得感光性聚醯亞胺前驅體 組合物(1至3)。將評價結果示於表2中。 139901.doc -42- 201006867 [化 23]To a two-neck separable flask, 9.8 g of bis(4-aminobenzoic acid) 1,3-propane diester and 12.9 g of poly(1,4-butanediol/3-methylq, 4) were added. • Butanediol) Ether bis(4-aminobenzoate), our 7-butyrolactone, stirred until a homogeneous solution. Then, 10 g of pentanediol-bis-trimellitic anhydride vinegar and 11_5 g of decanediol-bis-p-trimellitic anhydride were added while stirring for 1 hour while cooling in an ice bath, followed by stirring at room temperature for 6 hours. Then, the polyimine precursor 00 was obtained by pressure filtration of the product using a filter of 5 μM. 139901.doc -36- 201006867 molar ratio of the obtained polydiimine precursor (χ) acid dianhydride and diamine, solid content of the polyimine precursor (x) solution, and weight average molecular weight Shown in Table 1. Synthesis Example 11 Synthesis of Polyimine Precursor (xi) To a two-neck separable flask was added iO.lg of bis(4-aminobenzoate) 1,3-propanedicarboxylate, 133 g of poly Tetra-indenyl-di-p-aminobenzoic acid ester, 105.7 g of γ-butyrolactone was oxidized until it became a homogeneous solution. Then, 10 g of butanediol_bis-p-trimethanol anhydride, u.9 g of decanediol-p-trimellitic anhydride were added, and the mixture was stirred while being cooled in an ice bath for an hour, and then stirred at room temperature. hour. Then, the polyimide precursor (xi) was obtained by pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine oxime drive (xi) solution, and the weight average molecular weight of the obtained polyimine precursor (Xi) are shown in Table 1. Synthesis Example 12 Synthesis of Polyimine Precursor (χϋ) To a two-neck separable flask, 9.8 g of bis(4-aminobenzoic acid) 1,3-propanedicarboxylate and 12.9 g of polyoxytetraester were added. The fluorenylene-di-p-amino benzoate and 110.4 g of γ-butyrolactone were stirred until they became a homogeneous solution. Then, 10 g of pentanediol-p-trimellitic anhydride ester and 14.6 g of eicosanediol-bis-p-trimellitic acid ester were added, and the mixture was stirred for 1 hour while cooling in an ice bath, and then allowed to stand at room temperature. Mix for 6 hours. Then, a polyimine precursor (χΗ) was obtained by pressure filtration of the product using a filter of 5 μηη. The molar ratio of the acid two-needle to diamine molar ratio, the solid content of the polyamidene precursor (xii) solution, and the weight average molecular weight of the obtained polyimine precursor (xii) are shown in Table 1. 139901.doc •37- 201006867 Synthesis Example 13 Synthesis of Polyimine Precursor (xiii) 98 g of bis(4-aminobenzoic acid) 1,3-propanedicarboxylate, 12.9 was added to a three-neck separable flask. G, polytetramethylene di-p-aminobenzoate, 123.9 g of γ-butyrolactone was stirred until it became a homogeneous solution. Then, 10 g of pentanediol·bis-p-trimellitic anhydride ester and 2〇4 g of polypropylene glycol-p-trimellitic anhydride were added, and the mixture was stirred for one hour while cooling in an ice bath, and then the mixture was stirred at room temperature. hour. Then, the polyimine precursor was obtained by subjecting the product to a pressure of 5 μm of a transition vessel. Table 1 shows the molar ratio of the acid dioxan to diamine, the solid content of the polyamidene precursor (xiii) solution, and the weight average molecular weight of the obtained polyamidene precursor (xiii). Synthesis Example 14 Synthesis of Polyimine Precursor (xiv) To a two-neck separable flask, 9.4 g of 1,3_bis(3-aminophenoxy)benzine and 73 g of γ-butane S were added. The purpose is to carry out the mixing until it becomes a homogeneous solution. Then, 10 g of 4,4,-oxydiphthalic dianhydride was added, and the mixture was stirred for 1 hour while cooling in an ice bath, followed by stirring at room temperature for 6 hours. Then, the polyimine precursor (xiv) was obtained by pressure filtration of the product using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xiv) solution, and the weight average molecular weight of the obtained polyimine precursor (xiv) are shown in Table 1. Synthesis Example 15 Synthesis of Polyimine Precursor (χν) To a three-neck separable flask, 7.1 g of 1,3-bis(3-aminobenzone) stupid and 64.3 g of γ-butyrolactone were added. Stir until it becomes a homogeneous solution. Then, 10 g of ethylene glycol-bis-p-benzoic acid ester was added and cooled in an ice bath 139901.doc _ _ _ . 201006867 One side was mixed for 1 hour, and then stirred at room temperature for 6 hours. Then, the polyimide precursor (XV) is obtained by pressure filtration of the product using a filter of 5 μη! ° The obtained acid dianhydride precursor of the polyimine precursor (χν) and the diamine The solid content of the molar ratio, the polyimide intermediate (xv) solution, and the weight average sub-quantity are shown in Table 1. Synthesis Example 16 Synthesis of Polyimine Precursor (Xvi) To a two-neck separable flask, 2·7 g of 1,3-bis(3-aminophenyloxy)benzene and 26.3 g of polyoxygen oxide were added. The fluorenylene-di-p-amino benzoate, 91 g of γ-butyrolactone was scrambled until it became a homogeneous solution. Then, 10 g of 4,4,-oxydiphthalic dianhydride was added, and the mixture was stirred for 1 hour while cooling in an ice bath, followed by stirring at room temperature for 6 hours. Then, the polyimine precursor (xvi) was obtained by pressure filtration of the product using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xvi) solution, and the weight average molecular weight of the obtained polyimine precursor (?νί) are shown in Table 1. Synthesis Example 17 Synthesis of Polyimine Precursor (χνπ) To a three-neck separable flask, 2 〇§丨, 3_bis(3_aminophenoxy)benzene, and 19.9 g of polyoxytetramethylene were added. The bis-di-amino benzoate, 74.4 g of γ-butyrolactone, was stirred until it became a homogeneous solution. Then, 10 g of ethylene glycol-bipartic acid tricarboxylate was added, and the mixture was stirred for 1 hour while cooling in an ice bath. Thereafter, the mixture was stirred at room temperature for 6 hours. Then, the polyimine precursor (xvii) was obtained by pressure filtration using a 5 μm filter. The molar ratio of the acid dianhydride to the diamine, the solid content of the polyimine precursor (xvii) solution, and the weight of the obtained polybendimimine precursor (xvii), 139901.doc •39· 201006867, the average molecular weight Shown in Table 1. (Combination of Photosensitive Polyimine Precursor Composition) First, a specific amount of the polyimide precursor is divided into small portions and placed in a container such as a glass bottle. Then, a specific amount of an additive such as a photosensitizer or a dissolution inhibitor is formulated and stirred by a rotary mixer or the like until uniform. A photosensitive polyimide intermediate precursor composition can be obtained by these operations. (Measurement of weight average molecular weight) 1 : Determination of molecular weight of polyimine precursor The measured polyamidiamine precursor 〇〇丨g was measured by a precision balance and dissolved in 10 g of dimethyl decylamine (and pure light) Manufactured by the Pharmaceutical Industry Corporation). The solution was passed through a 10 μm transition vessel, and the molecular weight was measured by a gel permeation chromatography instrument (manufactured by Tosoh Corporation) having a tsk-GEL SUPER® (trade name, manufactured by Tosoh Corporation). 2. Determination of the weight average molecular weight of the photosensitive polyamid A-body composition coating: by placing a polysulfon film (manufactured by Unitika Co., Ltd.) on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, The polyester film was attached by vacuum suction. On the polyester film, a photosensitive polyimide intermediate precursor composition was coated using an applicator having a gap of 67 5 μm (manufactured by Pine Science Co., Ltd.). Desolvation: Desolvation was carried out at 95 ° C for 30 minutes using a dryer (SPH-201, manufactured by Espec). Molecular weight measurement: 0.01 g of a photosensitive polyimine imprint composition obtained by measuring a solvent after a precision balance was dissolved in 10 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.). The solution was filtered through a 10 μπ1 139901.doc -40·201006867 filter, and a gel permeation chromatograph (Scheme Spectrometer) equipped with TSIC_GEL SUPER HM-H (trade name 'T〇s〇h Co., Ltd.) was used. The company manufactures) Determination of molecular weight. The molecular weight ratio is calculated by setting the weight average molecular weight of the photosensitive polyimide precursor composition varnish to M1, and setting the weight average molecular weight of the photosensitive polyimide intermediate precursor composition after the solvent removal to M2. The molecular weight ratio was calculated by the following formula 1. Molecular weight ratio = M2 / M1 m _ (bending test) Coating: A polyester film (manufactured by Unitika & Seychelles) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed. The polyester film is attached. On the polyester film, a photosensitive polyimide intermediate precursor composition was applied using an applicator having a gap of 1 μm (manufactured by Pine Science Co., Ltd.). Solvent removal: Desolvation was carried out by using a dryer (SPH-201, manufactured by ESPEC), φ at 95 ° C for 30 minutes. Bending test: The film obtained by removing the solvent was bent by 18 ( (curl-folded) to visually observe cracking and peeling of the photosensitive layer. The case where there is no crack or peeling is referred to as 〇', and the case where cracking or peeling is performed is referred to as X. (Evaluation of warpage) Coating: The polyester film was attached by vacuum adsorption by placing a polyester film (manufactured by Unitika Co., Ltd.) on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated. On the polyester film, a photosensitive polyimide intermediate precursor group 139901.doc-41 - 201006867 was coated with an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.). Desolvation: The solvent was removed by a dryer (SPH-2®, manufactured by ESPEC) at 95 ° C for 30 minutes. Vacuum pressing: The substrate was subjected to a solvent removal step using a polyimide film (Kapt〇n EN_l〇〇, trade name, manufactured by T〇ray-DUpont Co., Ltd.) using a vacuum press (sa_5〇i, manufactured by Tester Industries, Inc.). The photosensitive dry film obtained was subjected to vacuum pressing at a pressing temperature of 1 Torr (TC, a pressing pressure of 〇5 Mpa, a vacuum of 15 kPa, and a pressing time of i minutes. Baking: using a dryer (8ΡΗ- 2 (Η 'Manufactured by Aspec Co., Ltd.), curing was carried out under the conditions shown in Table 5. Measurement of warpage: The film obtained after baking was cut to a length of 5 cm and a width of 5 cm, and after removing static electricity, the ruler was used. The warpage of ruthenium was measured. (Example 1) Evaluation of a photosensitive polyimide intermediate precursor composition comprising a polyimide intermediate and a sensitizer The polyimine precursor obtained in Examples 1 to 3 was prepared. The solution 丨〇g, the sensitizer is 2 parts by mass of the brewed diazide compound (formula 16) 0·42 g with respect to the solid content of the polyimide intermediate, and is mixed at a ratio shown in Table 2, Put in 2 〇"^ glass bottles, using a rotary mixer (MR-5, As One Shuzo) for granted stirred until homogeneous, to obtain a photosensitive polyimide precursor composition (1-3) The evaluation results are shown in Table 2. 139901.doc -42- 201006867 [of 23]

溶解抑制劑使用3,_羥基乙醯笨胺之感光性聚醯亞胺前驅 體組合物之評價 將合成例1至3中獲得之聚醯亞胺前驅體溶液1〇 g、作為 感光劑之相對於聚酿亞胺前驅體固形分而為質量份之酿 二豐氮化合物(式16)〇·42 g、相對於聚醯亞胺前驅體而為 12·5質里伤之3_备基乙醯笨胺〇26邑,&表3所示之比例加 ' 放入至2〇 “玻璃瓶♦,利用旋轉混合器(MR-5, △司製進盯攪拌直至均勻,獲得感光性聚醯亞 胺前驅體組合物(4至6)。將評價結果示於表3中。 139901.doc -43- 201006867 [化 23]Evaluation of a photosensitive polyimine precursor composition using 3,-hydroxyethyl sulfonamide as a dissolution inhibitor 1 〇g of the polyamidene precursor solution obtained in Synthesis Examples 1 to 3 as a sensitizer In the mass fraction of the brewing imine precursor, it is a mass fraction of the brewing nitrogen compound (formula 16) 〇·42 g, and the microbial imide precursor is 12.5 mass injuring 3_preparation base B醯 〇 〇 〇 邑 邑 & & & & & & & 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表The imine precursor composition (4 to 6). The evaluation results are shown in Table 3. 139901.doc -43- 201006867 [Chem. 23]

(16) (實施例3) 使用酚化合物之感光性聚醯亞胺前驅體組合物之評價 將合成例1至3中獲得之聚醯亞胺前驅體溶液1〇 g、作為 感光劑之相對於聚醯亞胺前驅體固形分而為2〇質量份之由 上述通式(16)所表示之醌二疊氮化合物〇 42 g、相對於聚 醯亞胺前驅體而為20質量份之由下述通式(丨7)所表示之酚 化合物0.42 g,以表4所示之比例加以混合,放入至2〇 ο。 玻璃瓶中,利用旋轉混合器(mr_5,As One公司製造)進行 攪拌直至均勻,獲得感光性聚醯亞胺前驅體組合物(7至 9)。將評價結果示於表4中。 139901.doc 201006867 [化 24](16) (Example 3) Evaluation of Photosensitive Polyimine Precursor Composition Using Phenol Compound 1 μg of the polyimide precursor solution obtained in Synthesis Examples 1 to 3 as a sensitizer The amount of the quinonediazide compound 〇42 g represented by the above formula (16) and 20 parts by mass relative to the polyamidene precursor is 2 parts by mass of the polyamidene precursor solid content. 0.42 g of the phenol compound represented by the above formula (丨7) was mixed at a ratio shown in Table 4, and placed in 2 〇. In the glass bottle, the mixture was stirred until uniform by a rotary mixer (mr_5, manufactured by As One Co., Ltd.) to obtain a photosensitive polyimide intermediate composition (7 to 9). The evaluation results are shown in Table 4. 139901.doc 201006867 [Chem. 24]

(17) (比較例1) 除使用合成例14至15中獲得之聚醯亞胺前驅體溶液1〇 g 之外,以與實施例1同樣之方式獲得表丨所示之感光性聚醯 亞胺前驅體組合物(10至11)。將評價結果示於表2中。 (比較例2) 除使用合成例14至15中獲得之聚醯亞胺前驅體溶液1〇 g(17) (Comparative Example 1) The photosensitive polyazide shown in Table 获得 was obtained in the same manner as in Example 1 except that the polyimide polyimide precursor solution obtained in Synthesis Examples 14 to 15 was used in an amount of 1 〇g. Amine precursor composition (10 to 11). The evaluation results are shown in Table 2. (Comparative Example 2) In addition to the polyethylenimine precursor solution obtained in Synthesis Examples 14 to 15, 1 〇 g

之外,以與實施例2同樣之方式獲得表2所示之感光性聚醯 亞胺前驅體組合物(12至13)。將評價結果示於表3中。 (比較例3) 除使用合成例14至15中獲得之聚醯亞胺前驅體溶液1〇 g 之外,以與實施例3同樣之方式獲得表4所示之感光性聚醯 亞胺前驅體組合物(14至15)。將評價結果示於表4中。 於將感光性聚酿亞胺前驅體組合物用於撓性印刷電路板 之覆盖膜專之情形時,必需牙丨丨田 禺利用包含鹼性水溶液之顯影液 139901.doc -45· 201006867 進行微影而獲得所需圖案。又,除該組合物之分子量不隨 時間變化之外,亦尋求黏性優異,烘烤後積層有覆蓋膜之 積層體無翹曲,即便彎曲亦不產生剝離、破裂,積層體不 燃燒等性能。 (感光性聚醯亞胺前驅體組合物之性能評價) 1)材料穩定性之評價 塗敷:藉由於可真空吸附及加熱之塗敷台(松木科學公 司製造)上放置聚酯膜(Unitika公司製造),進行真空吸附而 貼附該聚酯膜。於該聚酯膜上,使用間隙為67.5 μιη之敷 料器(松木科學公司製造)來塗佈感光性聚醯亞胺前驅體組 合物。 去溶劑:利用乾燥機(SPH-201,愛斯佩克公司製造), 以9 5 C下3 0分鐘之條件進行去溶劑。 分子量測定:利用精密天平測量去溶劑後所獲得之感光 性聚醯亞胺前驅體組合物0.01 g,溶解於1〇 g之二甲基甲 醯胺(和光純藥工業公司製造)中。將該溶液通過 10 μιη 之 過濾、器進行過濾,利用具備TSK-GEL SUPER ΗΜ-Η(商品 名’ T〇s〇h公司製造)之凝膠滲透層析儀(日本分光公司製 造)測定分子量。 刀子量比之算出.將感光性聚醯亞胺前驅體組合物清漆 之重量平均分子量設為Ml,且將去溶劑後該感光性聚醯 亞胺前駆體組合物之重量平均分子量設為M2時,利用以 下式1算出分子量比。 分子量比=M2/M1 139901.doc -46 · 201006867 2:微影性能評價 塗敷:藉由於可真空吸附及加熱之塗敷台(松木科學公 司製造)上放置聚醋膜(Unitika公司製造),進行真空吸附而 貼附該聚酯膜。於該聚酯膜上,使用間隙為67·5 μϊη之敷 料器(松木科學公司製造)來塗佈感光性聚醯亞胺前驅體組 合物。The photosensitive polyimide intermediate precursor compositions (12 to 13) shown in Table 2 were obtained in the same manner as in Example 2. The evaluation results are shown in Table 3. (Comparative Example 3) The photosensitive polyimine precursors shown in Table 4 were obtained in the same manner as in Example 3, except that 1 μg of the polyimide precursor solution obtained in Synthesis Examples 14 to 15 was used. Composition (14 to 15). The evaluation results are shown in Table 4. In the case where the photosensitive polyimide intermediate precursor composition is used for a cover film of a flexible printed circuit board, it is necessary to carry out microfiltration using a developing solution containing an alkaline aqueous solution 139901.doc -45· 201006867 Obtain the desired pattern. Further, in addition to the fact that the molecular weight of the composition does not change with time, the adhesiveness is also excellent, and the laminate having the cover film after baking has no warpage, and even if it is bent, no peeling or cracking occurs, and the laminated body does not burn. . (Evaluation of Performance of Photosensitive Polyimine Precursor Composition) 1) Evaluation of Material Stability Coating: Polyester film was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated (Unitika Corporation) Manufacturing), vacuum-adsorbing and attaching the polyester film. On the polyester film, a photosensitive polyimide intermediate composition was coated with an applicator having a gap of 67.5 μm (manufactured by Pine Science Co., Ltd.). Desolvation: The solvent was removed by a dryer (SPH-201, manufactured by ESPEC) under the conditions of 30 ° C for 30 minutes. Molecular weight measurement: 0.01 g of a photosensitive polyimide intermediate precursor composition obtained by measuring a solvent after a precision balance was dissolved in 1 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.). The solution was filtered through a filter of 10 μm, and the molecular weight was measured by a gel permeation chromatograph (manufactured by JASCO Corporation) equipped with TSK-GEL SUPER® (trade name: manufactured by T〇s〇h Co., Ltd.). The ratio of the amount of the knife is calculated. The weight average molecular weight of the photosensitive polyimide intermediate composition varnish is M1, and the weight average molecular weight of the photosensitive polyimide intermediate composition after the solvent removal is M2. The molecular weight ratio was calculated by the following formula 1. Molecular weight ratio = M2 / M1 139901.doc -46 · 201006867 2: lithographic performance evaluation coating: by placing a polyester film (manufactured by Unitika Co., Ltd.) on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, The polyester film was attached by vacuum suction. On the polyester film, a photosensitive polyimide intermediate composition was applied using an applicator having a gap of 67·5 μϊη (manufactured by Pine Science Co., Ltd.).

去溶劑:利用乾燥機(SPH_201,愛斯佩克公司製造), 以95 °C下3 0分鐘之條件進行去溶劑。 真空壓製.首先利用15 wt%之過硫酸鈉水溶液清洗 FCCL。繼而,利用真空壓製機(SA-501,1Tester產業公司 製造)’將去溶劑步驟中獲得之感光性乾式膜,以壓製溫 度為10(TC、壓製壓力為〇5 Mpa、真空度為15 kpa、壓製 k間為1分鐘之條件進行真空壓製。 活性光線照射:剥離真空壓製步驟中獲得之積層體之支 持膜,使用超尚壓水銀燈(HMW_2〇1KB,〇仏公司製造), 以曝光量為1.5 J/cm2之條件照射紫外線。 微影:利用喷霧型顯影機,顯影液使用i 之碳酸納 水溶液,以顯影溫度為机、喷霧壓力為G i8 Mb之條 件,測置直至UV照射部 >完全溶解為止之時間(以下記載 為斷點(break point))。繼❿,以斷點之12倍顯影時間進行 H 用噴霧式清洗器’於蒸德水中進行顯影 ]1/3之凊洗,進而利用0.2wt%之硫酸水溶液進行3〇秒 之清洗。 微影性能 根據顯影時間、殘膜率及圖案形狀來判斷微 13990l.doc -47- 201006867 影性能。 顯影時間··將顯影時間為90秒以下之感光性聚醯亞胺前 驅體組合物記為〇,將超過90秒之感光性聚醯亞胺前驅體 組合物記為X。 殘膜率測定:將顯影前之感光層之膜厚設為T1,且將顯 影後之感光層之膜厚設為T2,利用以下數學公式算出。 殘膜率=T2/Tlxl〇〇(%)Desolvation: The solvent was removed by a dryer (SPH_201, manufactured by ESPEC) at a temperature of 95 ° C for 30 minutes. Vacuum pressing. The FCCL was first washed with a 15 wt% aqueous solution of sodium persulfate. Then, using a vacuum press (SA-501, manufactured by 1 Tester Industries, Inc.), the photosensitive dry film obtained in the solvent removal step was pressed at a temperature of 10 (TC, a pressing pressure of 〇5 Mpa, a vacuum of 15 kPa, Vacuum pressing was performed under the condition of pressing for 1 minute between k. Active light irradiation: The support film of the laminate obtained in the vacuum pressing step was peeled off, and an excess pressure mercury lamp (HMW 2 〇 1 KB, manufactured by Sigma) was used, and the exposure amount was 1.5. The conditions of J/cm2 are irradiated with ultraviolet rays. The lithography: using a spray type developing machine, the developing solution is a sodium carbonate aqueous solution of i, and the developing temperature is set as the machine, and the spray pressure is G i8 Mb, and the measurement is performed until the UV irradiation unit > The time until it is completely dissolved (hereinafter referred to as a break point). Following the enthalpy, the development time is 12 times the break point, and the H is sprayed with a spray cleaner 'developed in steamed water'. Further, the cleaning was carried out for 3 seconds using a 0.2 wt% aqueous sulfuric acid solution. The lithography performance was judged according to the development time, the residual film ratio, and the shape of the pattern, and the development performance was observed. The photosensitive polyimide intermediate precursor composition having a time of 90 seconds or less is referred to as ruthenium, and the photosensitive polyimide intermediate precursor composition of more than 90 seconds is referred to as X. Residual film rate measurement: Photosensitive layer before development The film thickness was set to T1, and the film thickness of the photosensitive layer after development was set to T2, and was calculated by the following mathematical formula: Residual film rate = T2 / Tlxl 〇〇 (%)

圖案形狀:使用光學顯微鏡(ECLIPS LV100,尼康公司 製造),對微影後之圖案,以明視野、100倍之條件實施 100 μπι圓圈圖案之形狀觀察。將保持圖案形狀者記為〇, 將圖案變形者記為X。 3 :感光性乾式膜之黏性評價 塗敷:藉由於可真空吸附及加熱之塗敷台(松木科學公 司製造)上放置聚酯膜(Unitika公司製造),進行真空吸附而 貼附該聚酯膜。於該聚酯膜上,使用間隙為67 5 pm之敷 料器(松木科學公司製造)來塗佈感光性聚醯亞胺前驅體組 合物。 去'合劑.利用乾燥機(SPH_2〇 1,愛斯佩克公司製迕), 以95。(:下30分鐘之條件進行去溶劑。 。 黏性評價:以觸診評價去溶劑後之感光層之黏著有無。 將沾上才日紋者έ己為χ,冑未沾上指紋者記為。。 4 :耐折性評價 愛斯佩克公司製 固化.微影後,使用乾燥機(SPH-201 造),以表5所示之條件進行固化。 139901.doc •48- 201006867 彎折試驗:將固化後所獲得之膜彎折(捲邊摺疊)丨80 度,以目視觀察覆蓋膜之破裂、剝離。將無破裂、剝離之 情形記為〇’將有破裂、剝離之情形記為X。 5 :翹曲評價 塗敷:藉由於可真空吸附及加熱之塗敷台(松木科學公 司製造)上放置聚酯膜(Unitika公司製造),進行真空吸附而 貼附該聚醋膜。於該聚酯膜上’使用間隙為67 5 μιη之敷 # 料器(松木科學公司製造)來塗佈感光性聚醯亞胺前驅體組 合物。 去溶劑:利用乾燥機(SPH-201,愛斯佩克公司製造), 以95°C下30分鐘之條件進行去溶劑。 真二壓製.基材使用聚醯亞胺膜(Kapt〇ri εν- 1 〇〇,商品 名,T〇ray-DuP〇nt公司製造)’利用真空壓製機(sa_5〇i,Pattern shape: An optical microscope (ECLIPS LV100, manufactured by Nikon Corporation) was used to observe the shape of the 100 μπι circle pattern on the lithographic pattern with a clear field of view and 100 times. The person who keeps the pattern shape is denoted as 〇, and the person who changes the pattern is denoted by X. 3: Viscosity evaluation coating of the photosensitive dry film: a polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating station (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to attach the polyester. membrane. On the polyester film, a photosensitive polyimide intermediate precursor composition was coated using an applicator having a gap of 67 5 pm (manufactured by Pine Science Co., Ltd.). Go 'mixture. Use a dryer (SPH_2〇1, manufactured by Espeke) to 95. (: Desolvation in the next 30 minutes. Viscosity evaluation: The adhesion of the photosensitive layer after solvent removal is evaluated by palpation. 4: Folding resistance evaluation After curing by espec company, lithography was carried out using a dryer (manufactured by SPH-201) and cured under the conditions shown in Table 5. 139901.doc •48- 201006867 Bending test : The film obtained after curing was bent (folded and folded) 丨 80 degrees to visually observe the cracking and peeling of the cover film. The case of no cracking or peeling was recorded as 〇 'The case of cracking and peeling was recorded as X 5: Warpage evaluation coating: A polyester film (manufactured by Unitika Co., Ltd.) was placed on a coating table (manufactured by Pine Science Co., Ltd.) which can be vacuum-adsorbed and heated, and vacuum-adsorbed to adhere the polyester film. On the polyester film, a photosensitive polyimide polyimide precursor composition was applied using a spacer of 67 5 μm (manufactured by Pine Science Co., Ltd.). Desolvent: using a dryer (SPH-201, Espe Made by the company, it is carried out at 95 ° C for 30 minutes. Agent. Shinji press. Substrate using polyimide film (Kapt〇ri thousand and εν- 1, trade name, manufactured by T〇ray-DuP〇nt) 'using a vacuum press machine (sa_5〇i,

Tester產業公司製造)’將去溶劑步驟中獲得之感光性乾式 膜,以壓製溫度為1〇〇。〇、壓製壓力為〇·5 Mpa、真空度為 Φ 15 kPa、壓製時間為1分鐘之條件進行真空壓製。 烘烤:使用乾燥機(SPH-201,愛斯佩克公司製造),以 表5所示之條件進行固化。 麵曲之測定:將供烤後所獲得之膜切取長5 cm、寬5 cm,除去靜電後,使用尺測定膜之翹曲。 6 :阻燃性評價 直至塗敷、去溶劑為止,以與翹曲之評價 施。 只 真空壓製:基材使用聚酿亞胺膜(Κ3ρ_购⑼,商品 139901.doc 49· 201006867 名’ T〇ray-Dup〇nt公司製造),利用真空壓製機似州,Tester Industries, Inc.) The photosensitive dry film obtained in the solvent removal step was pressed at a temperature of 1 Torr. Vacuum pressing was carried out under the conditions of 〇, pressing pressure of M·5 Mpa, vacuum of Φ 15 kPa, and pressing time of 1 minute. Baking: Curing was carried out under the conditions shown in Table 5 using a dryer (SPH-201, manufactured by ESPEC). Measurement of facial curvature: The film obtained after baking was cut to a length of 5 cm and a width of 5 cm, and after removing static electricity, the warpage of the film was measured using a ruler. 6 : Evaluation of flame retardancy Evaluation of warpage was carried out until coating and solvent removal. Vacuum pressing only: The substrate is made of a polyimide film (Κ3ρ_购(9), commercial 139901.doc 49·201006867 'T〇ray-Dup〇nt company), using a vacuum press like a state,

Tester產業公司製造)’將去溶劑步驟中獲得之感光性乾式 膜’以壓製溫度為1G(rc、壓㈣力狀5 Mpa、真空度為 15 ^、壓料間為1分鐘之條件,對《亞胺膜之兩面 進行真空壓製。 供烤:使用乾燥機(SPH_2〇1,愛斯佩克公司製造),以 表5所示之條件進行固化。 阻燃性試驗:將烘烤步驟中獲得之膜切取寬1 em、長5 繼而以目視觀察試驗片之一端著火且火勢蔓延之過鲁 程。將中途媳滅之試料記為。,將全部燒完之試料記為X。 (實施例4至22) 相對於a成例2至13中獲得之聚醯亞胺前驅體溶液1〇 g ’將各種添加劑以表6-1所示之比例加以混合,放入至20 CC玻璃瓶中’利用旋轉混合器(MR-5,As One公司製造)進 行授掉直至均勻’獲得感光性聚醯亞胺前驅體組合物(16 至34)。將該等感光性聚醯亞胺前驅體組合物之評價結果 示於表7-1中。 醫 (比較例4至7) 才目對於合成例16至17中獲得之聚醯亞胺前驅體溶液1〇 g,將各種添加劑以表62所 示之比例加以混合’放入至20 CC玻璃瓶中’利用旋轉混合器(MR-5,As One公司製造)進 行授掉直至均勻,獲得感光性聚醯亞胺前驅體組合物(35 至38)。將該等感光性聚醯亞胺前驅體組合物之評價結果 示於表7-2中。 139901.doc • 50· 201006867 [表l] 合成例編號 聚醯亞胺前驅體溶液 酸二酐/二胺 (莫耳比) 固形分 重量平均分子量 1 ⑴ 100/100 21 wt% 80,000 2 (ii) 100/100 21 wt% 108,000 3 (iii) 100/100 21 wt% 113,000 4 (iv) 100/91 30 wt% 41,000 5 (v) 100/96 30 wt% 78,000 6 (vi) 100/94 30 wt% 58,000 7 (vii) 100/91 30 wt% 42,000 8 (viii) 100/94 30 wt% 61,000 9 (ix) 100/94 30 wt% 59,500 10 (x) 100/94 30 wt% 57,000 11 (xi) 100/94 30 wt% 58,500 12 (xii) 100/94 30 wt% 61,200 13 (xiii) 100/94 30 wt% 61,000 14 (xiv) 100/100 21 wt% 100,000 15 (xv) 100/100 21 wt% 85,000 16 (xvi) 100/94 30 wt% 65,000 17 (xvii) 100/94 30 wt% 62,000 [表2] 實施例1及比較例1之結果Tester Industries, Inc.) 'Photosensitive dry film obtained in the solvent removal step' is pressed at a temperature of 1 G (rc, pressure (4) force 5 Mpa, vacuum 15 ^, and 1 minute between presses) Vacuum pressing on both sides of the imide film. For baking: using a dryer (SPH_2〇1, manufactured by ESPEC), curing was carried out under the conditions shown in Table 5. Flame retardancy test: obtained in the baking step The film was cut to a width of 1 em and a length of 5, and then one of the test pieces was visually observed to ignite and the fire spread over the course. The sample annihilated in the middle was recorded as the sample, and all the burned samples were recorded as X. (Example 4 to 22) Relative to a polyimine precursor solution obtained in Examples 2 to 13 1〇g 'mix various additives in the ratios shown in Table 6-1 and put them into a 20 CC glass bottle. A mixer (MR-5, manufactured by As One Co., Ltd.) was dispensed until uniform to obtain a photosensitive polyimide intermediate composition (16 to 34). Evaluation of the photosensitive polyimide precursor compositions The results are shown in Table 7-1. The doctors (Comparative Examples 4 to 7) were for the synthesis examples 16 to 17. 1 μg of the obtained polyimide precursor solution was prepared, and various additives were mixed in the ratio shown in Table 62 and placed in a 20 CC glass bottle using a rotary mixer (MR-5, manufactured by As One Co., Ltd.). The photosensitive polyimide precursor composition (35 to 38) was obtained until it was uniform. The evaluation results of the photosensitive polyimide precursor compositions are shown in Table 7-2. 139901.doc • 50· 201006867 [Table 1] Synthesis Example No. Polyimine precursor solution Acid dianhydride/diamine (Morby) Solid weight average molecular weight 1 (1) 100/100 21 wt% 80,000 2 (ii) 100/100 21 Wt% 108,000 3 (iii) 100/100 21 wt% 113,000 4 (iv) 100/91 30 wt% 41,000 5 (v) 100/96 30 wt% 78,000 6 (vi) 100/94 30 wt% 58,000 7 (vii 100/91 30 wt% 42,000 8 (viii) 100/94 30 wt% 61,000 9 (ix) 100/94 30 wt% 59,500 10 (x) 100/94 30 wt% 57,000 11 (xi) 100/94 30 wt % 58,500 12 (xii) 100/94 30 wt% 61,200 13 (xiii) 100/94 30 wt% 61,000 14 (xiv) 100/100 21 wt% 100,000 15 (xv) 100/100 21 wt% 85,000 16 (xvi) 100/94 30 wt% 65,000 17 (xvii) 100/94 30 wt% 62,000 [Table 2] Results of Example 1 and Comparative Example 1

\ 感光性聚醯亞胺 前驅體組合物 聚醯亞胺前驅體 溶液 感光劑 M2/M1 捲邊摺疊 實施例1 1 合成例1 l〇g 0.42 g 0.98 〇 2 合成例2 10 g 0.42 g 0.97 〇 3 合成例3 10 g 0.42 g 0.97 〇 比較例1 10 合成例14 10 g 0.42 g 0.56 X 11 合成例15 10 g 0.42 g 0.51 XPhotosensitive Polyimine Precursor Composition Polyimine Precursor Solution Sensitizer M2/M1 Crimping Folding Example 1 Synthesis Example 1 l〇g 0.42 g 0.98 〇2 Synthesis Example 2 10 g 0.42 g 0.97 〇 3 Synthesis Example 3 10 g 0.42 g 0.97 〇Comparative Example 1 10 Synthesis Example 14 10 g 0.42 g 0.56 X 11 Synthesis Example 15 10 g 0.42 g 0.51 X

[表3] 實施例2及比較例2之結果[Table 3] Results of Example 2 and Comparative Example 2

\ 感光性聚醯亞胺 前驅體組合物 聚醯亞胺前驅體 溶液 感光劑 3'-羥基乙 醯笨胺 M2/M1 捲邊摺疊 實施例2 4 合成例1 10 g 0.42 g 0.26 g 0.95 〇 5 合成例2 10 g 0.42 g 0.26 g 0.95 〇 6 合成例3 10 g 0.42 g 0.26 g 0.95 〇 比較例2 12 合成例14 10 g 0.42 g 0.26 g 0.55 X 13 合成例15 10 g 0.42 g 0.26 g 0.50 X 139901.doc -51 - 201006867 [表4] 實施例3及比較例3之結果Photosensitive Polyimine Precursor Composition Polyimine Precursor Solution Sensitizer 3'-Hydroxyethylhydrazine M2/M1 Crimping Folding Example 2 4 Synthesis Example 1 10 g 0.42 g 0.26 g 0.95 〇5 Synthesis Example 2 10 g 0.42 g 0.26 g 0.95 〇6 Synthesis Example 3 10 g 0.42 g 0.26 g 0.95 〇Comparative Example 2 12 Synthesis Example 14 10 g 0.42 g 0.26 g 0.55 X 13 Synthesis Example 15 10 g 0.42 g 0.26 g 0.50 X 139901.doc -51 - 201006867 [Table 4] Results of Example 3 and Comparative Example 3

\ 或光性聚醯亞胺 前驅趙組合物 聚醯亞胺前驅體 溶液 感光劑 酚化合物 M2/M1 捲邊摺疊 實施例3 7 合成例1 10g 0.42 g 0.42 g 0.92 Ο 8 合成例2 10 g 0.42 g 0.42 g 0.95 〇 9 合成例3 10 g 0.42 g 0.42 g 0.90 〇 比較例3 14 合成例14 10 g 0.42 g 0.42 g 0.51 X 15 合成例15 10 g 0.42 g 0.42 g 0.49 X\ or Photoreactive Polyimine Precursor Zhao Composition Polyimine Precursor Solution Sensitizer Phenol Compound M2/M1 Crimping Folding Example 3 Synthesis Example 1 10g 0.42 g 0.42 g 0.92 Ο 8 Synthesis Example 2 10 g 0.42 g 0.42 g 0.95 〇9 Synthesis Example 3 10 g 0.42 g 0.42 g 0.90 〇Comparative Example 3 14 Synthesis Example 14 10 g 0.42 g 0.42 g 0.51 X 15 Synthesis Example 15 10 g 0.42 g 0.42 g 0.49 X

[表5] 固化條件 溫度 40°C —> 110°C —> 160°C 保持時間 10分鐘 - 60分鐘 - 60分鐘 升溫速度 - 5。。/分鐘 5°C/分鐘 - [表 6-1] 感光性聚醯亞胺前驅體組合物之調配表 實施例 組合物 No. 聚醯胺酸 添加劑(單位g) 溶解抑制劑1 溶解抑制劑2 阻燃劑 熱鹼產生劑 感先劑 4 16 合成例2 - 式26 0.262 式29 0.21 - 式34 0.47 5 17 合成例3 - 式26 0.262 式29 0.21 - 式34 0.47 6 18 合成例4 式25 0.075 式26 0.225 式29 0·3 式32 0.09 式34 0_9 7 19 合成例5 式25 0.075 式26 0.225 式29 0.3 - 式34 0_9 8 20 合成例6 - - 式29 0.3 式32 0.06 式34 0.9 9 21 合成例6 式25 0.075 式26 0.225 殳29 0.3 式32 0.06 式34 0.9 10 22 合成例6 - 式26 0.375 式29 0_3 式32 0.045 式34 0.68 11 23 合成例7 式25 0.075 式26 0.225 式29 0_3 式32 0.09 式34 0.9 12 24 合成例7 式25 0.075 式26 0.225 式29 0.3 式32 0.09 式34 0.9 13 25 合成例7 式25 0.075 式26 0.225 式30 0.3 式32 0.09 式34 0.9 14 26 合成例7 式25 0.075 式26 0.225 ^,31 0.3 式32 0.09 式34 0.9 15 27 合成例7 式25 0.075 式27 0.225 式29 0_3 式32 0.09 式34 0.9 16 28 合成例7 式25 0.075 式28 0.225 式29 0.3 式32 0.09 式34 0.9 17 29 合成例8 - 式27 0.3 式29 0.3 式34 0.75 18 30 合成例9 式25 0.075 式26 0.225 式29 0.3 式32 0.06 式34 0.9 19 31 合成例10 式25 0.075 式26 0.225 式29 0.3 式32 0.06 式34 0.9 20 32 合成例11 式25 0.075 式26 0.225 夫29 0.3 式32 0.06 式34 0.9 21 33 合成例12 式25 0.075 式26 0.225 式29 0.3 式32 0.06 式34 0.9 22 34 合成例13 式25 0.075 式26 0.225 式29 0.3 式32 0.06 式34 0.9 -52- 139901.doc 201006867 [表 6-2] 感光性聚酿亞胺如驅體组合物之調配表[Table 5] Curing conditions Temperature 40 ° C -> 110 ° C -> 160 ° C Holding time 10 minutes - 60 minutes - 60 minutes Heating rate - 5. . /min 5 ° C / min - [Table 6-1] Preparation of photosensitive polyimide intermediate composition Table Example Composition No. Poly-proline additive (unit g) Dissolution inhibitor 1 Dissolution inhibitor 2 Flame Retardant Hot Alkali Producer Sensitive Agent 4 16 Synthesis Example 2 - Formula 26 0.262 Formula 29 0.21 - Formula 34 0.47 5 17 Synthesis Example 3 - Formula 26 0.262 Formula 29 0.21 - Formula 34 0.47 6 18 Synthesis Example 4 Formula 25 0.075 Formula 26 0.225 Formula 29 0·3 Formula 32 0.09 Formula 34 0_9 7 19 Synthesis Example 5 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 - Formula 34 0_9 8 20 Synthesis Example 6 - - Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 9 21 Synthesis Example 6 Formula 25 0.075 Formula 26 0.225 殳29 0.3 Formula 32 0.06 Formula 34 0.9 10 22 Synthesis Example 6 - Formula 26 0.375 Formula 29 0_3 Formula 32 0.045 Formula 34 0.68 11 23 Synthesis Example 7 Formula 25 0.075 Formula 26 0.225 Formula 29 0_3 Formula 32 0.09 Formula 34 0.9 12 24 Synthesis Example 7 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.09 Formula 34 0.9 13 25 Synthesis Example 7 Formula 25 0.075 Formula 26 0.225 Formula 30 0.3 Formula 32 0.09 Formula 34 0.9 14 26 Synthesis Example 7 Equation 25 0.075 Equation 26 0.225 ^, 31 0.3 Equation 32 0.09 Formula 34 0.9 15 27 Synthesis Example 7 Formula 25 0.075 Formula 27 0.225 Formula 29 0_3 Formula 32 0.09 Formula 34 0.9 16 28 Synthesis Example 7 Formula 25 0.075 Formula 28 0.225 Formula 29 0.3 Formula 32 0.09 Formula 34 0.9 17 29 Synthesis Example 8 - Formula 27 0.3 Formula 29 0.3 Formula 34 0.75 18 30 Synthesis Example 9 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 19 31 Synthesis Example 10 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 20 32 Synthesis Example 11 Formula 25 0.075 Formula 26 0.225 Fraction 29 0.3 Formula 32 0.06 Formula 34 0.9 21 33 Synthesis Example 12 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 22 34 Synthesis Example 13 Formula 25 0.075 Formula 26 0.225 Formula 29 0.3 Formula 32 0.06 Formula 34 0.9 - 52- 139901.doc 201006867 [Table 6-2 Photosensitive polyamines such as the composition of the composition of the body composition

[表 7-1] 覽 實施例之結果[Table 7-1] Overview Results of the examples

201006867 由表2表4所示,使用本發明之聚醯亞胺前驅體之實施 J實知例3表現出分子量(M2/M1)未下降。又,捲邊摺疊 強度亦良好。一般認為該結果之原因在於,藉由使用本發 明之酸二酐,而抑制去溶劑時之聚醯亞胺前驅體之分解, 且抑制分子量下降。另一方面,已知使用其他酸二酐之比 較例1〜比較例3不僅分子量下降並且捲邊摺疊強度下降。 又,如表7-1、表7-2所示,使用本發明之聚醯亞胺前驅 體組合物之實施例4〜實施例22表現出殘膜率良好。尤其於 實施例8中,未添加溶解抑制劑而殘膜率成為9〇%。一般 s忍為該等結果之原因在於,藉由使用本發明之酸二酐,而 抑制顯影步驟争之聚醯亞胺前驅體之分解。實施例4〜實施 例22表現出黏性亦良好。另一方面’於使用其他酸二酐之 任一條件下均表現出殘膜率下降且黏性差。 [產業上之可利用性] 本發明之聚醯亞胺前驅體可適宜用作半導體裝置之表面 保護膜、層間絕緣膜、及再配線用絕緣膜、具有凸塊結構 之裝置之保護膜、多層電路之層間絕緣膜、撓性銅羯板之 面塗層、以及液晶配向膜等。 139901.doc 54-201006867 As shown in Table 4 of Table 2, the use of the polyimine precursor of the present invention was carried out. J Example 3 showed that the molecular weight (M2/M1) did not decrease. Moreover, the curling strength is also good. It is considered that the result is that the decomposition of the polyimine precursor in the case of solvent removal is suppressed by using the acid dianhydride of the present invention, and the molecular weight is suppressed from being lowered. On the other hand, it is known that the ratio of the other acid dianhydrides to the comparative examples 1 to 3 not only lowers the molecular weight but also lowers the curling strength. Further, as shown in Table 7-1 and Table 7-2, Examples 4 to 22 using the polyimide intermediate composition of the present invention exhibited a good residual film ratio. In particular, in Example 8, the dissolution inhibitor was not added and the residual film ratio was 9% by weight. The reason why the general s endures such a result is that the decomposition of the polyimide precursor is inhibited by the development step by using the acid dianhydride of the present invention. Examples 4 to 22 showed good adhesion. On the other hand, under any of the conditions of using other acid dianhydrides, the residual film ratio was lowered and the viscosity was poor. [Industrial Applicability] The polyimide precursor of the present invention can be suitably used as a surface protective film for a semiconductor device, an interlayer insulating film, an insulating film for rewiring, a protective film of a device having a bump structure, and a multilayer. An interlayer insulating film of a circuit, a top coat of a flexible copper plate, and a liquid crystal alignment film. 139901.doc 54-

Claims (1)

201006867 七、申請專利範圍: 一種聚醯亞胺前驅體,其特徵在於包含由下述通式(1)所 表示之酸二軒: [化1]201006867 VII. Patent application scope: A polyimine precursor, which is characterized by comprising an acid dianthine represented by the following general formula (1): [Chemical Formula 1] (1) ❿ (X係具有碳數為3至30之伸烷基之2價有機基;Rl表示氫 原子、碳數為1至⑺之丨價烷基、烷氧基、或鹵基)。 2.如凊求項1之聚醯亞胺前驅體,其中上述聚醯亞胺前驅 體包含由下述通式(2)所表示之二胺: [化2](1) ❿ (X is a divalent organic group having an alkylene group having 3 to 30 carbon atoms; R1 is a hydrogen atom; an alkyl group having 1 to 7 carbon atoms; an alkoxy group; or a halogen group). 2. The polyimine precursor according to claim 1, wherein the polyimine precursor comprises a diamine represented by the following formula (2): (Y係具有碳數為2至2〇之伸烷基之2價有機基;&表示氫 原子、碳數為1至10之1價烷基、垸氧基、或齒基)。 3·如印求項1或2之聚醯亞胺前驅體,其中上述聚醯亞胺前 驅體包含由下述通式(3)所表示之酸二酐: 139901.doc (3) 201006867 [化3](Y is a divalent organic group having an alkylene group having 2 to 2 carbon atoms; & represents a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, a decyloxy group, or a dentate group). 3. The polyimine precursor according to claim 1 or 2, wherein the polyimine precursor comprises an acid dianhydride represented by the following formula (3): 139901.doc (3) 201006867 3] (a表示1至20之整數;b表示3至30之整數;R3表示氫原子 或碳數為1至10之1價烷基)。 4.如請求項1或2之聚醢亞胺前驅體,其中上述聚醯亞胺前 驅體包含由下述通式(4)所表示之二胺: [化4](a represents an integer of 1 to 20; b represents an integer of 3 to 30; and R3 represents a hydrogen atom or a monovalent alkyl group having a carbon number of 1 to 10). 4. The polyimine precursor according to claim 1 or 2, wherein the polyimine precursor comprises a diamine represented by the following formula (4): (4) (Z係碳數為2至20之伸烷基;I表示氫原子、碳數為丄至 10之1價烷基、烷氧基、或齒基;c表示2至3〇之整數)。 5. 如請求項2之聚醯亞胺前驅體,其中上述聚酿亞胺前驅 體包含由下述通式(3)所表示之酸二酐: [化5](4) (Z is a C 2 to 20 alkyl group; I represents a hydrogen atom, a carbon number of 丄 to 10 valence alkyl, alkoxy, or a dentate group; c represents an integer of 2 to 3 〇 ). 5. The polyimine precursor according to claim 2, wherein the above-mentioned polyimine precursor comprises an acid dianhydride represented by the following formula (3): [Chemical 5] 139901.doc (3) 201006867 (a表不1至15之整數;b表示5至20之整數;I表示氫原子 或碳數為1至10之1價烷基)。 6. 如請求項4之聚醯亞胺前驅體,其中由上述通式(4)所表 不之二胺於所有二胺成分中為25莫耳%至75莫耳%。 7. 一種感光性聚醯亞胺前驅體組合物,其特徵在於:其係 含有1〇〇質量份之如請求項i、2或5之聚醯亞胺前驅體、 及5質量份〜35質量份之感光劑。 8. 如請求項7之感光性聚醯亞胺前驅體組合物,其中上述 感光劑包含醌二疊氮結構。 9. 如請求項7之感光性聚醯亞胺前驅體組合物,其中包含 具有酚性羥基之溶解抑制劑。 10. 一種感光性乾式膜’其特徵在於:其係藉由將如請求項 7之感光性聚醯亞胺前驅體組合物塗佈於支持膜上、進 行去溶劑,繼而積層覆蓋膜而得者。 11. 一種撓性印刷電路基板,其特徵在於其係使用如請求項 1〇之感光性乾式膜而形成。 12. 種聚醯亞胺前驅體,其特徵在於清漆之重量平均分子 量(Mwl)與於12(rc以下去溶劑後的重量平均分子量 (Mw2)之間的比(Mw2/Mwl)為0.7以上。 1399Dl.doc 201006867 四、指定代表圖: (一) 本案指定代表圖為:(無) (二) 本代表圖之元件符號簡單說明: 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式:139901.doc (3) 201006867 (a represents an integer from 1 to 15; b represents an integer from 5 to 20; and I represents a hydrogen atom or a monovalent alkyl group having a carbon number of 1 to 10). 6. The polyimine precursor according to claim 4, wherein the diamine represented by the above formula (4) is from 25 mol% to 75 mol% in all diamine components. A photosensitive polyimide intermediate composition comprising 1 part by mass of a polyimine precursor according to claim i, 2 or 5, and 5 parts by mass to 35 mass A portion of the sensitizer. 8. The photosensitive polyimide intermediate precursor composition of claim 7, wherein the sensitizer comprises a quinonediazide structure. 9. The photosensitive polyimide intermediate precursor composition of claim 7, which comprises a dissolution inhibitor having a phenolic hydroxyl group. A photosensitive dry film which is obtained by applying a photosensitive polyimide intermediate composition according to claim 7 to a support film, performing solvent removal, and then laminating a cover film. . A flexible printed circuit board characterized in that it is formed using the photosensitive dry film of claim 1. 12. A polyimine precursor, characterized in that the ratio (Mw2/Mwl) of the weight average molecular weight (Mwl) of the varnish to the weight average molecular weight (Mw2) after desolvation of 12 (rc or less) is 0.7 or more. 1399Dl.doc 201006867 IV. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 139901.doc139901.doc
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