TW201801932A - Polyimide dry film and application thereof - Google Patents

Abstract

A polyimide dry film including a substrate and a polyimide layer is provided. The polyimide layer contains (a) a polyimide precursor or soluble polyimide and (b) a solvent. The solvent includes a hydrophilic solvent and a hydrophobic solvent and the weight ratio of the hydrophilic solvent to the hydrophobic solvent is in the range from about 0.05 to about 2. The polyimide dry film of the present disclosure has water absorbability and is relatively stable even in the presence of water, and the surface thereof is not sticky. The resulting polyimide has excellent physical properties and can be used in the process in which water or an aqueous solution is involved to form a coverlay with excellent physical properties.

Description

Polyimine dry film and use thereof

The present invention relates to a dry film of a polyimide film, in particular to a dry film of a polyimide film suitable for a wet process, and to a method of using the above dry film.

In recent years, as electronic products emphasize light, thin, short, and small, the size of various electronic components must also be smaller and smaller. Under this development trend, soft printed circuit boards with light, thin and high temperature resistance characteristics and mass production have more room for development. The current popular electronic products such as mobile phones, liquid crystal displays and organic light-emitting diodes can be seen in the traces of flexible printed circuit boards. A flexible printed circuit (FPC) is obtained by arranging wires and other electronic components on a flexible substrate, and has better flexibility than a printed circuit board using a conventional germanium substrate or a glass substrate. Also known as a soft board. A coverlay is usually added to the surface of the flexible board to serve as an insulating protective layer to protect the copper wiring on the surface of the flexible board and increase the bending resistance of the line. Suitable cover film materials must have better heat resistance, dimensional stability, insulation properties and chemical resistance. In general, the method of laminating a cover film on a soft board is as follows: first, the cover film is processed into a prescribed shape so that the cover film has an opening corresponding to the line on the flexible board, and a layer of adhesive is applied on the surface on the side of the cover film. Then, the cover film is aligned with the corresponding position of the soft board, and is laminated in a lamination manner. However, since the above method requires processing such as processing, opening, and the like on a very thin cover film, and the cover film and the flexible board are almost always subjected to manual operation, problems such as low process yield and high cost are not satisfied. More precise assembly requirements; in addition, there are adhesive problems. In order to overcome the above problems, it is known that it can be improved by using a photo-imageable coverlay (PIC), and the photosensitive cover film does not need to be pre-opened, and the originally complicated and complicated process will be greatly simplified. However, when a dry-type press-bonding process is used to bond the photosensitive cover film to a patterned circuit board, an undesired gas may remain between the patterned circuit board and the photosensitive cover film, which may affect the reliability of the final product. Degree and quality. In order to remove the gas between the circuit board and the photosensitive cover film, some industries use a high pressure degassing machine to eliminate bubbles generated during the bonding process, but it is difficult to completely remove the bubbles, and it is easy to generate complex Foaming phenomenon, or vacuum laminating equipment (for example, vacuum laminator or vacuum hot press), the air is discharged first, and then pressure-bonded, however, vacuum pressure is used. Most methods of membrane equipment can only be pressed in a single piece, that is, after each completion of the pressing step, a period of time is required to remove the test piece that has been pressed and replace it with another test piece. Not only is it time consuming, it can't achieve the goal of rapid production, and the equipment is expensive and not cost effective. The wet press process first applies a liquid (usually water or an aqueous solution) to the surface to be pressed to fill the recessed area of the surface, thereby eliminating the air present between the cover film material and the surface to be pressed. However, most of the photosensitive cover films are photosensitive dry film solder masks (DFSM), which are mostly composed of epoxy resin or acrylate resin; however, epoxy resin and acrylate The cover film made of resin has insufficient heat resistance, insulation, chemical resistance and mechanical strength for high-order products, and since the organic solvent content of the photosensitive solder resist dry film is less than 1 wt%, it is not Suitable for wet pressing process. Another photosensitive cover film is a solvent-containing dry film such as a polyimide film dry film, although the polyimide film has good heat resistance, dimensional stability, insulation properties and chemical resistance. However, if the solvent selected is not compatible with water or an aqueous solution, it is not suitable for the wet pressing process, and the polyimide and its precursors (such as polyglycolic acid or polyamidomate) Because of the easy hydrolysis, the chain scission occurs or the premature yttrium imidization produces undesired low molecular weight polyimine precipitation, which affects the properties of the obtained cover film. Therefore, it is considered that the polyimide dry film generally needs to be at a low temperature. It can be stored or processed in a waterless environment, and it is not suitable for wet pressing processes. Therefore, there is a need in the art for a novel dry film that can be easily laminated to a patterned surface without excessive gas residue and that provides good heat resistance, insulation, chemical resistance, and mechanical strength coverage. membrane. In addition, there is a need in the art for a more economical and convenient press-fit method for applying a cover film to a patterned surface.

One aspect of the present invention provides a polyimine dry film comprising a substrate and a polyimide layer, wherein the polyimide layer comprises: (a) a polyimine precursor or a soluble polyimine and b) a solvent, wherein the solvent comprises a hydrophilic solvent and a hydrophobic solvent, and the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between about 0.05 and about 2. Another aspect of the present invention is to provide a method of applying the above dry film on a substrate. The polyimine dry film of the invention can be applied to the substrate without using a high-pressure defoaming machine or a vacuum laminating device of the prior art, and can be applied to a wet process, and retains good heat resistance of the polyimine dry film. , dimensional stability, insulation properties and chemical resistance, not only simple process, easy to obtain equipment, it is more cost-effective than the prior art.

式(A) 其中， G為四價有機基團； P為二價有機基團； n為大於0之整數，較佳是1至1000之整數。 可視需要使用不同基團對上述聚醯亞胺前驅物進行改質。例如，藉由感光性基團進行改質可製備感光型聚醯亞胺前驅物；或藉由調整與式(A)重複單元鍵結之末端基團，可改良聚醯亞胺前驅物之反應性及改良後續製得之聚醯亞胺之性質。 舉例言之，中華民國發明專利第100149594號申請案揭示具有以下式(1)至(4)表示之重覆單元之聚醯亞胺前驅物：

(1)，

(2)，

(3)，或

(4)， 其中，G₁ 獨立為四價有機基團； R_x 各自獨立為H或乙烯系不飽和基； R各自獨立為C₁ -C₁₄ 烷基、C₆ -C₁₄ 芳基、C₆ -C₁₄ 芳烷基、酚基或乙烯系不飽和基； D各自獨立為含氮之雜環基團或為OR*基團，其中R*為C₁ -C₂₀ 烷基； m為0至100之整數，較佳是5至50之整數，更佳是10至25之整數；及 G及P係如本文先前所定義。 上述乙烯系不飽和基，並無特殊限制，其實例包括(但不限於)乙烯基、丙烯基、甲基丙烯基、正丁烯基、異丁烯基、乙烯基苯基、丙烯基苯基、丙烯氧基甲基、丙烯氧基乙基、丙烯氧基丙基、丙烯氧基丁基、丙烯氧基戊基、丙烯氧基己基、甲基丙烯氧基甲基、甲基丙烯氧基乙基、甲基丙烯氧基丙基、甲基丙烯氧基丁基、甲基丙烯氧基戊基、甲基丙烯氧基己基、具下式(5)的基團及具下式(6)的基團：

(5)

(6)， 其中R₁₂ 為伸苯基、C₁ -C₈ 伸烷基、C₂ -C₈ 伸烯基、C₃ -C₈ 伸環烷基或C₁ -C₈ 羥基伸烷基；且R₁₃ 為氫或C₁ -C₄ 烷基。 (b) 可溶性聚醯亞胺 一般聚醯亞胺雖具有耐熱性及耐化學性佳之優點，但卻有加工性不良之缺點，且能溶解聚醯亞胺之溶劑不多。因此，在應用時多半係使用以聚醯亞胺前驅物進行加工，並在製程後期將其醯亞胺化成聚醯亞胺。可溶性聚醯亞胺則是在聚醯亞胺結構上進行改良，增加聚醯亞胺與溶劑間之溶解度，以改善其加工性。上述溶劑之種類可例如本文以下所述者。 本發明之可溶性聚醯亞胺並無特殊限制，且可為本發明所屬技術領域中具有通常知識者所習知者，如中華民國發明專利第097101740號、第099105794號、第097138725號或第097138792號申請案。上述文獻係全文併入本文中做為參考。 本發明之可溶性聚醯亞胺主要係具有以式(B)表示之重複單元：

式(B) 其中， C'為四價有機基團； E'為二價有機基團； t'為大於0之整數，較佳是1至1000之整數。 上述C'四價有機基團之態樣可如本文先前對G基團所定義者。 上述E'二價有機基團之態樣可如本文先前對P基團所定義者。 可視需要使用不同基團對上述可溶性聚醯亞胺進行改質。例如藉由感光性基團進行改質可製備感光型聚醯亞胺；或藉由調整與式(B)重複單元鍵結之末端基團，可改良可溶性聚醯亞胺之性質。 藉由調整與式(B)重複單元鍵結之末端基團之可得經改質可溶性聚醯亞胺，其結構例如(但不限於)：

(1') ；

(2')；

(3')； 其中， R₂₀ '為C₂ -C₂₀ 飽和或不飽和之2價有基機團，較佳為-C=C-、

、

； R₂₁ '為C₂ -C₂₀ 可為雜原子取代之具不飽和基之1價有基機團或-OH C'、E'及t'’係如本文先前所定義。 藉由感光性基團進行改質之可溶性聚醯亞胺較佳（但不限於）係第099105794號、第099105794號、第097138725號或第097138792號申請案所揭示者。 3. 溶劑 一般而言，聚醯亞胺前驅物及可溶性聚醯亞胺係在極性非質子有機溶劑下製備或調配。 習知技術中為避免乾膜在使用時產生高濃度之揮發性有機物及降低乾膜在儲存時發生塗布膠液流動的溢膠(excessive glue)現象，會將完成塗佈之乾膜半成品送入烘箱，使樹脂層乾燥並與基材完全貼合。有機溶劑於此步驟幾乎完全揮發，因此，一般而言，習知乾膜產品之有機溶劑含量小於1 wt%。此外，乾膜產品需儲存於低溫環境，以降低水解現象。 不同於以往技術，本發明之乾膜可含有溶劑，且本案發明人經廣泛研究和反覆實驗後發現：藉由控制溶劑種類及含量比例，所得聚醯亞胺乾膜具有吸水性，且縱使在水存在下其性質相對穩定，且表面不沾黏，轉印能力佳，且由其固化所製得之聚醯亞胺具有良好的物性。因此，不但可增加儲存安定性，且可應用至需使用水或水性溶液的加工製程。 本發明所用之溶劑包含親水溶劑與疏水溶劑，其中該親水溶劑與該疏水溶劑之重量比係介於約0.05至約2之間，較佳介於約0.1至約1之間，更佳係介於約0.25至約0.8之間，所得乾膜具有吸水性，良好轉印能力，表面不沾黏，且性質穩定，並具有良好物性。當親水溶劑與疏水溶劑之重量比過低時（例如低於0.05時），聚醯亞胺乾膜吸水性不佳，且聚醯亞胺層對基板之密著性較差；當親水溶劑與疏水溶劑之重量比過高時，尤其是大於2時，將使乾膜表面易有沾黏現象，操作性較差，不易對位，且不利於重工。 本發明添加疏水溶劑可與液體(水或醇類)互溶，可用於本發明之親水溶劑包含：二甲基亞碸(DMSO)、二乙基亞碸、N,N-二甲基甲醯胺(DMF)、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺(N,N-dimethylacetamide，DMAc)、N,N-二乙基乙醯胺、N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone，NMP)、N-乙基-2-吡咯烷酮(N-ethyl-2-pyrrolidone，NEP)、N-丙基-2-吡咯烷酮、N-乙烯基-2-吡咯烷酮、苯酚、鄰甲酚、間甲酚、對甲酚、二甲苯酚、鹵代苯酚、鄰苯二酚、四氫呋喃(THF)、二噁烷、二氧戊環、環丙二醇甲醚(PGME)、四乙二醇二甲醚(TGDE)、丁基溶纖劑、γ-丁內酯(γ-butyrolactone；GBL)、二甲苯(xylene)、甲苯(toluene)、六甲基鄰醯胺、丙二醇甲醚醋酸酯(PGMEA)或其混合物。 根據本發明之一實施例，所用親水溶劑較佳包含：二乙基亞碸、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N,N-二乙基乙醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-丙基-2-吡咯烷酮、環丙二醇甲醚、γ-丁內酯、丙二醇甲醚醋酸酯或其混合物。更佳包含：N,N-二甲基甲醯胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、γ-丁內酯或其混合物。 本發明添加疏水溶劑可提升乾膜對水之穩定性外，同時可使乾膜表面不易有沾黏現象，操作性較佳。可用於本發明之疏水溶劑包含：

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、或其組合， 其中： R₁ ''、R₉ ''及R₁₀ ''各自獨立為C₁ -C₂₀ 烷基、C₂ -C₂₀ 烯基或C₂ -C₂₀ 炔基； R₇ ''為H或C₁ -C₃ 烷基； R₂ ''為C₁ -C₁₀ 烷基； R₃ ''為C₄ -C₂₀ 烷基或-C₂ -C₁₀ 烷基-O-C₂ -C₁₀ 烷基； R₄ ''及R₅ ''各自獨立為C₁ -C₁₀ 烷基，或R₄ ''及R₅ ''與其所連接之氧原子一起形成5至6員雜環； R₆ ''為C₄ -C₁₅ 烷基、C₄ -C₈ 環烷基或

； R₈ ''為C₂ -C₁₀ 伸烷基； R₁₁ ''及R₁₂ ''各自獨立為C₁ -C₁₀ 烷基； R₁₃ ''及R₁₄ ''各自獨立為C₁ -C₁₀ 烷基，或R₁₃ ''及R₁₄ ''與其所連接之氮原子一起形成5至6員雜環； R₁₅ ''為C₄ -C₁₅ 烷基或C₄ -C₈ 環烷基； R₁₆ ''為C₁ -C₄ 烷基；且 R₁₇ ''為C₄ -C₁₀ 烷基。 根據本發明之一實施例，所用疏水溶劑較佳包含：

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、N,N-二甲基癸醯胺((N,N- dimethylcapramide，簡稱DMC))或其組合。 在本發明中，溶劑總含量並無特殊限制，可視乾膜之製造程序或者後續加工製程所需進行調整。在本發明之一實施態樣中，以聚醯亞胺層總重量計，溶劑之總含量係介於約30 wt%至約70 wt%之間，較佳係介於約35 wt%至約65 wt%之間，更佳係介於約40 wt%至約60 wt%之間。 4. 添加劑 本發明之聚醯亞胺層可視需要含有本發明所屬技術領域中具有通常知識者習知之任何適當添加劑，例如(但不以此為限)：穩定劑(stabilizer)、閉環促進劑、整平劑、消泡劑、偶合劑、催化劑、丙烯酸酯類單體及光起始劑等。上述添加劑之含量亦為本發明所屬技術領域中具有通常知識者可經由例行實驗調整者。 在本發明之一實施態樣中，本發明之聚醯亞胺層可視需要含有選自下列之穩定劑：

、

或其組合， 其中： R₁₇ ''、R₁₈ ''、R₁₉ ''及R₂₀ ''各自獨立為C₁ -C₄ 烷基，或者R₁₉ ''及R₂₀ ''與其連接之氧原子一起形成5至6員雜環，或者R₁₉ ''及R₁₇ ''或 R₂₀ ''及R₁₈ ''與其連接之氧原子及氮原子一起形成5至6員雜環； R₂₁ ''及R₂₂ ''各自獨立為C₁ -C₄ 烷基，或者R₂₁ ''與R₂₂ ''與其連接之碳原子一起形成5至6員碳環；且 R₂₃ ''及R₂₄ ''各自獨立為C₁ -C₄ 烷基。 根據本發明之一較佳實施例，該穩定劑較佳包含：

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或其組合。 添加穩定劑有助於提升乾膜的穩定性及操作性，並進一步提升後續形成之聚醯亞胺的物性。在本發明之一實施態樣中，以聚醯亞胺層總重量計，穩定劑之總含量係介於約0.01wt%至約5wt%之間，較佳係介於約0.05wt%至約3wt%之間。若含量超過5wt%可能導致形成之聚醯亞胺物性(例如可撓曲性)降低 在本發明之一實施態樣中，該聚醯亞胺層為感光型聚醯亞胺，可視需要選用添加劑包含光起始劑、丙烯酸酯類單體。 上述光起始劑可單獨使用或混合多種使用。適用於本發明之光起始劑係用來經光照射以產生自由基，透過自由基之傳遞來引發聚合反應。可用於本發明之光起始劑並無特殊限制。較佳地，所用之光起始劑係包含可吸收波長約350奈米至約500奈米之光而產生自由基的化合物。 光起始劑之用量，以100重量份之聚醯亞胺前驅物或可溶性聚醯亞胺固含量計，係約0.01至約20重量份，較佳係約0.05至約5重量份。適用於本發明之光起始劑可例如選自以下群組：二苯甲酮、二苯乙醇酮、2-羥基-2-甲基-1-苯丙酮、2,2-二甲氧基-1,2-二苯基乙-1-酮、1-羥基-環己基-苯基酮、2,4,6-三甲基苯甲醯基二苯基膦氧化物、肟酯、2,4,6-三甲基苯甲醯基二苯基膦氧化物（2,4,6-trimethylbenzoyl diphenyl phosphine oxide）、雙4,4'-二乙基胺基苯甲酮（bis-4,4'-diethylaminobenzophenone）、苯甲酮（benzophenone）、樟腦酮（camphorquinone）、3,5-雙(二乙基胺基苯亞甲基)-N-甲基-4-哌啶酮（3,5-bis(diethylaminobenzylidene)- N-methyl-4-piperidone）、3,5-雙(二甲基胺基苯亞甲基)-N-甲基-4-哌啶酮（3,5-bis(dimethylaminobenzylidene)-N-methyl-4- piperidone）、3,5-雙(二乙基胺基苯亞甲基)-N-乙基-4-哌啶酮（3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone）、3,3'-羰基-雙(7-二乙基胺基)香豆素（3,3'-carbonyl- bis(7-diethylamino)cumarin）、3,3'-羰基-雙(7-二甲基胺基)香豆素(3,3'-carbonyl-bis(7-dimethylamino)cumarin)、核黃素四丁酸酯(riboflavin tetrabutyrate)、2-甲基-1-[4-(甲基硫代)苯基]-2-嗎啉基丙-1-酮(2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan -1-one)、2,4-二甲基硫基氧雜蒽酮(2,4-dimethylthioxanthone)、2,4-二乙基硫基氧雜蒽酮(2,4-diethylthioxanthone)、2,4-二異丙基硫基氧雜蒽酮(2,4-diisopropylthioxanthone)、3,5-二甲基硫基氧雜蒽酮(3,5-dimethylthioxanthone)、3,5-二異丙基硫基氧雜蒽酮(3,5-diisopropylthioxanthone)、1-苯基-2-(乙氧基羰基)氧亞胺基丙-1-酮(1-phenyl-2-(ethoxycarbonyl)oxyiminopropan-1-one)、安息香醚(benzoin ether)、安息香異丙基醚(bezoin isopropyl ether)、苯繞蔥酮(benzanthrone)、5-硝基苊(5-nitroacenaphthene)、2-硝基芴(2-nitrofluorene)、菎酮(anthrone)、1,2-苯並并蒽(1,2-benzanthraquinone)、1-苯基-5-巰基-1H-四氮唑(1-phenyl-5-mercapto-1H-tetrazole)、噻噸-9-酮(thioxanthen- 9-one)、10-噻噸酮(10-thioxanthenone)、3-吲哚乙醯(3-acetylindole)、2,6-二(對二甲基胺基苯亞甲基)-4-羧基環己酮(2,6-di(p-dimethylaminobenzal)-4-carboxycyclohexanone)、2,6-二(對二甲基胺基苯亞甲基)-4-羥基環己酮(2,6-di (p-dimethylaminobenzal)-4-hydroxycyclohexanone)、2,6-二(對二乙基胺基苯亞甲基)-4-羧基環己酮(2,6-di(p-diethylaminobenzal) -4-carboxcyclohexanone)、2,6-二(對二乙基胺基苯亞甲基)-4-羥基環己酮(2,6-di(p-diethylaminobenzal))-4-hydroxycyclohexanone)、4,6-二甲基-7-乙基胺基香豆素(4,6-dimethyl-7- ethylaminocumarin)、7-二乙基胺基-4-甲基香豆素(7-diethylamino-4-methylcumarin)、7-二乙基胺基-3-(1-甲基苯并咪唑基)香豆素(7-diethylamino-3-(1-methylbenzoimidazolyl) cumarin)、3-(2-苯并咪唑基)-7-二甲乙基胺基香豆素(3-(2-benzoimidazolyl)-7-diethylaminocumarin)、3-(2-苯並并噻唑基)-7-二甲乙基胺基香豆素(3-(2-benzothiazolyl)-7- diethylaminocumarin)、2-(對二甲基胺基苯乙烯基)苯並噁唑(2-(p-dimethylaminostyryl)benzooxazole)、2-(對二甲基胺基苯乙烯基)喹啉(2-(p-dimethylaminostyryl)quinoline)、4-(對二甲基胺基苯乙烯基)喹啉(4-(p-dimethylaminostyryl)quinoline)、2-(對二甲基胺基苯乙烯基)苯並并噻唑(2-(p-dimethylaminostyryl) benzothiazole)、2-(對二甲基胺基苯乙烯基)-3,3-二甲基-3H-吲哚(2-(p-dimethylaminostyryl)-3,3- dimethyl-3H-indole)及其組合。較佳之光起始劑為二苯甲酮、2,4,6-三甲基苯甲醯基二苯基膦氧化物、二苯乙醇酮、2-羥基-2-甲基-1-苯丙酮、2,2-二甲氧基-1,2-二苯基乙-1-酮、1-羥基-環己基-苯基酮、2,4,6-三甲基苯甲醯基二苯基膦氧化物、肟酯或其組合。 上述丙烯酸酯類單體，係具有至少一個-C=C-之丙烯酸酯類單體，較佳為具有兩個或兩個以上-C=C-之多官能基丙烯酸酯單體(multi-functional acrylate monomer)，添加這類單體能使分子與分子間形成交聯，便於提高組合物的實用度。較佳地，本發明使用選自以下群組之丙烯酸酯類單體：乙二醇二(甲基丙烯酸)酯、乙二醇二丙烯酸酯、雙酚A乙二醇-改質二丙烯酸酯、雙酚A乙二醇-改質二(甲基丙烯酸)酯、雙酚F乙二醇-改質二丙烯酸酯、雙酚F乙二醇-改質二(甲基丙烯酸)酯、丙二醇二(甲基丙烯酸)酯、三丙烯乙二醇二丙烯酸酯、乙氧基化三羥甲基丙烷三丙烯酸酯、二季戊四醇六丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三(甲基丙烯酸)酯、四羥基甲烷三丙烯酸酯、四羥基甲烷三(甲基丙烯酸)酯、及其組合。當丙烯酸酯類單體存在時，以100重量份之聚醯亞胺前驅物或可溶性聚醯亞胺固含量計，其添加量係約5至約80重量份，較佳為約10至約40重量份。 可用於本發明之偶合劑可選自由以下所組成之群組(但不以此為限)：3-胺基丙基三甲氧基矽烷(APrTMOS)、3-三胺基丙基三乙氧基矽烷(APrTEOS)、3-胺基苯基三甲氧基矽烷(APTMOS)、3-胺基苯基三乙氧基矽烷(APTEOS)及其組合。 根據本發明之一實施態様，可視需要在本發明之聚醯亞胺前驅物之製備過程中加入閉環促進劑。較佳選用能在加熱，產生鹼性化合物，提供鹼性環境促進醯亞胺化(imidization)反應進行之閉環促進劑。可用於本發明之閉環促進劑包含:

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Y^θ 、

Y^θ 、

Y^θ 、

Y^θ 或

Y^θ ，其中Y^θ 為陰離子基團。 形成乾膜之方法 本發明之聚醯亞胺乾膜可藉由例如下列步驟製備： (1) 準備聚醯亞胺調配物，混合包含聚醯亞胺前驅物或可溶性聚醯亞胺和親水溶劑； (2) 添加適量之疏水溶劑、及視需要之添加劑至前述調配物中； (3) 將步驟(2)所得之調配物塗佈於基材形成一乾膜半成品； (4) 將乾膜半成品送入烘烤爐，加熱乾燥移除部份溶劑，藉此調整聚醯亞胺層中之溶劑含量；形成一聚醯亞胺乾膜； (5) 可視需要於聚醯亞胺乾膜上施加一保護膜。 上述步驟(4)加熱所需溫度及時間並無特殊限制，其主要目的係以減少在樹脂層中的溶劑含量，例如可使用介於60℃至150℃間中之一適合溫度，歷時30秒至10分鐘進行加熱乾燥。在傳統製備乾膜過程中，為避免使用乾膜時產生高濃度之揮發性有機物，在相對於前述步驟(4)的移除溶劑步驟中，常加熱致使溶劑達幾乎完全揮發程度(含量小於1 wt%)，然而，與習知步驟相反地，本發明並未在此步驟中將溶劑完全移除，反而保留適量比例之親水溶劑及疏水性溶劑於乾膜中。 上述步驟(4)的溶劑包含親水溶劑及疏水溶劑。一般而言，藉由不同溶劑種類的沸點差異，適當地調整加熱溫度及時間，可控制所欲得到之乾膜中溶劑之總含量及比例，例如將親水溶劑與疏水溶劑之重量比係介於約0.05至約2之間。 上述步驟(5)的保護膜，其例如但不限於：聚酯樹脂(polyester resin)，如聚對苯二甲酸乙二酯(polyethylene terephthalate, PET)或聚萘二甲酸乙二酯(polyethylene naphthalate, PEN)；聚甲基丙烯酸酯樹脂(polymethacrylate resin)，如聚甲基丙烯酸甲酯(polymethyl methacrylate, PMMA)；聚醯亞胺樹脂(polyimide resin)；聚苯乙烯樹脂(polystyrene resin)；聚環烯烴樹脂(polycycloolefin resin)；聚烯烴樹脂(polycycloolefin resin)；聚碳酸酯樹脂(polycarbonate resin)；聚胺基甲酸酯樹脂(polyurethane resin)；三醋酸纖維素(triacetate cellulose, TAC)；或彼等之混合物。較佳為聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚環烯烴樹脂、三醋酸纖維素或其混合物，更佳為聚對苯二甲酸乙二酯。 於基板上施加乾膜之方法 本發明另提供一種於基板上施加聚醯亞胺乾膜之方法，其包含：於移除視需要添加之保護膜後，將上述聚醯亞胺乾膜以聚醯亞胺層之面與基板進行壓合。上述基板可為印刷電路板、晶圓、玻璃、顯示器或觸控面板，或其他基板。根據本發明之一實施態樣，上述基板係為印刷電路板，尤佳為軟性印刷電路板(Flexible Print Circuit；FPC)，且乾膜之聚醯亞胺層係壓合至該圖案化表面。 於基板上施加乾膜可選任何方式，較佳以卷對卷(roll to roll)方式進行操作壓合，捲對捲之操作係本發明所屬技術領域中具有通常知識者所熟知者，係指透過自呈捲繞形式之樣品拉出樣品，經處理後再以捲繞方式將經處理後之樣品收回。舉例言之，如圖1所示，呈捲繞形式之基板A於拉出後，在滾輪2及3之間與來自乾膜捲1之乾膜進行滾輪壓合，再以捲繞方式收回形成產品B。本發明之乾膜可使用連續製程壓合至基板，有利於簡化製程及加快製程速度。上述壓合方式，例如但不限於：滾輪壓合(roller lamination)、熱板壓合(hot press)、真空壓合(vacuum lamination)、真空快壓(vacuum press)或濕式壓合(wet lamination)。 如前所述，藉由控制適當的溶劑種類及含量比例，本發明之聚醯亞胺乾膜具有吸水性，且表面不沾黏，並且所形成之覆蓋膜具有優異的物性。此外，縱使在水存在下，也能保持穩定，不會影響所得聚醯亞胺之性質，因此適用於濕式壓合，且藉由濕式壓合可提升乾膜對於圖案化基板之均覆性。 圖2為本發明之乾膜應用於濕式壓合之示意圖。如圖2所示，本發明提供一種藉由濕式壓合於基板上施加乾膜之方法，該方法包含： (1) 於該基板10待壓合之表面11上施加液體30；及 (2) 將本發明之乾膜20（包含基材21及聚醯亞胺層22）以聚醯亞胺層之面壓合至該基板10待壓合之表面11。 步驟(1)中所用之液體包含水、醇類溶劑或其組合，以使製程更為環保且更經濟。較佳液體為甲醇、乙醇、異丙醇、丁醇、水或其混合物。該液體可填覆於待壓合表面11上之凹陷區域，形成一層液體膜，藉此趕走原存在於凹陷區域中之空氣。 在步驟(2)中，係藉由滾輪將乾膜20壓合至該基板10待壓合之表面11。此時步驟(1)中所用之液體可被吸收至本發明之聚醯亞胺層中。較佳係在加熱下進行步驟(2)，例如在60^o C至100^o C之溫度，以提升聚醯亞胺層與帶壓合表面間之均覆性及密著性。 若有液體殘留時，可視需要進行一靜置步驟(3)，在壓合後靜置一段時間（例如，5分鐘至240分鐘），將殘留之液體充分吸收至乾膜中。 本發明另提供一種濕式壓合用系統，其包含: (1) 本發明之乾膜； (2) 基板；及 (3) 液體。 上述之基板、液體係如前所述。 本發明之乾膜，特別係使用於濕式製程時，具有良好均覆性，並且相較於習知的乾膜，可以有效填覆厚銅線路。 本發明乾膜之應用 本發明之聚醯亞胺乾膜，可在不使用高壓脫泡機或真空壓膜設備的情況下，使用一般壓合技術（特別是濕式壓合）與如印刷電路板、晶圓、玻璃、顯示器或觸控面板之基板進行壓合，因此可在相較於先前技術簡單之製程步驟下進行操作，所用設備亦較先前技術所使用者更容易取得。因此，相較於使用真空壓膜機或其他製程設備之先前技術更為符合成本效益。 本發明之乾膜適用於印刷電路板，作為供保護印刷電路板上之塗膜用的覆蓋膜，具絕緣性，可保護線路，且具有避免線路氧化及焊接短路之優異效能。此外，本發明之乾膜因具有高解析度、顯影速度快、耐電解電鍍性、耐無電解電鍍性及耐高溫高濕性等特性，因此也可以使用於晶圓製程中作為光阻劑。 此外，本發明之聚醯亞胺乾膜，縱使在水存在下其性質相對穩定，且表面不沾黏，轉印能力佳。此外，乾膜中的水份或溶劑可於後續製程中移除，不會影響所得聚醯亞胺之物理性質，因此，當用作覆蓋膜時尤具優勢。有鑑於此，在本發明之一較佳實施態樣中，係使用濕式製程將本發明之聚醯亞胺乾膜施加至基板上作為覆蓋膜。 圖3係以使用本發明之感光型聚醯亞胺乾膜作為軟性印刷電路板覆蓋膜為例，進一步說明其後續加工步驟（但不以此為限）： (1) 利用濕式壓合，將本發明之聚醯亞胺乾膜20與基板10壓合； (2) 在光罩40存在下，進行曝光，使本發明之聚醯亞胺前驅物或可溶性聚醯亞胺上之感光性基團（如具有乙烯系不飽和基之基團）發生交聯反應； (3) 移除乾膜20之支撐基材21，並進行曝後烤(Post-exposure Bake)； (4) 進行顯影，以移除非曝光區之聚醯亞胺層；及 (5) 視需要將聚醯亞胺前驅物醯亞胺化(固化)成聚醯亞胺。 上述步驟(2)之曝光步驟可以任何本發明所屬領域具有通常知識者所知之方式進行，例如，使用紫外線、可見光、電子束或雷射照射，較佳係使用紫外線。曝光能量及時間並無特別限制，為本發明所屬技術領域中具有通常知識者可視需要依其經驗調整者。根據本發明之一實施態樣，所用之曝光能量約50至1200mJ/cm² 。 上述步驟(3)之曝後烤係藉由加熱增加曝光區與非曝光區在顯影時的溶解度差異。加熱溫度及時間並無特殊限制，可視需要調整，只要能達成前述目的即可。加熱可以單階段或多階段進行。在本發明之一具體實施例中，係於60至150^o C之溫度範圍持續加熱5至90分鐘。聚醯亞胺層中所含之溶劑（例如前述親水、疏水溶劑）以及於濕式壓合時所吸收之液體可在此加熱步驟中部分排出。 上述步驟(4)係藉由顯影步驟使未經曝光區域之樹脂(使用負型感光型聚醯亞胺乾膜時)溶解去除或使經曝光區域之樹脂(使用正型感光型聚醯亞胺乾膜時)溶解去除，再以水進行清洗(rinse)，而得到所需之圖案。所使用之顯影劑，係本發明所屬技術領域中具有通常知識者所熟知者。顯影劑之實例例如(但不限於)K₂ CO₃ 水溶液、Na₂ CO₃ 水溶液、KOH水溶液、NaOH水溶液、四甲基氫氧化銨(TMAH)水溶液。 此外，當聚醯亞胺層包含聚醯亞胺前驅物時，進行步驟(5)，例如藉由加熱，使該聚醯亞胺前驅物環化、聚合成聚醯亞胺。並且將聚醯亞胺層中尚存的溶劑或液體，進一步移除。 以下實施例係用於對本發明作進一步說明，唯非用以限制本發明之範圍。任何熟悉此項技藝之人士可輕易達成之修飾及改變均包括於本案說明書揭示內容及所附申請專利範圍之範圍內。 實施例 以下實施例中所提及的縮寫定義如下： DA1：

1-MI：1-甲基咪唑(1-methylimidazole) PTZ：吩噻嗪(10H-phenothiazine) DA3：

DMC：N,N-二甲基癸醯胺

NOP：

NOEP：

D-PC：

醋酸癸酯：

1,6-己二醇二丙烯酸酯：

製備例 1 ：合成感光型聚醯亞胺前驅樹脂PAA-1 將21.81克(0.1莫耳)的均苯四酸二酐(pyromellitic dianhydride，下文簡稱為PMDA)溶於200克的N-甲基吡咯烷酮(N-methyl-2- pyrrolidone；下文簡稱為NMP)中，加熱所得混合物至50℃且反應攪拌兩個小時。慢慢滴入1.161克(0.01莫耳)的丙烯酸2-羥基乙酯(2-hydroxyethyl acrylate，下文簡稱為HEA)，於50℃的固定溫度下反應攪拌兩個小時。其後，將20.024克(0.1莫耳)的4,4'-氧化二苯胺(4,4'-oxydianiline，下文簡稱為ODA) 加至溶液中，待完全溶解後，再於50℃的固定溫度下反應攪拌六個小時，可得到感光型聚醯亞胺前驅樹脂PAA-1，固形份約17wt%（在250或300℃下烘烤1小時移除所有溶劑後，量測烘烤前後的重量差，便可得到非揮發性物質的重量，計算其在PAA-1中的重量百分含量即為固形份）。製備例 2 ：合成感光型聚醯亞胺前驅樹脂PAA-2 將21.81克(0.1莫耳)的PMDA溶於200克的N-乙基吡咯烷酮(N-methyl-2-pyrrolidone；下文簡稱為NEP)中，加熱所得混合物至50℃且反應攪拌兩個小時。慢慢滴入1.161克(0.01莫耳)的HEA，於50℃的固定溫度下反應攪拌兩個小時。其後，將20.024克(0.1莫耳)的ODA加至溶液中，待完全溶解後，再於50℃的固定溫度下反應攪拌六個小時可得到感光型聚醯亞胺前驅樹脂PAA-2，固形份約17wt%（在250或300℃下烘烤1小時，量測其烘烤前後的重量差，便可得到實際非揮發性物質的重量，計算其在PAA-2中的重量百分含量即為固形份）。製備例 3 ：合成感光型聚醯亞胺前驅樹脂PAA-3 將21.81克(0.1莫耳)的PMDA溶於200克的NMP中，加熱至50℃且反應攪拌兩個小時。慢慢滴入13.01克(0.01莫耳)的甲基丙烯酸2-羥基乙酯(2-hydroxyethyl methacrylate；下文簡稱為HEMA)，於50℃的固定溫度 下反應攪拌兩個小時。再將20.024克(0.1莫耳)的ODA加至溶液中，待完全溶解後，再於50℃的固定溫度下反應攪拌六個小時，可得感光型聚醯亞胺前驅樹脂PAA-3，固形份約21wt%。製備例 4 ：合成感光型聚醯亞胺前驅樹脂PAA-4 將29.42克(0.1莫耳)的3,3,4,4-聯苯四甲酸二酐(4,4'-Biphthalic dianhydride；下文簡稱為BPDA)溶於200克的NMP中，加熱至50℃且反應攪拌兩個小時。慢慢滴入13.01克(0.01莫耳)的HEMA，於50℃的固定溫度 下反應攪拌24小時。再將32.024克(0.1莫耳)的間二(三氟甲基)對二胺基聯苯(2,2'-bis(trifluoromethyl) benzidine；下文簡稱為TFMB)加至溶液中，待完全溶解後，再於50℃的固定溫度下反應攪拌六個小時，可得感光型聚醯亞胺前驅樹脂PAA-4，固形份約20wt%。製備例 5 ： 合成聚醯亞胺前驅樹脂PAA-5 將21.81克(0.1莫耳)的PMDA溶於200克的NMP中，加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)的異丙醇，於50℃的固定溫度下反應攪拌兩個小時。再將32.02克(0.1莫耳)的TFMB加至溶液中，待完全溶解後，再於50℃的固定溫度下反應攪拌六個小時，可得聚醯亞胺前驅樹脂PAA-5，固形份約21wt%。製備例 6 ：合成聚醯亞胺前驅樹脂PAA-6 將29.42克(0.1莫耳)的BPDA溶於200克的NMP中，加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)的異丙醇，於50℃的固定溫度下反應攪拌兩個小時。再將20.024克(0.1莫耳)的ODA加至溶液中，待完全溶解後，再於50℃的固定溫度下反應攪拌六個小時，可得聚醯亞胺前驅樹脂PAA-6，固形份約19 wt %。製備例 7 ：合成具有羧基(-COOH)的可溶性聚醯亞胺SPI-1 稱取43.62克(0.2莫耳)的PMDA與30.43 g (0.2莫耳)的3,5-二胺基苯甲酸(3,5-diamino benzoic acid；下文簡稱為DABA)，加入300 mL NMP，於室溫下攪拌1小時，再升溫至50℃後攪拌4小時。4小時後，加入50 mL甲苯，在150℃下，以迪安-斯塔克(dean-stark)裝置除水。待除水完全後再去除甲苯，便可得到具有羧基的聚醯亞胺溶液SPI-1，固形份約19 wt%。製備例 8 ：合成異氰酸酯改質的可溶性聚醯亞胺SPI-2 稱取64.85克(0.2莫耳)的DA1與42.46克(0.2莫耳)的2,2'-二甲基聯苯基-4,4'-二胺(2,2'-dimethylbiphenyl-4,4'-diamine，下文簡稱為DMDB)，加入300 mL NMP，於室溫下攪拌1小時，再升溫至50°C後攪拌4小時。4小時後，加入50 mL甲苯，在130°C下，以迪安-斯塔克裝置除水。待除水、除甲苯完全後，將溶液降至室溫，再加入7克(0.05莫耳) 的丙烯酸2-異氰酸基乙酯(2-isocyanatoethyl acrylate，下文簡稱為2-IEA)、0.05克1-MI與0.06克PTZ。加完後將溶液升溫至80℃，攪拌8小時。即可得異氰酸酯改質的可溶性聚醯亞胺SPI-2，固形份約27 wt %。 製備例9：合成具有羧基(-COOH)的可溶性聚醯亞胺SPI-3 稱取100.074克(0.2莫耳)的DA3與42.46克(0.2莫耳)的DMDB，加入450毫升NMP，於室溫下攪拌1小時，再升溫至50℃後攪拌4小時。之後，加入50毫升甲苯，在130℃下，以迪安-斯塔克裝置除水。待除水、除甲苯完全後，得到具有-COOH基的可溶性聚醯亞胺SPI-3，固形份約24 wt %製備例 10 ：合成環氧改質的可溶性感光型聚醯亞胺SPI-4 稱取142.5克的由製備例9所制得的聚醯亞胺SPI-3，再加入6.11克(0.05莫耳)的甲基丙烯酸縮水甘油酯(glycidyl methacrylate，下文簡稱為GMA)、0.015克溴化四丁基銨(tetrabutylammonium bromide，下文簡稱為TBAB)與0.06克對苯二酚單甲醚(Hydroquinone Monomethyl Ether，下文簡稱為MEHQ)。加完後將溶液升溫至90°C，攪拌12小時，獲得環氧改質的可溶性感光型聚醯亞胺SPI-4，固型份約25 wt %。製備例 11 ： 合成具有壓克力感光基團的聚醯亞胺溶液SPI-5 稱取32.023克(0.1莫耳)的TFMB與48.8664克(0.11 mol)的4,4'-(六氟異丙烯)二酞酸酐(4,4'-(Hexafluoroisopropylidene)diphthalic anhydride，下文簡稱為6FDA)，加入300 mL NMP，於室溫下攪拌1小時。再升溫至50℃攪拌4小時。4小時後，加入50 mL的甲苯，在150°C下，以迪安-斯塔克裝置除水。待完全除水及除甲苯後，將2.322克(0.02莫耳)的HEA在50℃下，加入攪拌4小時，便可得到具有壓克力感光基團的聚醯亞胺溶液SPI-5，固形份約21 wt %。製備例 12 ：合成聚醯亞胺前驅樹脂PAA-7 將21.81克(0.1莫耳)的PMDA溶於200克的N,N-二甲基乙醯胺(N,N-dimethylacetamide；下文簡稱為DMAc)中，加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)的異丙醇，於50℃的固定溫度下反應攪拌兩個小時。再將32.02克(0.1莫耳)的TFMB加至溶液中，待完全溶解後，再於50℃的固定溫度下反應攪拌六個小時，可得聚醯亞胺前驅樹脂PAA-7，固形份約20 wt %。製備例 13 ：合成聚醯亞胺前驅樹脂PAA-8 將21.81克(0.1莫耳)的PMDA溶於200克的γ-丁內酯中，加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)的異丙醇，於50℃的固定溫度下反應攪拌三個小時。再將32.02克(0.1莫耳)的TFMB加至溶液中，待完全溶解後，再於50℃的固定溫度下反應攪拌六個小時，可得聚醯亞胺前驅樹脂PAA-8，固形份約21 wt %。製備例 14 ：合成具有羧基(-COOH)的可溶性聚醯亞胺SPI-6 稱取43.62克(0.2莫耳)的PMDA與30.43 g (0.2莫耳)的DABA，加入300 mL DMAc，於室溫下攪拌1小時，再升溫至50℃後攪拌4小時。4小時後，加入50 mL甲苯，在150℃下，以迪安-斯塔克(dean-stark)裝置除水。待除水完全後再去除甲苯，便可得到具有羧基的聚醯亞胺溶液SPI-6，固形份約20 wt %。乾 膜的製備 取上述製備例1至14製備的聚醯亞胺前驅物溶液或可溶性聚醯亞胺溶液100重量份，以表1至表5所示比例（重量份）加入疏水溶劑或視需要之穩定劑，並加入2重量份的熱鹼產生劑（

）。此外，另若為感光型聚醯亞胺前驅物溶液或感光型可溶性聚醯亞胺溶液(例如PAA-1至PAA-4、SPI-2、SPI-4及SPI-5)時，則再加入1重量份光起始劑（2,4,6-三甲基苯甲醯基二苯基膦氧化物及二苯乙醇酮，比例為1:1），製成塗料組合物。 將各塗料組合物以刮刀均勻塗布在聚對苯二甲酸乙二酯（型號：R310，三菱製）基材上，以烘箱烘烤，烘烤溫度與時間如各表所示。隨後將塗有前述塗料組合物之面覆蓋上離型膜(型號：L150L，南亞製)，即可得到具有聚醯亞胺前驅物塗層或可溶性聚醯亞胺塗層的乾膜，塗層厚度約40μm。 塗佈前的親水溶劑含量及疏水溶劑添加量(重量份)均基於每100重量份聚醯亞胺前驅物溶液或可溶性聚醯亞胺溶液計，而經烘烤乾燥後的親水溶劑及疏水溶劑含量(wt%)則基於樹脂層總重量計。乾膜的測試 檢測上述乾膜之溶劑含量並測試乾膜之物性，如沾黏性、轉印完整性、溶水性、耐折性以及感光性，各項測試詳述如下：1. 溶劑含量檢測 取0.01克聚醯亞胺前驅物塗層或可溶性聚醯亞胺塗層(即不包含PET基材及離型膜)，溶解於二甲基亞碸(DMSO)中，使用安捷倫公司的7890GC氣相層析儀，毛細管(column)型號：DB1701(0.53mm, 30mm, 1.5μm)，實施氣相色層定量分析。 2. 乾膜沾黏性檢測 取各實施例及比較例之乾膜，撕除離型膜，觀察離型膜上是否有殘留的聚醯亞胺層樹脂。完全無殘留為0，＜10%殘留為1，10%~20%殘留為2，＞20%殘留為NG。 3. 轉印測試 取20*20cm之乾膜，撕除離型膜後，分別以下述乾式壓合及濕式壓合方法，將乾膜膜塗覆有聚醯亞胺層之面壓合至已製作線路的銅箔基板上（L/S=30/30μm；L/S為線寬/線距）： (a) 濕式壓合 於銅箔基板具線路之表面上，施覆去離子水，使用熱滾輪，以60℃及5kg的下壓力進行壓合。 (b) 乾式壓合 於銅箔基板具線路之表面上，使用熱滾輪，以60℃及5kg的下壓力進行壓合。 分別靜置10分鐘後撕除乾膜上之PET膜，觀察PET膜是否有殘留的聚醯亞胺層樹脂，PET膜上完全無殘留為0，＜10%殘留為1，10%~20%殘留為2，＞20%殘留在PET膜為NG。4. 溶水性測試 取20*20cm之乾膜，以上述濕式壓合方法，將乾膜塗覆有聚醯亞胺層的一面壓合至銅箔基板具有線路之面上，靜置並使用顯微鏡觀察銅箔基板上之水被完全吸收之時間。第一小時內每5分鐘觀察一次，之後每30分鐘觀察一次。5. 氣泡測試 取20*20cm之乾膜，分別以上述濕式壓合與乾式壓合方法，將乾膜塗覆有聚醯亞胺層的一面壓合至銅箔基板具有線路之面上，靜置10分鐘後觀察氣泡殘留狀況。無氣泡為Pass，有氣泡為NG。 6. 物性測試 ( 耐折測試 1) 取20*20cm之乾膜，分別以上述濕式壓合與乾式壓合方法，將乾膜塗覆有聚醯亞胺層的一面壓合至銅箔基板具有線路之面上，靜置120分鐘後，以250^o C烘烤120分鐘，隨後降至室溫，並以耐折檢驗機(Measure Infect Turn (MIT) test machine，金德豪公司)設備，以彎折角度135度，彎曲半徑R=0.38mm，荷重500g進行耐折測試，記錄電路板至電路性質失效時所承受之彎曲次數。耐折測試次數越大表示所形成之聚醯亞胺層物性越好。7. 物性測試 ( 耐折測試 2- 感光性材料用 ) 取20*20cm之乾膜，分別以上述濕式壓合與乾式壓合方法，將乾膜塗覆有聚醯亞胺層的一面壓合至銅箔基板具有線路之面上，靜置120分鐘後，以UV曝光機進行曝光（曝光能量400mJ/cm² ），之後撕除PET膜以90^o C烘烤10分鐘，以1wt%濃度的K₂ CO₃ 水溶液進行圖案顯影，再以250^o C烘烤120分鐘，隨降至室溫後，並以耐折檢驗機(Measure Infect Turn (MIT) test machine，金德豪公司)設備，以彎折角度135度，彎曲半徑R=0.38mm，荷重500g進行耐折測試，記錄電路板至電路性質失效時所承受之彎曲次數。耐折測試次數越大表示所形成之聚醯亞胺層物性越好。 8. 物性測試 ( 耐折測試 3) ： 取20*20cm之乾膜(各實施例分別取4片)，放置於室溫下，之後在分別在第1、3、5、7天以上述濕式壓合方法，將乾膜塗覆有聚醯亞胺層的一面貼附於銅箔基板具線路之表面上，靜置120分鐘後以250^o C烘烤120分鐘，待降至室溫後，以耐折檢驗機(Measure Infect Turn (MIT) test machine，金德豪公司)設備，以彎折角度135度，彎曲半徑R=0.38mm，荷重500g進行耐折測試，紀錄耐折測試小於200次的放置天數，放置天數越長表示乾膜儲存穩定性越佳。 9. 物性測試 ( 耐折測試 4) ： 將取20*20cm之乾膜，之後以上述濕式壓合方法，將乾膜塗覆有聚醯亞胺層的一面貼附於銅箔基板具線路之表面上，之後於室溫下靜置，每6小時取2*10cm之壓合後基板以250^o C烘烤120分鐘，待降至室溫後，以耐折檢驗機(Measure Infect Turn (MIT) test machine，金德豪公司)設備，以彎折角度135度，彎曲半徑R=0.38mm，荷重500g進行耐折測試，紀錄耐折測試小於200次的放置時數，放置時數越長表示乾膜製程穩定性越佳。 10. 感光測試： 取20*20cm之乾膜，分別以上述濕式壓合與乾式壓合方法，將乾膜塗覆有聚醯亞胺層的一面壓合至銅箔基板具線路之表面上，靜置120分鐘後，使用L/S為60/60µm和開孔(via)大小為60µm之玻璃光罩，分別以不同UV能量(50mJ/cm² 、100mJ/cm² 、150 J/cm² 、200 J/cm² 、250 J/cm² )對聚醯亞胺層進行曝光。 曝光後撕除PET膜，置入烘箱以90^o C烘烤10分鐘，再以1wt%濃度的K₂ CO₃ 水溶液進行圖案顯影，隨後以SEM量測顯影後聚醯亞胺層上L/S(µm)和via(µm)之解析度，紀錄解析度符合要求之曝光能量，曝光能量較低表示材料的感光性較佳。 各實施例及比較例的測試結果記錄如表1至表7。 表1 ＜比較不同疏水溶劑之效果＞

NA：無法量測 表2 ＜比較不同樹脂/不同親水溶劑之效果＞

表3 ＜比較不同親水/疏水溶劑比例之效果＞

表4 ＜比較添加穩定劑之效果＞

表5 ＜比較不同溶劑總量之效果＞

表6 ＜比較不同壓合方法之效果＞

表7 ＜感光測試＞

表1顯示沒有添加疏水溶劑與添加不同疏水溶劑之效果。由表1可知，若僅使用製備習知聚醯亞胺前驅物或可溶聚醯亞胺時的常用溶劑（如NMP），則聚醯亞胺樹脂大幅沾黏在離型膜上，難以應用至後續加工，添加疏水溶劑則可改善沾黏現象，並且有良好的轉印能力與溶水性，適用於濕式壓合製程。 表2顯示選擇特定親水溶劑與疏水溶劑搭配，並控制其比例在本發明所述範圍內時，所得乾膜不沾黏，且具有良好轉印能力與溶水性，適用於濕式壓合製程。 表3顯示當親水溶劑及疏水溶劑之重量比例過高（如，超過2）時，乾膜過度沾黏，無法使用，且乾膜的儲存穩定性不佳(耐折測試3)；當親水溶劑及疏水溶劑之重量比例過低（如，低於0.05）雖可增加儲存穩定性，但此時乾膜轉印能力與溶水性不佳，由表3結果顯示調整適當之親水溶劑及疏水溶劑之重量比例(如，0.05~2，較佳0.1~1)所得之乾膜同時具有抗沾黏性、優良的轉印能力與溶水性，且乾膜的儲存穩定性佳(耐折測試3)，後續所形成之聚醯亞胺層亦具有優異的物性(耐折測試1)。 表4顯示添加適當用量之穩定劑，有助於提升乾膜的製程穩定性(耐折測試4)與溶水率，且不影響後續所得聚醯亞胺層之物性(耐折測試1)。 表5顯示乾膜溶劑總量控制在30wt%至70wt%之間時，乾膜沾黏性、轉印能力及溶水性較佳，且縱使在水存在下，最後製得的聚醯亞胺層亦具有良好物性（耐折測試1）。溶劑總量低於30wt%時，乾膜無法通過轉印測試，溶水性差，且最後製得的聚醯亞胺層物性亦不佳（耐折測試1）。溶劑總量高於70wt%時，乾膜過度沾黏，無法進行後續加工製程。 表6及7顯示，本發明之乾膜適用於濕式壓合方法，不但不會在圖案化表面與聚醯亞胺樹脂層間留下氣泡，且所得聚醯亞胺層物性較佳。此外，使用本發明之乾膜搭配濕式壓合方法相較於乾式壓合方法，可以用較低的曝光能量達到相同的解析度。To facilitate an understanding of the disclosure set forth herein, several terms are defined below. The term "about" means an acceptable error as the specific value determined by those skilled in the art, which is determined in part by how the value is measured or determined. In the present invention, the term "alkyl" means a saturated straight or branched hydrocarbon group, preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms; examples of which include, but are not limited to, methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl and the like. In the present invention, the term "alkenyl" means an unsaturated straight or branched hydrocarbon group having at least one carbon-carbon double bond, preferably having 2 to 30 carbon atoms, more preferably 10 to 20 carbon atoms; Examples thereof include, but are not limited to, ethenyl, propenyl, methacryl, isopropenyl, pentenyl, hexenyl, heptenyl, 1-propenyl, 2-butenyl, 2-methyl 2-butenyl group and the like. In the present invention, the term "alkynyl" means an unsaturated straight or branched hydrocarbon group having at least one carbon-carbon bond, preferably having 2 to 30 carbon atoms, more preferably 10 to 20 carbon atoms; Examples thereof include, but are not limited to, ethynyl, propargyl, 3-methyl-1-pentynyl, 2-heptynyl, and the like. In the present invention, the term "aryl" or "aromatic compound" means, for example, a monocyclic, bicyclic or tricyclic aromatic carbocyclic group having 6 to 14 carbon ring atoms, and examples thereof include, but are not limited to, benzene. Base, tolyl, naphthyl, anthracenyl, fluorenyl, phenanthryl and the like. In the present invention, the term "haloalkyl" means an alkyl group substituted by halogen, wherein "halogen" means fluorine, chlorine, bromine or iodine, preferably fluorine and chlorine. In the present invention, the term "alkoxy" means an alkyl group attached to an oxygen atom, and examples thereof include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy Base, isobutoxy, pentyloxy, hexyloxy, benzyloxy, fluorenylmethoxy and the like. In the present invention, the term "heterocyclic group" means a saturated, partially saturated (for example, a radical dihydrogen, a trihydrogen, a tetrahydrogen) composed of a carbon atom and at least one hetero atom selected from N, O or S. a hexahydro group or the like, or an unsaturated 3 to 14 membered ring group, preferably a 4 to 10 membered ring group, more preferably a 5 or 6 membered ring group; preferably having 1 to 4 hetero atoms, more preferably 1 to 3 heteroatoms. The heterocyclic group can be a monocyclic, bicyclic or tricyclic ring system comprising a fused ring (eg, a fused ring formed with another heterocyclic ring or another aromatic carbocyclic ring). Unless otherwise specified, in the present invention, "heterocyclic group" may be substituted or unsubstituted. Substituents such as, but not limited to, halogen, hydroxy, oxo, alkyl, hydroxyalkyl, -NO₂ Wait. In the present invention, the term "nitrogen-containing heterocyclic group" means a 3 to 14 membered heterocyclic group in which at least one ring carbon atom is replaced by a N atom, preferably a 4 to 10 member nitrogen-containing heterocyclic group, more preferably 5 or 6 members contain a nitrogen-containing heterocyclic group. Examples thereof include, but are not limited to, pyrrolyl, imidazolyl, pyrazolyl, pyrimidinyl, thiazolyl, pyridyl, indolyl. , isoindolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, and the like. Unless otherwise specified, in the present invention, the "nitrogen-containing heterocyclic group" may be substituted or unsubstituted. The substituents are as defined above for "heterocyclyl". In the present invention, the term "polyimine layer" means a resin layer containing a polyimide imine resin, a polyimine precursor or a polyetherimide (PEI) resin, "polyimine" It may be a polyamidene homopolymer or copolymer. The present invention provides a polyimine dry film comprising a substrate and a polyimide layer, wherein the polyimide layer comprises a polyimide precursor or a soluble polyimine and a solvent, and the solvent comprises a hydrophilic solvent and a hydrophobic solvent having a total content of the solvent of between about 30% by weight and about 70% by weight based on the total weight of the polyimine layer, and the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between about 0.05 and About 2 between. Polyimine dry film of the invention 1. Substrate The substrate used in the present invention may be any one known to those of ordinary skill in the art to which the present invention pertains, such as glass or plastic. The plastic substrate is not particularly limited, and is not limited to, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (polyethylene naphthalate). PEN); polymethacrylate resin, such as polymethyl methacrylate (PMMA); polyimide resin; polystyrene resin; polycycloolefin Polycycloolefin resin;polycycloolefin resin;polycarbonate resin;polyurethane resin; triacetate cellulose (TAC); or the like mixture. Preferred is polyethylene terephthalate, polymethyl methacrylate, polycycloolefin resin, cellulose triacetate or a mixture thereof, more preferably polyethylene terephthalate. The thickness of the substrate typically depends on the desired electronic product, preferably between about 16 μm and about 250 μm. 2. Polyimine layer The polyimine dry film of the present invention can be applied to different elements, so the polyimide layer can be a photosensitive polyimide layer or a non-photosensitive polyimide layer. The polyimine layer in the dry film of the present invention may comprise a polyimine precursor or a soluble polyimine. The thickness of the polyimide layer in the dry film of the present invention is not particularly limited and is generally preferably between about 10 μm and about 60 μm, preferably between about 20 μm and about 40 μm. (a) Polyimine precursor The polyimine precursor used in the present invention is not particularly limited and may be well known to those of ordinary skill in the art to which the present invention pertains, such as polyglycolic acid, polyamidamine, or any polymerizable reaction. A material of an imine or a mixture thereof. A variety of different polyimine precursors have been developed in the art, such as the inventions of the Republic of China, No. 095, 138, 481, No. 095, 141, 664, No. 096, 127, 743, No. 097, 151, 913, or No. 100, 149, 594. The above documents are incorporated herein by reference in their entirety. The polyimine precursor mainly has a repeating unit represented by the formula (A):

Wherein G is a tetravalent organic group; P is a divalent organic group; n is an integer greater than 0, preferably an integer from 1 to 1000. The above polyimine precursors may be modified using different groups as needed. For example, a photosensitive polyimide precursor can be prepared by modification with a photosensitive group; or the reaction of the polyimide precursor can be improved by adjusting a terminal group bonded to a repeating unit of the formula (A). Sexuality and improvement of the properties of the subsequent preparation of polyimine. For example, the application of the Republic of China Patent No. 100149594 discloses a polyimine precursor having a repeating unit represented by the following formulas (1) to (4):

(1),

(2),

(3), or

(4), where, G₁ Independently a tetravalent organic group; R_x Each is independently H or an ethylenically unsaturated group; R is independently C₁ -C₁₄ Alkyl, C₆ -C₁₄ Aryl, C₆ -C₁₄ An aralkyl group, a phenol group or a ethylenically unsaturated group; each D is independently a nitrogen-containing heterocyclic group or an OR* group, wherein R* is C₁ -C₂₀ Alkyl; m is an integer from 0 to 100, preferably an integer from 5 to 50, more preferably an integer from 10 to 25; and G and P are as previously defined herein. The above ethylenically unsaturated group is not particularly limited, and examples thereof include, but are not limited to, ethenyl, propenyl, methacryl, n-butenyl, isobutenyl, vinylphenyl, propenylphenyl, propylene. Oxymethyl, propyleneoxyethyl, propyleneoxypropyl, propyleneoxybutyl, propyleneoxypentyl, propyleneoxyhexyl, methacryloxymethyl, methacryloxyethyl, a methacryloxypropyl group, a methacryloxybutyl group, a methacryloxypentyl group, a methacryloxyhexyl group, a group having the following formula (5), and a group having the following formula (6) :

(5)

(6), where R₁₂ For stretching phenyl, C₁ -C₈ Alkyl, C₂ -C₈ Alkenyl, C₃ -C₈ Cycloalkyl or C₁ -C₈ Hydroxyalkylene; and R₁₃ For hydrogen or C₁ -C₄ alkyl. (b) Soluble polyimine In general, polyimides have the advantages of good heat resistance and chemical resistance, but they have disadvantages of poor processability, and there are not many solvents capable of dissolving polyimine. Therefore, in the application, most of the processing is carried out using a polyimide precursor, and the ruthenium is imidized into a polyimine at a later stage of the process. The soluble polyimine is modified on the structure of polyimine to increase the solubility between the polyimide and the solvent to improve the processability. The kind of the above solvent can be, for example, as described herein below. The soluble polyimine of the present invention is not particularly limited and may be known to those having ordinary skill in the art to which the present invention pertains, such as the Republic of China invention patent No. 097101740, No. 099105794, No. 097138725 or No. 097138792. Application number. The above documents are incorporated herein by reference in their entirety. The soluble polyimine of the present invention mainly has a repeating unit represented by the formula (B):

Wherein C' is a tetravalent organic group; E' is a divalent organic group; t' is an integer greater than 0, preferably an integer from 1 to 1000. The above-described C' tetravalent organic group can be as defined previously for the G group. The above-described aspect of the E' divalent organic group can be as defined herein for the P group. The above soluble polyimine may be modified using different groups as needed. The photosensitive polyimine can be prepared, for example, by modification with a photosensitive group; or by adjusting the terminal group bonded to the repeating unit of the formula (B), the properties of the soluble polyimine can be improved. The modified soluble polyimine can be obtained by adjusting the terminal group bonded to the repeating unit of the formula (B), the structure of which is, for example, but not limited to:

(1') ;

(2');

(3'); where R₂₀ 'for C₂ -C₂₀ The saturated or unsaturated 2 valence has a base group, preferably -C=C-,

,

; R_{twenty one} 'for C₂ -C₂₀ The monovalent group having an unsaturated group which may be substituted with a hetero atom or a group of -OH C', E' and t'' is as defined herein before. The soluble polyimine which is modified by a photosensitive group is preferably, but not limited to, those disclosed in the application No. 099105794, No. 099105794, No. 097138725, or No. 097138792. 3. Solvent In general, the polyimine precursor and the soluble polyimide are prepared or formulated in a polar aprotic organic solvent. In the prior art, in order to avoid the high concentration of volatile organic substances in the dry film during use and to reduce the excess glue of the coating film flowing during storage, the coated dry film semi-finished product is fed into the prior art. The oven is used to dry the resin layer and completely conform to the substrate. The organic solvent is almost completely volatilized in this step, and therefore, in general, the conventional dry film product has an organic solvent content of less than 1 wt%. In addition, dry film products need to be stored in a low temperature environment to reduce hydrolysis. Different from the prior art, the dry film of the present invention may contain a solvent, and the inventors of the present invention have extensively studied and repeated experiments and found that by controlling the kind and content ratio of the solvent, the obtained polyimide dry film has water absorption, and even in the case of In the presence of water, its properties are relatively stable, the surface is not sticky, the transfer ability is good, and the polyimine prepared by the curing thereof has good physical properties. Therefore, not only can the storage stability be increased, but also it can be applied to a processing process in which water or an aqueous solution is required. The solvent used in the present invention comprises a hydrophilic solvent and a hydrophobic solvent, wherein the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between about 0.05 and about 2, preferably between about 0.1 and about 1, and more preferably between Between about 0.25 and about 0.8, the obtained dry film has water absorption property, good transfer ability, non-stick surface, stable property, and good physical properties. When the weight ratio of the hydrophilic solvent to the hydrophobic solvent is too low (for example, less than 0.05), the polyilylimide dry film has poor water absorption, and the polyimide layer has poor adhesion to the substrate; when the hydrophilic solvent and the hydrophobic When the weight ratio of the solvent is too high, especially when it is more than 2, the surface of the dry film is liable to be sticky, the workability is poor, the alignment is not easy, and it is not suitable for heavy work. The hydrophobic solvent added in the present invention can be miscible with a liquid (water or alcohol), and the hydrophilic solvent usable in the present invention comprises: dimethyl hydrazine (DMSO), diethyl hydrazine, N, N-dimethylformamide (DMF), N,N-diethylformamide, N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N-propyl-2-pyrrolidone, N-vinyl- 2-pyrrolidone, phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, catechol, tetrahydrofuran (THF), dioxane, dioxolane, cyclopropanediol methyl ether ( PGME), tetraethylene glycol dimethyl ether (TGDE), butyl cellosolve, γ-butyrolactone (GBL), xylene, toluene, hexamethyl-o-amine, propylene glycol Methyl ether acetate (PGMEA) or a mixture thereof. According to an embodiment of the present invention, the hydrophilic solvent used preferably comprises: diethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethyl Acetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, cyclopropanediol methyl ether, γ-butyl Lactone, propylene glycol methyl ether acetate or a mixture thereof. More preferably, it comprises: N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone or a mixture thereof. The addition of the hydrophobic solvent of the invention can improve the stability of the dry film to water, and at the same time, the surface of the dry film is less likely to be sticky, and the operability is better. Hydrophobic solvents useful in the present invention include:

,

,

,

,

,

Or a combination thereof, wherein: R₁ '', R₉ ''and R₁₀ ''Separately for C₁ -C₂₀ Alkyl, C₂ -C₂₀ Alkenyl or C₂ -C₂₀ Alkynyl; R₇ ''for H or C₁ -C₃ Alkyl; R₂ ''for C₁ -C₁₀ Alkyl; R₃ ''for C₄ -C₂₀ Alkyl or -C₂ -C₁₀ alkyl-O-C₂ -C₁₀ Alkyl; R₄ ''and R₅ ''Separately for C₁ -C₁₀ Alkyl, or R₄ ''and R₅ '' forms a 5- to 6-membered heterocyclic ring together with the oxygen atom to which it is attached; R₆ ''for C₄ -C₁₅ Alkyl, C₄ -C₈ Cycloalkyl or

; R₈ ''for C₂ -C₁₀ Alkyl; R₁₁ ''and R₁₂ ''Separately for C₁ -C₁₀ Alkyl; R₁₃ ''and R₁₄ ''Separately for C₁ -C₁₀ Alkyl, or R₁₃ ''and R₁₄ '' forms a 5- to 6-membered heterocyclic ring together with the nitrogen atom to which it is attached; R₁₅ ''for C₄ -C₁₅ Alkyl or C₄ -C₈ Cycloalkyl; R₁₆ ''for C₁ -C₄ Alkyl; and R₁₇ ''for C₄ -C₁₀ alkyl. According to an embodiment of the invention, the hydrophobic solvent used preferably comprises:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, N,N-dimethylcapramide (DMC) or a combination thereof. In the present invention, the total solvent content is not particularly limited and may be adjusted depending on the manufacturing process of the dry film or the subsequent processing. In one embodiment of the invention, the total solvent content is between about 30 wt% and about 70 wt%, preferably between about 35 wt% and about the total weight of the polyimine layer. Between 65 wt%, more preferably between about 40 wt% and about 60 wt%. 4. additive The polyimine layer of the present invention may optionally contain any suitable additives known to those of ordinary skill in the art to which the present invention pertains, such as, but not limited to, stabilizers, ring closure promoters, leveling agents. , defoamers, coupling agents, catalysts, acrylate monomers and photoinitiators. The amount of the above additives is also a person who has ordinary knowledge in the art to which the present invention pertains can be adjusted by routine experimentation. In one embodiment of the invention, the polyimine layer of the invention may optionally contain a stabilizer selected from the group consisting of:

,

Or a combination thereof, wherein: R₁₇ '', R₁₈ '', R₁₉ ''and R₂₀ ''Separately for C₁ -C₄ Alkyl, or R₁₉ ''and R₂₀ '' forms a 5- to 6-membered heterocyclic ring together with the oxygen atom to which it is attached, or R₁₉ ''and R₁₇ ''or R₂₀ ''and R₁₈ '' forms a 5- to 6-membered heterocyclic ring together with the oxygen and nitrogen atoms to which it is attached; R_{twenty one} ''and R_{twenty two} ''Separately for C₁ -C₄ Alkyl, or R_{twenty one} ''and R_{twenty two} '' forms a 5 to 6 member carbon ring with its attached carbon atoms; and R_{twenty three} ''and R_{twenty four} ''Separately for C₁ -C₄ alkyl. According to a preferred embodiment of the invention, the stabilizer preferably comprises:

,

,

,

,

,

Or a combination thereof. The addition of a stabilizer helps to improve the stability and handleability of the dry film, and further enhances the physical properties of the subsequently formed polyimine. In one embodiment of the invention, the total amount of stabilizer is from about 0.01% to about 5% by weight, based on the total weight of the polyimine layer, preferably from about 0.05% to about 5% by weight. Between 3wt%. If the content exceeds 5% by weight, the formed polyimine property (for example, flexibility) may be lowered. In one embodiment of the present invention, the polyimide layer is a photosensitive polyimide, and an additive may be selected as needed. It contains a photoinitiator and an acrylate monomer. The above photoinitiators may be used singly or in combination of two or more. Photoinitiators suitable for use in the present invention are used to illuminate light to generate free radicals, which are initiated by the transfer of free radicals. The photoinitiator which can be used in the present invention is not particularly limited. Preferably, the photoinitiator used comprises a compound which absorbs light having a wavelength of from about 350 nm to about 500 nm to generate free radicals. The photoinitiator is used in an amount of from about 0.01 to about 20 parts by weight, preferably from about 0.05 to about 5 parts by weight, based on 100 parts by weight of the polyethylenimine precursor or soluble polyamidene solid content. Photoinitiators suitable for use in the present invention may, for example, be selected from the group consisting of benzophenone, benzophenone, 2-hydroxy-2-methyl-1-propiophenone, 2,2-dimethoxy- 1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, oxime ester, 2,4 , 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, bis 4,4'-diethylaminobenzophenone (bis-4, 4' -diethylaminobenzophenone), benzophenone, camphorquinone, 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone (3,5-bis (diethylaminobenzylidene)-N-methyl-4-piperidone), 3,5-bis(dimethylaminobenzylidene)-N-methyl-4-piperidone (3,5-bis(dimethylaminobenzylidene)- N-methyl-4-piperidone), 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone (3,5-bis(diethylaminobenzylidene)-N-ethyl- 4-piperidone), 3,3'-carbonyl-bis(7-diethylamino) cumarin, 3,3'-carbonyl-double (7-dimethylamino) coumarin ( 3,3'-carbonyl-bis(7-dimethylamino)cumarin), riboflavin tetrabutyrate, 2-methyl-1-[4-(methylthio)phenyl]-2- 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), 2,4-dimethylthioxanthone (2,4 -dimethylthioxanthone), 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5 -3,5-dimethylthioxanthone, 3,5-diisopropylthioxanthone, 1-phenyl-2-(ethoxy 1-phenyl-2-(ethoxycarbonyl)oxyiminopropan-1-one, benzoin ether, bezoin isopropyl ether, benzene onion Benzanthrone, 5-nitroacenaphthene, 2-nitrofluorene, anthrone, 1,2-benzanthraquinone, 1 -Phenyl-5-mercapto-1H-tetrazole, thioxanthen-9-one, 10-thioxanthenone ), 3- 3-acetylindole, 2,6-di(p-dimethylaminobenzal)-4-carboxycyclohexanone, 2,6-di(p-dimethylaminobenzal)-4-hydroxycyclohexanone, 2,6-di (p-diethyl) 2-,6-di(p-diethylaminobenzal)-4-carboxcyclohexanone, 2,6-di(p-diethylaminobenzylidene)- 4-hydroxycyclohexanone (4,6-di(p-diethylaminobenzal)-4-hydroxycyclohexanone), 4,6-dimethyl-7-ethylamine coumarin (4,6-dimethyl-7-) Ethylaminocumarin), 7-diethylamino-4-methylcumarin, 7-diethylamino-3-(1-methylbenzimidazolyl)coumarin 7-diethylamino-3-(1-methylbenzoimidazolyl) cumarin), 3-(2-benzimidazolyl)-7-dimethylethylamino coumarin (3-(2-benzoimidazolyl)-7-diethylaminocumarin) , 3-(2-benzothiazolyl)-7-dimethylphenylamino coumarin (3-(2-benzothiazolyl)-7- diethylaminocumarin), 2-(p-dimethylaminostyryl) Benzooxazole (2-(p-dimethy) Laminostyryl)benzoxazole), 2-(p-dimethylaminostyryl)quinoline, 4-(p-dimethylaminostyryl)quinoline (4-(p-dimethylaminostyryl)quinoline) P-dimethylaminostyryl)quinoline), 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)-3 , 3-(p-dimethylaminostyryl)-3,3-dimethyl-3H-indole) and combinations thereof. Preferred photoinitiators are benzophenone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, benzophenone, 2-hydroxy-2-methyl-1-propenone , 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2,4,6-trimethylbenzimidyl diphenyl A phosphine oxide, an oxime ester or a combination thereof. The above acrylate monomer is an acrylate monomer having at least one -C=C-, preferably a polyfunctional acrylate monomer having two or more -C=C- Acrylate monomer), the addition of such monomers enables the formation of crosslinks between molecules and molecules, which facilitates the utility of the composition. Preferably, the present invention uses an acrylate monomer selected from the group consisting of ethylene glycol di(methacrylate), ethylene glycol diacrylate, bisphenol A ethylene glycol-modified diacrylate, Bisphenol A ethylene glycol-modified di(methacrylic acid) ester, bisphenol F ethylene glycol-modified diacrylate, bisphenol F ethylene glycol-modified di(methacrylic acid) ester, propylene glycol II Methacrylate, tripropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, trimethylolpropane tri Methacrylate, tetrahydroxymethane triacrylate, tetrahydroxymethane tris(methacrylate), and combinations thereof. When the acrylate monomer is present, it is added in an amount of from about 5 to about 80 parts by weight, preferably from about 10 to about 40, based on 100 parts by weight of the polyamidene precursor or soluble polyimine solid content. Parts by weight. The coupling agent which can be used in the present invention can be selected from the group consisting of, but not limited to, 3-aminopropyltrimethoxydecane (APrTMOS), 3-triaminopropyltriethoxylate. Decane (APrTEOS), 3-aminophenyltrimethoxydecane (APTMOS), 3-aminophenyltriethoxydecane (APTEOS), and combinations thereof. According to one embodiment of the present invention, a ring closure promoter may be added during the preparation of the polyimine precursor of the present invention as needed. A ring closure accelerator which can be heated to produce a basic compound and which provides an alkaline environment to promote the imidization reaction is preferably used. The closed loop promoter useful in the present invention comprises:

,

,

,

,

,

,

,

,

,

,

Y^θ ,

Y^θ ,

Y^θ ,

Y^θ or

Y^θ , where Y^θ It is an anionic group. Method of forming a dry film The polyimine dry film of the present invention can be prepared, for example, by the following steps: (1) preparing a polyimide composition, mixing a polyimine precursor or a soluble polyimine and a hydrophilic solvent; (2) adding a suitable amount of a hydrophobic solvent, and an optional additive to the above formulation; (3) applying the formulation obtained in the step (2) to the substrate to form a dry film semi-finished product; (4) feeding the dry film semi-finished product into the baking furnace Heating and drying to remove part of the solvent, thereby adjusting the solvent content in the polyimine layer; forming a polyimine dry film; (5) applying a protective film on the polyimine dry film as needed. The temperature and time required for the above step (4) are not particularly limited, and the main purpose thereof is to reduce the solvent content in the resin layer, for example, one of the temperatures between 60 ° C and 150 ° C can be used for 30 seconds. Heat and dry to 10 minutes. In the conventional process of preparing a dry film, in order to avoid the use of a dry film to produce a high concentration of volatile organic compounds, in the solvent removal step relative to the aforementioned step (4), the usual heating causes the solvent to reach almost complete volatilization (content less than 1) Wwt%) However, contrary to the conventional steps, the present invention does not completely remove the solvent in this step, but instead retains an appropriate amount of a hydrophilic solvent and a hydrophobic solvent in the dry film. The solvent of the above step (4) contains a hydrophilic solvent and a hydrophobic solvent. In general, by adjusting the heating temperature and time by different boiling point differences of different solvent types, the total content and ratio of the solvent in the dry film to be obtained can be controlled, for example, the weight ratio of the hydrophilic solvent to the hydrophobic solvent is Between about 0.05 and about 2. The protective film of the above step (5), which is, for example but not limited to, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (polyethylene naphthalate). PEN); polymethacrylate resin, such as polymethyl methacrylate (PMMA); polyimide resin; polystyrene resin; polycycloolefin Polycycloolefin resin;polycycloolefin resin;polycarbonate resin;polyurethane resin; triacetate cellulose (TAC); or the like mixture. Preferred is polyethylene terephthalate, polymethyl methacrylate, polycycloolefin resin, cellulose triacetate or a mixture thereof, more preferably polyethylene terephthalate. Method of applying a dry film on a substrate The present invention further provides a method for applying a polytheneimide dry film on a substrate, comprising: after removing the protective film to be added as needed, using the polyimine dry film as a surface of the polyimide layer and the substrate Press fit. The substrate may be a printed circuit board, a wafer, a glass, a display or a touch panel, or other substrate. According to an embodiment of the present invention, the substrate is a printed circuit board, particularly preferably a flexible printed circuit (FPC), and a dry film polyimide layer is pressed onto the patterned surface. The dry film may be applied to the substrate in any manner, preferably in a roll-to-roll manner. The roll-to-roll operation is well known to those of ordinary skill in the art to which the present invention pertains. The sample is pulled through the sample in a self-wrapping form, and after processing, the treated sample is taken back by winding. For example, as shown in FIG. 1, after the substrate A in a wound form is pulled out, the dry film from the dry film roll 1 is rolled between the rollers 2 and 3, and then retracted by winding. Product B. The dry film of the present invention can be pressed to the substrate using a continuous process, which is advantageous for simplifying the process and speeding up the process. The above pressing method, such as but not limited to: roller lamination, hot press, vacuum lamination, vacuum press or wet lamination ). As described above, the polyilylimide dry film of the present invention has water absorbing property by controlling the appropriate solvent type and content ratio, and the surface is not sticky, and the formed cover film has excellent physical properties. In addition, even in the presence of water, it can remain stable without affecting the properties of the obtained polyimine, so it is suitable for wet pressing, and the dry film can be used to enhance the uniformity of the patterned substrate by wet pressing. Sex. 2 is a schematic view of the dry film of the present invention applied to wet pressing. As shown in FIG. 2, the present invention provides a method for applying a dry film by wet pressing on a substrate, the method comprising: (1) applying a liquid 30 on a surface 11 of the substrate 10 to be pressed; and (2) The dry film 20 of the present invention (including the substrate 21 and the polyimide layer 22) is laminated to the surface 11 of the substrate 10 to be laminated with the surface of the polyimide layer. The liquid used in the step (1) contains water, an alcohol solvent or a combination thereof to make the process more environmentally friendly and economical. Preferred liquids are methanol, ethanol, isopropanol, butanol, water or mixtures thereof. The liquid can be filled in the recessed area on the surface 11 to be pressed to form a liquid film, thereby escaping the air originally present in the recessed area. In the step (2), the dry film 20 is pressed by the roller to the surface 11 of the substrate 10 to be pressed. The liquid used in the step (1) at this time can be absorbed into the polyimine layer of the present invention. Preferably, step (2) is carried out under heating, for example at 60^o C to 100^o The temperature of C to enhance the uniformity and adhesion between the polyimide layer and the pressed surface. If liquid remains, a standing step (3) may be carried out as needed, and after standing for a certain period of time (for example, 5 minutes to 240 minutes), the residual liquid is sufficiently absorbed into the dry film. The present invention further provides a wet press-bonding system comprising: (1) a dry film of the present invention; (2) a substrate; and (3) a liquid. The above substrate and liquid system are as described above. The dry film of the present invention is particularly useful for wet processing, has good uniformity, and can effectively fill thick copper lines compared to conventional dry films. Application of dry film of the invention The polyimine dry film of the invention can be used in general pressing technology (especially wet pressing) and such as printed circuit board, wafer, glass without using high pressure defoaming machine or vacuum laminating equipment. The substrate of the display or the touch panel is pressed, so that it can be operated in a process process which is simpler than the prior art, and the equipment used is more easily obtained by users of the prior art. Therefore, it is more cost effective than prior art using a vacuum laminator or other process equipment. The dry film of the invention is suitable for a printed circuit board, and is used as a cover film for protecting a coating film on a printed circuit board, has insulation, can protect a circuit, and has excellent performance for avoiding line oxidation and solder short circuit. Further, since the dry film of the present invention has characteristics such as high resolution, fast development speed, electrolytic plating resistance, electroless plating resistance, and high temperature and high humidity resistance, it can also be used as a photoresist in a wafer process. Further, the polyimine dry film of the present invention has a relatively good transfer property even when the properties are relatively stable in the presence of water and the surface is not sticky. In addition, the moisture or solvent in the dry film can be removed in subsequent processes without affecting the physical properties of the resulting polyimine, and therefore, it is particularly advantageous when used as a cover film. In view of the above, in a preferred embodiment of the present invention, the polyimine dry film of the present invention is applied to a substrate as a cover film by a wet process. 3 is an example of using a photosensitive polyimide film of the present invention as a flexible printed circuit board cover film, and further describes the subsequent processing steps (but not limited thereto): (1) using wet pressing, The polyimine dry film 20 of the present invention is pressed against the substrate 10; (2) exposure is carried out in the presence of the mask 40 to impart photosensitivity to the polyimine precursor or soluble polyimine of the present invention. a group (such as a group having an ethylenically unsaturated group) undergoes a crosslinking reaction; (3) removing the support substrate 21 of the dry film 20, and performing post-exposure Bake; (4) performing development To remove the polyimine layer of the non-exposed area; and (5) if the polyimine precursor is imidized (cured) into a polyimine. The exposure step of the above step (2) can be carried out in any manner known to those skilled in the art to which the present invention pertains, for example, ultraviolet light, visible light, electron beam or laser irradiation, preferably ultraviolet light. The exposure energy and time are not particularly limited, and those who have ordinary knowledge in the technical field to which the present invention pertains may be adjusted according to their experience. According to an embodiment of the invention, the exposure energy used is about 50 to 1200 mJ/cm.² . The post-exposure bake of the above step (3) increases the difference in solubility of the exposed and non-exposed areas during development by heating. The heating temperature and time are not particularly limited, and may be adjusted as needed, as long as the above purpose can be achieved. Heating can be carried out in one or more stages. In one embodiment of the invention, it is between 60 and 150^o The temperature range of C is continuously heated for 5 to 90 minutes. The solvent contained in the polyimide layer (for example, the aforementioned hydrophilic, hydrophobic solvent) and the liquid absorbed during wet pressing can be partially discharged in this heating step. The above step (4) is a method of dissolving or removing the resin in the unexposed area (when a dry film of a negative photosensitive polyimide is used) by a developing step or using a resin of an exposed region (using a positive photosensitive polyimide) When the film is dry, it is dissolved and removed, and then rinsed with water to obtain a desired pattern. The developer used is well known to those of ordinary skill in the art to which the present invention pertains. Examples of developers such as, but not limited to, K₂ CO₃ Aqueous solution, Na₂ CO₃ An aqueous solution, an aqueous KOH solution, an aqueous NaOH solution, and an aqueous solution of tetramethylammonium hydroxide (TMAH). Further, when the polyimine layer comprises a polyimine precursor, the step (5) is carried out, for example, by heating, the polyimine precursor is cyclized and polymerized into a polyimine. And the solvent or liquid remaining in the polyimide layer is further removed. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Modifications and variations that may be readily made by those skilled in the art are included within the scope of the disclosure of the present disclosure and the scope of the appended claims. Example The abbreviations mentioned in the following examples are defined as follows: DA1:

1-MI: 1-methylimidazole PTZ: phenothiazine (10H-phenothiazine) DA3:

DMC: N,N-dimethyl decylamine

NOP:

NOEP:

D-PC:

Ethyl acetate:

1,6-hexanediol diacrylate:

Preparation example 1 : Synthetic photosensitive polyimine precursor resin PAA-1 21.81 g (0.1 mol) of pyromellitic dianhydride (hereinafter abbreviated as PMDA) was dissolved in 200 g of N-methylpyrrolidone (N- Methyl-2-pyrrolidone; hereinafter abbreviated as NMP), the resulting mixture was heated to 50 ° C and stirred for two hours. 1.161 g (0.01 mol) of 2-hydroxyethyl acrylate (hereinafter abbreviated as HEA) was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Thereafter, 20.024 g (0.1 mol) of 4,4'-oxydianiline (hereinafter referred to as ODA) was added to the solution, and after completely dissolved, it was further fixed at 50 ° C. The reaction was stirred for six hours to obtain a photosensitive polyimine precursor resin PAA-1 having a solid content of about 17% by weight (bake at 250 or 300 ° C for 1 hour to remove all solvents, and measure the weight before and after baking) Poor, the weight of the non-volatile material can be obtained, and the weight percentage in PAA-1 is calculated as the solid content).Preparation example 2 : Synthetic photosensitive polyimine precursor resin PAA-2 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of N-methyl-2-pyrrolidone (hereinafter referred to as NEP), and heated. The resulting mixture was brought to 50 ° C and the reaction was stirred for two hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Thereafter, 20.024 g (0.1 mol) of ODA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours to obtain a photosensitive polyimine precursor resin PAA-2. The solid content is about 17% by weight (bake at 250 or 300 ° C for 1 hour, and the weight difference before and after baking is measured to obtain the weight of the actual non-volatile matter, and the weight percentage in PAA-2 is calculated. It is a solid part).Preparation example 3 : Synthetic photosensitive polyimine precursor resin PAA-3 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP, heated to 50 ° C and stirred for two hours. 13.01 g (0.01 mol) of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Then, 20.024 g (0.1 mol) of ODA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours to obtain a photosensitive polyimine precursor resin PAA-3, which was solid. The portion is about 21% by weight.Preparation example 4 : Synthetic photosensitive polyimine precursor resin PAA-4 29.42 g (0.1 mol) of 3,3,4,4-biphthalic dianhydride (hereinafter referred to as BPDA) Dissolved in 200 g of NMP, heated to 50 ° C and stirred for two hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for 24 hours. Further, 32.024 g (0.1 mol) of bis(trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl) benzidine; hereinafter referred to as TFMB) was added to the solution, after being completely dissolved. The reaction was further stirred at a fixed temperature of 50 ° C for six hours to obtain a photosensitive polyimine precursor resin PAA-4 having a solid content of about 20% by weight.Preparation example 5 : Synthesis of Polyimine Precursor Resin PAA-5 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP, heated to 50 ° C and stirred for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Then, 32.02 g (0.1 mol) of TFMB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours to obtain a polyimine precursor resin PAA-5. 21wt%.Preparation example 6 : Synthesis of Polyimine Precursor Resin PAA-6 29.42 g (0.1 mol) of BPDA was dissolved in 200 g of NMP, heated to 50 ° C and stirred for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Then, 20.024 g (0.1 mol) of ODA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours to obtain a polyimine precursor resin PAA-6. 19 wt %.Preparation example 7 : Synthesis of soluble polyimine SPI-1 with carboxyl group (-COOH) Weighed 43.62 g (0.2 mol) of PMDA and 30.43 g (0.2 mol) of 3,5-diaminobenzoic acid (3,5 -diamino benzoic acid; hereinafter abbreviated as DABA), 300 mL of NMP was added, and the mixture was stirred at room temperature for 1 hour, and then heated to 50 ° C and stirred for 4 hours. After 4 hours, 50 mL of toluene was added and the water was removed at 150 ° C with a dean-stark apparatus. After the water is completely removed, the toluene is removed to obtain a polyimine solution SPI-1 having a carboxyl group, and the solid content is about 19 wt%.Preparation example 8 : Synthesis of Isocyanate Modified Soluble Polyimine SPI-2 Weigh 64.85 g (0.2 mol) of DA1 and 42.46 g (0.2 mol) of 2,2'-dimethylbiphenyl-4,4' Diamine (2,2'-dimethylbiphenyl-4,4'-diamine, hereinafter abbreviated as DMDB), 300 mL of NMP was added, and the mixture was stirred at room temperature for 1 hour, and then heated to 50 ° C and stirred for 4 hours. After 4 hours, 50 mL of toluene was added and the water was removed at 130 ° C with a Dean-Stark apparatus. After the water was removed and the toluene was completely removed, the solution was cooled to room temperature, and 7 g (0.05 mol) of 2-isocyanatoethyl acrylate (hereinafter referred to as 2-IEA), 0.05 was added. Gram 1-MI and 0.06 g PTZ. After the addition was completed, the solution was warmed to 80 ° C and stirred for 8 hours. The isocyanate-modified soluble polyimine SPI-2 is obtained with a solid content of about 27 wt%. Preparation Example 9: Synthesis of soluble polyimine SPI-3 having a carboxyl group (-COOH) Weigh 100.074 g (0.2 mol) of DA3 and 42.46 g (0.2 mol) of DMDB, and add 450 ml of NMP at room temperature. The mixture was stirred for 1 hour, heated to 50 ° C, and stirred for 4 hours. Thereafter, 50 ml of toluene was added, and at 130 ° C, water was removed by a Dean-Stark apparatus. After the water is removed and the toluene is completely removed, a soluble polyimine SPI-3 having a -COOH group is obtained, and the solid content is about 24 wt%.Preparation example 10 : Synthetic epoxy-modified soluble photosensitive polyimine SPI-4 142.5 g of the polyimine SPI-3 prepared in Preparation Example 9 was weighed, and 6.11 g (0.05 m) of methyl group was added. Glycidyl methacrylate (hereinafter referred to as GMA), 0.015 g of tetrabutylammonium bromide (hereinafter abbreviated as TBAB) and 0.06 g of hydroquinone Monomethyl Ether (hereinafter referred to as MEHQ) ). After the addition, the solution was heated to 90 ° C and stirred for 12 hours to obtain an epoxy-modified soluble photosensitive polyimine SPI-4 having a solid content of about 25 wt %.Preparation example 11 : Synthesis of Polyimine Solution SPI-5 with Acrylic Photosensitive Group Weigh 32.023 g (0.1 mol) of TFMB and 48.8664 g (0.11 mol) of 4,4'-(hexafluoroisopropene) diacetic anhydride (4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, hereinafter referred to as 6FDA), was added with 300 mL of NMP, and stirred at room temperature for 1 hour. The mixture was further heated to 50 ° C and stirred for 4 hours. After 4 hours, 50 mL of toluene was added and the water was removed at 150 ° C with a Dean-Stark apparatus. After completely removing water and removing toluene, 2.322 g (0.02 mol) of HEA was added and stirred at 50 ° C for 4 hours to obtain a polyimine solution SPI-5 having an acrylic photosensitive group, which was solid. The share is about 21 wt%.Preparation example 12 : Synthetic Polyimine Precursor Resin PAA-7 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of N,N-dimethylacetamide (hereinafter abbreviated as DMAc). Heat to 50 ° C and stir the reaction for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Then, 32.02 g (0.1 mol) of TFMB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours to obtain a polyimine precursor resin PAA-7. 20 wt %.Preparation example 13 : Synthesis of Polyimine Precursor Resin PAA-8 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of γ-butyrolactone, heated to 50 ° C and stirred for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for three hours. Then, 32.02 g (0.1 mol) of TFMB was added to the solution. After completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours to obtain a polyimine precursor resin PAA-8. 21 wt %.Preparation example 14 : Synthesis of soluble polyimine SPI-6 with carboxyl group (-COOH) Weigh 43.62 g (0.2 mol) of PMDA and 30.43 g (0.2 mol) of DABA, add 300 mL of DMAc, and stir at room temperature. After an hour, the temperature was further raised to 50 ° C and stirred for 4 hours. After 4 hours, 50 mL of toluene was added and the water was removed at 150 ° C with a dean-stark apparatus. After the water is completely removed, the toluene is removed to obtain a polyimine solution SPI-6 having a carboxyl group, and the solid content is about 20 wt%.dry Membrane preparation Taking 100 parts by weight of the polyimine precursor solution or the soluble polyimine solution prepared in the above Preparation Examples 1 to 14, a hydrophobic solvent or a stabilizer as needed is added in a ratio (parts by weight) shown in Tables 1 to 5. And adding 2 parts by weight of a hot base generator (

). In addition, if it is a photosensitive polyimide precursor solution or a photosensitive soluble polyimide solution (such as PAA-1 to PAA-4, SPI-2, SPI-4 and SPI-5), then add 1 part by weight of a photoinitiator (2,4,6-trimethylbenzimidyldiphenylphosphine oxide and benzophenone, in a ratio of 1:1) to prepare a coating composition. Each of the coating compositions was uniformly coated on a polyethylene terephthalate (model: R310, manufactured by Mitsubishi Corporation) with a doctor blade, and baked in an oven. The baking temperature and time were as shown in the respective tables. Subsequently, the surface coated with the coating composition is covered with a release film (Model: L150L, manufactured by South Asia) to obtain a dry film having a polyimide or a polyimide coating. The thickness is about 40 μm. The hydrophilic solvent content before coating and the amount of hydrophobic solvent added (parts by weight) are based on 100 parts by weight of the polyimide solvent solution or the soluble polyimide solution, and the hydrophilic solvent and the hydrophobic solvent after baking and drying. The content (% by weight) is based on the total weight of the resin layer.Dry film test The solvent content of the above dry film was measured and the physical properties of the dry film such as tackiness, transfer integrity, water solubility, folding resistance and photosensitivity were tested. The tests are as follows:1. Solvent content detection Take 0.01 g of polyimine precursor coating or soluble polyimide coating (ie, no PET substrate and release film), dissolve in dimethyl hydrazine (DMSO), use Agilent's 7890 GC gas Phase chromatograph, capillary model: DB1701 (0.53mm, 30mm, 1.5μm), quantitative analysis of gas chromatography. 2. Dry film adhesion test The dry film of each of the examples and the comparative examples was taken, and the release film was peeled off to observe whether or not the residual polyimide film resin remained on the release film. There is no residue at all 0, <10% residue is 1, 10%~20% residue is 2, and >20% residue is NG. 3. Transfer test After taking a dry film of 20*20 cm and tearing off the release film, the surface of the dry film coated with the polyimide layer is pressed to the copper of the prepared line by the following dry pressing and wet pressing methods, respectively. On the foil substrate (L/S=30/30μm; L/S is the line width/line spacing): (a) Wet-pressed on the surface of the copper foil substrate with the line, apply deionized water, use a hot roller, Pressing was carried out at 60 ° C and a lower pressure of 5 kg. (b) Dry press-bonding on the surface of the copper foil substrate with a hot roller and pressing at 60 ° C and a lower pressure of 5 kg. After standing for 10 minutes, the PET film on the dry film was peeled off, and the PET film was observed to have residual polyimine layer resin. The residual residue on the PET film was 0, <10% residue was 1,10% to 20%. The residue is 2, and >20% remains in the PET film as NG.4. Water solubility test Taking a dry film of 20*20 cm, the side of the dry film coated with the polyimide layer is pressed to the surface of the copper foil substrate having the line by the above wet pressing method, and the copper foil substrate is observed by using a microscope. The time when the water is completely absorbed. Observe every 5 minutes in the first hour and then every 30 minutes.5. Bubble test Take a dry film of 20*20 cm, press the side of the dry film coated with the polyimide layer to the surface of the copper foil substrate with the line on the line by the above-mentioned wet pressing and dry pressing method, and let stand for 10 minutes. After observing the residual state of the bubbles. No bubbles are Pass and bubbles are NG. 6. Physical property test ( Folding test 1) A dry film of 20*20 cm was taken, and the side of the dry film coated with the polyimide layer was pressed to the surface of the copper foil substrate having the line by the above-mentioned wet pressing and dry pressing, respectively, and allowed to stand for 120 minutes. After, to 250^o C baking for 120 minutes, then down to room temperature, and using a Measure Infect Turn (MIT) test machine, with a bending angle of 135 degrees, a bending radius of R = 0.38 mm, and a load of 500 g. Fold-resistant test, recording the number of bends the board is subjected to when the circuit properties fail. The greater the number of folding test results, the better the physical properties of the formed polyimide layer.7. Physical property test ( Folding test 2- For photosensitive materials ) A dry film of 20*20 cm was taken, and the side of the dry film coated with the polyimide layer was pressed to the surface of the copper foil substrate having the line by the above-mentioned wet pressing and dry pressing, respectively, and allowed to stand for 120 minutes. After exposure with a UV exposure machine (exposure energy 400 mJ/cm² ), then peel off the PET film to 90^o C baking for 10 minutes, with a concentration of 1% by weight of K₂ CO₃ Aqueous solution for pattern development, then 250^o C baking for 120 minutes, and after falling to room temperature, and using a Measure Infect Turn (MIT) test machine, the bending angle is 135 degrees, the bending radius is R = 0.38 mm, and the load is 500 g. Perform a folding test to record the number of bends the board is subjected to when the circuit fails. The greater the number of folding test results, the better the physical properties of the formed polyimide layer. 8. Physical property test ( Folding test 3) : Take 20*20cm dry film (4 pieces in each embodiment), place at room temperature, and then apply the dry film on the first, third, fifth, and seventh days by the above wet pressing method. One side of the polyimide layer is attached to the surface of the copper foil substrate, and is allowed to stand for 120 minutes after standing for 250 minutes.^o C baking for 120 minutes, after being cooled to room temperature, using a Measure Infect Turn (MIT) test machine, with a bending angle of 135 degrees, a bending radius of R = 0.38 mm, and a load of 500 g. The folding test is to record the number of days in which the folding test is less than 200 times. The longer the number of days, the better the dry film storage stability. 9. Physical property test ( Folding test 4) : A dry film of 20*20 cm will be taken, and then one side of the dry film coated with the polyimide layer is attached to the surface of the copper foil substrate line by the above wet pressing method, and then allowed to stand at room temperature. , take 2*10cm of pressed substrate after every 6 hours to 250^o C baking for 120 minutes, after being cooled to room temperature, using a Measure Infect Turn (MIT) test machine, with a bending angle of 135 degrees, a bending radius of R = 0.38 mm, and a load of 500 g. For the folding test, record the folding time test less than 200 times, the longer the placement time, the better the dry film process stability. 10. Photosensitive test: Taking a dry film of 20*20 cm, the side of the dry film coated with the polyimide layer is pressed onto the surface of the copper foil substrate line by the above-mentioned wet pressing and dry pressing method, and allowed to stand for 120 minutes. After that, use a glass reticle with an L/S of 60/60 μm and a via size of 60 μm with different UV energies (50 mJ/cm).² , 100mJ/cm² , 150 J/cm² , 200 J/cm² 250 J/cm² The polyimide layer is exposed to light. Peel off the PET film after exposure and place it in an oven to 90^o C baking for 10 minutes, then 1% by weight of K₂ CO₃ The aqueous solution was subjected to pattern development, and then the resolution of L/S (μm) and via (μm) on the polyimide layer after development was measured by SEM, and the resolution was determined to meet the required exposure energy, and the lower exposure energy indicates the sensitization of the material. Better sex. The test results of the respective examples and comparative examples are recorded as shown in Tables 1 to 7. Table 1 <Comparing the effects of different hydrophobic solvents>

NA: Unmeasured Table 2 <Comparing the effects of different resins/different hydrophilic solvents>

Table 3 <Comparing the effects of different hydrophilic/hydrophobic solvent ratios>

Table 4 <Comparing the effect of adding stabilizer>

Table 5 <Comparing the effects of different solvents>

Table 6 <Comparing the effects of different pressing methods>

Table 7 <Photosensitive test>

Table 1 shows the effect of not adding a hydrophobic solvent and adding a different hydrophobic solvent. It can be seen from Table 1 that if only a common solvent (such as NMP) for preparing a conventional polyimine precursor or a soluble polyimine is used, the polyimide resin is greatly adhered to the release film, and it is difficult to apply to the subsequent process. Processing, adding a hydrophobic solvent can improve the sticking phenomenon, and has good transfer ability and water solubility, suitable for wet pressing process. Table 2 shows that when a specific hydrophilic solvent is selected in combination with a hydrophobic solvent and the proportion thereof is controlled within the range of the present invention, the obtained dry film is not sticky, and has good transfer ability and water solubility, and is suitable for a wet press-bonding process. Table 3 shows that when the weight ratio of the hydrophilic solvent and the hydrophobic solvent is too high (for example, more than 2), the dry film is excessively sticky, cannot be used, and the storage stability of the dry film is not good (resistant test 3); when the hydrophilic solvent If the weight ratio of the hydrophobic solvent is too low (for example, less than 0.05), the storage stability can be increased, but at this time, the dry film transfer ability and the water solubility are not good, and the results of Table 3 show that the appropriate hydrophilic solvent and hydrophobic solvent are adjusted. The dry film obtained by the weight ratio (for example, 0.05 to 2, preferably 0.1 to 1) has anti-adhesion property, excellent transfer ability and water solubility, and good storage stability of the dry film (resistant test 3). The subsequently formed polyimide layer also has excellent physical properties (Folding Resistance Test 1). Table 4 shows that the addition of an appropriate amount of stabilizer helps to improve the process stability (difference test 4) and water dissolution rate of the dry film, and does not affect the physical properties of the subsequently obtained polyimide layer (resistant test 1). Table 5 shows that when the total amount of dry film solvent is controlled between 30% by weight and 70% by weight, dry film adhesion, transfer ability and water solubility are preferred, and even in the presence of water, the finally obtained polyimide layer Also has good physical properties (resistant test 1). When the total amount of the solvent is less than 30% by weight, the dry film cannot pass the transfer test, the water solubility is poor, and the property of the finally obtained polyimide layer is also poor (deficiency test 1). When the total amount of the solvent is higher than 70% by weight, the dry film is excessively adhered, and subsequent processing cannot be performed. Tables 6 and 7 show that the dry film of the present invention is suitable for the wet pressing method, and not only does not leave bubbles between the patterned surface and the polyimide layer, and the obtained polyimine layer has better physical properties. Further, the use of the dry film of the present invention in combination with the wet pressing method can achieve the same resolution with a lower exposure energy than the dry pressing method.

A‧‧‧ substrate roll
B‧‧‧Product Roll
1‧‧‧ dry film roll
2‧‧‧Upper wheel
3‧‧‧Lower scroll wheel
10‧‧‧Substrate
11‧‧‧ Surface to be pressed
20‧‧‧ Polyimine dry film
21‧‧‧Substrate
22‧‧‧ Polyimine layer
30‧‧‧Photomask
40‧‧‧Photomask

Figure 1 is a schematic diagram of a roll-to-roll process. 2 is a schematic view of the dry film of the present invention applied to wet pressing. Figure 3 is a related processing step of the dry film of the present invention applied to a cover film.

A‧‧‧ substrate roll

B‧‧‧Product Roll

1‧‧‧ dry film roll

2‧‧‧Upper wheel

3‧‧‧Lower scroll wheel

Claims (14)

A polyimine dry film comprising a substrate and a polyimide layer, wherein the polyimide layer comprises: (a) a polyimine precursor or a soluble polyimine; and (b) a solvent, wherein The solvent comprises a hydrophilic solvent and a hydrophobic solvent, and the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between 0.05 and 2, wherein the hydrophilic solvent comprises dimethyl sulfoxide, diethyl hydrazine, N, N. - dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, catechol, tetrahydrofuran, dioxane , dioxolane, cyclopropanediol methyl ether, tetraethylene glycol dimethyl ether, butyl cellosolve, γ-butyrolactone, xylene, toluene, hexamethyl ortho-amine, propylene glycol methyl ether acetate or mixtures thereof, And wherein the hydrophobic solvent comprises: , , , , , Or a combination thereof, wherein: R ₁ '', R ₉ '' and R ₁₀ '' are each independently C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl; R ₇ '' is H or C ₁ -C ₃ alkyl; R ₂ '' is C ₁ -C ₁₀ alkyl; R ₃ '' is C ₄ -C ₂₀ alkyl or -C ₂ -C ₁₀ alkyl-OC ₂ -C ₁₀ alkyl; R ₄ '' and R ₅ '' are each independently C ₁ -C ₁₀ alkyl, or R ₄ '' and R ₅ '' together with the oxygen atom to which they are attached form a 5- to 6-membered heterocyclic ring ; R ₆ '' is C ₄ -C ₁₅ alkyl, C ₄ -C ₈ cycloalkyl or R ₈ '' is a C ₂ -C ₁₀ alkylene group; R ₁₁ '' and R ₁₂ '' are each independently a C ₁ -C ₁₀ alkyl group; R ₁₃ '' and R ₁₄ '' are each independently C ₁ - C ₁₀ alkyl, or R ₁₃ '' and R ₁₄ '' together with the nitrogen atom to which they are attached form a 5- to 6-membered heterocyclic ring; R ₁₅ '' is a C ₄ -C ₁₅ alkyl group or a C ₄ -C ₈ naphthenic ring R ₁₆ '' is C ₁ -C ₄ alkyl; and R ₁₇ '' is C ₄ -C ₁₀ alkyl. The dry film of claim 1, wherein the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between about 0.1 and 1. The dry film of claim 1, wherein the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between about 0.25 and about 0.8. The dry film of claim 1, wherein the solvent is present in an amount between about 30% by weight and about 70% by weight based on the total weight of the polyimine layer. The dry film of claim 1, wherein the hydrophobic solvent comprises: , , , , , , , , , , , , , , , , , , N,N-dimethyldecylamine or a combination thereof. The dry film of claim 1, further comprising (c) an additive, wherein the additive comprises: a stabilizer, a ring closure promoter, a pigment, a leveling agent, an antifoaming agent, a coupling agent, a catalyst, an acrylate monomer, and a light. Starting agent or a combination thereof. The dry film of claim 6, wherein the stabilizer comprises: , Or a combination thereof, wherein: R ₁₇ '', R ₁₈ '', R ₁₉ '' and R ₂₀ '' are each independently C ₁ -C ₄ alkyl, or R ₁₉ '' and R ₂₀ '' The atoms together form a 5 to 6 membered heterocyclic ring, or R ₁₉ '' and R ₁₇ '' or R ₂₀ '' and R ₁₈ '' together with the oxygen and nitrogen atoms to which they are attached form a 5 to 6 membered heterocyclic ring; R ₂₁ ''and R ₂₂ '' are each independently C ₁ -C ₄ alkyl, or R ₂₁ '' and R ₂₂ '' together with the carbon atom to which they are attached form a 5 to 6 membered carbocyclic ring; and R ₂₃ '' and R ₂₄ ''Each independently of C ₁ -C ₄ alkyl. A polyimine dry film comprising a substrate and a polyimide layer, wherein the polyimide layer comprises: (a) a polyimine precursor or a soluble polyimine; and (b) a solvent, wherein The solvent comprises a hydrophilic solvent and a hydrophobic solvent, and the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between 0.05 and 2, wherein the hydrophilic solvent is N-methyl-2-pyrrolidone, and wherein the hydrophobic solvent comprises : , , , , , Or a combination thereof, wherein: R ₁ '', R ₉ '' and R ₁₀ '' are each independently C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl; R ₇ '' is H or C ₁ -C ₃ alkyl; R ₂ '' is C ₁ -C ₁₀ alkyl; R ₃ '' is C ₄ -C ₂₀ alkyl or -C ₂ -C ₁₀ alkyl-OC ₂ -C ₁₀ alkyl; R ₄ '' and R ₅ '' are each independently C ₁ -C ₁₀ alkyl, or R ₄ '' and R ₅ '' together with the oxygen atom to which they are attached form a 5- to 6-membered heterocyclic ring ; R ₆ '' is C ₄ -C ₁₅ alkyl, C ₄ -C ₈ cycloalkyl or R ₈ '' is a C ₂ -C ₁₀ alkylene group; R ₁₁ '' and R ₁₂ '' are each independently a C ₁ -C ₁₀ alkyl group; R ₁₃ '' and R ₁₄ '' are each independently C ₁ - C ₁₀ alkyl, or R ₁₃ '' and R ₁₄ '' together with the nitrogen atom to which they are attached form a 5- to 6-membered heterocyclic ring; R ₁₅ '' is a C ₄ -C ₁₅ alkyl group or a C ₄ -C ₈ naphthenic ring R ₁₆ '' is C ₁ -C ₄ alkyl; and R ₁₇ '' is C ₄ -C ₁₀ alkyl, with the proviso that the hydrophobic solvent does not comprise: or . The dry film of claim 8, wherein the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between about 0.1 and 1. The dry film of claim 8, wherein the weight ratio of the hydrophilic solvent to the hydrophobic solvent is between about 0.25 and about 0.8. The dry film of claim 8, wherein the solvent is present in an amount between about 30% and about 70% by weight based on the total weight of the polyimine layer. The dry film of claim 8, wherein the hydrophobic solvent comprises: , , , , , , , , , , , , , , , , N,N-dimethyldecylamine or a combination thereof. The dry film of claim 8, further comprising (c) an additive, wherein the additive comprises: a stabilizer, a ring closure promoter, a pigment, a leveling agent, an antifoaming agent, a coupling agent, a catalyst, an acrylate monomer, and a light. Starting agent or a combination thereof. The dry film of claim 13, wherein the stabilizer comprises: , Or a combination thereof, wherein: R ₁₇ '', R ₁₈ '', R ₁₉ '' and R ₂₀ '' are each independently C ₁ -C ₄ alkyl, or R ₁₉ '' and R ₂₀ '' The atoms together form a 5 to 6 membered heterocyclic ring, or R ₁₉ '' and R ₁₇ '' or R ₂₀ '' and R ₁₈ '' together with the oxygen and nitrogen atoms to which they are attached form a 5 to 6 membered heterocyclic ring; R ₂₁ ''and R ₂₂ '' are each independently C ₁ -C ₄ alkyl, or R ₂₁ '' and R ₂₂ '' together with the carbon atom to which they are attached form a 5 to 6 membered carbocyclic ring; and R ₂₃ '' and R ₂₄ ''Each independently of C ₁ -C ₄ alkyl.