201202308 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樹脂及其製備方法，更具體而 言’係關於一種低溫可固化聚醯亞胺樹脂及其製備方法。 【先前技術】 近來，隨著電子設備向高集成度、高密度、高可靠性、高 速度等方向的發展趨勢在基於半導體的半導體設備領域及液 晶顯示器領域中的快速蔓延，對易於獲得加工性'高純度等的 有機材料的有利使用進行了積極研究。 特別地’聚醯亞胺樹脂具有許多優點’除了具有高耐熱 性、優良的機械強度、低介電常數（1〇λν permittivity)、高絕緣性 外’其還具有良好的塗覆表面極化特性’具有極低含量的降低 元件可靠性的雜質，並可以容易地構造成精細的形式’因此包 括含聚醯亞胺樹脂的光敏樹脂的光敏絕緣層的使用甚至延伸 到了顯示器領域。 爲合成聚醯亞胺，通常將一種二胺組分和一種二酐組分在 一種極性有機溶劑例如N-甲基-2-吡咯烷酮 (N-methyl-2-pyrolidone ， NMP)、二曱基乙醯胺 (dimethylacetamide ， DMAc)和二曱基曱醯胺 (dimethylformamide，DMF)中進行聚合，藉由2-步縮聚得到— 種聚醯亞胺前體溶液(polyimide precursor solution)，並將該得 到的聚醯亞胺前體溶液塗於矽片、玻璃等上面，然後在高溫下 進行熱處理從而使其固化（或硬化）。 4 201202308 用於電子材料的商業化聚醯亞胺産品以聚醯亞胺前體溶 液或聚醯亞胺薄膜的形態供給，並且在半導體裝置領域中，聚 醯亞胺産品主要以聚醯亞胺前體溶液的形態供給。 但是，製備聚醯亞胺聚合物的方法要求高的固化溫度（即 300°C或更高），問題在於，該方法無法用於對熱敏感的處理過 程。此外，雖然對聚醯亞胺前體溶液進行了高溫固化操作，但 仍無法將其完全轉變成聚醯亞胺。 因此，爲解決該問題，開發了一種通過使用催化劑在液態 實施化學醯亞胺化（imidizing)的聚合方法；但是該方法也使用 高沸點溶劑，並且其也需要高溫處理過程，因此在聚合過程之 後，必須再次實施高溫固化處理以除去溶劑。 此外，當預備實施高溫熱處理來製備聚醯亞胺樹脂時，需 要大型加熱設備以提高生産效率。 【發明内容】 本發明旨在解決所屬領域中存在的技術問題，本申請的發 明者注意到，在聚醯亞胺製備過程中，聚醯亞胺可藉由使用低 沸點溶劑、或連同低沸點溶劑一起添加基於胺（amine-based)的 具有低沸點和高活性的催化劑而在低溫下製備，並且經證實由 此製備的低溫聚醯亞胺仍具有優良的耐熱性和可加工性等品 質，從而完成了本發明。 因此，本發明的一個目標爲提供一種製備聚醯亞胺樹脂的 方法，該聚醯亞胺樹脂可通過使用低沸點溶劑甚至在低溫下進 行醯亞胺化（imidized)而製備。 201202308 本發明的另一個目標爲提供一種製備聚醯亞胺樹脂的方 法，該聚醯亞胺樹脂可通過連同所述低沸點溶劑一起使用一種 具有低沸點和高反應性的特定催化劑甚至在低溫下進行醯亞 胺化而製備。 本發明的又一個目標爲提供包含所述聚醯亞胺樹脂的一 種光敏組合物與一種印刷用油墨組合物。 本發明的再一個目標爲提供一種可在低溫下固化的聚醯 亞胺樹脂。 爲實現上述目標，提供了一種製備聚醯亞胺樹脂的方法， 該方法包括：使用沸點於130°C至80°C之範圍的低沸點溶劑而 聚合付到聚酿亞胺樹脂。 所述低沸點溶劑可爲選自以下的一種或多種：二甘醇甲基 乙基喊（diethyleneglycol methylethylether)、二甘醇二曱基喊 (diethyleneglycol dimethylether)、二甘醇二乙基醚 (diethyleneglycol diethylether)、雙丙甘醇二曱基謎 (dipropyleneglycol dimethylether)、3-甲氧基丙酸甲醋（methyl 3-methoxy propionate)、3-乙氧基丙酸乙醋（ethyl 3-ethoxy propionate)、丙二醇甲基謎丙酸醋（propylene glycol methylether propionate)、雙丙甘醇二曱基驢（dipropyleneglycol dimethylether)、環己_ (cyclohexanone)和丙二醇單曱基鍵乙酸 S旨（propyleneglycolmonomethyletheracetate，（PGMEA)) ° 基於100重量份製備聚醯亞胺樹脂的單體計，所述低沸點 溶劑的含量可爲20重量份至2000重量份。 6 201202308 聚醯亞胺樹脂可在不實施製備聚醯胺酸(polyamic acid)前 體的操作的情況下直接製備。 聚醯亞胺樹脂可在沸點於60°C至100°C之範圍的催化劑的 存在下製備。 所述催化劑可爲選自Ν,Ν-二乙基甲胺 (Ν,Ν-diethylmethyl amine) 、 Ν,Ν-二甲基異丙胺 (Ν,Ν-dimethyl isopropylamine) 、 N-曱基 0 比 口各 烧 (N-methylpyrrolidine)、。比卩各烧（pyrrolidine)和三乙胺 (triethylamine)的一種或多種。 基於100重量份聚醯亞胺樹脂的原料二胺和二酐計，所述 催化劑的含量可爲0.5重量份至30重量份。 所述聚合可在120°C至200°C範圍的溫度下實施。 所述聚醯亞胺樹脂可使用一種或多種選自以下的芳香族 二胺作爲原料：包含酌·經基（phenolic hydroxyl group)、緩基 (carboxyl group)或經基（hydroxyl group)的二價有機基團 (bivalent organic groups) 5 例如由 7 201202308 "0~ "9~ on ， coom 9 »201202308 VI. Description of the Invention: [Technical Field] The present invention relates to a polyimine resin and a preparation method thereof, and more particularly to a low-temperature curable polyimide resin and a preparation method thereof. [Prior Art] Recently, with the rapid development of electronic devices in the direction of high integration, high density, high reliability, high speed, etc. in the field of semiconductor-based semiconductor devices and liquid crystal displays, it is easy to obtain processability. The favorable use of organic materials such as high purity has been actively studied. In particular, 'polyimine resin has many advantages', in addition to high heat resistance, excellent mechanical strength, low dielectric constant (1〇λν permittivity), high insulation, it also has good coated surface polarization characteristics. 'There are extremely low contents of impurities which reduce the reliability of the element, and can be easily constructed into a fine form'. Therefore, the use of the photosensitive insulating layer including the photosensitive resin containing the polyimide resin even extends to the field of display. For the synthesis of polyimine, a diamine component and a dianhydride component are usually in a polar organic solvent such as N-methyl-2-pyrolidone (NMP), dimercapto B. Polymerization of dimethylacetamide (DMAc) and dimethylformamide (DMF) to obtain a polyimide precursor solution by 2-step polycondensation, and the obtained The polyimine precursor solution is applied to a crucible, glass, or the like, and then heat-treated at a high temperature to cure (or harden). 4 201202308 Commercially available polyimine products for electronic materials are supplied in the form of polyimine precursor solutions or polyimide membranes, and in the field of semiconductor devices, polyimine products are mainly polyimine. The form of the precursor solution is supplied. However, the method of preparing a polyimide pigment polymer requires a high curing temperature (i.e., 300 ° C or higher), and the problem is that the method cannot be used for a heat sensitive treatment process. In addition, although the polyamidene precursor solution was subjected to a high temperature curing operation, it was not completely converted into a polyimide. Therefore, in order to solve this problem, a polymerization method in which chemical imidization is carried out in a liquid state by using a catalyst has been developed; however, the method also uses a high boiling point solvent, and it also requires a high temperature treatment process, and thus after the polymerization process The high temperature curing treatment must be performed again to remove the solvent. Further, when a high-temperature heat treatment is prepared to prepare a polyimide resin, a large heating apparatus is required to increase production efficiency. SUMMARY OF THE INVENTION The present invention is directed to solving the technical problems in the art, and the inventors of the present application have noted that polyimine can be used in the preparation of polyimine by using a low boiling point solvent, or together with a low boiling point. The solvent is added together with an amine-based catalyst having a low boiling point and a high activity, and is prepared at a low temperature, and it has been confirmed that the low-temperature polyimine thus prepared still has excellent heat resistance and processability. The present invention has thus been completed. Accordingly, it is an object of the present invention to provide a process for preparing a polyimine resin which can be produced by imidization using a low boiling solvent even at a low temperature. 201202308 Another object of the present invention is to provide a process for preparing a polyimine resin which can be used together with the low boiling point solvent together with a specific catalyst having a low boiling point and high reactivity even at a low temperature It is prepared by carrying out hydrazine imidization. It is still another object of the present invention to provide a photosensitive composition comprising the polyimine resin and a printing ink composition. Still another object of the present invention is to provide a polyimide resin which can be cured at a low temperature. In order to achieve the above object, there is provided a process for producing a polyimine resin which comprises polymerizing a polyacrylonitrile resin by using a low boiling point solvent having a boiling point in the range of from 130 ° C to 80 ° C. The low boiling point solvent may be one or more selected from the group consisting of diethyleneglycol methylethylether, diethyleneglycol dimethylether, diethyleneglycol diethylether. ), dipropyleneglycol dimethylether, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, propylene glycol Propylene glycol methylether propionate, dipropyleneglycol dimethylether, cyclohexanone, and propylene glycol monomethyl thioacetate (PGMEA) ° based on propylene glycol methylether propionate (propylene glycol methylether propionate) The low boiling point solvent may be included in an amount of 20 parts by weight to 2000 parts by weight based on 100 parts by weight of the monomer for preparing the polyimide resin. 6 201202308 Polyimine resin can be prepared directly without the operation of preparing a polyamic acid precursor. The polyimine resin can be produced in the presence of a catalyst having a boiling point in the range of 60 °C to 100 °C. The catalyst may be selected from the group consisting of hydrazine, hydrazine-diethylmethylamine, hydrazine, dimethyl-isopropyl isopropylamine, N-mercapto-based N-methylpyrrolidine, each. One or more of pyrrolidine and triethylamine. The catalyst may be included in an amount of from 0.5 part by weight to 30 parts by weight based on 100 parts by weight of the raw material diamine and dianhydride of the polyimine resin. The polymerization can be carried out at a temperature ranging from 120 °C to 200 °C. The polyimine resin may use one or more aromatic diamines selected from the group consisting of: a phenolic hydroxyl group, a carboxyl group, or a hydroxyl group. Bivalent organic groups 5 for example by 7 201202308 "0~ "9~ on , coom 9 »
和3,5-二胺基苯甲酸(3,5-diaminobenzoic acid)得到的二價有機 基團；一種或多種選自以下的芳香族二胺（aromatic diamines): 對 苯二胺（p-phenylenediamine)、 間 苯二胺 (m-phenylenediamine) 、 2,4,6-三曱基-1,3-苯二胺 (2,4,6-trimethyl-l，3- phenylenediamine)、2,3,5,6-四曱基-1,4-苯 二胺（2,3,5,6-tetramethyl-l,4-phenylenediamine)、4,4’ -二胺基 二苯醚（4,4’-diaminodiphenylether)、3,4 ’ -二胺基二苯醚 (3,4’-diaminodiphenylether) 、3,3 -二胺基二苯醚 (3,3’-diaminodiphenylether)、4,4 -二胺基二苯硫輕 (4,4’-diaminodiphenylsulfide)、4,4 -二胺基二苯甲炫· (4,4’-diaminodiphenylmethane)、3,4 ’ -二胺基二苯甲烧 (3,4’-diaminodiphenylmethane)、3,3 ’ -二胺基二苯曱烧 (3,3’-diaminodiphenylmethane)、4,4’ -亞曱基-二（2-曱基苯胺） (4,4’-methylene-bis(2-methylaniline))、4,4’ -亞曱基-二（2-異丙 基 -6- 曱基 苯胺） 8 201202308 (4,4’-methylene-bis(2-isopropyl-6-methylaniline))、4,4’ -亞曱基 - -一 (2,6- -一 異 丙 基.苯 胺 ) (4,4’-methylene-bis(2,6-didsopropylaniline))、4,4’ -亞甲基-二 (2- 異丙基 -6- 甲基 苯胺） (4,4’-methylene-bis(2-isopropyl-6-methylaniline))、4,4’-亞甲基_ 二 （2,6- 二異丙 基苯胺 ） (4,4’-methylene-bis(2,6-diisopropylaniline))、4,4’-二胺基二笨石風 (4,4’-diaminodiphenylsulfone) 、 3,3’-二胺基二笨石風 (3，3’-diaminodiphenylsulfone)、聯苯胺（benzidine)、鄰-聯曱笨 胺（o-tolidine)、間-聯曱苯胺(m-tolidine)、3,3’,5,5’-四甲基聯苯 胺（3,3’，5,5’-tetramethylbenzidine)、2,2’-二.(三氟曱基）聯苯胺 (2,2’-bis(trifluoromethyl)benzidine)、1,4-二（4-胺基苯氧基）苯 (l，4-bis(4-amoniphenoxy)benzene)、1,3-二（4-胺基苯氧基）苯 (l，3-bis(4-aminophenoxy)benzene)、1,3-二（3-胺基苯氧基）苯 (l，3-bis(3-aminophenoxy)benzene)、二[4-(4-胺基苯氧基）苯基] 石風(bis[4-(4-aminophenoxy)phenyl]sulfone)、二[4-(3-胺基苯氧基) 笨基]石風（bis[4-(3-aminophenoxy)phenyl]sulfone)、2,2-二[4-(4-胺基苯 氧基）苯基] 丙烷 (2,2-bis[4-(4-aminophenoxy)phenyl]propane)和 2,2-二[4-(3-胺基 苯氧基 ） 苯基] 丙烧 (2,2-bis[4-(3-aminophenoxy)phenyl]propane);及一種或多種選 自以下的脂肪族二胺（aliphatic diamines) : 1，6-己二胺 (l，6-hexanedimane)、1,4-環己二胺（l，4-cyclohexanediamine)、 1，3-環己二胺（1,3-cyclohexanedimane)、1,4-二（胺曱基）環己烧 201202308 (l，4-bix(aminomethyl)cyclohexane)、1，3-二（胺甲基）環己烧 (1，3-bis(aminomethyl)cyclohexane)、4,4’-二胺基二環己基甲炫 (4,4’-diaminodicyclohexylmethane)、4,4’-二胺基-3,3’-二曱基二 環己基甲炫（4,4’-diamino-3,3’-dimethyldicyclohexylmethane)、 4,4’-二胺基-3,3’-二曱基二環己基甲烷 (4,4’-diamino-3,3’-dimethyldicyclohexylmethane)、1,2-二-(2-胺 基乙氧基）乙烧（1，2-bis-(2-aminoethoxy)ethane)、二（3-胺基丙基） 醚（bis(3-aminopropyl)ether)、1,4-二（3-胺基丙基）°瓜嗪 (1,4-bis(3-amonipropyl)piperazine) 、 3,9-二（3-胺基丙 基 ）-2,4,8，10- 四 氧雜螺 [5,5] 十一烷 (3,9-bis(3-amonopropyl)-2,4,8，l 0-tetraoxaspiro[5,5]undecane)和 1,3-二（3-胺基丙基）四甲基二矽氧烷 (l-3-bis(3-aminopropyl)tetramethyldisiloxane)。 所述聚醯亞胺樹脂可使用一種或多種選自以下的二酐作 爲原料：一種或多種選自無水1，2,4,5-苯四酸（anhydrous pyromellitic acid) 、3,3’，4,4’-二苯基四缓 S曼二肝 (3,3’，4,4’-biphenyltetracarboxylic acid dianhydride)、丁烧 -1，2,3,4-四缓酸二酐（butane-1,2,3,4-tetracarboxylic acid dianhydride) 、 3,3’，4,4’-二苯曱酮四羧酸二酐 (3,3’，4,4’-benzophenonetetracarboxylic acid dianhydride)、 3,3’4,4’- 二苯基 醚四羧 酸二酐 (3,3’4,4’-diphenylethertetracarboxylic dianhydride)、3,3’，4,4’-二苯基石風四敌酸二酐（3,3’,4,4’-diphenylsulfonetetracarboxylic acid dianhydride)、2,2-二（3,4-二叛基苯基）六氟異亞丙基二針 (2,2-bis(3,4,-dicarboxyphenyl)hexafluoroisopropylidine 201202308 dianhydride) 、 3,3’,4,4’-二笨基四叛酸二針 (3,3’，4,4’-biphenyltetracarboxylic acid dianhydride)、3,3’，4,4’-二苯甲酮四竣酸二 if (3,3’,4,4’-benzophenonetetracarboxylic acid dianhyride)、4,4’-六氟異亞丙基二醜酸二酐 (4,4,-hexafluoroisopropylidenediphthalic acid dianhydride)、 3,3’，4,4’- 二苯基 砜四羧 酸二酐 (3,3,,4,4,-diphenylsulfonetetracarboxylic acid dianhydride)、 1,2,3,4-環丁 烧四叛酸二 Sf (l，2,3,4-cyclobutanetetracarboxylic acid dianhydride)、1,2-二甲基-1，2,3，4-環丁 院四叛酸二針 (1,2,-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride)、1,2,3,4-四甲基-I，2,3,4-環丁 烧四缓酸二針 (1,2,3,4-tetramethyl-l ,2,3,4-cyclobutanetetracarboxylic acid dianhydride) 、 1,2,3,4-環戊烧四叛酸二酐 (1,2,3,4-cyclopentanetetracarboxylic acid dianhydride) ' 1,2,4,5-環己烧四竣酸二酐（1,2,4,5-cyclohexanetetracarboxylic acid dianhydride)、3,4-二叛基-1,2,3,4-四氫-1-萘烧丁二酸二酐 (3,4,-dicarboxy-l ,2,3,4-tetrahydro-l-naphthalane succinic acid dianhydride)、5-(2,5-二氧代四氫0夫喃基）-3-甲基-3-環己烯-1，2-二羧 酸二酐 (5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2,-dicar boxylic acid dianhydride)、2,3,5-三叛基-2-環戊院乙酸二酐 (2,3,5-tricarboxy-2-cyclopentane acetic acid dianhydride)、雙環 [2,2,2]辛-7-烯-2,3,5,6-四羧 酸二酐 (bicycle [2,2，2]octo-7-en-2,3,5，6-tetracarboxi lie acid dianhydride) 、 2,3,4,5-四氫吱喃四缓酸二針 201202308 (2,3,4,5-tetrahydropuranetetracarboxylic acid dianhydride)和 3,5,6- 三羧基 -2- 降冰片 炫乙酸二肝 (3,5,6-ti，icarboxy-2-norbornane acetic acid dianhydride)的酸肝， 及它們的衍生物。 爲實現上述目標，還提供了 一種藉由使用沸點於130°C至 180°C之範圍的低沸點溶劑製備的聚醯亞胺樹脂。 所述聚醯亞胺的玻璃化轉變溫度可在15〇°C至400°C範圍 内。 所述聚酿亞胺樹脂的重均分子量（weight-average molecular weight)可在1，〇〇〇 至1〇〇,〇〇〇範圍内。 殘留在聚醯亞胺樹脂中的催化劑的量可爲該聚醯亞胺樹 脂總重量的0.001重量％至0.1重量％。 爲實現上述目標，還提供了一種可在低溫下固化並包含根 據前述方法製備的聚醯亞胺樹脂的光敏樹脂組合物。 所述光敏樹脂組合物可在150°c至250°C範圍的溫度下固 化。 在所述光敏樹脂組合物固化之後，該光敏樹脂組合物中不 再殘留有溶劑。 在所述光敏樹脂組合物固化之後，殘留在該光敏樹脂組合 物中的溶劑可小於0.05重量％。 使用了所述光敏樹脂組合物的光敏薄膜可在預烘焙之後 藉由邊緣光刻膠去除溶劑（edge bead removal solvent)而除去。 當混合使用一種排出液(drain)時，會使光敏樹脂組合物溶 解而不會產生沈澱。 12 201202308 可提供含有根據前述方法製備的聚醯亞胺樹脂的印刷用 油墨組合物。 爲實現上述目標，還提供了一種含有根據前述方法製備的 聚醯亞胺樹脂的印刷用油墨組合物。 可提供製備爲含有所述光敏樹脂組合物的OLED、LCD或 半導體絕緣層。 此外，還可提供製備爲含有所述印刷用油墨組合物的 OLED、LCD或半導體絕緣層。 聚醯亞胺樹脂可藉由使用一種低沸點溶劑直接製備，無需 實施製備聚酿胺酸(poiyamic acid)、聚醯亞胺前體的操作。 此外，由此製備的聚醯亞胺樹脂甚至可在低溫下固化，因 此當使用該聚醯亞胺樹脂作爲電子材料時，可使原本由於高溫 操作而對設備造成的破壞最小化，此外，聚醯亞胺樹脂可廣泛 用作電子材料，例如用於塑膠基質等。 根據本發明方法製備的聚醯亞胺樹脂具有足夠的機械強 度、優良的可加工性和高的生產效率，因此其可有利地用於多 種顯示器的光敏樹脂組合物、印刷用油墨組合物等。 根據本發明的一個示例性實施方案，當聚醯亞胺樹脂包含 在光敏樹脂組合物中從而被用作電子材料的光敏薄膜時，其可 在預烘焙之後甚至在低溫下藉由邊緣光刻膠去除（edge bead removal，EBR)溶劑而容易地除去。 此外，根據本發明的一個示例性實施方案，當與一種排出 液混合時，包含聚醯亞胺樹脂的光敏樹脂組合物可溶解而不會 産生沈澱。 201202308 义從以下對本發明的詳細描述中，當結合附圖考慮時，本發 J述的及其他目&、特徵、方面和優點將變得更明顯。 【實施方式】 現將對本發明的示例性實施方案進行描述。 本申凊中所用的術語僅用於描述具體實施方案，並不意欲 限制本發明。單數形式的表述涵蓋複數形式除非其在使用它 的文中具有明顯不同的含義。 在本申請中，應理解的是，例如“包含（c〇mprise 〇r compnsmg)” #術語意欲指明在說明書中公開的特徵、數目、 操ί乍、作用、組分、份數、或其結合的存在’ 1不意欲排除可 能存在或可能增加-種或多種其他特徵、數目、操作、作用、 組分、份數、或其結合的可能性。 在本發明的示例性實施方案中，在藉由使二胺和二酐反應 來製備聚醯亞賴脂巾’使用具有低沸點的特定催化劑和溶 劑，由此而製得可在低溫下固化並可溶的聚醯亞胺樹脂。 本發明的示例性實施方案的聚醯亞胺樹脂可由二胺和二 酐直接製備，而不是如所屬領域一般藉由二胺和二酐（一種或 多種）製備聚醯胺酸前體然後使其固化而製成聚醯亞胺薄膜的 形式。 本發明的特徵在於’使用沸點於130。(：至18〇。(：：之範圍的低 沸點溶劑，以便在低溫下合成聚醯亞胺樹脂。 聚醯亞胺樹脂通常藉由製備一種聚醯胺酸前體然後在32〇 C或更高溫度下固化該前體而製得。比較而言，在本發明的示 例性實施方案中，聚醯亞胺樹脂可直接製備，無需實施製備聚 14 201202308 醯胺酸前體的操作’並且使用低沸點溶劑，從而可在與相關領 域相比較低的溫度下合成聚醒亞胺樹脂。 如上所述，沸點於n〇°C至1 80°C之範圍的低沸點溶劑可爲 例如選自以下的一種或多種：二甘醇甲基乙基醚 (diethyleneglycol methylethylether)、二甘醇二甲基鱗 (diethyleneglycol dimethylether)、二甘醇二乙基醚 (diethyleneglycol diethy 丨 ether)、雙丙甘醇二曱基鍵 (dipropyleneglycol dimethylether)、3-曱氧基丙酸甲酯（methyl 3-methoxy propionate)、3-乙氧基丙酸乙醋（ethyl 3-ethoxy propionate)、丙二醇甲基謎丙酸 g旨（pr〇pyiene giyC〇i meth.ylether propionate)、雙丙甘醇二曱基醚（dipropyleneglycol dimethylether)、環己鋼（cyclohexanone)和丙二醇單甲基謎乙酸 明不限於此’任何溶劑均可使用，只要其具有在上述溫度範圍 内的低沸點即可。 如果本發明示例性實施方案的溶劑的沸點低於130°C，則 不能提供製備聚醯亞胺的足夠的能量，可能會降低轉化率。此 外’如果溶劑的沸點超過180。(：，則必須爲固化操作提供200 。(：或更高的溫度，以防止溶劑殘留，導致無法降低固化溫度的 問題。 基於包含二胺和二酐的單體總計100重量份計，低沸點溶 劑的含量可爲2〇重量份至2〇00重量份、較佳1〇〇重量份至1〇〇〇 重畺伤、敢佳2〇〇重量份至4〇〇重量份。如果溶劑的含量小於2〇 重i伤’則聚酿亞胺無法充分溶解’如果溶劑含量超過2000 201202308 重量份’則當將聚醯亞胺塗於基質上時，無法形成具有足夠厚 度的塗膜。 在本發明示例性實施方案中，在製備聚醯亞胺樹脂中，可 含有低沸點催化劑。 對於催化劑’可按需要使用可在低溫下醯亞胺化、可在反 應後容易地除去、具有低沸點並具有高活性的催化劑。 詳言之’所述催化劑的沸點於60。(：:至120。(：:之範圍、較佳 70C至10〇。(：之範圍，並且最佳8〇°c至9〇°c之範圍。如果催化 劑的沸點低於6〇它，則該催化劑在聚合過程中將完全蒸發，而 如果催化劑的沸點高K120t，則該具有高反應性的催化劑在 反應完成後仍有餘留，可能會在製備組合物中引起副反應。 本發明示例性實施方案的催化劑可爲例如選自以下的一 種或多種.N，N-二乙基甲胺、N，N_:甲基異丙胺、N_甲基。比 咯烷、吡咯烷和三乙胺，但本發明不限於此。 基於稭由添加用於合成聚醯亞胺樹脂的二胺和二野而得 到，單體總計⑽重量份計，催化劑的含量可爲W重量份至扣 重里伤車又佳2重量份至2〇重量份，並且最佳5重量份至财量 伤。如果催化劑的含量小於G 5重量份，則由於 夠而降低轉化成聚酿亞胺的速率，並且如果催化劑的含量= 3〇重量份，難於殘”未反應的催_而可紐生不希 附加反應。 在本發明示例性實施方案的聚醯亞胺樹财使用的單體 —胺和二酐，可爲用於製備-般聚酿亞胺樹脂的那些，而無特 16 201202308 別限制。在此情況下，所述單體可針對某些目的而選擇性地使 用0 例如’酸酐或其衍生物可爲一種或多種選自以下的二酐： 一種或多種選自無水丨，2，々』-苯四酸、3,3，,4,4，-二笨基四羧酸二 酐、丁烷-1，2,3,4-四羧酸二酐、3,3，，4,4’_二笨甲酮四羧酸二酐、 3,3 4,4’-二笨基醚四羧酸二酐、3,3，，4,4，二苯基礙四羧酸二 肝2,2- — (3,4-一叛基笨基）六氣異亞丙基二酐、3,3,，4,4，-二笨 基四缓酸一酐、3,3’，4,4’-二笨甲嗣四緩酸二針、4,4，_六敗異亞 丙基—駄酸一酐、3,3’，4,4.-二苯基石風四叛酸二酐、1,2,3,4-環丁 烧四羧酸二酐、1，2-二甲基-l，2,3,4-環丁院四羧酸二酐、丨，2,3,4_ 四甲基-1，2,3,4-環丁烷四羧酸二酐、ι，2,3,4-環戊烷四羧酸二 酐、1，2,4,5-環己烷四羧酸二酐、3,4-二羧基·ι，2,3,4_四氫_丨萘 炫丁一酸二酐、5-(2,5-二氧代四氫咬喃基）_3_曱基環己烯 -1，2-—叛酸二針、2,3,5-三叛基-2-環戊烧乙酸二酐、雙環[2,2,2] 辛-7-稀-2,3,5,6-四羧酸一酐、2,3,4,5-四氫n夫喃四叛酸二針和 3,5,6-三羧基-2-降冰片烷乙酸二酐的酸酐。 對於二胺’可使用芳香族和脂肪族二胺，並且二胺化合物 可爲選自以下的一種或多種芳香族二胺：包含酚羥基、羧基或 羥基的二價有機基團，例如由 17 201202308And a divalent organic group obtained from 3,5-diaminobenzoic acid; one or more aromatic diamines selected from the group consisting of p-phenylenediamine (p-phenylenediamine) ), m-phenylenediamine, 2,4,6-trimethyl-l,3-phenylenediamine, 2,3,5 ,6-tetramethyl-l,4-phenylenediamine, 4,4'-diaminodiphenylether (4,4'-diaminodiphenylether) , 3,4 '-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4-diaminodiphenyl ether 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4 '-diaminobenzophenone (3,4'- Diaminodiphenylmethane), 3,3 '-diaminodiphenylmethane, 4,4'-indenylene-bis(2-mercaptoaniline) (4,4'-methylene-bis (2-methylaniline)), 4,4'-indenylene-bis(2-isopropyl-6-mercaptoaniline) 8 201202308 (4,4'-methylene-bis(2-isopropyl- 6-methylaniline)), 4,4'-indenylene--(2,4'-methylene-bis(2,6-didsopropylaniline)), 4, 4'-Methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene (4,4'-methylene-bis(2,6-diisopropylaniline), 4,4'-diaminodiphenyldiphenylsulfone (4,4'-diaminodiphenylsulfone) , 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine , 3,3',5,5'-tetramethylbenzidine (3,3',5,5'-tetramethylbenzidine), 2,2'-di.(trifluoromethyl)benzidine (2,2' -bis(trifluoromethyl)benzidine), 1, 4-bis(4-amoniphenoxy)benzene, 1,3-bis(4-aminophenoxy) Benzene (1,3-bis(4-aminophenoxy)benzene), 1,3-bis(3-aminophenoxy)benzene, bis[4-( 4-aminophenoxy)phenyl] bis[4-(4-aminophenoxy)phenyl]s Ulfone), bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-di[4-(4-aminobenzene) Oxy)phenyl]propane (2,2-bis[4-(4-aminophenoxy)phenyl]propane) and 2,2-bis[4-(3-aminophenoxy)phenyl]propanone (2 , 2-bis[4-(3-aminophenoxy)phenyl]propane); and one or more aliphatic diamines selected from the group consisting of 1,6-hexanediamine (1,6-hexanedimane), 1 , 4-cyclohexanediamine, 1,3-cyclohexanedimane, 1,4-bis(amine fluorenyl)cyclohexene 201202308 (l,4- Bix(aminomethyl)cyclohexane), 1,3-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylmethyl (4,4' -diaminodicyclohexylmethane), 4,4'-diamino-3,3'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino -3,3'-Dimercapto-dicyclohexylmethane, 1,2-di-(2-aminoethoxy)ethane (1,2) -bis-(2-aminoethoxy)ethane), (3-aminopropyl)ether, 1,4-bis(3-aminopropyl)piazine (1,4-bis(3-amonipropyl)piperazine), 3 ,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (3,9-bis(3-amonopropyl)-2,4,8 , l 0-tetraoxaspiro [5,5] undecane) and 1,3-bis(3-aminopropyl)tetramethyldisiloxane. The polyimine resin may use one or more dianhydrides selected from the group consisting of one or more selected from the group consisting of anhydrous hydrolyzed pyromellitic acid, 3, 3', 4 4'-diphenyltetracarboxylic acid dianhydride, butadiene-1,2,3,4-tetrazoic acid dianhydride (butane-1, 2,3,4-tetracarboxylic acid dianhydride), 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3' 4,4'-diphenylethertetracarboxylic dianhydride (3,3'4,4'-diphenylethertetracarboxylic dianhydride), 3,3',4,4'-diphenyl stone, tetrahydro acid dianhydride (3, 3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride), 2,2-bis(3,4-di-phenylphenyl)hexafluoroisopropylidene two-needle (2,2-bis(3,4,-dicarboxyphenyl) )hexafluoroisopropylidine 201202308 dianhydride), 3,3',4,4'-3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'- Benzophenone tetradecanoic acid di(3,3',4,4'-benzophenonetetra Carboxylic acid dianhyride), 4,4'-hexafluoroisopropylidenediphthalic acid dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid Anhydride (3,3,4,4,-diphenylsulfonetetracarboxylic acid dianhydride), 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2 -1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4- 1,2,3,4-tetramethyl-l,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3, 4-, 2,3,4-cyclopentanetetracarboxylic acid dianhydride ' 1,2,4,5-cyclohexanyltetracarboxylic dianhydride (1,2,4,5-cyclohexanetetracarboxylic) Acid dianhydride), 3,4-di-rebel-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (3,4,-dicarboxy-l, 2,3,4-tetrahydro- L-naphthalane succinic acid dianhydride), 5-(2,5-dioxotetrahydro-O-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride (5-( 2,5-dioxotetra Hydrofuryl)-3-methyl-3-cyclohexene-1,2,-dicar boxylic acid dianhydride), 2,3,5-tri-rebel-2-cyclopentanyl acetate dianhydride (2,3,5-tricarboxy-2 -cyclopentane acetic acid dianhydride), bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicycle [2,2,2]octo-7-en-2 ,3,5,6-tetracarboxi lie acid dianhydride), 2,3,4,5-tetrahydrofuran tetrasodium sulphate 201202308 (2,3,4,5-tetrahydropuranetetracarboxylic acid dianhydride) and 3,5,6 - Acidic liver of tricarboxy-2-norbornane acetic acid dianhydride, and their derivatives. In order to achieve the above object, there is also provided a polyimide resin prepared by using a low boiling point solvent having a boiling point in the range of 130 ° C to 180 ° C. The glass transition temperature of the polyimide may range from 15 °C to 400 °C. The weight-average molecular weight of the polyamidene resin may range from 1, 〇〇〇 to 1 〇〇, 〇〇〇. The amount of the catalyst remaining in the polyimide resin may be from 0.001% by weight to 0.1% by weight based on the total weight of the polyimide resin. In order to achieve the above object, there is also provided a photosensitive resin composition which can be cured at a low temperature and which comprises a polyimine resin prepared according to the aforementioned method. The photosensitive resin composition can be cured at a temperature ranging from 150 ° C to 250 ° C. After the photosensitive resin composition is cured, no solvent remains in the photosensitive resin composition. After the photosensitive resin composition is cured, the solvent remaining in the photosensitive resin composition may be less than 0.05% by weight. The photosensitive film using the photosensitive resin composition can be removed by pre-baking by an edge bead removal solvent. When a drain is used in combination, the photosensitive resin composition is dissolved without precipitation. 12 201202308 A printing ink composition containing the polyimide resin prepared according to the foregoing method can be provided. In order to achieve the above object, there is also provided a printing ink composition comprising the polyimine resin prepared according to the aforementioned method. An OLED, LCD or semiconductor insulating layer prepared to contain the photosensitive resin composition can be provided. Further, an OLED, LCD or semiconductor insulating layer prepared to contain the printing ink composition may also be provided. The polyimine resin can be directly prepared by using a low boiling point solvent, and it is not necessary to carry out the operation of preparing a poiyamic acid or polyimine precursor. In addition, the polyimine resin thus prepared can be cured even at a low temperature, so when the polyimine resin is used as an electronic material, damage to the apparatus originally caused by high-temperature operation can be minimized, and further, The quinone imine resin can be widely used as an electronic material, for example, for a plastic substrate. The polyimine resin prepared by the method of the present invention has sufficient mechanical strength, excellent workability, and high production efficiency, and thus it can be favorably used for photosensitive resin compositions, printing ink compositions, and the like of various displays. According to an exemplary embodiment of the present invention, when a polyimide resin is contained in a photosensitive resin composition to be used as a photosensitive film of an electronic material, it can be subjected to edge photoresist after prebaking or even at a low temperature. The edge bead removal (EBR) solvent is easily removed. Further, according to an exemplary embodiment of the present invention, when mixed with an effluent, the photosensitive resin composition containing the polyimide resin can be dissolved without causing precipitation. The present invention and other objects, features, aspects and advantages will become more apparent from the following detailed description of the invention. [Embodiment] An exemplary embodiment of the present invention will now be described. The terminology used in this application is for the purpose of describing particular embodiments and is not intended to limit the invention. The singular expression encompasses the plural unless it has a distinct meaning in the context in which it is used. In the present application, it is to be understood that the term "comprising (c〇mprise 〇r compnsmg)" is intended to indicate the features, number, operation, function, composition, number of parts, or combinations thereof disclosed in the specification. The existence of '1 is not intended to exclude the possibility that one or more other features, numbers, operations, actions, components, parts, or combinations thereof may or may not be added. In an exemplary embodiment of the present invention, a polyfluorene sorbite towel is prepared by reacting a diamine and a dianhydride to use a specific catalyst having a low boiling point and a solvent, thereby producing a curing at a low temperature and Soluble polyimide resin. The polyimine resin of an exemplary embodiment of the present invention may be directly prepared from a diamine and a dianhydride instead of preparing a polyproline precursor by a diamine and a dianhydride (one or more) as in the prior art. It is cured to form a film of a polyimide film. The invention is characterized by the use of a boiling point of 130. (: to 18 〇. (:: a range of low boiling solvents to synthesize polyimine resins at low temperatures. Polyimine resins are usually prepared by preparing a polyproline precursor and then 32 〇 C or more The precursor is cured by curing at a high temperature. In comparison, in an exemplary embodiment of the present invention, the polyimide resin can be directly prepared without performing the operation of preparing the poly 14 201202308 proline precursor and using a low boiling point solvent, so that the polyamidole resin can be synthesized at a lower temperature than the related art. As described above, the low boiling point solvent having a boiling point in the range of n 〇 ° C to 180 ° C can be, for example, selected from the following One or more of: diethyleneglycol methylethylether, diethyleneglycol dimethylether, diethyleneglycol diethy 丨ether, dipropylene glycol dioxime Dipropyleneglycol dimethylether, methyl 3-methoxy propionate, ethyl 3-ethoxy propionate, propylene glycol methyl mycophenolate Pr〇pyiene giy C〇i meth.ylether propionate), dipropyleneglycol dimethylether, cyclohexanone and propylene glycol monomethyl myristate are not limited to any solvent, as long as it has The low boiling point in the above temperature range may be. If the boiling point of the solvent of the exemplary embodiment of the present invention is lower than 130 ° C, sufficient energy for preparing the polyimide may not be provided, and the conversion may be lowered. The boiling point of more than 180. (:, must provide 200 for the curing operation. (: or higher temperature to prevent solvent residue, resulting in the problem of not reducing the curing temperature. Based on the monomer containing diamine and dianhydride total 100 weight The content of the low boiling point solvent may be from 2 parts by weight to 2 parts by weight, preferably from 1 part by weight to 1 part by weight, from 2 parts by weight to 4 parts by weight. If the content of the solvent is less than 2 〇 I, then the brewing imine cannot be sufficiently dissolved. 'If the solvent content exceeds 2000 201202308 parts by weight', when the polyimide is coated on the substrate, it cannot form a foot. Coating film of thickness. In an exemplary embodiment of the present invention, a low-boiling catalyst may be contained in the preparation of the polyimide resin. For the catalyst, it may be used at a low temperature to imidize at a low temperature, and may be easily after the reaction. The catalyst is removed, has a low boiling point and has high activity. In detail, the catalyst has a boiling point of 60. (:: to 120. (:: range, preferably 70C to 10〇. (: range, and the best range of 8〇 °c to 9〇 °c. If the boiling point of the catalyst is less than 6〇, then The catalyst will completely evaporate during the polymerization, and if the boiling point of the catalyst is high by K120t, the catalyst having high reactivity remains after the reaction is completed, possibly causing side reactions in the preparation composition. Exemplary embodiment of the present invention The catalyst of the scheme may be, for example, one or more selected from the group consisting of: N,N-diethylmethylamine, N,N-:methylisopropylamine, N-methyl, pyrrolidine, pyrrolidine and triethylamine, but The present invention is not limited thereto. The straw is obtained by adding a diamine and a dimer for synthesizing a polyimine resin, and the total amount of the catalyst is 10 parts by weight, and the content of the catalyst may be W parts by weight to the weight of the buckle. 2 parts by weight to 2 parts by weight, and most preferably 5 parts by weight to the amount of damage. If the content of the catalyst is less than G 5 parts by weight, the rate of conversion to the chitosan is lowered due to sufficient, and if the content of the catalyst = 3 〇 by weight, it is difficult to be disabled" unreacted urging _ but can not be born Additional Reactions The monomers-amines and dianhydrides used in the polyimines of the exemplary embodiments of the present invention may be those used for the preparation of the general-purpose polyurethane resin, without the limitation of 201202308. In this case, the monomer may be selectively used for some purposes. For example, the anhydride or its derivative may be one or more dianhydrides selected from the group consisting of one or more selected from the group consisting of anhydrous hydrazine, 2, hydrazine. - pyromellitic acid, 3,3,,4,4,-diphenyltetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 3,3,,4,4 '_二笨酮酮tetracarboxylic dianhydride, 3,3 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3,4,4,diphenyl-tetracarboxylic acid di-hepatic 2 2- — (3,4-A ruthenyl) hexa- isopropylidene dianhydride, 3,3,,4,4,-di-p-styl-tetras-acid anhydride, 3,3',4,4 '-二笨甲甲嗣四酸酸二针,4,4,_六败isopropylidene-decanoic acid anhydride, 3,3',4,4.-diphenyl stone wind four resorcinic dianhydride, 1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-l,2,3,4-cyclobutanine tetracarboxylic dianhydride, hydrazine, 2,3,4_ tetra Base-1,2,3,4-cyclobutanetetracarboxylic dianhydride, ι, 2, 3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy·ι, 2,3,4-tetrahydro-naphthalene Hyundian acid dianhydride, 5-(2,5-dioxotetrahydrotetrahydrocarbyl)_3_nonylcyclohexene-1,2--rebel two-needle, 2,3,5-triple -2-cyclopentane acetic acid dianhydride, bicyclo[2,2,2]oct-7-rare-2,3,5,6-tetracarboxylic acid monoanhydride, 2,3,4,5-tetrahydron-fu An acid anhydride of the two needles and 3,5,6-tricarboxy-2-norbornane acetic acid dianhydride. For the diamine, aromatic and aliphatic diamines can be used, and the diamine compound can be selected from the following One or more aromatic diamines: divalent organic groups containing a phenolic hydroxyl group, a carboxyl group or a hydroxyl group, for example, by 17 201202308
和3,5-二胺基苯甲酸得到的二價有機基團；一種或多種選自以 下的芳香族二胺：對苯二胺、間苯二胺、2,4,6-三甲基-1,3-笨二 胺、2,3,5,6-四甲基-1，4-苯二胺、4,4’ -二胺基二苯醚、3,4，_ 二胺基二苯醚、3,3’ -二胺基二苯醚、4,4’ -二胺基二笨硫醚、 4,4’ -二胺基二苯曱烷、3,4’ —二胺基二苯曱烷、3,3’ -二胺基 二笨曱烷、4,4’ -亞甲基-二(2-甲基苯胺）、4,4’ -亞曱基-二(2-異丙基-6-甲基苯胺）、4,4’ -亞甲基-二（2,6-二異丙基苯胺）、 4,4’ -亞甲基-二(2-異丙基-6-曱基苯胺）、4,4，-亞甲基-二(2,6-二 異丙基苯胺）、4,4’-二胺基二苯砜、3,3，-二胺基二苯砜、聯苯胺、 鄰-聯曱苯胺、間-聯曱苯胺、3,3’，5,5’-四甲基聯苯胺、2,2，-二（三 氟曱基)聯苯胺、1，4-二(4-胺基苯氧基）苯、U_二(4_胺基苯氧基) 苯、1,3-二(3-胺基苯氧基)苯、二[4-(4_胺基苯氧基)苯基]颯、二 [4-(3-胺基苯氧基）苯基]砜、2,2-二[4-(4-胺基苯氧基）苯基]丙烷 和2,2-二[4-(3-胺基苯氧基）苯基]丙烷；及一種或多種選自以下 的脂肪族二胺：1，6-己二胺、1，4-環己二胺、1,3-環己二胺、ι，4-二（胺甲基）環己烷、1，3-二（胺曱基）環己烷、4,4，_二胺基二環己 基曱烷、4,4’-二胺基-3,3’-二曱基二環己基甲烷、4,4，_二胺基 18 201202308 -3,3 -一甲基二環己基曱烷、二_(2_胺基乙氧基）乙烧、二(3_ 胺基丙基）醚、1，4-一（3_胺基丙基）σ瓜唤、3,9_二（3_胺基丙 基）-2,4’8，10-四氧雜螺[5,5]十一烷和丨，3二（3胺基丙基）四甲基 一矽氧烷，並且所述芳香族二胺和脂肪族二胺可混合使用，但 本發明不限於此。 同時，本發明示例性實施方案的聚醢亞胺樹脂可在i2〇t 至2〇〇C、較佳no°C至180°C，並且最佳14(TC至160°C的低溫 下聚合製得。 當根據上述方法製備聚醯亞胺時，較佳地’聚合過程中的 轉化率爲10 0 % ’並且殘留在聚醯亞胺樹脂中的催化劑的量爲該 聚醯亞胺樹脂的〇.〇〇 1重量％至〇· 1重量％。 雖然本發明示例性實施方案的聚酿亞胺在較低的溫度下 聚合製彳于，但其具有高的轉化率，並且殘留在最終製得的聚醯 亞胺樹脂中的催化劑的量較小，因此可以看到，根據本發明示 例性實施方案的製備方法可有效地製備聚醯亞胺樹脂。 在本發明示例性實施方案中根據順序操作而製備的聚醯 亞胺樹脂可在150°c至250。(：的低溫下固化，並且其是可溶的。 因此，可解決所屬領域的問題，例如在32〇。匸或更高溫度 下固化聚醯亞胺過程中的困難、其無法用於對熱敏感的方法、 儘管實施了高溫固化但聚醯胺酸前體溶液轉化爲聚醯亞胺樹 脂的轉化率仍較低等。 一般，聚醯亞胺樹脂相對於溶劑的可溶性通常極爲有限， 但根據本發明示例性實施方案製備的聚醯亞胺樹脂相對於具 有低可溶性的溶劑具有可用性。 19 201202308 通常，由於聚醯亞胺具有極低的可溶性，因此必須引入單 體以提供聚醯亞胺之溶解功能。然而，聚醯亞胺易於很好地溶 於具有高極性的高沸點溶劑中。 但是，本發明的示例性實施方案的低溫可固化聚醯亞胺具 有優良的可溶特徵，並且相對於低沸點溶劑具有優良的可溶 性，所述低沸點溶劑例如在本發明中使用的沸點於130°C至180 °(：之範圍的溶劑。 因此，爲生成醯亞胺（imide)環，無需在塗覆之後在高溫下 實施醯亞胺化反應，並且聚醯亞胺薄膜可藉由簡單除去溶劑而 得到。此外，由於預先的化學醯亞胺化反應的高轉化率，因此 可避免由於非醯亞胺化聚醯胺酸或聚醯胺酸自旨（polyamic acid ester)發生放氣而降低元件的可靠性。特別是，當低沸點溶劑在 使用中時，溫度可根據該溶劑的沸點進一步降低，因此該溶劑 可用於需要低溫處理的元件的加工，以形成具有高的機械穩定 性與熱穩定性例如目前的聚醯亞胺的機械穩定性與熱穩定性 的薄膜。 本發明的示例性實施方案的聚醯亞胺樹脂的玻璃化轉變 溫度可爲150°C至400°C。此外，所述聚醯亞胺樹脂的重均分子 量可爲 1,000至500,000，較佳5,000至100,000。 可提供含有根據上述方法製備的聚醯亞胺樹脂的低溫可 固化的光敏樹脂組合物，並且該光敏樹脂組合物的特徵在於， 其可在150°C至250°C的低溫下固化。 關於本發明的示例性實施方案的光敏樹脂組合物，在該光 敏樹脂組合物固化之後，殘留在該光敏樹脂組合物中的溶劑的 20 201202308 量小於0.05重量％，並且較佳在該光敏樹脂組合物固化之後， 無溶劑（0重量％)殘留在該光敏樹脂組合物中。 使用了所述光敏樹脂組合物的光敏薄膜的特徵在於，其可 在預烘焙之後藉由邊緣光刻膠去除(EBR)溶劑而除去。聚合過 程藉由使用例如甘醇二曱醚基溶劑（glyme-based solvent)、丙酸 酯（propionate)、PGMEA等溶劑來實施，所述溶劑常用於光阻 (photoresist)而不用於通常的聚醯亞胺聚合，因此該光敏薄膜可 藉由通常的EBR溶劑在低溫下容易地除去。 因此，在半導體生產線或顯示器生產線例如OLED、LCD 等的製造過程中，所述光敏樹脂組合物可藉由使用通常用於再 加工的溶劑而除去，並且當混合使用一種排出液(drain)時，所 述光敏樹脂組合物可溶解，而不會産生沈殿，由此可防止管道 被堵塞等問題。 對於印刷用組合物，不可使用用於通常的聚醯亞胺聚合的 溶劑’例如NMP、GBL、DM Ac、DMF等，但本發明示例性實 施方案的聚醯亞胺樹脂可有利地用於印刷用油墨組合物，因爲 其不使用所述溶劑。 因此，本發明示例性實施方案的聚醯亞胺樹脂可用作包括 OLED、LCD等在内的多種電子材料的光敏樹脂組合物的黏合 劑樹脂，和印刷用油墨組合物，但本發明不限於此。 因此’可提供藉由包含本發明示例性實施方案的光敏樹脂 組合物而製備的聚醯亞胺薄膜或藉由包含本發明示例性實施 方案的印刷用油墨組合物而製備的聚酿亞胺薄膜，此外，還可 21 201202308 提供藉由使用所述聚醯亞胺薄膜而製造的〇LED、LCD或半導 體絕緣層。 現將對本發明進行更詳細的描述。提供本發明的示例性實 施方案是爲了便於理解本發明，並且不應解釋爲限於附圖。本 發明的技術構思應該解釋爲除附圖之外還包括所有的變更、變 型和改變。 實施例1 :低溫聚醯亞胺聚合的實施例 將12.1克（g) 2,2-二（3-胺基羥苯基）六氟丙烷 (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoi.opropane)和 60 克（g) 丙 二醇單 甲基醚 乙酸酯 (propyleneglycolmonomethyletheracetate)順序放入一個 1〇〇 的圓底燒瓶中，然後對其進行緩慢攪拌至完全溶解。將該燒瓶 放入水浴中，然後緩慢添加10.2克（g)3,3’，4,4’ -二苯基醚四 叛酸二 gf (3,3 ,.4,4,-diphenylethertetracarboxylic acid dianhydride)，同時保持該燒瓶處於室溫。將丨丨克⑷甲苯(toluene) 和4克(g)三乙胺(triethylamine)放入該混合物溶液中，並在安裝 了迪安-斯達克(dean-stark)蒸餾裝置以除去水的情形下，將該混 合物溶液在150°C回流5小時。除去迪安-斯達克蒸餾裝置中的 水，並將得到的混合物溶液再回流2小時以除去催化劑，然後 將其在室溫下冷卻’從而得到可溶的聚醯亞胺溶液。 通過IR檢測聚醯亞胺的生成峰，證實通過GPC測量的聚醯 亞胺樹脂的重均分子量爲40,〇〇〇，並且多分散性指數 (poly-disperse index，（PDI))爲 1.5。 22 201202308 實施例2 :低溫聚醯亞胺聚合的實施例 將12.1克（g) 2,2-二（3-胺基-4-羥苯基）六氟丙烷和60克（g)丙 二醇單曱基醚乙酸酯順序放入一個丨00 ml的圓底燒瓶中，然後 對其進行緩慢攪拌至完全溶解。將該燒瓶放入水浴中，然後緩 慢添加 6.5 克（g) 1，2,3,4-四碳酸二酐（l,2,3,4-tetracarbonic acid dianhydride)，同時保持該燒瓶處於室溫。將11克（g)甲苯和4克 (g)三乙胺放入該混合物溶液中，並在安裝了迪安-斯達克蒸餾 裝置以除去水的情形下，將該混合物溶液在150°C回流5小時。 除去迪安-斯達克蒸餾裝置中的水，並將得到的混合物溶液再回 流2小時以除去催化劑，然後將其在室溫下冷卻，從而得到可 溶的聚醯亞胺溶液。 通過IR檢測聚醯亞胺的生成峰，證實通過GPC測量的聚醯 亞胺樹脂的重均分子量爲35,000，並且多分散性指數（PDI)爲 1.7。 比較例1 :高溫聚醯亞胺聚合的實施例 將12.1克（g) 2,2-二（3-胺基-4-羥苯基）六氟丙烷和60克（g) T - 丁内酷（γ -butyrolactone)順序放入一個100 ml的圓底燒瓶 中，然後對其進行緩慢攪拌至完全溶解。將該燒瓶放入水浴 中，然後緩慢添加10.2克（g) 3,3’ ，4,4’ -二苯基醚四羧酸二 酐，同時保持該燒瓶處於室溫。將該混合物溶液在室溫下攪拌 16小時，並將7克(g)甲苯放入該混合物溶液中，在安裝了迪安-斯達克蒸餾裝置以除去水的情形下，將該混合物溶液在180°C 回流3小時。除去迪安-斯達克蒸餾裝置中的水，並將得到的混 23 201202308 合物溶液再回流2小時以除去催化劑，然後將其在室溫下冷 卻，從而得到可溶的聚醯亞胺溶液。 通過丨R檢測聚醯亞胺的生成峰，證實通過GPc測量的聚醯 亞胺樹脂的重均分子量爲4〇 〇〇〇，並且多分散性指數（pD丨）爲 1.6。 比較例2:聚醯亞胺前體聚合的實施例 將 73.3 克（g) 4,4-二胺基二笨醚（4,4，-〇xydianilene)和 300 克（g) γ-丁内酯（T-butyrolactone)順序放入一個1 L的圓底夾套 反應器中，然後對其進行緩慢攪拌至完全溶解。在保持反應器 的夾套溫度爲20°C的情况下，緩慢添加55·8 g 3,3，,4,4，_二苯基 石風四叛酸一酐（3,3，,4,4，_diphenylsulf〇netetracarb〇xyHC chanhydnde)並攪拌。將該混合物溶液攪拌2小時’以使其充分 反應，然後在室溫下再攪拌16小時，從而製得聚醯胺酸。通過 IR檢測聚醯胺酸的生成峰，證實通過Gpc測量的聚醯亞胺樹脂 的重均分子量爲50,000，並且多分散性指數(PDI)爲丨6。 實驗實施例1 1 ·醯亞胺化率的評估 -對在120°C預烘焙4分鐘之後的情形和在25(rc硬烘焙 (hardbaking)l小時之後的情形，藉由使用Ff_IR測量。 _假定在300°C固化1小時的試驗試樣的(：^^帶積分值（CN band integration value)表示1 〇〇〇/。的轉化率，藉由在各自的固化 條件下固化的試驗試樣的CN帶積分值來檢測每種情況的醯亞 胺化率。 24 201202308 [表i] 在120°C預烘焙4分 鐘之後 在250\：硬烘焙1小 時之後 實施例1 100% 100% 實施例2 98% 98% 比較例1 98% 98% 比較例1 0% 0% 根據表1所不的結果，可看出，與其中在高溫下製備聚醯 亞胺樹te的此較例丨相比，在低溫下直接製備聚醯亞胺樹脂的 本發明實施例1和2具有相同或更優的醯亞胺化率。 2.催化劑殘留量的分析 藉由GC-MS分析對催化劑殘留量進行定量分析，並將結果 示於下表2中。 ___ 殘留催化劑的量 實施例1 二 Λ 胳 0 0?% 比較例1 吡啶0.5% 如表2中所7F ’可看出’當使用本發明的低沸點催化劑時， 殘留在聚醯亞胺巾的催化劑的量與比較賴目比顯著降低。因 此，從所述結果可看出，根據本發明方法可有效製備聚醯亞胺。 實知例3 ·光敏樹脂組合物（聚醯亞胺組合物）的製備實施例 25 201202308 將0.5克（g)作爲光活性化合物的重氮基萘醌酯化合物 (diazonaphthoquinone ester compound)(其 OH和 〇D根據 TPPA 320: OD/(OD+OH)=2/3這一比例選擇性地給出）和4克（g)丙二 醇單甲基醚乙酸酯（PGMEA)添加到1.6克（g)在前述實施例]中 合成的可溶性聚醯亞胺中，然後將其在室溫下攪拌1小時，並 用孔大小爲1微米（μιη)的濾器過濾’從而製得一種光敏樹脂組合 物。 比較例3:光敏樹脂組合物（聚醯亞胺組合物）的製備實施例 將0.5克（g)作爲光活性化合物的重氮基萘醌酯化合物（其 OH和OD根據TPPA 320: OD/(OD+OH)=2/3這一比例選擇性地 給出）和4克（g) γ-丁内酯（GBL)添加到1.6克（g)在前述比較例i 中合成的可溶性聚醯亞胺中，然後將其在室溫下攪拌】小時 並用孔大小爲1微米（μϊη)的濾器過濾’從而製得—種光敏樹月匕会 合物。 實驗實施例2:溶劑殘留量的分析 將實施例3和比較例3的組合物塗於一種基皙 丄。 Μ丄，然後分別 在120C預烘焙2分鐘和在200t硬烘焙丨小時，從而形成塗 將該塗膜在2航靜置，分析在2小時、3小時和4小時之後 獲溶劑的量，如圖1和2中所示。 圖1爲展示對實施例3的溶劑殘留量的分析的圖，圖2 示對比較例3的溶劑殘留量的分析的圖。如圖i中所示θ :展 到，實施例3中殘留溶液未有波峰，只有—個與組合:的^ 26 201202308 相對應的峰。而在圖2中，可 叫時之後，仍出現GBL峰，即使當將溶液在赋捕獲 ^知屬於殘留溶劑的峰。 =偏離本發日㈣徵的情況下，轉日村 ^=1解:是’除非另有指明，否則上述實施例不應 丄=7,而产在所附權利要求書限定的範圍内進行寬 …*此’洛人_要求書範_的所有變化和變型、 5所述範圍料效物均意欲包括麵Μ利要求書中。 【圖式簡單說明】 圖1爲展不在本發明實施例的光敏樹脂組合物固化之後對 剩餘溶劑量的分析的圖。 圖2爲展示在比較例的光敏樹脂組合物固化之後對剩餘溶 劑量的分析的圖。 【主要元件符號說明】 無 27And a divalent organic group obtained from 3,5-diaminobenzoic acid; one or more aromatic diamines selected from the group consisting of p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl- 1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4,-diaminodiphenyl Ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl decane, 3,4'-diaminodiphenyl Decane, 3,3'-diaminodibuxane, 4,4'-methylene-bis(2-methylaniline), 4,4'-indenylene-di(2-isopropyl -6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 4,4'-methylene-bis(2-isopropyl-6-oxime) Aniline), 4,4,-methylene-bis(2,6-diisopropylaniline), 4,4'-diaminodiphenyl sulfone, 3,3,-diaminodiphenyl sulfone, Benzidine, o-benzidine, m-benzidine, 3,3',5,5'-tetramethylbenzidine, 2,2,-bis(trifluoromethyl)benzidine, 1,4- Bis(4-aminophenoxy)benzene, U_bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-amine) Phenoxy group) phenyl] fluorene, di [ 4-(3-Aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 2,2-bis[4-(3-amine) a phenoxy)phenyl]propane; and one or more aliphatic diamines selected from the group consisting of: 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, ι , 4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomercapto)cyclohexane, 4,4,-diaminodicyclohexyldecane, 4,4'-diamino- 3,3'-dimercaptodicyclohexylmethane, 4,4,-diamino group 18 201202308 -3,3-methyldicyclohexyldecane, bis(2-aminoethoxy)ethene , bis(3_aminopropyl)ether, 1,4-mono(3-aminopropyl) σ, 3,9-bis(3-aminopropyl)-2,4'8,10- Tetraoxaspiro[5,5]undecane and anthracene, 3 bis(3aminopropyl)tetramethylmonooxane, and the aromatic diamine and the aliphatic diamine may be used in combination, but The invention is not limited to this. Meanwhile, the polyimide resin of the exemplary embodiment of the present invention may be polymerized at a temperature of from i2〇t to 2〇〇C, preferably from no °C to 180 °C, and preferably at a low temperature of TC to 160 °C. When the polyimine is prepared according to the above method, it is preferred that the conversion rate during the polymerization is 100%' and the amount of the catalyst remaining in the polyimide resin is the enthalpy of the polyimide resin. 〇〇1% by weight to 〇·1% by weight. Although the polystyrene of the exemplary embodiment of the present invention is polymerized at a lower temperature, it has a high conversion rate, and remains in the final production. The amount of the catalyst in the polyimide resin is small, and thus it can be seen that the preparation method according to the exemplary embodiment of the present invention can efficiently prepare the polyimide resin. In the exemplary embodiment of the present invention, it is operated according to the sequence. The prepared polyimide resin can be cured at a low temperature of 150 ° C to 250 ° and is soluble. Therefore, problems in the art can be solved, for example, at 32 Torr or higher. Difficulties in curing polyimine, which cannot be used for heat The method of sensation, although the high temperature curing is carried out, the conversion rate of the polyproline precursor solution to the polyimide resin is still low, etc. Generally, the solubility of the polyimide resin with respect to the solvent is usually extremely limited, but according to The polyimine resin prepared by the exemplary embodiment of the present invention has usability with respect to a solvent having low solubility. 19 201202308 In general, since polyquinone has a very low solubility, it is necessary to introduce a monomer to provide a polyimide. The dissolution function. However, the polyimine is easily dissolved in a high boiling solvent having high polarity. However, the low temperature curable polyimide of the exemplary embodiment of the present invention has excellent solubility characteristics and is relatively It has excellent solubility in a low boiling point solvent such as a solvent having a boiling point in the range of 130 ° C to 180 ° (in the range of 130 ° C to 180 ° used in the present invention. Therefore, in order to form an imide ring, it is not necessary to The ruthenium imidization reaction is carried out at a high temperature after coating, and the polyimide film can be obtained by simply removing the solvent. Further, due to the prior chemistry High conversion of the imidization reaction, thereby avoiding the reliability of the element due to degassing of the non-imidized poly-proline or polyamic acid ester. In particular, when the boiling point is low When the solvent is in use, the temperature can be further lowered depending on the boiling point of the solvent, so the solvent can be used for processing of an element requiring low temperature treatment to form a machine having high mechanical stability and thermal stability such as current polyimine. Film having stability and thermal stability. The polyimide resin of the exemplary embodiment of the present invention may have a glass transition temperature of from 150 ° C to 400 ° C. Further, the weight average molecular weight of the polyimide resin It may be from 1,000 to 500,000, preferably from 5,000 to 100,000. A low-temperature curable photosensitive resin composition containing the polyimine resin prepared according to the above method may be provided, and the photosensitive resin composition is characterized in that it may be at 150° Curing at a low temperature of C to 250 °C. With regard to the photosensitive resin composition of the exemplary embodiment of the present invention, after the photosensitive resin composition is cured, the amount of the solvent remaining in the photosensitive resin composition of 20 201202308 is less than 0.05% by weight, and preferably in the photosensitive resin composition After the material was cured, no solvent (0% by weight) remained in the photosensitive resin composition. The photosensitive film using the photosensitive resin composition is characterized in that it can be removed by edge photoresist removal (EBR) solvent after prebaking. The polymerization process is carried out by using a solvent such as a glycole-based solvent, propionate, PGMEA, etc., which is often used for photoresist without being used for usual polyfluorene. The imine is polymerized, so that the photosensitive film can be easily removed at a low temperature by a usual EBR solvent. Therefore, in the manufacturing process of a semiconductor production line or a display production line such as an OLED, an LCD, or the like, the photosensitive resin composition can be removed by using a solvent which is usually used for reworking, and when a drain is used in combination, The photosensitive resin composition can be dissolved without causing a pedestal, thereby preventing problems such as clogging of the pipe. For the printing composition, a solvent for usual polyimine polymerization, such as NMP, GBL, DM Ac, DMF, or the like, cannot be used, but the polyimide resin of the exemplary embodiment of the present invention can be advantageously used for printing. The ink composition is used because it does not use the solvent. Therefore, the polyimide resin of the exemplary embodiment of the present invention can be used as a binder resin of a photosensitive resin composition of various electronic materials including an OLED, an LCD, etc., and an ink composition for printing, but the present invention is not limited this. Therefore, a polyimide film prepared by a photosensitive resin composition containing an exemplary embodiment of the present invention or a polyimide film prepared by using the printing ink composition of the exemplary embodiment of the present invention can be provided. In addition, 21 201202308 can also provide a 〇LED, LCD or semiconductor insulating layer fabricated by using the polyimide film. The invention will now be described in more detail. The exemplary embodiments of the present invention are provided to facilitate the understanding of the present invention and should not be construed as being limited to the drawings. The technical idea of the present invention should be construed as including all changes, modifications and changes in addition to the drawings. Example 1: Example of Low Temperature Polyimine Polymerization 12.1 g (g) of 2,2-bis(3-aminohydroxyphenyl)hexafluoropropane (2,2-bis(3-amino-4-hydroxyphenyl) Hexafluoi.opropane) and 60 g (g) of propyleneglycolmonomethyletheracetate were placed in a 1 圆 round bottom flask and slowly stirred until completely dissolved. The flask was placed in a water bath, and then 10.2 g (g) of 3,3',4,4'-diphenyl ether tetraglycolic acid di-gf (3,3,.4,4,-diphenylethertetracarboxylic acid dianhydride) was slowly added. While keeping the flask at room temperature. Tocopherium (4) toluene and 4 g (g) of triethylamine were placed in the mixture solution, and a dean-stark distillation apparatus was installed to remove water. The mixture solution was refluxed at 150 ° C for 5 hours. The water in the Dean-Stark distillation apparatus was removed, and the resulting mixture solution was refluxed for further 2 hours to remove the catalyst, which was then cooled at room temperature to obtain a soluble polyimine solution. The peak of polyimine imine formation was examined by IR, and it was confirmed that the weight average molecular weight of the polyimine resin measured by GPC was 40, 〇〇〇, and the poly-disperse index (PDI) was 1.5. 22 201202308 Example 2: Example of low temperature polyimine polymerization 12.1 g (g) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 60 g (g) of propylene glycol monoterpene The base ether acetate was placed in a 00 ml round bottom flask in sequence and then slowly stirred until completely dissolved. The flask was placed in a water bath, and then 6.5 g (g) of 1,2,3,4-tetracarbonic acid dianhydride was slowly added while keeping the flask at room temperature. 11 g (g) of toluene and 4 g (g) of triethylamine were placed in the mixture solution, and in the case where a Dean-Stark distillation apparatus was installed to remove water, the mixture solution was at 150 ° C. Reflux for 5 hours. The water in the Dean-Stark distillation apparatus was removed, and the resulting mixture solution was refluxed for another 2 hours to remove the catalyst, which was then cooled at room temperature to obtain a soluble polyimine solution. The formation peak of polyimine was detected by IR, and it was confirmed that the polyamidene resin measured by GPC had a weight average molecular weight of 35,000 and a polydispersity index (PDI) of 1.7. Comparative Example 1: Example of high temperature polyimine polymerization 12.1 g (g) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 60 g (g) of T-butylene (γ-butyrolactone) was placed in a 100 ml round bottom flask in sequence and then slowly stirred until completely dissolved. The flask was placed in a water bath, and then 10.2 g (g) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was slowly added while keeping the flask at room temperature. The mixture solution was stirred at room temperature for 16 hours, and 7 g (g) of toluene was placed in the mixture solution, and the mixture solution was placed in the case where a Dean-Stark distillation apparatus was installed to remove water. Reflux at 180 ° C for 3 hours. The water in the Dean-Stark distillation apparatus was removed, and the obtained mixed 23 201202308 solution was further refluxed for 2 hours to remove the catalyst, which was then cooled at room temperature to obtain a soluble polyimine solution. . The formation peak of polyimine was detected by 丨R, and it was confirmed that the polyaniline resin measured by GPc had a weight average molecular weight of 4 Å and a polydispersity index (pD 丨) of 1.6. Comparative Example 2: Example of Polymerization of Polyimine Precursor 73.3 g (g) 4,4-diaminodiphenyl ether (4,4,-〇xydianilene) and 300 g (g) γ-butyrolactone (T-butyrolactone) was placed in a 1 L round bottom jacketed reactor in sequence and then slowly stirred until completely dissolved. While maintaining the jacket temperature of the reactor at 20 ° C, slowly add 55·8 g of 3,3,4,4,_diphenyl stone and four resorcinic anhydride (3,3,,4,4 , _diphenylsulf〇netetracarb〇xyHC chanhydnde) and stirred. The mixture solution was stirred for 2 hours' to allow it to react sufficiently, and then stirred at room temperature for further 16 hours to obtain a polyamic acid. The peak of polyproline formation was examined by IR, and it was confirmed that the polyamidene resin measured by Gpc had a weight average molecular weight of 50,000 and a polydispersity index (PDI) of 丨6. Experimental Example 1 1 Evaluation of oxime imidization ratio - the case after prebaking at 120 ° C for 4 minutes and the case after 25 (rc hardbaking) for 1 hour, measured by using Ff_IR. The CN band integration value of the test sample cured at 300 ° C for 1 hour represents a conversion rate of 1 〇〇〇 /. by the test sample cured under the respective curing conditions. The CN band integral value was used to detect the sulfhydrylation rate in each case. 24 201202308 [Table i] After prebaking at 120 ° C for 4 minutes at 250 °: hard baking for 1 hour Example 1 100% 100% Example 2 98% 98% Comparative Example 1 98% 98% Comparative Example 1 0% 0% According to the results of Table 1, it can be seen that compared with the comparative example in which the polyimine tree te is prepared at a high temperature, Examples 1 and 2 of the present invention in which a polyimide resin was directly prepared at a low temperature had the same or superior yield of ruthenium imidization. 2. Analysis of catalyst residual amount Quantitative analysis of catalyst residual amount by GC-MS analysis And the results are shown in the following Table 2. ___ Amount of residual catalyst Example 1 Two Λ 0 0 0?% Comparative Example 1 Pyridine 0.5% As can be seen from 7F' in Table 2, when the low boiling point catalyst of the present invention is used, the amount of the catalyst remaining in the polyimide lens is significantly lower than the comparatively low ratio. Therefore, from the results, It is seen that the polyimine can be efficiently produced according to the method of the present invention. Example 3: Preparation of photosensitive resin composition (polyimine composition) Example 25 201202308 0.5 g (g) is used as the weight of the photoactive compound A diazonaphthoquinone ester compound (whose OH and 〇D are selectively given according to TPPA 320: OD/(OD+OH)=2/3) and 4 g (g) of propylene glycol monomethyl Ethyl ether acetate (PGMEA) was added to 1.6 g (g) of the soluble polyimine synthesized in the foregoing Example], and then it was stirred at room temperature for 1 hour, and the pore size was 1 μm (μιη). The filter was filtered to produce a photosensitive resin composition. Comparative Example 3: Preparation of photosensitive resin composition (polyimine composition) 0.5 g (g) of diazo naphthyl ester as a photoactive compound Compound (the ratio of OH and OD according to TPPA 320: OD/(OD+OH)=2/3 Optionally given) and 4 g (g) of γ-butyrolactone (GBL) were added to 1.6 g (g) of the soluble polyimine synthesized in the aforementioned comparative example i, and then stirred at room temperature 】 hours and filter with a pore size of 1 micron (μ ϊ η) filter to produce a photosensitive tree sap. Experimental Example 2: Analysis of solvent residual amount The compositions of Example 3 and Comparative Example 3 were applied to a base hydrazine. Μ丄, then pre-baked at 120C for 2 minutes and hard baked at 200t for a few hours to form a coating. The coating was placed in 2, and the amount of solvent obtained after 2 hours, 3 hours, and 4 hours was analyzed. Shown in 1 and 2. Fig. 1 is a graph showing the analysis of the residual amount of the solvent of Example 3, and Fig. 2 is a graph showing the analysis of the residual amount of the solvent of Comparative Example 3. As shown in Fig. i, θ: shows that the residual solution in Example 3 has no peaks, and only one peak corresponding to the combination: 26 201202308. In Fig. 2, after the time of the call, the GBL peak still appears, even when the solution is captured and the peak of the residual solvent is known. = Deviation from the date of the first day (four), the transfer of the village ^ = solution: is 'unless otherwise specified, the above embodiment should not be 丄 = 7, and the production is wide within the scope defined by the appended claims ...* All changes and modifications of this 'Luoren _ request book _ _, the range of material effects are intended to include the face profit request. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing an analysis of the amount of remaining solvent after the photosensitive resin composition of the embodiment of the invention is not cured. Fig. 2 is a graph showing the analysis of the remaining solvose amount after the photosensitive resin composition of the comparative example was cured. [Main component symbol description] None 27