200944563 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種製造具有利用聚醯亞胺組成物而形 成之聚醯亞胺層的可撓性配線板之方法。 【先前技術】 通常，聚醯亞胺樹脂係將高聚合度之聚酿亞胺前驅物 成形為膜等，進行加熱或者化學醯亞胺化而獲得，該高聚 ❹ 合度之聚酿亞胺前驅物係使均笨四叛酸二針（pyromellitie dianhydride)等芳香族四羧酸二酐與二胺基二苯醚等芳香族 二胺於二甲基乙醯胺等非質子性極性溶劑中進行等莫耳反 - 應而輕易獲得。 - 並且，該聚酿亞胺樹脂由於兼具優異之耐熱性、耐藥 品性、耐放射線性、電氣絕緣性、機械性質等性質，故而 形成於銅箔等導體上，被廣泛利用於可撓性配線板等各種 電子元件中。 ® 使用上述醯亞胺樹脂之可撓性配線板係利用下述專利 文獻1中所示之方法來製造。首先，將使二胺與酸二酐於 溶液中聚合而獲得之聚醯亞胺組成物塗佈於不鏞鋼羯上。 並且，將所塗佈之聚醯亞胺組成物藉由於空氣、氮、氬等 之環境氣氛下，於60〜600°C之溫度下之加熱乾燥而於不鏽 鋼箔上形成聚醢亞胺層，藉由圖案形成或鍍敷等而製造特 定之可撓性配線板。 先前技術文獻 3 200944563 專利文獻 專利文獻1 :日本專利特開2〇〇61〇33〇4號公報 【發明内容】 發明所欲解決之朗顙 可撓性配線板等中所利用之感光性聚酿亞胺組成物， 為了於導趙上形成特定形狀而利用驗性顯影進行圖案形 成。例如’可藉氫氧錢錢氧化鉀等驗溶液來去除特定 部位，以形成圖案。 然而，已知若於聚醯亞胺組成物中預先添加交聯劑， 且於圖案形成後，A了使聚醯亞胺層與導體之密合性提高 而使聚醯亞胺樹脂與交聯劑反應，則在由於圖案形成而使 導體露出-部分之狀態下進行加熱，t導致所露出之導體 經氧化而變色。該變色並不僅止於㈣之露出自，亦會擴 散至聚醯亞胺層與導體之界面，若於該狀態下進行無電 鍍’則雖由前處理而去除變色M旦會於產生變色之聚醯亞 胺層與導艘之界面形成間隙。即導致產生聚醯亞胺層之浮 起0 於上述專利文獻丨中所示之可撓性配線板之製造方法 中，為了使形成於不鏽鋼猪上之聚酿亞胺層硬化、乾燥而 進行惰性氣體中之加熱，但並未進行用以使聚酼亞胺化合 物與交聯劑反應之加熱。因此，並未對聚醯亞胺層與導體 之不鏽鋼箔之界面的變色進行研究。 因此’發明者黎於上述課題而進行銳意研究。由此， 200944563 本發明之目的在於為了防止鍍敷後之聚醢亞胺層之浮起的 產生，而提供一種即便於聚醯亞胺樹脂與交聯劑之反應 後，聚醯亞胺層與導體之界面亦不會變色的可撓性配線板 之製造方法。 解決問題之拮術丰埒 解決上述課題的本發明之可撓性配線板之製造方法， 其特徵在於’包括以下步驟：製備含有藉由酸二酐與二胺 之反應而獲得之聚醯亞胺化合物、感光劑、及交聯劑的聚 〇 醯亞胺組成物之步驟；將上述聚醯亞胺組成物塗佈於導體 電路上而形成聚醯亞胺層之步驟；將上述聚酿亞胺層藉由 曝光及鹼性顯影處理而形成特定圖案，並且使導體電路之 ' 特定區域露出之步驟；上述圖案形成後，於氧濃度為1 vol% 以下之環境氣氛下進行加熱處理而使聚醯亞胺化合物與交 聯劑反應之步驟。 發明之效果 本發明之可撓性配線板之製造方法係藉由曝光、鹼性 顯影處理將聚醯亞胺層形成特定圖案之後，使構成該聚醯 亞胺層之聚醯亞胺化合物與交聯劑反應之加熱處理於氧濃 度為1 vol%以下之環境氣氛下進行。藉由於1 v〇1%以下之 極端缺氧之狀態下進行加熱處理，不僅於導體電路之露出 面’並且於導體與聚醢亞胺層之界面亦可防止由於氧化而 產生之導體變色。 【實施方式】 5 200944563 以下’對本發明之可撓性配線板之製造方法加以說 明。再者，本發明並非限定於以下之說明者，可於不脫離 本發明之主旨的範圍内加以適當變更。 本發明之可撓性配線板之製造方法，係藉由對形成有 聚醯亞胺層之圓案的導體之加熱於極端之缺氧狀態下進 仃，以防止導體與聚醯亞胺層之界面之變色的方法。於本 發明之方法中，形成聚醯亞胺層之聚醯亞胺組成物係含有 藉由酸二酐與二胺之反應而獲得之聚醯亞胺化合物、感光 劑、及交聯劑而成者。 為了獲得以本發明之方法所製備之聚醢亞胺組成物而 使用之酸二酐，例如可列舉：3,3,，4,4，_二苯基颯四羧酸二酐 (DSDA)、均苯四羧酸二酐（pMDA) 、2,3 6 7_萘四羧酸 一酐（NTCDA) 、4,4，_(六氟異亞丙基）雙鄰苯二甲酸酐 (6FDA )、3,4,3'，4’-二苯甲酮四羧酸二酐（BTDA )、3,4,3，，4，_ 聯笨基四羧酸二酐（BPDA或S_BPDA) 、44，氧雙鄰苯二 曱酸酐（ODPA) 、9,9-雙[4-(3,4-二羧基苯氧基）苯基]苐二 奸（BPF-PA) 、1，2,3,4-環丁烷四羧酸二酐（CBDA)、雙 環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐等的芳香族酸二酐及 月旨環式酸二酐。 其中，一般認為DSDA具有電負度大之硫原子 '氧原 子，該等原子之影響經由共軛而影響到醯亞胺羰基碳，並 且谷易受到鹼之親核攻擊，因此驗溶解性提高，係較佳之 酸二 gf。 為了提高顯影性，與上述酸二酐反應而生成聚醯亞胺 200944563 化合物之二胺較佳為於分子中具有經基者。例如可列舉： 3,3’-二胺基-4,4’-二羥基二苯基颯（BSDA)44，·二胺基 聯苯基二醇（HAB)、9,9-雙（3-胺基-4-經基苯基）苐 (BAHF )作為不損及聚酿亞胺層之驗性顯影性及低彈性 者，較佳為使用BSDA。 本發明之方法中所製備之聚酿亞胺組成物，由於亦用 作可撓性配線板之覆蓋層材料，故而作為形成聚酿亞胺組 成物之聚醯亞胺化合物，較佳為彈性模數比較低之聚醯亞 © 胺化合物，具體而言為具有揚氏模數為1 GPa以下之彈性 模數的聚醯亞胺化合物。作為此種具有低彈性模數之聚醯 亞胺化合物，例如可列舉具有矽與氧交替鍵結之矽氧烷結 構的聚醯亞胺化合物❶具有矽氧烷結構之聚醯亞胺化合物 - 可使用於酸二酐成分及/或二胺成分之一部分中具有矽與氧 交替鍵結之矽氧烷結構之單體而生成。相對於酸二野及二 胺之總重量（全部單體總重量），該具有矽氧烷結構之單 體的含量較佳為55 wt%以上且72 wt%以下之範圍，更佳為 60 wt%以上且70 wt%以下之範圍。於具有矽氧烷結構之單 體之重量範圍未滿55 wt%，或者大於72 wt%之情形時，會 有驗性顯影性降低，或者無法達成低彈性之一標準即i Gpa 的情況。 於習知之可撓性配線板之製造中產生的導鱧之變色 域’根據元素分析之結果可確認氧化，一般認為導體之變 色係由氧引起。通常矽氧烷結構具有氧穿透性，因此若為 了獲得低彈性之聚醯亞胺化合物而使用具有矽氧烧結構之 7 200944563 單體，則氧會變得易於穿 2. ^ s ^ w 眾醯亞胺層，使得導體與聚醯 亞胺層之界面之轡辛空太 介囬之燹色合易產生。於本發明中，即便 種具有提高氧穿透性之發氧燒社 軋沉、^構的卓體，亦可防止導體 與聚醯亞胺層之界面之變色。 作為矽氧烧二胺之一例 示之具有二甲基亞矽烷基骨 氧院二胺β ，可列舉由下述結構式丨所表 架與二苯基亞石夕烧基骨架之矽BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of producing a flexible wiring board having a polyimide layer formed using a polyimide composition. [Prior Art] Generally, a polyimine resin is obtained by forming a high-polymerization degree polyiminoimide precursor into a film or the like, heating or chemically imidating, and the high-concentration degree of the chitosan precursor is obtained. The aromatic diamines such as aromatic tetracarboxylic dianhydrides such as pyromellitie dianhydride and adiamine diphenyl ethers are allowed to be used in an aprotic polar solvent such as dimethylacetamide. Moore - should be easily obtained. - The polyiminoimine resin is widely used in flexible conductors because it has excellent heat resistance, chemical resistance, radiation resistance, electrical insulation, and mechanical properties. Among various electronic components such as wiring boards. ® A flexible wiring board using the above quinone imide resin is produced by the method shown in the following Patent Document 1. First, a polyimide composition obtained by polymerizing a diamine and an acid dianhydride in a solution is applied onto a stainless steel crucible. Further, the coated polyimide composition is formed by forming a polyimide layer on a stainless steel foil by heating and drying at a temperature of 60 to 600 ° C in an atmosphere of air, nitrogen, argon or the like. A specific flexible wiring board is produced by patterning, plating, or the like. PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT LIST OF THE INVENTION The imine composition is patterned by use of an in-progressive development in order to form a specific shape on the guide. For example, a specific solution can be removed by a test solution such as oxyhydrogen and potassium hydroxide to form a pattern. However, it is known that when a cross-linking agent is added in advance to a polyimine composition, and after pattern formation, A improves the adhesion between the polyimine layer and the conductor, and the polyimine resin is crosslinked. In the case of the agent reaction, heating is performed in a state in which the conductor is exposed to a portion due to pattern formation, and t causes the exposed conductor to be discolored by oxidation. The discoloration does not only occur when (4) is exposed, but also spreads to the interface between the polyimide layer and the conductor. If electroless plating is performed in this state, the color change will be removed by pretreatment. The interface between the quinone imine layer and the guide vessel forms a gap. That is, the floating of the polyimine layer is caused. In the method for producing a flexible wiring board as shown in the above patent document, the polyimide layer formed on the stainless steel pig is hardened and dried to be inert. Heating in the gas, but heating for reacting the polyimine compound with the crosslinking agent is not performed. Therefore, the discoloration at the interface between the polyimide layer and the stainless steel foil of the conductor was not investigated. Therefore, the inventor of the inventor has conducted intensive research on the above topics. Thus, the purpose of the present invention is to provide a polyimine layer and a reaction between the polyimine resin and the crosslinking agent in order to prevent the occurrence of floating of the polyimide layer after plating. A method of manufacturing a flexible wiring board in which the interface of the conductor does not change color. The present invention provides a method for producing a flexible wiring board according to the present invention, which comprises the following steps: preparing a polyimine obtained by a reaction of an acid dianhydride and a diamine a step of a polyimine composition of a compound, a sensitizer, and a crosslinking agent; a step of applying the above polyimine composition to a conductor circuit to form a polyimide layer; a step of forming a specific pattern by exposure and alkali development treatment, and exposing a specific region of the conductor circuit; after the pattern is formed, heat treatment is performed in an atmosphere having an oxygen concentration of 1 vol% or less to cause polymerization The step of reacting an imine compound with a crosslinking agent. Advantageous Effects of Invention The method for producing a flexible wiring board according to the present invention is to form a polyimine layer of a polyimine layer by forming a specific pattern by exposure and alkali development treatment. The heat treatment of the joint reaction is carried out in an atmosphere having an oxygen concentration of 1 vol% or less. By heat treatment in a state of extreme oxygen deficiency of 1 v 〇 1% or less, not only the exposed surface of the conductor circuit but also the interface between the conductor and the polyimide layer can prevent discoloration of the conductor due to oxidation. [Embodiment] 5 200944563 Hereinafter, a method of manufacturing a flexible wiring board of the present invention will be described. The present invention is not limited to the following description, and may be appropriately modified without departing from the spirit and scope of the invention. The method for producing a flexible wiring board according to the present invention is to prevent the conductor and the polyimide layer by heating the conductor of the round formed with the polyimide layer in an extreme oxygen-deficient state. The method of discoloration of the interface. In the method of the present invention, the polyimine composition forming the polyimine layer comprises a polyimine compound obtained by the reaction of an acid dianhydride and a diamine, a sensitizer, and a crosslinking agent. By. The acid dianhydride used to obtain the polyimine composition prepared by the method of the present invention may, for example, be 3,3,4,4,diphenylphosphonium tetracarboxylic dianhydride (DSDA), Pyromellitic dianhydride (pMDA), 2,3 6 7-naphthalenetetracarboxylic acid monohydride (NTCDA), 4,4,_(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,4,3',4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,4,3,,4,_biphenyltetracarboxylic dianhydride (BPDA or S_BPDA), 44, oxygen Di-phthalic anhydride (ODPA), 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]anthracene (BPF-PA), 1,2,3,4-ring Aromatic acid dianhydrides such as butane tetracarboxylic dianhydride (CBDA), bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, etc. anhydride. Among them, it is generally believed that DSDA has a sulfur atom with a large electronegativity, and the influence of these atoms affects the quinone imine carbonyl carbon via conjugate, and the valley is susceptible to nucleophilic attack by the alkali, so that the solubility is improved. A preferred acid di gf. In order to improve the developability, it is preferred to react with the above-mentioned acid dianhydride to form a polyimine. The diamine of the compound of the compound 4444563 is preferably a base having a base in the molecule. For example, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfonium (BSDA) 44, diaminobiphenyl diol (HAB), 9,9-bis (3- Amino-4-pyridylphenyl)anthracene (BAHF) is preferably used as BSDA without impairing the developability and low elasticity of the polyimide layer. Since the polyiminoimine composition prepared by the method of the present invention is also used as a covering material for a flexible wiring board, it is preferably a polyimine compound which is a composition of a polystyrene composition. The relatively low poly-polyamine compound, specifically, a polyimine compound having an elastic modulus of Young's modulus of 1 GPa or less. As such a polyimine compound having a low modulus of elasticity, for example, a polyimine compound having a rhodium structure in which an anthracene and oxygen are alternately bonded, a polyfluorene compound having a rhodium structure can be cited. It is produced by using a monomer having a decane structure in which an oxime and oxygen are alternately bonded to one of an acid dianhydride component and/or a diamine component. The content of the monomer having a decane structure is preferably in the range of 55 wt% or more and 72 wt% or less, more preferably 60 wt%, based on the total weight of the acid di-subfield and the diamine (total total monomer weight). More than % and less than 70 wt%. When the weight of the monomer having a decane structure is less than 55 wt% or more than 72 wt%, the developability is lowered, or one of the low elasticity standards, i Gpa, cannot be achieved. The discoloration field of the guide which is produced in the manufacture of the conventional flexible wiring board 'is confirmed by the result of elemental analysis. It is considered that the color change of the conductor is caused by oxygen. Usually, the oxane structure has oxygen permeability, so if a low-elastic polyimine compound is used in order to obtain a low-elastic polyimine compound, the oxygen can become easy to wear. 2. ^ s ^ w The quinone imine layer makes the interface between the conductor and the polyimide layer easy to produce. In the present invention, the discoloration of the interface between the conductor and the polyimide layer can be prevented even if the seed crystal having the oxygen permeability is improved. The dimethyl sulfonium oxide oxo-diamine β which is exemplified as one of the oxynoxydiamines is exemplified by the structure of the following structural formula and the diphenyl sulfite skeleton.
上述結構式1中，R1及R2為可經取代之伸烷基，作為 其具體例，可列舉亞甲基、伸乙基、三亞甲基、四亞甲基、 五亞甲基、六亞甲基。作為取代基，可列舉甲基、乙基等 低級烷基，笨基等芳基。其中，自容易獲得原材料的觀點 來考慮，較理想為三亞甲基。又，Rl及R2可相同，亦可相 互不同’由於難以獲得原材料，故而較理想為相同。 又’上述結構式1中，扪為1〜30之整數，較佳為1〜 2〇、更佳為2〜20之整數。其原因在於，若m為〇，則難以 獲得原材料，若超過30 ’則不會混合於溶劑中而分離。另 一方面，η為0〜20之整數’較佳為卜⑽、更佳為 之整數。其原因在於’若η為1以上，則阻燃性優異之二 笨基矽氧烷單位被導入，而與未導入之情況相比較，阻燃 200944563 性會提高，若超過20，則對賦予低彈性之作用會變小。 由於具有如上所述之二甲基亞矽烷基骨架，而對由本 發明之聚酿亞胺組成物層所構成之覆蓋層賦予較佳之低彈 性’結果可減小可撓性配線板之翹曲。 尤其是使用具有二甲基亞矽烷基骨架與二笨基亞矽烷 基骨架之矽氧烷二胺的聚醯亞胺組成物，被賦予低彈性與 阻燃性，適合於可撓性配線板之覆蓋層材料。作為如上所 述之矽氧烷二胺之具體例，可列舉具有二甲基亞矽烷基骨 架之KF-8010、具有二甲基亞矽烷基骨架及二苯基亞矽烷基 骨架之X-22-9409、X-22-1660B-3 (均為信越化學工業（股） 製造）。 ~ 聚醯亞胺組成物中所含之聚醯亞胺化合物係於N甲基 ·2·η比略咬_(NMP)、三乙二醇二甲醚（triglyme) 、γ_ 丁内酯等溶劑中，使如上所述之酸二酐與二胺溶解以使溶 劑中之酸二酐與二胺進行加成聚合後，藉由環化脫水反應 (溶液中之加熱醯亞胺化或由脫水劑引起之化學醯亞胺 化）而生成。藉由於聚醯亞胺前驅物中添加甲苯二甲苯 等共沸劑，於180°C以上加熱攪拌而進行聚醯胺酸成分之脫 水反應’形成聚醯胺酸之一部分或者全部閉環之聚醯亞胺 成分。此時，可視需要而添加三乙胺等三級胺，芳香族系 異喹啉、吡啶等鹼性觸媒，苯甲酸、對羥基笨甲酸等酸觸 媒來作為酿亞胺化之觸媒，可將該等化合物單獨使用，亦 可併用多種化合物。又，亦可利用作為脫水環化試劑之乙 酸酐/°比咬系或一環己基碳二醯亞胺等化學醯亞胺化劑來使 9 200944563 聚醯胺酸閉環》 聚酿亞胺組成物中含有感光劑。藉由含有該感光劑， 可對所形成之聚醯亞胺組成物賦予感光性。作為該感光 劑，例如可列舉重氮萘酿化合物。含有上述重氮萘醌化合 物之聚醯亞胺組成物的鹼溶解性會由於曝光而變化。曝光 之前，於鹼性水溶液中之溶解性低。另一方面，經曝光之 後，重氮萘醌化合物之分子結構變化而產生乙稀酮，與驗 性水溶液反應而產生叛酸。並且’所生成之叛酸與水進一 步反應而溶解。因此，藉由光照射，於鹼性水溶液中之溶 解性會提高。 於聚酿亞胺化合物具有羥基之情形時，若聚醯亞胺組 成物含有作為感光劑之重氮萘醌化合物，則聚醯亞胺化合 物之羥基與重氮萘醌化合物會形成氫鍵。聚醯亞胺化合物 由於具有羥基，故而本來鹼溶解性比較高，但藉由與重氮 萘醌化合物形成氫鍵，易於溶解於鹼中之羥基受到保護， 因此鹼溶解性會降低。若對該狀態之聚醯亞胺化合物進行 曝光’則如上所述重氮萘醌化合物之分子結構變化，表現 出聚醯亞胺化合物之鹼溶解性。因此，藉由使其含有重氮 萘醌化合物作為感光劑，可於對可撓性配線板之曝光後， 利用氫氧化鈉（Na0H)、氫氧化鉀、礙酸納、碳酸氣納、 氫氧化四甲基銨（TMAH)等鹼性水溶液來形成圖案。 作為感光劑重氮萘醌化合物，若為具有重氮萘鲲骨架 之化合物，則無特別限定，例如可列舉：2,3,4_三羥基二笨 甲嗣-鄰萘酿二疊氮·4·續酸醋、2,3,4·三經基二苯甲酮-鄰蔡 200944563 職二疊氮-5-續酸酯、2,3,4-三羥基二苯甲嗣-鄰苯醌二疊氮 -4-確酸酿等。 聚醯亞胺組成物中含有具有複數個環氧基之交聯劑。 該交聯劑可與利用鹼溶液之驗性顧影後之聚醯胺化合物在 200 C以下之低溫下產生加成反應’以將聚醯亞胺化合物交 聯°务為具有複數個環氧基之官能基，則可於比較低之溫 度下使其與具有胺基或羧基之聚酿亞胺化合物反應，即便 用於可撓性配線板中亦可減少由對其他構件之加熱所引起In the above structural formula 1, R1 and R2 are a substituted alkylene group, and specific examples thereof include a methylene group, an exoethyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. base. Examples of the substituent include a lower alkyl group such as a methyl group or an ethyl group, and an aryl group such as a strepyl group. Among them, from the viewpoint of easy availability of raw materials, it is preferred to be a trimethylene group. Further, R1 and R2 may be the same or different from each other. Therefore, since it is difficult to obtain a raw material, it is preferable to be the same. Further, in the above structural formula 1, 扪 is an integer of 1 to 30, preferably 1 to 2 Å, more preferably 2 to 20 integer. The reason for this is that if m is yttrium, it is difficult to obtain a raw material, and if it exceeds 30 Å, it is not mixed in a solvent and is separated. On the other hand, η is an integer of 0 to 20', preferably an integer of (10), more preferably. The reason is that if the η is 1 or more, the unit of the bismuth oxymethane having excellent flame retardancy is introduced, and the flame retardancy 200944563 is improved as compared with the case where it is not introduced, and if it is more than 20, the imparting is low. The effect of elasticity will be smaller. By having the dimethylarylene alkyl skeleton as described above, it is preferable to impart a low elasticity to the coating layer composed of the layer of the polyanilin composition of the present invention, whereby the warpage of the flexible wiring board can be reduced. In particular, a polyimide composition having a methoxyalkylene diamine having a dimethyl sulfenylene skeleton and a bis-alkylidene alkyl skeleton is imparted with low elasticity and flame retardancy, and is suitable for a flexible wiring board. Cover material. Specific examples of the oxirane diamine as described above include KF-8010 having a dimethylarylene group skeleton, X-22- having a dimethyl sulfenylene skeleton and a diphenylalkylene group skeleton. 9409, X-22-1660B-3 (all manufactured by Shin-Etsu Chemical Co., Ltd.). ~ Polyimine compound contained in the composition of polyimine is based on solvents such as Nmethyl·2·η ratio slightly (NMP), triethylene glycol dimethyl ether (triglyme), γ-butyrolactone After dissolving the acid dianhydride and the diamine as described above to carry out the addition polymerization of the acid dianhydride and the diamine in the solvent, the cyclization dehydration reaction (heating in the solution, imidization or dehydrating agent) Produced by the chemical hydrazine imidization). By adding an azeotropic agent such as toluene xylene to the polyimine precursor, the polydecalic acid component is dehydrated by heating and stirring at 180 ° C or higher to form a part or all of the closed polycondensate of the polyamic acid. Amine component. In this case, a tertiary amine such as triethylamine, an alkaline catalyst such as an aromatic isoquinoline or pyridine, or an acid catalyst such as benzoic acid or p-hydroxybenzoic acid may be added as a catalyst for the amination. These compounds may be used singly or in combination of a plurality of compounds. Further, it is also possible to use a chemical ruthenium imide such as acetic anhydride/° ratio or monocyclohexylcarbodiimide as a dehydration cyclization reagent to make 9 200944563 poly-proline closed-loop polyacrylamide composition. Contains sensitizer. By containing the sensitizer, photosensitivity can be imparted to the formed polyimide composition. As the sensitizer, for example, a diazo naphthalene compound can be cited. The alkali solubility of the polyimine composition containing the above diazonaphthoquinone compound changes depending on the exposure. The solubility in an aqueous alkaline solution was low before exposure. On the other hand, after exposure, the molecular structure of the diazonaphthoquinone compound changes to produce ethylene ketone, which reacts with the aqueous test solution to produce a tick. And the resulting rebel acid dissolves in a further reaction with water. Therefore, the solubility in an alkaline aqueous solution is improved by light irradiation. In the case where the polyamidene compound has a hydroxyl group, if the polyimine composition contains a diazonaphthoquinone compound as a sensitizer, the hydroxyl group of the polyimine compound and the diazonaphthoquinone compound form a hydrogen bond. Since the polyimine compound has a hydroxyl group, the base solubility is relatively high. However, by forming a hydrogen bond with the diazonaphthoquinone compound, the hydroxyl group which is easily dissolved in the base is protected, and thus the alkali solubility is lowered. When the polyimine compound in this state is exposed, the molecular structure of the diazonaphthoquinone compound changes as described above, and the alkali solubility of the polyimine compound is exhibited. Therefore, by using the diazonaphthoquinone compound as a sensitizer, after exposure to the flexible wiring board, sodium hydroxide (NaOH), potassium hydroxide, sodium sulphate, sodium carbonate, and hydration can be used. An alkaline aqueous solution such as tetramethylammonium (TMAH) is used to form a pattern. The diazonaphthoquinone compound as the sensitizer is not particularly limited as long as it is a compound having a diazonaphthoquinone skeleton, and examples thereof include 2,3,4-trihydroxydibenzyl-n-naphthalene-dihalide·4 ·Continuous acid vinegar, 2,3,4·trisyl benzophenone-o-Chan 200944563 O-diazide-5-decanoate, 2,3,4-trihydroxybenzophenone-o-benzoquinone Azide-4-acid solubilization, etc. The polyimine composition contains a crosslinking agent having a plurality of epoxy groups. The cross-linking agent can form an addition reaction with a polyamine compound after the use of an alkali solution at a low temperature of 200 C or less to crosslink the polyimine compound to have a plurality of epoxy groups. The functional group can be reacted with a poly-imine compound having an amine group or a carboxyl group at a relatively low temperature, and can be reduced by heating of other members even in a flexible wiring board.
❹ 的影響。又，利用該交聯劑，可使銅箔等導體與聚醯亞胺 之密合性提高。 作為使聚醯亞胺組成物中含有該交聯劑之量，相對於 聚醯亞胺化合物100重量份，較佳為20重量份以下。於含 有20重量份以上之交聯劑之情形時，聚醯亞胺组成物之穩 定性變差，且黏度會上升，因此聚醯亞胺組成物之操作性 變差。又，由於感光性降低，故而鹼性顯影變難。另一方 面’環氧基存在產生由鹼性水溶液引起之水解之虞，因此 為了維持交聯效果，較理想為添加丨重量份以上之交聯劑。 -有環氧基之交聯劑，若為對於所形成之聚酿亞胺組 成物的相容性良好者，則無特別限定，例如可列舉如下所 述之化合物。作為交聯劑，可列舉：雙齡F型環氧化合物、 雙酚A型環氧化合物、34掙备# β ^ ^ ’環氧基環己烯基甲基_3',4，·環氧 基環己稀甲酸醋等脂環式環爱几 飞壤氣化合物’山梨糖醇聚縮水甘 油醚、聚甘油聚縮水甘油醚、 ^ 手戊四醇聚縮水甘油醚、二 甘油聚縮水甘油醚、甘油脊始l 由聚縮水甘油醚、三羥甲基丙烷聚 200944563 縮水甘油醚、間苯二酚二縮水甘油醚、新戊二醇二縮水甘 油醚、1，6-己二醇二縮水甘油醚、氫化雙酚A二縮水甘油 越、聚乙二醇縮水甘油喊、聚丙二醇二縮水甘油醚、對苯 一齡二縮水甘油醚等縮水甘油醚化合物，鄰苯二甲酸_縮 水甘油酯、對苯二甲酸縮水甘油酯等縮水甘油酯化合物’， 二溴新戊二醇縮水甘油醚等經齒化之阻燃性環氧基化合 物，甲酚酚醛清漆環氧樹脂、苯酚酚醛清漆環氧樹脂等。 聚醯亞胺組成物中亦可含有噁嗪化合物。噁嗪化合物 係刀子内之噁嗪骨架因熱而開環，從而硬化。藉由使本發 ❹ 明之聚醢亞胺組成物中含有該嗔唤化合物，可發揮交聯劑 :作:，使聚酿亞胺組成物中阻燃性、及對銅等金屬之密 合性提高。例如相對於聚醯亞胺化合物100重量份，該噁 嗪化合物之添加量為5重量份以下之少量即可。 - 作為该鳴'嘻化合物’例如可列舉：雙酚F型苯并噁嗪 次甲基）雙[3,4·二氫I苯基-2H]，3-苯并》惡嗪])、 ^ i笨并噁嗪（6,6·-磺醯基雙[3,4-二氫-3-苯基-2H-1，3-笨并噪秦])、雙紛A型笨并噪嗪（下述結構式2)、苯紛® 盼料漆型苯并。惡嘻（下述結構式3)等。The impact of ❹. Further, by using the crosslinking agent, the adhesion between the conductor such as copper foil and the polyimide can be improved. The amount of the crosslinking agent to be contained in the polyimide composition is preferably 20 parts by weight or less based on 100 parts by weight of the polyimine compound. When the crosslinking agent is contained in an amount of 20 parts by weight or more, the stability of the polyimide composition is deteriorated, and the viscosity is increased, so that the handleability of the polyimide composition is deteriorated. Moreover, since the photosensitivity is lowered, alkaline development becomes difficult. On the other hand, the epoxy group has a hydrazine which is hydrolyzed by an aqueous alkaline solution. Therefore, in order to maintain the crosslinking effect, it is preferred to add a crosslinking agent or more. The crosslinking agent having an epoxy group is not particularly limited as long as it has good compatibility with the formed polyimide intermediate composition, and examples thereof include the compounds described below. Examples of the crosslinking agent include a two-year-old F-type epoxy compound, a bisphenol A-type epoxy compound, and 34 earned #β^^'epoxycyclohexenylmethyl_3',4,·epoxy An alicyclic ring-like compound such as a ring-shaped dilute formic acid vinegar, a sorbitol polyglycidyl ether, a polyglycerol polyglycidyl ether, a hand-pentylene glycol polyglycidyl ether, a diglycerol polyglycidyl ether, Glycerol ridges start from polyglycidyl ether, trimethylolpropane poly 200944563 glycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether , hydrogenated bisphenol A diglycidyl, polyethylene glycol glycidol, polypropylene glycol diglycidyl ether, glycidyl ether compounds such as benzoic acid diglycidyl ether, phthalic acid _ glycidyl ester, benzene A glycidyl ester compound such as glycidyl dicarboxylate, a flame-retardant epoxy compound such as dibromopentyl glycol glycidyl ether, a cresol novolac epoxy resin, a phenol novolac epoxy resin, or the like. The polyamidiamine composition may also contain an oxazine compound. The oxazine compound is an oxazine skeleton in a knife which is opened by heat and hardens. By including the stimulating compound in the polyimine composition of the present invention, a crosslinking agent can be used to: make the flame retardancy of the polyimide component and the adhesion to metals such as copper. improve. For example, the amount of the oxazide compound to be added is preferably 5 parts by weight or less based on 100 parts by weight of the polyimine compound. - Examples of the 嘻 '嘻 compound" include bisphenol F type benzoxazine methine bis [3,4 · dihydro I phenyl-2H], 3-benzoxazine], ^ i stupid and oxazide (6,6·-sulfonyl bis[3,4-dihydro-3-phenyl-2H-1,3-bung and qiqin]), double bismuth A type stupid and noisy ( The following structural formula 2), Benzene® is expected to be lacquer-type benzo. Evil (the following structural formula 3) and the like.
結構式2 12 200944563Structural formula 2 12 200944563
結構式3 聚醯亞胺組成物中亦可含有防銹劑。作為該防錄劑， 例如可列舉作為醯肼系金屬減活劑之2,3-雙[3-(3,5-二第三The structure 3 polyimine composition may also contain a rust inhibitor. As the anti-recording agent, for example, 2,3-bis[3-(3,5-two, third) which is a lanthanide metal deactivator can be cited.
丁基-4-經基苯基）丙醯]肼（CDA-10)，於用於可撓性配線 板之情形時’可防止與金屬接觸之聚醯亞胺組成物之樹脂 劣化。 作為CDA-10以外之防銹劑，可列舉作為醯肼系防銹劑 之癸二曱酸二鄰羥苯甲醯肼、作為三唑系防銹劑之3-(沁鄰 羥苯曱醯基）胺基-1，2,4-三唑等，但並不限定於該等。 利用本發明之方法所製造之可撓性配線板如圖丨所 不，於基材2上以覆蓋形成為具有特定圖案之銅等導體4 的方式’利用公知之塗佈法來塗佈含有如上所述之化合物 的聚酿亞胺組成物，加以乾燥以使溶劑蒸發，從而 酿胺層3(未硬化狀態）。 於聚醯亞胺層3形成後，如圖2所干，|取 之欲土a 岡Z所不，對聚醯亞胺層3 〈欲去除之部分設置光所照射之光罩 由曝# a * 早層5而進行曝光。藉 由曝先，使聚醯亞胺層3中之感光劑 經晛* * * W <結構變化’以提高 、曝先之部位的鹼溶解性。並且， 中，而如…示，將經曝光之部位去2浸潰於驗溶液 (正型圖案一基材2上之導體去：:二特定圖案 电略之一部分露出。 13 200944563 圖案形成後，例如利用氮或氦等惰性氣體，使所加熱 之可撓性配線板1之周圍之氧濃度成為1 vol%以下之極端 缺氧之狀態，較佳為0.1 vol%以下之更缺氧之狀態。該氧濃 度可利用賈法尼電池（galvanic cell )方式之燃燒排氣分析 儀進行測定。 於氧濃度成為1 vol%以下後，加熱至聚醯亞胺層3内 之交聯劑與聚醯亞胺化合物反應之溫度，藉此利用聚醯亞 胺層3内之交聯劑使聚醯亞胺化合物進行交聯，而使聚醯 亞胺層3成為硬化狀態。於本發明中，所謂硬化狀態，係 表示藉由對聚醯亞胺層加熱而使交聯劑交聯之狀態，所謂 未硬化狀態’係指尚未達到硬化狀態之狀態。 藉由該加熱’於氧濃度高於1 V〇l%之情形時，由於周 圍之氧之影響’不僅導體4之露出面，並且導艎4與聚醯 亞胺層3之界面亦經氧化而變色。又，若利用例如硫酸_過 氧化氫等來去除變色’則於導體4與聚醯亞胺層3之界面 會形成間隙。如本發明所述，藉由於氧濃度為丨v〇1%以下 之極端缺氧之環境氣氛下對可撓性配線板丨加熱，由於氧 穿透聚醯亞胺層而引起的導體4之氧化亦得到抑制，因此 不僅可防止導體4之露出面之變色，並且亦可防止導體4 與聚醯亞胺層3之界面的變色。再者，藉由使氧濃度成為 〇.1 vol%以下，可大致完全抑制導體4之氧化，故而更適宜。 先前，於可撓性配線板之加熱庫内導入氮氣等惰性氣 體’以使庫内之氧濃度降低’但為了使庫内之氧濃度為ι vol%以下，必需有習知之惰性氣體之導入量的數倍左右之 200944563 例如’於庫内之容積為90〜100〔左右之情形時， 將氣等惰性氣體流量設為較佳為8·5 L/min且3G分鐘以 上，更佳為12 L/min且3〇分鐘以上。 如此，本發明之可撓性配線板之製造方法中， 光後之驗性顯影可形成特定圖案，且可防止所露出之導體 由於氧化而變色。尤其，即便使用由上述結構4 i所表干 之具有石夕氧烷骨架之單體的氧穿透性高之聚酿亞胺層，亦 ❿ ❺ 可藉由使氧濃度成為i VGl%以下，來防止導體之露出面以 及導體與聚醯亞胺層之界面的變色。因此，於圖案形成後 即便進行無騎，亦無導艘與聚醯亞胺層之界面浮起之情 況，可防止鍍敷液流入聚酿亞胺層與導體之間。因此 由將以該方法製造之配線板用於電子零件，可提供可靠性 高之電子零件。 [實施例；1 (聚酿亞胺組成物之製作） [實施例1] 將137.47 g ( 100.48 mmol )作為矽氧烷二胺之 X-22-9409 (信越化學工# (股）製造）、i64ig(純度為 99.5%，58,26mm〇1)之BSDA投入至安裝有〜抓彻k之 500 nU四口可分離式燒瓶中，於氮氣環境氣氛下以]“ 5 § 之N-甲基吡咯啶酮使其完全溶解。其後，添加”以“純 度為99.7%，160.33 mmol)之〇犯八，於8代下㈣2小 時後，添加70 ml用以將醯亞胺化縮合水去除之共沸劑甲 苯，於油浴中於18(TC下攪拌5小時，使其保持回流.，獲得 15 200944563 目標物^ 相對於上述所獲得之聚酿亞胺化合物溶液之固體成分 100重量份，添加10重量份之重氮萘鲲感光劑（4NT 3〇〇， 東洋合成工業（股）製造）、以及2重量份作為交聯劑之 雙酚F型環氧樹脂（jER807,曰本環氧樹脂股份有限公司 製造）’製成目標之聚醯亞胺組成物。 [實施例2] 將143.34 g ( 104.78 mmol )作為矽氧烷二胺之 X-22-9409 C信越化學工業（股）製造）、18 71g(純度為 ❹ 99.5%，06.41 mmol)之 BSDA 投入至安裝有 Dean-Stark 之 500 ml四口可分離式燒瓶中，於氮氣環境氣氛下以229 5 g 之N-甲基吼咯啶酮使其完全溶解。其後，添加58·45 g (純 度為 99.7%，162.65 mmol)之 DSDA，於 80°C 下挽拌 2 小 時後，添加70 ml用以將醯亞胺化縮合水去除之共沸劑甲 苯’於油浴中於180。(：下攪拌5小時，使其保持回流，獲得 目標物。 相對於上述所獲得之聚醯亞胺化合物溶液之固體成分 ❹ 100重量份，添加10重量份之重氮萘醌感光劑（4ΝΤ-300， 東洋合成工業（股）製造）、以及2重量份之環氧樹脂 (jER807 ’日本環氡樹脂股份有限公司製造），製成目標 之聚醯亞胺組成物。 [實施例3] 將 106.41 g( 77.78 mmol )作為石夕氧炫二胺之 X-22-9409 (信越化學工業（股）製造）、25.72 g(純度為99.5%、91.30 16 200944563 mmol )之BSDA投入至安裝有Dean-Stark之500 ml四口可 分離式燒瓶中，於氮氣環境氣氛下以256.5 g之N-甲基吡咯 啶酮使其完全溶解。其後，添加61 37 g (純度為99 7%， 170.77 mmol)之DSDA，於8(TC下攪拌2小時後，添加7〇 ml用以將醯亞胺化縮合水去除之共沸劑甲苯，於油浴中於 1 80 C下攪拌5小時，使其保持回流，獲得目標物。 相對於上述所獲得之聚醢亞胺化合物溶液之固體成分 100重量份’添加10重量份之重氮萘醌感光劑（4NT-300， 東洋合成工業（股）製造）、以及2重量份之環氧樹脂 (jER807，日本環氧樹脂股份有限公司製造），製成目標 之聚酿亞胺組成物。 ^ [實施例4] 相對於實施例1中所獲得之聚醯亞胺化合物溶液之固 體成分100重量份，添加10重量份之重氮萘醌感光劑 (4NT-300 ’東洋合成工業（股）製造）、以及5重量份之 ❹ 環氧樹脂（jER807，日本環氧樹脂股份有限公司製造）， 製成目標之聚酿亞胺組成物Q [比較例1 ] 相對於實施例1中所獲得之聚酿亞胺化合物溶液之固 體成分100重量份，添加10重量份之重氮萘醌感光劑 (4NT-3G0，東洋合成卫業（股）製造）、以及2重量份之 環氧樹脂UER807’日本環氧樹脂股份有限公司製造）， 製成目標之聚醯亞胺組成物。 [比較例2] 17 200944563 相對於實施例3中所獲得之聚醯亞胺化合物溶液之固 體成分100重量份，添加1〇重量份之重氮蔡醒感光劑 (4NT-300,東洋合成工業（股）製造）、以及2重量份之 環氧樹脂（jER807，曰本環氧樹脂股份有限公司製造）， 製成目標之聚醯亞胺紐成物。 (顯影性之確認） 將實施例1至實施例4、以及比較例i或比較例2之聚 醯亞胺組成物，於預先經過相當於〇々瓜之化學研磨處理 的銅泊之單面上塗佈為1〇# m，於8〇β(：下使其乾燥1〇分鐘。❹ 繼而’經由解析度評價用之正型光罩（3〇{^m/3〇〇〆 m之線與間隔（line and space )圖案），利用超高壓水銀燈 X 2500 mJ/cm之累计光量進行曝光，浸潰於氫氧化鈉3 wt%之贼水溶液中，其後於贼之溫水中浸潰2分鐘， 藉此進行鹼性顯影。其後，以蒸餾水充分清洗，使其乾燥， 元成一系列之顯影步驟。顯影性之評價係根據3〇〇以爪/ // m之線與間隔開口時之浸潰最小時間、及將浸潰時間設為 60秒時的線與間隔之開口狀態來評價。將結果示於表i中。❹ 實施例1至實施例4、以及比較例！或比較例2之聚醯 亞胺組成物如表1所示，均可於4〇秒以内鹼性顯影。實施 例4中，將浸潰時間設至6〇秒時，可觀察到曝光部外之開 口，因此作業性差。對浸潰時間進行研究之結果可知，較 理想為40秒以内。 18 200944563 【1^1 比較例2 45.9 54.1 60 wt% ο ο <Ν 35秒 開口 高於1%且 <5%以下 有變色 比較例1 36.7 63.3 65 wt% Ο ο CS 40秒 開口 高於1%且 <5%以下 有變色 實施例4 36.7 63.3 65 wt% ο ο ι〇 20秒 膜劣化 0.1%以下 無變色 實施例3 〇 45.9 «〇 60 wt% ο Τ"Μ ο (Ν 35秒 開口 0.1%以下 無變色 實施例2 v> σ\ 38.8 61.2 65 wt% ο ο r*H (Ν 35秒 D 5? 0.1%以下 無變色 實施例1 ο 36.7 63.3 65 wt% ο «"Η ο <Ν 40秒 D 0.1%以下 無變色 DSDA BSDA X-22-9409 總單體中之X-22-9409之重量比率 聚醢亞胺樹脂 4ΝΤ-300 jER807 最小浸潰時間 60秒 200°C烘烤開始時之氧濃度 200°C烘烤後之外觀 酸二酐單體（mol%) ^ fS * / 、 i c . g 1 i- 娶 1 感光性樹脂組成（重量份） > 40°C 聚醞亞胺 μ A Jt nr 玲 f 3 ^ 5 i- 顯影評價 3%NaOHaq 跻玉W 60_6-ζ(ΝΙ-χ 铢 vasOQw +令噠绪 M : z* f4i3w 猶'*· fe u 溆 s 岔荦#|. WO/OOUI 001 嫦钵一:璨 ^?令噠鸽4案：1* 200944563 (開口部之變色之確認） 將實施例1之聚醯亞胺組成物，於預先經過相當於〇 3 之化學研磨處理的銅箔之單面上塗佈成10以 ^ 於8〇 。(：下使其乾燥10分鐘。繼而，經由正型光罩，利用超高壓 水銀燈以25〇0 mJ/cm2之累計光量進行曝光，浸潰於氣氧化 鈉3 wt%之40°C水溶液中，其後於40。(：之溫水中浸潰2八 鐘，藉此進行鹼性顯影。圖案形成後，將銅箔投入至情性 烘箱（inert oven)DN410I( Yamato Scientific(股）製造）中，Butyl-4-phenylphenyl)propanol]oxime (CDA-10), when used in a flexible wiring board, prevents deterioration of the resin of the polyimide composition in contact with the metal. Examples of the rust preventive agent other than CDA-10 include bismuth bismuth phthalate which is a ruthenium-based rust preventive agent, and 3-(an o-hydroxyphenyl fluorenyl group as a triazole-based rust preventive agent. Amino-1,2,4-triazole, etc., but is not limited thereto. The flexible wiring board manufactured by the method of the present invention is coated on the substrate 2 so as to cover the conductor 4 formed of a specific pattern on the substrate 2 by a known coating method. The polyamidene composition of the compound is dried to evaporate the solvent to thereby coat the amine layer 3 (unhardened state). After the polyimine layer 3 is formed, as shown in Fig. 2, it is taken from the soil of the polyimine layer 3, and the photomask irradiated by the light to be removed is exposed. * Exposure is performed on the early layer 5. By exposure, the sensitizer in the polyimide layer 3 is subjected to 晛***W <structural change' to improve the alkali solubility of the exposed portion. And, as shown in the figure, the exposed portion is immersed in the test solution (the conductor of the positive pattern-substrate 2 is removed:: one of the two specific patterns is partially exposed. 13 200944563 After the pattern is formed, For example, a state of extreme oxygen deficiency in which the oxygen concentration around the heated flexible wiring board 1 is 1 vol% or less is preferably an oxygen-deficient state of 0.1 vol% or less by using an inert gas such as nitrogen or helium. The oxygen concentration can be measured by a galvanic cell type combustion exhaust gas analyzer. After the oxygen concentration is 1 vol% or less, the crosslinking agent and polypyrene are heated to the polyimine layer 3. The temperature at which the amine compound reacts, whereby the polyimine compound is crosslinked by the crosslinking agent in the polyimide layer 3, and the polyimine layer 3 is made into a hardened state. In the present invention, the hardened state The state in which the crosslinking agent is crosslinked by heating the polyimine layer, the so-called unhardened state means a state in which the hardened state has not yet been reached. By the heating, the oxygen concentration is higher than 1 V〇1 In the case of %, due to the influence of surrounding oxygen' Only the exposed surface of the conductor 4, and the interface between the crucible 4 and the polyimide layer 3 is also discolored by oxidation. Further, if the discoloration is removed by, for example, sulfuric acid-hydrogen peroxide or the like, the conductor 4 and the polyimine are used. A gap is formed at the interface of the layer 3. As described in the present invention, the flexible wiring board is heated by an extremely anoxic atmosphere having an oxygen concentration of less than 1%, due to oxygen penetrating the polyimide. The oxidation of the conductor 4 caused by the layer is also suppressed, so that discoloration of the exposed surface of the conductor 4 can be prevented, and discoloration at the interface between the conductor 4 and the polyimide layer 3 can be prevented. Further, by making the oxygen concentration It is more preferable to reduce the oxidation of the conductor 4 substantially 〇1 vol% or less. Previously, an inert gas such as nitrogen gas was introduced into the heating chamber of the flexible wiring board to reduce the oxygen concentration in the chamber. When the oxygen concentration in the reservoir is ι vol% or less, it is necessary to have a conventional gas inert gas introduction amount of about several times. For example, 'the volume in the reservoir is 90 to 100. Set to preferably 8·5 L/min and 3G points More preferably, it is 12 L/min and more than 3 minutes. Thus, in the method of manufacturing a flexible wiring board of the present invention, the post-lighting developability can form a specific pattern and prevent the exposed conductor from being oxidized. And discoloration. In particular, even if the polyaniline layer having a high oxygen permeability of the monomer having the oxalate skeleton which is dried by the above structure 4 i is used, the 氧 can be made to have an oxygen concentration of i VGl % or less, to prevent discoloration of the exposed surface of the conductor and the interface between the conductor and the polyimide layer. Therefore, even after riding without patterning, there is no floating interface between the guide and the polyimide layer. The plating solution can be prevented from flowing between the polyimide layer and the conductor. Therefore, the wiring board manufactured by the method can be used for electronic parts, and the electronic parts with high reliability can be provided. [Examples; 1 (Production of Polyanilin Composition) [Example 1] 137.47 g (100.48 mmol) of X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a decanediamine The iBSig (purity of 99.5%, 58, 26 mm 〇 1) BSDA was put into a 500 nU four-port separable flask equipped with a n-gram, and the N-methylpyrrole of 5 § was used under a nitrogen atmosphere. The ketone was completely dissolved. Thereafter, the "purity of 99.7%, 160.33 mmol" was added, and after 8 hours of the 8th generation (4), 70 ml was added to remove the ruthenium condensed water. The boiling agent toluene was stirred in an oil bath at 18 (TC for 5 hours, and kept at reflux. The obtained 15 200944563 target compound was added with respect to 100 parts by weight of the solid component of the above obtained polyamidene compound solution, and 10 was added. Parts by weight of diazonaphthoquinone sensitizer (4NT 3〇〇, manufactured by Toyo Synka Kogyo Co., Ltd.), and 2 parts by weight of bisphenol F type epoxy resin as crosslinker (jER807, limited share of Epoxy Epoxy Resin) The company manufactures 'a target polyimine composition. [Example 2] 143.34 g (104.78 mmol) was used as a crucible. Alkyldiamine X-22-9409 C manufactured by Shin-Etsu Chemical Co., Ltd.), 18 71 g (purity of 99.5%, 06.41 mmol) of BSDA was placed in a 500 ml four-neck separable flask equipped with Dean-Stark. It was completely dissolved with 229 5 g of N-methylpyrrolidone under a nitrogen atmosphere. Thereafter, 58.45 g (purity: 99.7%, 162.65 mmol) of DSDA was added and the solution was taken at 80 ° C. After mixing for 2 hours, 70 ml of an azeotropic toluene for removing the hydrazide-condensed water was added in an oil bath at 180° (: stirring for 5 hours, keeping it under reflux to obtain a target. 100 parts by weight of the obtained solid component of the polyimine compound solution, 10 parts by weight of a diazonaphthoquinone sensitizer (4ΝΤ-300, manufactured by Toyo Synka Kogyo Co., Ltd.), and 2 parts by weight of epoxy resin (jER807 'manufactured by Nippon Resin Co., Ltd.) to prepare a target polyimine composition. [Example 3] 106.41 g (77.78 mmol) was used as X-22-9409 of Shixioxydiamine ( Shin-Etsu Chemical Co., Ltd.), 25.72 g (purity of 99.5%, 91.30 16 200944563 mmo The BSDA of l) was placed in a 500 ml four-neck separable flask equipped with Dean-Stark, and completely dissolved with 256.5 g of N-methylpyrrolidone under a nitrogen atmosphere. Thereafter, 61 37 g (purity of 99 7%, 170.77 mmol) of DSDA was added, and after stirring at 8 (TC for 2 hours, 7 〇ml of azeotrope toluene for removing hydrazide-condensed water was added. The mixture was stirred at 80 ° C for 5 hours in an oil bath, and kept under reflux to obtain a target product. 10 parts by weight of diazonaphthoquinone was added to 100 parts by weight of the solid component of the polyimine compound solution obtained above. A sensitizer (4NT-300, manufactured by Toyo Synka Kogyo Co., Ltd.) and 2 parts by weight of epoxy resin (jER807, manufactured by Nippon Epoxy Resin Co., Ltd.) were used to prepare a target polyimine composition. ^ [ Example 4] 10 parts by weight of a diazonaphthoquinone sensitizer (4NT-300 'Toyo Synthetic Industrial Co., Ltd.) was added to 100 parts by weight of the solid content of the polyimine compound solution obtained in Example 1. And 5 parts by weight of oxime epoxy resin (jER807, manufactured by Nippon Epoxy Resin Co., Ltd.), the target polyiminoimine composition Q [Comparative Example 1] Compared with the polystyrene obtained in Example 1 100 parts by weight of the solid component of the imine compound solution, 10 parts by weight of diazonaphthoquinone sensitizer (4NT-3G0, manufactured by Toyo Synthetic Industries Co., Ltd.), and 2 parts by weight of epoxy resin UER807' manufactured by Nippon Epoxy Co., Ltd.) Yttrium imide composition. [Comparative Example 2] 17 200944563 To 100 parts by weight of the solid content of the polyimine compound solution obtained in Example 3, 1 part by weight of diazo-cai sensitizer (4NT-300, Toyo Seiki Co., Ltd.) was added. (manufacturing), and 2 parts by weight of epoxy resin (jER807, manufactured by Sakamoto Epoxy Co., Ltd.), to make the target polyimine complex. (Confirmation of developability) The polyimine compositions of Examples 1 to 4 and Comparative Example i or Comparative Example 2 were subjected to a single surface of copper borobin which was subjected to chemical polishing treatment in advance. It is coated as 1〇# m, and dried at 8〇β(:1 for 1 minute. ❹ Then 'for positive evaluation of the mask by resolution (3〇{^m/3〇〇〆m line and The line and space pattern is exposed by using the accumulated light amount of the ultrahigh pressure mercury lamp X 2500 mJ/cm, immersed in a 3 wt% aqueous solution of sodium squid, and then immersed in the warm water of the thief for 2 minutes. The alkali development was carried out by this, and then it was sufficiently washed with distilled water to be dried, and the product was subjected to a series of development steps. The evaluation of the developability was based on the immersion of the 3 〇〇 claw//m line and the opening. The minimum time and the state of the opening of the line and the interval when the immersion time was 60 seconds were evaluated. The results are shown in Table i. 实施 Example 1 to Example 4, and Comparative Example! or Comparative Example 2 The quinone imine composition can be alkaline developed within 4 sec seconds as shown in Table 1. In Example 4, the immersion time was When the opening is outside the exposure portion, the workability is poor, and the results of the study on the immersion time are preferably within 40 seconds. 18 200944563 [1^1 Comparative Example 2 45.9 54.1 60 wt% ο ο < Ν 35 seconds opening is higher than 1% and < 5% or less has color change Comparative Example 1 36.7 63.3 65 wt% Ο ο CS 40 seconds opening is higher than 1% and <5% or less is discolored Example 4 36.7 63.3 65 wt% ο ο ι 〇 20 seconds film deterioration 0.1% or less without discoloration Example 3 〇 45.9 «〇60 wt% ο Τ"Μ ο (Ν 35 seconds opening 0.1% or less without discoloration Example 2 v> σ\ 38.8 61.2 65 wt% ο ο r*H (Ν 35 seconds D 5? 0.1% or less without discoloration Example 1 ο 36.7 63.3 65 wt% ο «"Η ο <Ν 40 seconds D 0.1% or less without discoloration DSDA BSDA X -22-9409 Weight ratio of X-22-9409 in total monomer Polyimide resin 4ΝΤ-300 jER807 Minimum impregnation time 60 seconds 200°C Oxygen concentration at the beginning of baking 200°C Appearance after baking Acid dianhydride monomer (mol%) ^ fS * / , ic . g 1 i- 娶1 photosensitive resin composition (parts by weight) > 40 ° C polyimine μ A Jt nr f 3 ^ 5 i- Development evaluation 3% NaOHaq 跻玉W 60_6-ζ(ΝΙ-χ 铢vasOQw +令哒绪 M : z* f4i3w 犹'*· fe u 溆s 岔荦#|. WO/OOUI 001 嫦钵一:璨^?令哒鸽4: 1* 200944563 (Confirmation of discoloration of the opening) The polyimine composition of Example 1 was previously subjected to a chemically polished copper foil equivalent to 〇3. Apply 10 on one side to 8 〇. (: Let it dry for 10 minutes. Then, through a positive-type mask, use an ultra-high pressure mercury lamp to expose the accumulated light amount of 25 〇 0 mJ/cm 2 , and immerse it in a 40 ° C aqueous solution of 3 wt % of sodium oxyhydroxide. Thereafter, it was immersed in 40% of warm water for 2 hours to perform alkaline development. After the pattern formation, the copper foil was placed in an inert oven DN410I (manufactured by Yamato Scientific Co., Ltd.).
❹ 以強制送風循環方式’將氮氣以15 L/min導入至庫内（容 積為95 L ) ’將庫内溫度設為40。〇且保持3〇分鐘。利用燃 燒排氣分析儀（TESTO-325M，Testo股份有限公司製造） 來測定此時庫内之氧濃度，結果為〇 5 v〇1%。經過3〇分鐘 後，以14分鐘自40°C升溫至2〇0<t。此時庫内之氧濃度為 0.1 vol%以下。然後，繼續導入氮氣，使庫内之氧濃度保持 為0.1 vol%以下，於該狀態下以2〇〇<>c加熱i小時放置冷 卻。將該溫度變化及庫内之氧濃度之時間變化示於圖4中。 對自庫内取出之銅猪以目視加以確認，結果如圖5所示， 未確認到銅箔之露出面有變色。此於實施例2至4之聚酿 亞胺組成物的情況下亦為相同之結果。 作為比較’將導入至庫内之氮氣之流量設為3 L/min， 以與上述相同《方式控制庫内之溫度而進行加熱處理後， 確遇到加熱後之銅f|之露出面之變色。投人至惰性洪箱中 者係'使用與上述變色之確認中所使用者相同地於聚酿亞 胺層上形成有圖案之鋼箔。將該溫度變化及庫内之氧濃度 20 200944563 之時間變化示於圖4中。放置冷卻後，對自庫内取出之銅 泊以目視加以確認’結果如圖6所示，銅箔之露出面變色 為象色。將該銅箔之剖面示於圖7中。如圖7所示，可於 銅4與聚醯亞胺層之界面確認到變色域（不明物）^對該 變色域進行元素分析’結果檢測出銅與氧，因此可知該變 色域經氧化。 如圖4所示’藉由在達到交聯劑與聚酿亞胺化合物反 應之溫度即200 C之前使庫内之氧濃度成為〇〗v〇1%以下， © 可防止銅箔之變色以及銅箔與聚醯亞胺層之界面之變色， 相對與此’即便庫内之氧濃度高於1 v〇1%且為5 ν〇ι%以 下’降溫至低於交聯劑與聚酿亞胺化合物之反應溫度的溫 度為止氧濃度亦不會降低至丨v〇1%w下’結果可知’銅箱 * 與聚酿亞胺層之界面經氧化，確認為變色域。該結果於將 相對於總單體重量之矽氧烷二胺量改變的實施例2至4之 聚酿亞胺組成物的情況下亦相同，若考慮到顯影性，則相 對於總體之單體重量，矽氧烷二胺較佳為55以％以上且為 72 wt/。以下’更佳為6〇 wt%以上且7〇 wt%以下。 【圖式簡單說明】 圖1係表不利用本發明之方法，將聚醯亞胺組成物塗 佈於導體上之狀態的剖面圖。 圖2係表示利用本發明之方法經曝光之狀態的剖面圖。 圖3係表不利用本發明之方法進行鹼性處理後之狀態 的剖面圖。 21 200944563 圖4係表示氧濃度與溫度之時間變化的圖。 圖5係表示於氧濃度為1 v〇1%以下之環境氣氛下進行 加熱之可撓性配線板之銅箔露出面之狀態的照片。 圖6係表示於氧濃度為高於1 vol%之環境氣氛下進行 加熱之可撓性配線板之銅箔露出面之狀態的照片。 圖7係表示圖6所示之可撓性配線板之變色域附近之 剖面的照片。 【主要元件符號說明】 1 可撓性配線板 2 基材 3 聚醯亞胺層 4 導體 5 光罩層导入 Introduce nitrogen into the reservoir at a rate of 15 L/min (with a volume of 95 L) in a forced air circulation mode to set the internal temperature to 40. And keep it for 3 minutes. The oxygen concentration in the chamber at this time was measured by a combustion exhaust gas analyzer (TESTO-325M, manufactured by Testo Co., Ltd.) and found to be 〇 5 v 〇 1%. After 3 minutes, the temperature was raised from 40 ° C to 2 〇 0 lt; t in 14 minutes. At this time, the oxygen concentration in the reservoir is 0.1 vol% or less. Then, nitrogen gas was continuously introduced to maintain the oxygen concentration in the reservoir at 0.1 vol% or less, and in this state, it was heated by 2 Torr <>c for 1 hour to be cooled. The temperature change and the time change of the oxygen concentration in the reservoir are shown in Fig. 4. The copper pigs taken out from the library were visually confirmed. As a result, as shown in Fig. 5, it was not confirmed that the exposed surface of the copper foil was discolored. The same results were obtained in the case of the polyaniline compositions of Examples 2 to 4. As a comparison, the flow rate of the nitrogen gas introduced into the reservoir was set to 3 L/min, and after the heat treatment was performed in the same manner as described above, the exposed surface of the exposed copper f| . In the case of the person who has been thrown into the inert flood container, a pattern of steel foil is formed on the polyimide layer in the same manner as the user of the above-mentioned color change confirmation. The time variation of this temperature change and the oxygen concentration in the reservoir 20 200944563 is shown in Fig. 4. After standing to cool, the copper pouch taken out from the library was visually confirmed. As a result, as shown in Fig. 6, the exposed surface of the copper foil was discolored to a pictorial color. A cross section of the copper foil is shown in Fig. 7. As shown in Fig. 7, it was confirmed that the discoloration domain (unidentified object) was subjected to elemental analysis at the interface between the copper 4 and the polyimide layer, and copper and oxygen were detected. Therefore, it was found that the color gamut was oxidized. As shown in Fig. 4, the oxygen concentration in the reservoir is made 〇v〇1% or less before reaching the temperature at which the crosslinking agent reacts with the polyanilin compound, that is, 200 C, and the copper foil is prevented from discoloring and copper. The discoloration of the interface between the foil and the polyimide layer, relative to this, even if the oxygen concentration in the reservoir is higher than 1 v〇1% and less than 5 ν〇%%, the temperature is lowered to lower than the crosslinking agent and the polystyrene. The oxygen concentration at the temperature of the reaction temperature of the compound was not lowered to 丨v 〇 1% w. As a result, it was found that the interface between the copper box* and the polyaniline layer was oxidized and confirmed to be a color-changing domain. This result is also the same in the case of the polyanilin composition of Examples 2 to 4 in which the amount of the decane diamine relative to the total monomer weight is changed, and in consideration of developability, the monomer relative to the whole The weight, the oxane diamine is preferably 55% or more and 72 wt/. The following 'better is 6 〇 wt% or more and 7 〇 wt% or less. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a state in which a polyimide composition is coated on a conductor without using the method of the present invention. Figure 2 is a cross-sectional view showing a state in which exposure is performed by the method of the present invention. Fig. 3 is a cross-sectional view showing a state in which the alkaline treatment is not carried out by the method of the present invention. 21 200944563 Figure 4 is a graph showing the temporal change in oxygen concentration and temperature. Fig. 5 is a photograph showing a state in which the copper foil exposed surface of the flexible wiring board is heated in an atmosphere having an oxygen concentration of 1 v 〇 1% or less. Fig. 6 is a photograph showing a state in which the copper foil exposed surface of the flexible wiring board which is heated in an atmosphere having an oxygen concentration higher than 1 vol%. Fig. 7 is a photograph showing a cross section of the vicinity of the discoloration region of the flexible wiring board shown in Fig. 6. [Main component symbol description] 1 Flexible wiring board 2 Substrate 3 Polyimine layer 4 Conductor 5 Photomask layer