Claims (1)
1220901 申請日期： IPC分類 申請案號： 發明專利說明書 發明名稱 中文 英文 發明人 (共6人） 姓名 (中文） 4. 向富袄 5. 陳健祥 6. 吳聲昌 姓名 (英文） 4. Shiang, Fu-Ti 5. Chen, chien-Hsiang 1 6. Wu, S. C. Paul 國籍 (中英文) 4.中華民國TW 5.中華民國TW 6.中華民國TW 住居所 (中文〕 4. 新竹市科學園區力行四路2號 5. 新竹市科學園區力行四路2號 6. 新竹市科學園區力行四路2號 住居所 (英文: 4. 5. 6. 申請人 (共1人） 名稱或 姓名 (中文） 名稱或 姓名 (英文） 國籍 (中英文) 住居所 (營業所) (中文) 住居所 (營業所) (英文) 代表人 (中文） 代表人 (英文）1220901 Application Date: IPC Classification Application Number: Invention Patent Specification Invention Name Chinese English Inventor (6 in total) Name (Chinese) 4. Xiang Fuyu 5. Chen Jianxiang 6. Wu Shengchang Name (English) 4. Shiang, Fu-Ti 5. Chen, chien-Hsiang 1 6. Wu, SC Paul Nationality (Chinese and English) 4. Republic of China TW 5. Republic of China TW 6. Residence of TW (Chinese) 4. No. 2, Lixing 4th Road, Science Park, Hsinchu City 5. Hsinchu Science Park, No. 2 Lixing Fourth Road 6. Residence, Hsinchu Science Park, No. 2 Lixing Fourth Road (English: 4. 5. 6. Applicant (1 person in total) Name or Name (Chinese) Name or Name ( English) Nationality (Chinese and English) Residence (Business Office) (Chinese) Residence (Business Office) (English) Representative (Chinese) Representative (English)
1220901 一、本案已向 國家（地區）申請專利 申請日期 案號 主張專利法第二十四條第一項優先權 無 1 二、□主張專利法第二十五條之一第一項優先權： 申請案號： 無 曰期： 三、主張本案係符合專利法第二十條第一項□第一款但書或□第二款但書規定之期間 曰期： 四、□有關微生物已寄存於國外： 寄存國家 寄存機構 • 益 寄存曰期 寄存號碼 i □有關微生物已寄存於國内（本局所指定之寄存機構）： 寄存機構 寄存曰期 寄存號碼 . 鉦 □熟習該項技術者易於獲得，不須寄存。 III 11 1220901 五、發明說明Ο) 本創作 面具有良好 聚醯亞胺積 創作另係提 解芳香族四 成聚醯胺酸 害聚醯亞胺 料，添加少 胺樹脂對銅 近年來 喜好 明確 色， 的連 求都 在， 時滿 及時 度、 產品 的介 無接 與銅 ，一種 ，在這 傳統印 結，無 有賴軟 但是適 足各種 有了改 耐溶劑 ，更明 此謂聚 電層與 著劑地 箔必須 係關 接著 層板 供一 羧酸 溶液 薄膜 量之 箔之 ，由 高密 股趨 刷電 法有 性印 用的 特性 變， 性及 確的 酸亞 銅羯 將其 緊密 於一 性之 ，可 含丙 二酐 進行 ，本 該無 接著 於行 度化 勢潮 路板 效運 刷電 材料 要求 聚醯 对熱 說是 胺積 為主 結合 結合 種具有 聚醯亞 供應軟 _之極 及芳香 亞醯胺 創作還 機填充 效果。 動通訊 、輕小 流中軟 存在有 用電子 路板來 取得不 ，這情 亞胺基 特性， 軟性印 層板者 的導電 為 否則 良好高溫安定性及對銅箔表 胺樹脂，其主要係用於製作 性印刷電路板工業之用，本 性非質子溶劑系，能有效溶 族二胺，同時，有利於所合 化時溶劑之移除，並不致傷 提供一適當的無機填充材 材料即可有效提升該聚醯亞 及可攜 化及高 性印刷 無法彎 產品的 升級， 易，乃 形在聚 的材料 因而被 刷電路 簡單而 層，兩 聚醯亞 無論是 式電 效能 電路曲， 空間 其實 至於 醯亞 有其 廣泛 板所言， 層之 胺積 印刷 子產 化的 板扮 無法 等缺 這需 相關 胺基 獨特 應用 必需 包含 間或 層板 電路 品廣 趨勢 演極 被用 慽， 求早 材料 的材 的高 於電 的積 有聚 有接 之聚 板生 為大眾 已非常 重要角 於動態 這類需 已存 未能同 料漸普 機械強 子工業 層板。 酉亞胺 著劑或 醯亞胺 產過程1220901 I. This case has been applied to the country (region) for the date of patent application. The case number claims the first priority of Article 24 of the Patent Law. No. 12, claims the first priority of Article 25 of the Patent Law: Application number: No date: 3. The claim is that the period in accordance with Article 20 (1) of the Patent Law □ Paragraph 1 of the Patent Law or □ Paragraph 2 of the Patent Law: □ The relevant microorganism has been deposited in Abroad: National depository institution of depository • Benefit deposit date deposit number i □ The relevant microorganisms have been deposited in the country (the deposit institution designated by this bureau): Deposit institution deposit date deposit number. 钲 □ Those who are familiar with this technology are easy to obtain, No deposit required. III 11 1220901 V. Description of the invention 〇) This creative aspect has a good polyimide product, and the other is to extract aromatic polyisocyanuric acid, which harms polyimide, and the addition of oligoamine resin has a clear preference for copper in recent years. All the requirements are there, when the time is up, the product is not connected with copper, a kind of, in this traditional printing, there is nothing to rely on, but there are a variety of solvent resistance, more clearly this is called the polymer layer and the The agent floor foil must be a foil that is connected to the laminate for the amount of a carboxylic acid solution film. The characteristics of the high-density strand brushing method for sexual printing are changed. It can be carried out with malonic anhydride, which should not be followed by the potential of the tide board to transport the electric materials. Polypyrene is said to be an amine product. The main combination is a combination of polypyrene and aromatic. The amidine creation also has an organic filling effect. There is a useful electronic circuit board in the mobile communication, light and small streams to obtain no. In this case, the characteristics of the imide group, the conductivity of the flexible printed board is otherwise good high temperature stability and copper foil epiamine resin, which is mainly used for For the manufacture of printed circuit boards, the aprotic solvent system is effective in dissolving diamines. At the same time, it is beneficial for the removal of solvents during compounding, and it does not hurt to provide an appropriate inorganic filler material. The Polyurethane and portable and high-performance printing cannot be upgraded. It is easy, but the material that is shaped in the poly is thus simple and layered. The two Polyurethanes are both electrical circuit circuits with space. Yayou has a wide range of boards. The layered amine product printed board cannot be incomplete. This needs to be related to the unique application of the amine group. It must include the use of interlayer circuit boards. The trend is widely used. The higher accumulation of electricity than the accumulation of electricity has become very important for the public. It is dynamic and needs to be saved. Laminates. Arsenimine or arsenimide production process
第5頁 1220901 五、發明說明（2) 或是組裝完畢之產品，只稍有剝離就可能形成嚴重損 害，換言之，聚醯亞胺與銅箔之有足夠的結合力是聚醯 亞胺積層板品質的保證，也是軟性印刷電路板之品質保 證。 軟性印刷電路板的生產過程中，至少存在二處操作 會挑戰聚醯亞胺積層板的品質，一為蝕刻過程，例如將 部份銅箔蝕除，留下電傳導線圖，當蝕刻完畢兩層之間 有應力產生時就會形成變形，若聚醯亞胺積層板之尺寸 安定性不佳，則聚醯亞胺樹脂層與導電的銅箔會發生應 力，甚至其錢膜導通孔也會受損；二為焊錫過程，電子零 件與積層板連接處以南溫將錫料融化’使之黏結’此過 程所拌隨的高溫會產生熱應力或可能會破壞其非聚醯亞 胺基的接著劑，因此，生產良好品質的聚醯亞胺積層板 必須尋求與銅箔能具有良好接著效果之聚醯亞胺樹脂， 同時也應具備有良好高溫安定性。 由於聚醯亞胺非常耐高溫，其成形或操作很困難， 因此，耐高溫的聚醯亞胺樹脂之製備方法通常是先合成 聚醯胺酸前驅體，以聚醯胺酸前驅體成形或操作，然後 以高熱處理聚醯胺酸前驅體，使之亞醯胺化生成聚醯亞 胺，其中該聚醯胺酸前驅體之製備係由芳香族四羧酸二 酐及芳香族二胺在極性非質子溶劑中反應合成。 一般而言，聚醯亞胺之性質取決於所使用的四羧酸 二酐及二胺，包括其取代官能基或其立體結構等，有些 特性仍難解釋，因此嚐試改變四羧酸二酐及二胺之組Page 5 1220901 V. Description of the invention (2) or the assembled product may cause serious damage with only a little peeling, in other words, the sufficient bonding force between polyimide and copper foil is polyimide laminated board Quality assurance is also the quality assurance of flexible printed circuit boards. During the production of flexible printed circuit boards, there are at least two operations that will challenge the quality of polyimide laminates. One is the etching process, such as etching away part of the copper foil, leaving a pattern of electrical conduction lines. When there is stress between the layers, deformation will occur. If the polyimide laminate has poor dimensional stability, the polyimide resin layer and the conductive copper foil will be stressed, and even the money film vias will be formed. Damage; the second is the soldering process. The solder is melted to the south of the junction between the electronic part and the laminate to 'bond it'. The high temperature followed by this process will generate thermal stress or may damage its non-polyimide-based bonding. Therefore, to produce a good quality polyimide laminate, it is necessary to find a polyimide resin that can have good adhesion with copper foil, and it must also have good high temperature stability. Because polyimide is very resistant to high temperature, its forming or operation is difficult. Therefore, the preparation method of high temperature resistant polyimide resin is usually to first synthesize a polyamic acid precursor, and use the polyamino acid precursor to form or operate. Then, the polyfluorinated acid precursor is subjected to high heat treatment to amidate to form a polyfluorinated imine. The preparation of the polyfluorinated acid precursor is based on the aromatic tetracarboxylic dianhydride and the aromatic diamine. Synthesis by reaction in aprotic solvents. In general, the properties of polyfluorene imine depend on the tetracarboxylic dianhydride and diamine used, including its substituted functional group or its stereo structure. Some characteristics are still difficult to explain, so try to change the tetracarboxylic dianhydride and Diamine group
第6頁 1220901 五、發明說明（3) 合，或更常見的是組合二個或二個以上的芳香族二胺來 尋求所欲之聚醯亞胺特性；至於極性非質子溶劑主要係溶 解四羧酸二酐及二胺及其所反應生成的聚醯胺酸，形成 聚醯胺酸溶液，聚醯胺酸溶液是進一步反應生成聚醯亞 胺的原料，其性質須配合所欲形成聚醯亞胺之形式，因 此聚醯胺酸溶液之黏度、分子量或固含量乃至於溶劑移 除速度或溫度都是考慮重點。 本質上，聚醯亞胺樹脂對銅箔之接著效果並非很 好，或尺寸安定性不理想，因而有為數眾多的專利文獻 揭露以經特別官能基修飾過的單體合成聚醯亞胺，或加 入其它單體形成共聚合之聚醯亞胺，按，財團法人工業 技術研究院，台灣專利2 3 8，3 1 8即揭露以引入含馬來醯亞 胺的單體到聚醯胺酸進行共聚合，雖然其結果可形成π 無膠式”聚醯亞胺積層板，但如此方法可能會造成員出較 昂貴代價以取得特別官能基修飾過的單體，或因添加較 不耐高溫的有機成份而犧牲聚醯亞胺部份耐高溫特性， 然而本創作未添加其它有機成份或使用特別官能基修飾 過的單體，不必犧牲聚醯亞胺樹脂耐高溫或耐溶劑特性； 其次，該方法須操作兩層的塗佈亦明顯較本創作複雜。 本創作之聚醯亞胺積層板對於前述之先前技藝之缺 點與不足之問題，有相當進步及改良的優點。 本創作之主要目的係提供一種有良好高溫安定性及 對銅箔表面有良好接著性之聚醯亞胺樹脂，可適用於各 種軟性印刷電路板之製作。Page 6 1220901 V. Description of the invention (3) Combine, or more commonly, combine two or more aromatic diamines to find the desired polyimide characteristics; as for the polar aprotic solvent, it is mainly dissolved in four. Carboxylic dianhydride and diamine and the polyfluorinated acid formed by the reaction form a polyfluorinated acid solution. The polyfluorinated acid solution is a raw material for further reaction to form polyimide, and its properties must be matched with the desired polyfluorene. In the form of imine, the viscosity, molecular weight or solid content of the polyamic acid solution, and even the speed or temperature of solvent removal are all important considerations. In essence, polyimide resins do not adhere well to copper foil, or their dimensional stability is not ideal. Therefore, a large number of patent documents disclose the synthesis of polyimide from monomers modified with special functional groups, or Adding other monomers to form the copolymerized polyimide, according to the Institute of Industrial Technology, Taiwan Patent 2 3, 3 1 8 is disclosed to introduce the maleimide-containing monomer to the polyimide Copolymerization, although the result can form π glue-free "polyfluorene imide laminates, but this method may result in more expensive costs to obtain monomers modified with special functional groups, or because of the addition of less high temperature resistant Organic ingredients are sacrificed to the high temperature resistance of polyimide. However, this work does not add other organic ingredients or monomers modified with special functional groups. It is not necessary to sacrifice the high temperature or solvent resistance of polyimide resins. Second, the The method requires two layers of coating to be applied, which is also significantly more complicated than this one. The polyimide laminates for this work have considerable progress and improvement over the disadvantages and deficiencies of the previous techniques. The main object of the present Creation system provides a good high temperature stability and has a good adhesive property of the copper foil surface of the polyimide resin, it can be applied to various kinds of flexible printed circuit board production.
第7頁 1220901 五、發明說明（4) 本創作之另一目的係提供一種無膠式的雙層聚醯亞 胺積層板，由於無中間之接著劑層，因此無習用以環氧 樹脂或壓克力系樹脂作為接著劑層致不利於印刷電路板 的高溫製程的問題，另，因無中間之接著劑層，可得較 薄之聚臨亞胺積層板。 本創作之另一目的係提供一種尺寸安定性較高的聚 酿亞胺積層板，其有較高的尺寸安定性者對於軟性印刷 電路板之設計及製造都很重要，尤其對於導通孔對位之 精密要求。 本創作之另一目的係提供一種有較高剝離強度的聚 醯亞胺積層板，其有較高剝離強度者所製得之印刷電路 板有較佳品質，有利於軟性印刷電路板應用之可靠性。 本創作之另一目的係提供一種有較好平坦度的聚醯 亞胺積層板，其積層板成形時有平坦外觀且對於蝕刻製 程後也不產生捲曲，可以滿足軟性印刷電路板製程之嚴 格要求。 本創作之另一目的亦提供一種製備聚醯胺酸溶液及以π 塗佈到銅箔”方式製造聚醯亞胺積層板之方法，此方法可 以免除鍍金屬膜之電鍍程序所發生之生產成本及環保的 困擾。 本創作一種聚S&亞胺積層板，包含一聚酸亞胺層及一 銅箔層，其中該聚醯亞胺積層板係由塗佈聚醯胺酸前驅 體到銅箔表面，然後以2 5 0 ° C以上高溫使之亞醯胺化， 同時，聚醯胺酸轉化為聚醯亞胺樹脂，且在銅箔表面形Page 7 1220901 V. Description of the invention (4) Another purpose of this creation is to provide a non-adhesive double-layer polyimide laminated board. Because there is no intermediate adhesive layer, it is not customary to use epoxy resin or press. Acrylic resin as the adhesive layer causes problems in the high-temperature process of printed circuit boards. In addition, because there is no intermediate adhesive layer, a thinner polyimide laminate can be obtained. Another purpose of this creation is to provide a polyimide laminate with high dimensional stability. Those with high dimensional stability are important for the design and manufacture of flexible printed circuit boards, especially for the alignment of vias. Precision requirements. Another purpose of this creation is to provide a polyimide laminate with higher peel strength. The printed circuit board produced by those with higher peel strength has better quality, which is conducive to the reliability of flexible printed circuit board applications. Sex. Another purpose of this creation is to provide a polyimide laminated board with better flatness. The laminated board has a flat appearance during forming and does not cause curl after the etching process, which can meet the strict requirements of the flexible printed circuit board manufacturing process. . Another purpose of this creation is also to provide a method for preparing polyamic acid solution and coating polyimide laminates with π coating on copper foil. This method can eliminate the production cost incurred in the plating process of metal plating. This is a poly S & imide laminate, which contains a polyimide layer and a copper foil layer, where the polyimide laminate is coated with a polyimide precursor to copper foil. Surface, and then imidized at a temperature of more than 250 ° C. At the same time, polyamic acid is converted into polyimide resin, and the shape of copper foil on the surface
第8頁 1220901 五、發明說明（5) 成一聚醯亞胺薄膜。於本創作中用以製造聚醯亞胺積層 板之聚醯胺酸，係由芳香族四羧酸二酐與芳香族二胺於 極性非質子溶劑中合成反應而成。 本創作中所可用於製備聚醯亞胺樹脂之芳香族四羧 酸二酐有聯二苯四羧酸二酐（3，3 *， 4,4*-Biphenyltetracarboxylicdianhydride)，均苯四 酸二酐（Pyromellitic dianhydride)，二苯 g同四魏酸二 酐（Benzophenonetetracarboxylic dianhydride ， BTDA)，二苯鱗四魏酸二 Sf(4，4*-oxydiphthalic anhydride)，二苯基石夙四竣酸二酐（3，3氺， 4， 4*-diphenylsulfonetetracarboxylic dianhydride) ，二胺基二苯甲烧 (b i s(3，4-dicarboxyphenyl) methane dianhydride) ，萘基四酸二酐（1，2，5，6- naphthalene tetracarboxy 1 i c dianhydride)以及其組合 。 本創作中所可用於製備聚醯亞胺樹脂之芳香族二胺有 二胺基二苯醚（oxydianiline) ，對苯二胺（ p-phenylenediamine) ，二苯胺甲烧 (N,N,-diphenylmethylenediamine) ，二胺基二苯酮 (diaminobenzophenone) ，二胺基二苯基石風 (d i am i nod i pheny 1 su 1 f one ) ，二萘二胺（1 ，5*-naphthalene diamine) ，二胺基二苯硫醚 (4，4氺一diamino diphenyl s u 1 f i d e )以及其組合。Page 8 1220901 V. Description of the invention (5) A polyimide film is formed. The polyamidic acid used in the production of polyimide laminates in this work is a synthetic reaction of an aromatic tetracarboxylic dianhydride and an aromatic diamine in a polar aprotic solvent. The aromatic tetracarboxylic dianhydrides that can be used in the preparation of polyimide resins are biphenyltetracarboxylic dianhydride (3,3 *, 4,4 * -Biphenyltetracarboxylicdianhydride), pyromellitic dianhydride ( Pyromellitic dianhydride), diphenyl g isotetraweilic acid dianhydride (BTDA), diphenyl scale tetraweiric acid dianhydride Sf (4,4 * -oxydiphthalic anhydride), diphenylcarboxylic acid dianhydride 3 氺, 4, 4 * -diphenylsulfonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, naphthalene tetracarboxylic dianhydride (1,2,5,6-naphthalene tetracarboxy 1 ic dianhydride) and combinations thereof. The aromatic diamines that can be used in the preparation of polyimide resins include diamine diphenyl ether (oxydianiline), p-phenylenediamine, and diphenylamine (N, N, -diphenylmethylenediamine). , Diaminobenzophenone, diam i nod i pheny 1 su 1 f one, dinaphthalene diamine (1,5 * -naphthalene diamine), diamine diamine Phenylsulfide (4,4 氺 -diamino diphenyl su 1 fide) and combinations thereof.
1220901 五、發明說明（6) 選擇各種不同芳香族四羧酸二酐或芳香族二胺之組合 進行反應，其所製備之聚醯亞胺樹脂會有不同的物理特 性，例如高溫安定性，熱膨脹係數，玻璃轉移溫度，對 金屬之接著性，尺寸安定性等，其不同特性之結果將 影響其所製成之聚醯亞胺樹脂之應用範圍，亦即影響其 所製成之聚醯亞胺積層板使用情形，同時也可能影響其 聚醯亞胺積層板生產製程，這些影響因素有時無法兼 顧，對於商業用途及生產程序之不同需求，製備聚醯亞 胺時通常會加入其他成份來修飾其中某項特性，例如以 特定基團或分子修飾其中部份高分子單體，用以增進聚 醯亞胺對銅箔之接著效果，或用以改善其尺寸安定性， 此方法因加入有機成份，通常會降低一些其它重要物理 特性，而且利用此方法前題是需尋求較不普遍之特別修 飾高分子單體，生產成本自然相對提高。 本創作之方案是先尋求適當的芳香族四羧酸二酐或 芳香族二胺之組合，係為兼顧所製成聚醯亞胺樹脂之特 性及容易取得之高分子單體，實施例中以聯二苯四羧酸 二酐/二苯酮四羧酸二酐以及對苯二胺/二胺基二苯醚之 組合所製成之聚醯亞胺樹脂享有良好的耐高溫特性及理 想的電氣特性，該項耐高溫特性及電氣特性對於聚醯亞 胺應用於印刷電路板用途時尤其重要，同時，本實施例 中合成聚醯亞胺所使用之各項高分子單體皆係極為普遍 之工業原料，並且其所合成之聚醯亞胺之各種性質亦明 確，因此，此等聯二苯四羧酸二酐/二苯酮四羧酸二酐以1220901 V. Description of the invention (6) Various kinds of aromatic tetracarboxylic dianhydride or aromatic diamine are selected for the reaction. The polyimide resin prepared by them has different physical characteristics, such as high temperature stability and thermal expansion. Coefficient, glass transition temperature, adhesion to metal, dimensional stability, etc. The results of different characteristics will affect the application range of the polyimide resin made by it, that is, the polyimide made by it The use of laminates may also affect the production process of polyimide laminates. These factors can sometimes not be taken into account. For different needs of commercial applications and production processes, other ingredients are usually added to modify polyimide. One of the properties, such as modifying some of the polymer monomers with specific groups or molecules, to improve the adhesion of polyimide to copper foil, or to improve its dimensional stability. This method requires the addition of organic ingredients , Usually reduce some other important physical properties, and the premise of using this method is to find a less common special modified polymer monomer, The relative cost of natural increase. The solution of this creation is to first find an appropriate combination of aromatic tetracarboxylic dianhydride or aromatic diamine, which is to take into account the characteristics of the polyfluorene imide resin and the easily available polymer monomers. In the examples, Polyimide resins made from a combination of biphenyl tetracarboxylic dianhydride / benzophenone tetracarboxylic dianhydride and p-phenylenediamine / diamino diphenyl ether enjoy good high temperature resistance and ideal electrical properties Characteristics, the high temperature resistance and electrical characteristics are particularly important when polyimide is used in printed circuit board applications. At the same time, the various polymer monomers used in the synthesis of polyimide in this embodiment are extremely common. Industrial raw materials, and various properties of the polyimide synthesized by them are also clear. Therefore, these biphenyltetracarboxylic dianhydrides / benzophenonetetracarboxylic dianhydrides are
第10頁 1220901 五、發明說明（7) 及對苯二胺/二胺基二苯醚之組合對於生產聚醯亞胺積層 板是較經濟的選擇，至於修飾其合成反應程序或其它物 理特性，則選擇以溶劑系及無機添加材料之方法進行改 良。 此外，聚驢亞胺積層板之尺寸安定性對於軟性印刷 電路板之設計及製造都很重要，尤其對於導通孔對位之 精密要求。聚醯亞胺積層板於軟性印刷電路板之製作過 程中伴有蝕刻及焊錫之程序，經過該程序聚醯亞胺積層 板會出現尺寸上的變化，此即尺寸安定性的問題，其印 刷電路板積層板導通孔之對位尤其重要，尺寸安定性不 良之聚醯亞胺積層板無法配合精密的印刷電路板設計。 另外，聚醯亞胺積層板經過蝕刻及焊錫之程序亦有可能 發生邊緣捲曲的現像，程序中的聚醯亞胺積層板若發生 邊緣捲曲往往會卡在輸送設備之入口，無法順利完成操 作。 本創作係以聯二苯四羧酸二酐/二苯酮四羧酸二酐以 及對苯二胺/二胺基二苯醚之組合為例，製備聚醯亞胺積 層板後，進而依I P C及J I S之相關檢測方法分析結果，依 實驗結果顯示，其中改變對苯二胺/二胺基二苯醚之比 例，其相對之聚醯亞胺積層板之尺寸安定性會跟著改 變，但其剝離強度則呈相反的變化，為設定聚醯亞胺積 層板之尺寸安定性與剝離強度，必須調整對苯二胺/二胺 基二苯醚之比例，取得較佳之二胺組合；雖然本創作所列 舉之實施例中，僅提示對苯二胺/二胺基二苯醚之二胺組Page 10 1220901 V. Description of the invention (7) and the combination of p-phenylenediamine / diamine diphenyl ether is a more economical choice for the production of polyimide laminates. As for the modification of its synthetic reaction process or other physical characteristics, Then the method of solvent-based and inorganic additive materials is selected for improvement. In addition, the dimensional stability of the polydonimide laminated board is very important for the design and manufacture of flexible printed circuit boards, especially for the precise requirements of the via alignment. Polyimide laminates are accompanied by a process of etching and soldering during the production of flexible printed circuit boards. After this process, the polyimide laminates will change in size. This is a problem of dimensional stability. The printed circuit The alignment of the vias of the board laminated board is particularly important, and the polyimide laminated board with poor dimensional stability cannot match the precise printed circuit board design. In addition, the polyimide laminates may undergo edge curling after the process of etching and soldering. If the polyimide laminates in the procedure have edge curls, they often get stuck at the entrance of the conveying equipment and cannot be successfully completed. This creation is based on the combination of biphenyltetracarboxylic dianhydride / benzophenonetetracarboxylic dianhydride and p-phenylenediamine / diaminodiphenyl ether as an example. According to the analysis results of related testing methods of JIS and JIS, according to the experimental results, if the ratio of p-phenylenediamine / diaminodiphenyl ether is changed, the dimensional stability of polyimide laminates will change, but the peeling The strength changes in the opposite direction. In order to set the dimensional stability and peel strength of the polyimide laminate, the ratio of p-phenylenediamine / diamine diphenyl ether must be adjusted to obtain a better diamine combination. In the listed examples, only the diamine group of p-phenylenediamine / diaminodiphenyl ether is suggested.
第11頁 1220901 五、發明說明（8) 合，但實際上，尚有其它單獨之二胺或不同二胺之組合 亦可被本創作所使用。 本創作可以各種不同芳香族四羧酸二酐或芳香族二 胺之組合進行。其中，最佳實施例之聚醯亞胺樹脂係由 聯二苯四羧酸二酐/二苯酮四羧酸二酐以及對苯二胺/二 胺基二苯醚之組合所製成，進一步說，本創作之聚醯亞 胺樹脂係以聯二苯四羧酸二酐6 0至9 0莫耳％，二苯酮四羧 酸二酐10至40莫耳％以及對苯二胺50至95莫耳％，二胺基二 苯醚5至5 0莫耳％所製成，對於如此之單體組合所製備之 聚醯胺酸可以滿足本創作製造聚醯亞胺積層板的目的要 求。 關於可被使用於本創作之極性非質子溶劑有N -甲基 咯酮（NMP)，N，N-二甲基乙醯胺（DMAc)，N，N-二甲基甲醯 胺（DMF)，丙酿1，及丁内酯（g-butyrolactone)等，該等 溶劑可以單獨或混合使用，有些混合溶劑組合的選擇是 為了完全溶解四羧酸二酐原料及二胺原料，以及能順利 於聚醯胺酸溶液進行亞醯胺化時移除所含之溶劑。 如前所述，本創作之實施例係以聯二苯四羧酸二酐/ 二苯酮四魏酸二酐以及對苯二胺/二胺基二苯醚之組合為 例製備聚醯亞胺樹脂，因此選用之溶劑急須完全溶解該 四羧酸二酐原料及二胺原料，於合成聚醯胺酸反應時若 有一成份未能完全溶解時，無法依化學計量之組成進行 反應，反應生成物之聚合物分子量也無法提高，因此傳 統合成聚醯胺酸時常為完全溶解各項單體原料，總是須Page 11 1220901 V. Description of the invention (8), but in fact, there are other separate diamines or combinations of different diamines that can also be used in this creation. This creation can be performed with a combination of various aromatic tetracarboxylic dianhydrides or aromatic diamines. Among them, the polyimide resin of the preferred embodiment is made of a combination of biphenyltetracarboxylic dianhydride / benzophenonetetracarboxylic dianhydride and p-phenylenediamine / diaminodiphenyl ether, further It is said that the polyimide resin of this creation is based on biphenyl tetracarboxylic dianhydride 60 to 90 mole%, benzophenone tetracarboxylic dianhydride 10 to 40 mole%, and p-phenylenediamine 50 to It is made of 95 mol% and diamino diphenyl ether from 5 to 50 mol%. The polyamic acid prepared from such a monomer combination can meet the requirements of the purpose of manufacturing polyimide laminates. About the polar aprotic solvents that can be used in this creation are N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF) , Propylene alcohol 1, and butyrolactone (g-butyrolactone), etc. These solvents can be used alone or in combination. Some mixed solvent combinations are selected to completely dissolve the tetracarboxylic dianhydride raw materials and diamine raw materials, and can be smoothly used in When the polyamidic acid solution is amidated, the solvent is removed. As mentioned above, the example of this creation is based on the combination of biphenyltetracarboxylic dianhydride / benzophenonetetraweilic dianhydride and p-phenylenediamine / diaminodiphenyl ether as an example to prepare polyimide. Resin, so the selected solvent is urgently required to completely dissolve the tetracarboxylic dianhydride raw material and diamine raw material. If a component is not completely dissolved during the synthesis of polyamino acid, the reaction cannot be performed according to the stoichiometric composition, and the reaction product The molecular weight of the polymer cannot be increased, so traditional synthetic polyamines are often used to completely dissolve all monomer materials.
第12頁 1220901 五、發明說明（9) 長時間攪拌溶 例即以不同之 有少量之酮類 有助於完全溶 類溶劑之含量 低，含過量此 造成溶劑揮發 加熱處理的困 之目的，本創 溶劑系，其中 酐原料及二胺 於所合成聚醯 不致於傷害聚 增加其它溶劑 於1%則無法顯 配方所合成之 值皆為1. 2dl/ 量已經很高， 醯胺酸生成的 非質子溶劑僅 其它不同之極 溶劑是丙酮者 聚醯胺酸 溶液性質以利Page 1212901 V. Explanation of the invention (9) The example of long-term stirring dissolution means that a small amount of ketones helps to completely dissolve the solvent. The content of the solvent is too low, and the purpose of excessively causing solvent volatilization and heat treatment is difficult. Wound solvent system, in which the anhydride raw material and diamine in the synthesized polyfluorene will not harm the polymerization. Adding other solvents to 1% will not show the value of the formula. The values synthesized are 1. 2dl / amount is very high Protonic solvents are the only other polar solvents which are acetone or polyamidic acid solution.
解，但終究不是理想的合成條件，本實施 溶劑系改良此困擾，成功的新溶劑系中含 溶劑，例如丙S同，該含少量酮類之溶劑系 解該四羧酸二酐原料及二胺原料，其中酮 應可達5 0重量％，惟有些酮類溶劑之沸點較 類酮類溶劑於後續之聚醯胺酸成膜過程會 太快的困擾，丙酮含量越3 0 %則會增加後續 難，若酮類溶劑含量太少亦無達成本創作 作之實施例即以N -甲基咯酮混合丙酮作為 丙酮含量約為1 5 %，可以滿足溶解四羧酸二 原料與適度的溶劑揮發速度的要求，有利 胺酸溶液進行亞醯胺化時溶劑之移除，且 醯亞胺薄膜，以含有3 0 %丙酮之混合溶劑依 之比例而降低丙ϊ同之比例，若丙_含量低 示本創作之目的功效，同時，依本創作之 聚醯胺酸溶液由其固有黏度測試所得之數 g以上，此顯示該反應形成聚醯胺酸之分子 亦即本創作之含酮溶劑系已明顯有促進聚 效果；雖然，本創作實施例中所使用之極性 提示N-甲基咯酮與丙酮之組合，實際上， 性非質子溶劑組合，只要含有部份成份的 亦可為本創作所使用。 溶液加入無機填充材可用來調整聚醯胺酸 生產製程，有時也可以增進聚醯亞胺樹脂Solution, but in the end it is not the ideal synthesis conditions. The solvent in this implementation is to improve this problem. The successful new solvent system contains solvents, such as propylene. The solvent containing a small amount of ketones is used to resolve the tetracarboxylic dianhydride raw materials and Amine raw materials, of which ketones should be up to 50% by weight. However, the boiling point of some ketone solvents is much faster than that of ketone solvents in the subsequent polyamic acid film formation process. The 30% increase in acetone content will increase It is difficult to follow up. If the ketone solvent content is too small and the cost is not reached, the example created is to use N-methylpyrrolidone mixed with acetone as the acetone content is about 15%, which can satisfy the dissolution of the tetracarboxylic acid two raw materials and a moderate solvent. The requirement of the volatilization rate is beneficial for the removal of the solvent during the imidization of the amine acid solution, and the acetonitrile film is reduced by the same proportion of the mixed solvent with a mixed solvent containing 30% acetone. Low showing the purpose and efficacy of this creation, and at the same time, the polyamine solution according to this creation is more than g by its inherent viscosity test, which shows that the molecule that forms polyamic acid by this reaction is the ketone-containing solvent system of this creation Has promoted aggregation Effect; Although, the polarity used in this creative example suggests the combination of N-methylpyrrolidone and acetone. In fact, the combination of sexual aprotic solvents, as long as it contains some ingredients, can also be used for this creative. Adding inorganic filler to the solution can be used to adjust the production process of polyamic acid, and sometimes it can improve the polyimide resin.
m 第13頁 1220901 五、發明說明（ίο) 的物性，本創作則利用加入二氧化矽粉或雲母粉至聚醯 胺酸溶液，用以增進聚醯亞胺對銅箔的接著效果。本創 作之聚醯亞胺積層板，係包含一聚醯亞胺層及一銅箔 層，其中問並無接著劑層，因此，聚醯亞胺層須對銅箔 層有良好的接著力，否則聚醯亞胺積層板於生產印刷電 路板過程中或該印刷電路板實際使用時皆可能發生剝離 情形，這是不容許發生的瑕疵。對於本創作之”無膠式” 聚醯亞胺積層板，首先要增進聚醯亞胺對銅箔的接著 力，經實驗探討結果得知聚醯亞胺樹脂添加少量之雲母 粉，發現其對於銅箔之接著力有明顯增進之效果，探其 原因應是聚醯胺酸溶液塗佈在銅箔表面後，需經2 5 0 ° C 以上的加熱亞醯胺化成聚醯亞胺樹脂層，在高溫情況下 聚醯亞胺樹脂内的雲母粉阻絕了氧氣的滲透，減少聚醯 亞胺樹脂層與銅箔間界面發生氧化，接著效果因而不致 劣化，依本創作實施例所製作之聚醯亞胺積層剝離強度 測試，皆可輕易的達到0 · 8 k g f / c m以上（J I S 6 4 7 1 - 8 · 1 )， 然而未含雲母粉之聚醯亞胺積層板則其剝離強度相對較 低，同時，依本創作實施例所製作之聚醯亞胺積層板尺 寸安定性測試，亦顯示無機填充材之添加有助於改善尺 寸安定性，其它無機填充材例如碳酸鈣粉，磷酸鈣粉， 矽酸鈣粉及二氧化矽粉亦可以有相同效果。 一般而言，應用於軟性印刷電路板之聚醯亞胺積層 板包含有聚驢亞胺的介電層與銅箔為主的導電層，兩層 之間可用接著劑將其結合為一體，亦有無接著劑層而令m page 13 1220901 V. The physical properties of the invention description (ίο). In this work, silicon dioxide or mica powder is added to the polyamic acid solution to improve the adhesion of polyimide to copper foil. The polyimide laminate of this creation consists of a polyimide layer and a copper foil layer. There is no adhesive layer. Therefore, the polyimide layer must have good adhesion to the copper foil layer. Otherwise, the polyimide laminated board may be peeled off during the production of the printed circuit board or the printed circuit board is actually used, which is an impermissible defect. For the “rubber-free” polyimide laminated board of this creation, we must first improve the adhesion of polyimide to copper foil. After experimental investigation, we know that polyimide resin adds a small amount of mica powder. The adhesion of copper foil has a significant effect. The reason is that after the polyamic acid solution is coated on the surface of the copper foil, it needs to be heated to a temperature of more than 250 ° C to form a polyimide resin layer. Under high temperature conditions, the mica powder in the polyimide resin blocks the penetration of oxygen, and reduces the oxidation of the interface between the polyimide resin layer and the copper foil, and the effect is not deteriorated. The imine laminate peel strength test can easily reach above 0.8 kgf / cm (JIS 6 4 7 1-8 · 1), but the polyimide laminate without mica powder has a relatively low peel strength. At the same time, the dimensional stability test of polyimide laminates made according to this creative example also shows that the addition of inorganic fillers helps improve dimensional stability. Other inorganic fillers such as calcium carbonate powder, calcium phosphate powder, Silicic acid Calcium powder and silica powder can also have the same effect. Generally speaking, polyimide laminates used in flexible printed circuit boards include a polydonimide dielectric layer and a copper foil-based conductive layer. The two layers can be combined into one with an adhesive. With or without adhesive layer
第14頁 1220901 五、發明說明（11) 兩層直接結合製成聚酸亞胺積層板，前者因多出一層接 著劑，積層板之厚度相對會比較厚，柔軟性也較差，且 因聚醯亞胺樹脂接著劑需較高溫處理，加工困難，因而 往往要使用環氧樹脂接著劑而犧牲高溫特性，品質上較 有問題，應用上也較受限制；後者形成層膜方法不同尚可 分為在聚醯亞胺膜上鍍金屬膜與再金屬膜上形成聚醯亞 胺膜，前者因生產過程涉及電鍍程序，過程複雜且有環 保的困擾；後者製程單純且經濟，但品質及生產不易控制 是現有的問題，理想的聚醯亞胺前驅體溶液可以確保提 高生產的良率及產量。 本創作之聚醯亞胺積層板係由塗佈聚醯胺酸前驅體 到銅箔表面，然後以3 0 0 ° C以上高溫使之亞醯胺化，同 時，聚醯胺酸轉化為聚醯亞胺樹脂，且在銅箔表面形成 一聚醯亞胺薄膜，此處之亞醯胺化溫度亦可降至2 5 0 °C， 惟其亞醯胺化時程較長，聚醯胺酸前驅體之製備係由聯 二苯四羧酸二酐/二苯酮四羧酸二酐以及對苯二胺/二胺 基二苯醚之組合，並以N -甲基咯酮與丙酮混合溶劑作為 溶劑系，並添加雲母粉，經攪拌反應形成聚醯亞胺前驅 體溶液，同時控制聚醯亞胺前驅體之固含量在1 0 %以上， 檢驗該溶液之黏度決定終止反應，通常聚醯亞胺前驅體 溶液黏度到達1 0 0 0 0 c p s即可使用來進行塗佈工作，將聚 醯胺酸前驅體均勻塗佈到銅箔表面，以漸進升溫之加熱 程序將溶劑移除，繼之，聚醯胺酸被加熱至3 0 0 °C以上使 之亞酸胺化，又因無使用其它接著劑，此亞驢胺化過程Page 14 1220901 V. Description of the invention (11) The two layers are directly combined to make a polyimide laminated board. The former has an extra layer of adhesive, the thickness of the laminated board is relatively thick, the softness is also poor, and The imine resin adhesive requires higher temperature processing and is difficult to process. Therefore, epoxy resin adhesive is often used to sacrifice high temperature characteristics. The quality is more problematic and the application is more limited. The latter can be divided into different methods for forming a film. The polyimide film is formed on the polyimide film and the polymetallic film is formed on the polyimide film. The former involves a plating process, which is complicated and environmentally difficult. The latter is simple and economical, but the quality and production are not easy to control. It is an existing problem. The ideal polyimide precursor solution can ensure the improvement of production yield and yield. The polyimide laminates created in this work are made by coating a polyamic acid precursor on the surface of copper foil, and then amidating the polyimide at a high temperature above 300 ° C. At the same time, the polyimide is converted into polyimide Imine resin, and a polyimide film is formed on the surface of the copper foil. Here, the imidization temperature of the polyimide can also be reduced to 250 ° C, but its imidization time is longer, and the polyimide precursor The preparation is based on a combination of biphenyltetracarboxylic dianhydride / benzophenonetetracarboxylic dianhydride and p-phenylenediamine / diaminodiphenyl ether, and a mixed solvent of N-methylpyrrolidone and acetone as Solvent system, adding mica powder, and stirring to form a polyimide precursor solution. At the same time, the solid content of the polyimide precursor is controlled to be above 10%. The viscosity of the solution is determined to terminate the reaction. The viscosity of the amine precursor solution reaches 1 0 0 0 0 cps, and it can be used for coating work. The polyamine precursor is evenly coated on the surface of the copper foil, and the solvent is removed by a heating process of gradually increasing temperature, followed by, Polyamic acid is heated to more than 300 ° C to make it acidified, but without using other bonding This sub amination donkey
第15頁 1220901 五、發明說明（12) 可加熱至4 5 0 °C使亞醯胺化更有效率。 為因應工業生產的方式與配合工業生產的設備，本 創作之聚醯胺酸前驅體均勻塗佈到銅箔表面之方式亦可 以自動化裝置定量供給，藉狹缝裝量塗佈至銅箔表面， 銅箔則可採用連續輸送方式接受塗佈，此方法所得塗層 厚度均勻，其塗層厚度可依定量供給量及銅箔輸送、、 而定，不受聚醯亞胺溶液之黏度影響聚醯亞胺樹脂層勺 厚度可以由聚醯醯酸前驅體供給量及銅箔輸送速而設 定，並經此設定而決定最終聚醯亞胺層之厚度，此對工 業規模的連續生產及品質控制有重大意義。 現在，配合以下實施例進一步說明本創作之結果， 但本創作不應受限於這些實施例 例一 1 70毫升N-甲基咯酮及30毫升丙酮加入反應容器中 攪拌成混合溶劑，再將對苯二胺6 · 5克（0 · 0 6莫耳）及二胺 基二苯醚6 · 5克（0 · 0 3莫耳）加入於混合溶劑中攪拌溶解 成二胺溶液，此溶解過程在低温下進行3小時使之完全溶 解。將二苯酮四羧酸二酐8.7克（0.027莫耳）及聯二苯四 羧酸二酐1 8 · 5克（0 . 0 6 3莫耳）逐漸加入二胺溶液中，反應 生成聚醯胺酸溶液，反應生成之聚醯胺酸溶液之黏度大 約為2 5 0 0 0 c p s，將聚醯胺酸溶液移出反應容器停止反 應。 前述製備之聚醯胺酸溶液均勻塗佈於銅箔表面，塗 佈聚醯胺酸溶液之厚度約0. 3毫米，將塗有聚醯胺酸溶液Page 15 1220901 V. Description of the invention (12) It can be heated to 4 50 ° C to make imidization more efficient. In order to respond to the industrial production method and the equipment compatible with industrial production, the method of uniformly coating the polyurethane precursor on the surface of the copper foil of this creation can also be quantitatively supplied by an automated device. Copper foil can be coated by continuous conveyance. The thickness of the coating obtained by this method is uniform. The thickness of the coating can be determined by the quantitative supply and copper foil conveyance. It is not affected by the viscosity of the polyimide solution. The thickness of the imide resin layer can be set by the supply of polyacrylic acid precursors and the copper foil conveying speed, and the final thickness of the polyimide layer is determined by this setting. This has industrial continuous production and quality control. Great significance. Now, the results of this creation will be further explained with the following examples, but this creation should not be limited to these examples Example 1 70 ml of N-methylpyrrolidone and 30 ml of acetone are added to the reaction container and stirred to form a mixed solvent, and then 6.5 g (0.06 mol) of p-phenylenediamine and 6.5 g (0.03 mol) of diamine diphenyl ether are added to a mixed solvent and stirred to dissolve into a diamine solution. This dissolution process It was allowed to completely dissolve at a low temperature for 3 hours. 8.7 g (0.027 mol) of benzophenone tetracarboxylic dianhydride and 18.5 g (0.063 mol) of biphenyltetracarboxylic dianhydride were gradually added to the diamine solution to form polyfluorene. The viscosity of the polyamic acid solution produced by the reaction is approximately 25,000 cps. The polyamino acid solution is removed from the reaction container to stop the reaction. The prepared polyamic acid solution was evenly coated on the surface of the copper foil, and the thickness of the coated polyamino acid solution was about 0.3 mm, which would be coated with a polyamino acid solution
第16頁 1220901 五、發明說明（13) 之銅箔置於烘箱加熱處理，烘箱溫度設定5 0 °C漸至2 0 0 ° C以移除聚醯胺酸溶液中之溶劑，繼續加熱至3 5 0 °C令聚 醯胺酸完全亞醯胺化，製成聚醯亞胺-銅箔積層板。 所製備之聚醞亞胺-銅箔積層板依J1S 6 4 7卜8.1之規 定測試其剝離強度，得平均剝離強度為1 . 3kg f/cm，依 I P C - Τ Μ - 6 5 0，M e t h o d 2 · 2，4之規定測試其尺寸安定性，得 尺寸安定性平均值為-0 . 1 6，另，該積層板經蝕試驗後外 觀平坦，無邊緣捲曲現象。 例二 本例之聚醯胺酸合成程序與塗佈方法與烘箱溫度之 設定與四羧酸二酐之組成與比例均與例一相同，但所使 用之二胺比率不同，其二胺溶液含對苯二胺8.0克（0.07 莫耳）及二胺基二苯醚5.0克（0.02莫耳），將二苯酮四羧 酸二酐8.7克（0.027莫耳）及聯二苯四羧酸二酐18.5克（ 0，0 6 3莫耳）逐漸加入二胺溶液反應生成聚醯胺溶液， 其製成積層板之剝離強度值為1.0kgf/cm，尺寸安定性為 - 0 . 0 9，蝕後外觀平坦。 例三 本例之聚醯胺酸合成程序與塗佈方法與烘箱溫度之 設定與四羧酸二酐之組成與比例均與例一相同，但二胺 比率不同，其二胺溶液含對苯二胺9 · 1克（0 · 0 8莫耳）及二 胺基二苯醚3 · 1克（0 . 0 1莫耳），其製成積層板之剝離強度 值為0. 8kg f/cm，尺寸安定性為+ 0. 06，但蝕後外觀有微 捲情形。Page 16 1220901 V. Description of the invention (13) The copper foil is placed in an oven for heating. The temperature of the oven is set to 50 ° C to 200 ° C to remove the solvent in the polyamic acid solution. Continue heating to 3 Polyimide was completely imidized at 50 ° C to make a polyimide-copper foil laminate. The prepared polyimide-copper foil laminated board was tested for peel strength according to J1S 6 4 7 and 8.1, and the average peel strength was 1.3 kg f / cm, according to IPC-ΤΜ-6 50, Method. The dimensional stability was tested according to the requirements of 2 · 2 and 4 and the average value of dimensional stability was -0.16. In addition, the appearance of the laminated board after the corrosion test was flat without edge curling. Example 2 The synthesis procedure and coating method of the polyamic acid and the setting of the oven temperature and the composition and ratio of the tetracarboxylic dianhydride in this example are the same as in Example 1, but the diamine ratio used is different, and the diamine solution contains 8.0 g (0.07 mol) of p-phenylenediamine and 5.0 g (0.02 mol) of diaminodiphenyl ether, 8.7 g (0.027 mol) of benzophenone tetracarboxylic dianhydride and diphenyl dicarboxylic acid 18.5 grams of anhydride (0.03 mol) was gradually added to the diamine solution to form a polyamidoamine solution. The peel strength of the laminated board was 1.0 kgf / cm, and the dimensional stability was -0.09. The rear appearance is flat. Example 3 The synthesis procedure and coating method of the polyamic acid and the setting of the oven temperature and the composition and ratio of the tetracarboxylic dianhydride in this example are the same as in Example 1, but the diamine ratio is different, and the diamine solution contains p-phenylenediamine. 8kg f / cm ， The peel strength of the laminated board is 9.1 g (0.08 mol) and diamine diphenyl ether 3.1 g (0.01 mol). The dimensional stability is + 0.06, but there is a slight rolling situation after the etch.
第17頁 1220901 五、發明說明（14) 本質上，聚醯亞胺之性質乃由其所組成之四羧酸二 酐及二胺之成份來決定，但，實用上，常利用改變二胺 成份來調整聚醯亞胺之特性，並且以選用二個或二個以 上二胺單體之組合可更靈活應用，本創作之實施例一、 二及三即以不同比例之二胺組合說明本創作之内容與實 施，該各例中並無添加無機填充材，請參考表一，其中 實施例一結果顯示雖然其剝離強度頗為理想，蝕後外觀 亦平坦，惟，其尺寸安定性不佳，實用性有問題；再其中 實施例三之結果顯示，其剝離強度與尺寸安定性均屬理 想，但蝕後外觀有些微捲曲。 表- # 例一 例二 例三 p-PDA 莫耳0/〇 65 80 90 Ρ-PDA(克） 6. 5 8. 0 9. 1 0DA(克） 6. 5 5.0 3. 1 剝離強度（k g f / c m ) 1 . 3 1 . 0 0. 8 尺寸安定性（％ ) -0.16 -0.09 0.06 1虫刻後外觀 平坦 平坦 微捲 P D A :對苯二胺； 0 D A : 二胺基. 二苯醚 例四Page 17 1220901 V. Explanation of the invention (14) In essence, the properties of polyimide are determined by the composition of the tetracarboxylic dianhydride and the diamine. However, in practice, it is often used to change the composition of the diamine. To adjust the characteristics of polyimide, and use two or more diamine monomer combinations for more flexible application, the first, second and third examples of this creation use different proportions of diamine combinations to explain this creation For the content and implementation, no inorganic filler is added in each case. Please refer to Table 1. The results of Example 1 show that although the peel strength is quite satisfactory, the appearance after etching is also flat, but its dimensional stability is not good. There is a problem with practicability; the results of Example 3 show that the peel strength and dimensional stability are ideal, but the appearance is slightly curled after etching. Table-# Example 1 Example 2 Example 3 p-PDA Moore 0 / 〇65 80 90 P-PDA (g) 6. 5 8. 0 9. 1 0DA (g) 6. 5 5.0 3. 1 Peel Strength (kgf / cm) 1. 3 1. 0 0. 8 Dimensional stability (%) -0.16 -0.09 0.06 1 Appearance flat and flat microvolume PDA: p-phenylenediamine; 0 DA: diamine. Diphenyl ether Example 4
第18頁 1220901 五、發明說明（15) 本例之聚醯胺酸合成程序與塗佈方法與烘箱溫度設 定與四羧酸二酐之組成與比例均與例一相同，但其二胺 溶液含對苯二胺7.6克（0.07莫耳）及二胺基二苯醚4.7克（ 0. 02莫耳），其製成積層板之剝離強度值為1. 1 kg f/cm， 尺寸安定性為-0 . 0 8，蝕後外觀平坦。 例五 本例之聚醯胺酸合成程序與塗佈方法與烘箱溫度設 定均與例一相同，而且四羧酸二酐與二胺之組成比例均 與例四相同，其聚醯胺酸溶液中另含雲母粉4. 0克 (10%)，其製成積層板之剝離強度值為1. 5kg f/cm，尺寸 P 安定性為-0 . 0 7，蝕後外觀平坦。 例六 本例之聚醯胺酸合成程序與塗佈方法與烘箱溫度設 定均與例一相同，而且四羧酸二酐與二胺之組成比例均 與例四相同，其聚醯胺酸溶液中另含雲母粉8. 0克 (2 0%)，其製成積層板之剝離強度值為1 · 7 kgf/cm，尺寸 安定性為-0 . 0 3，蝕後外觀平坦。 例七 I· 本例之聚醯胺酸合成程序與塗佈方法與烘箱溫度設 定均與例一相同，而且四羧酸二酐與二胺之組成比例均 與例四相同，其聚醯胺酸溶液中另含二氧化矽粉4. 0克（Page 18 1220901 V. Description of the invention (15) The synthesis procedure and coating method of polyamic acid, the oven temperature setting, and the composition and ratio of tetracarboxylic dianhydride in this example are the same as in Example 1, but the diamine solution contains 7.6 grams (0.07 moles) of p-phenylenediamine and 4.7 grams (0.02 moles) of diaminodiphenyl ether, the peel strength of the laminated board is 1.1 kg f / cm, and the dimensional stability is -0. 0 8, the appearance after etching is flat. Example 5 The synthesis procedure, coating method and oven temperature setting of this example are the same as in Example 1, and the composition ratio of tetracarboxylic dianhydride and diamine are the same as in Example 4. In the polyamic acid solution, It also contains 4.0 m (10%) of mica powder, which has a peel strength value of 1.5 kg f / cm, a dimension P stability of -0.07, and a flat appearance after etching. Example 6 The synthesis procedure, coating method, and oven temperature setting of this example are the same as in Example 1, and the composition ratio of tetracarboxylic dianhydride and diamine are the same as in Example 4. In the polyamic acid solution, It also contains 8.0 g (20%) of mica powder, which has a peel strength of 1 · 7 kgf / cm and a dimensional stability of -0.03. The appearance after etching is flat. Example 7 I · The polyamine synthesis procedure and coating method and oven temperature setting of this example are the same as in Example 1, and the composition ratio of tetracarboxylic dianhydride and diamine is the same as in Example 4. The polyamine 0 克 （Silicon dioxide powder in the solution
第19頁 1220901 五、發明說明（16) 10%)，其製成積層板之剝離強度值為1.5 kgf/cm，尺寸 安定性為-0 . 0 7，蝕後外觀平坦。 例八 本 例 之 聚 Si 胺 酸 合成程序與塗佈方法 與 烘 箱溫 度 δ又 定 均 與 例 一 相 同 而 四羧酸二酐與二胺之 組 成 比例 均 與 例 四 相 同 ， 其 聚 Si 胺 酸溶液中另含二氧化 矽 粉8 . 0克 (20%) ，其製成積層板之剝離強度值為1. 6 kg f / cm ， 尺 寸 安 定 性 為 -0 .05 ，蝕後外觀平坦。 實 施 例 四 至 八 說 明本創作之無機填充 材 效 果， 同 樣 選 擇 以 對 苯 二 胺 佔 二 胺總量之7 5 %為基礎之單體組合為 例 即 對 苯 二 胺75%及二胺基二苯醚2 5%為 二 胺 成份 5 再 加 入 不 同 比 例 量 之 雲 母粉或二氧化矽粉為 益 機 填充 材 ， 觀 察 無 機 填 充 材 對 聚 醯亞胺積層板特性之 影 響 ，請 參 考 表 二 及 表 三 其 中 實 施例四、五及六顯示 其 剝 離強 度 與 尺 寸 安 定 性 均 屬 理 想 ，且蝕後外觀也都屬 平 坦 ，更 說 明 了 本 創 作 可 以 添 加 雲 母粉增進聚醯亞胺積 層 板 之特 性 再 於 實 施 例 七 及 八 中添加二氧化矽時亦 呈 相 同結 果 與 趨 向 〇 表 例四 例五 例六 P- PDA莫耳％ 7 5 7 5 75Page 19 1220901 V. Description of the invention (16) 10%), the peel strength of the laminated board is 1.5 kgf / cm, the dimensional stability is -0.07, and the appearance after etching is flat. Example 8 The synthesis procedure and coating method and oven temperature δ of this example are the same as those of Example 1. The composition ratio of the tetracarboxylic dianhydride and diamine is the same as that of Example 4. The polySi amine solution is the same. It also contains 8.0 g (20%) of silicon dioxide powder, which has a peel strength of 1.6 kg f / cm and a dimensional stability of -0.05 as a laminated board. The appearance after etching is flat. Examples 4 to 8 illustrate the effect of the inorganic fillers of this creation. Similarly, a monomer combination based on p-phenylenediamine accounting for 75% of the total diamine is selected as an example, that is, p-phenylenediamine 75% and diamine dibenzene. Ether 2 5% is the diamine component 5 Then add mica powder or silicon dioxide powder in different proportions as filling materials. To observe the effect of inorganic fillers on the characteristics of polyimide laminates, please refer to Tables 2 and 3. Among them, Examples 4, 5 and 6 show that the peel strength and dimensional stability are ideal, and the appearance after etching is also flat. It also explains that this creation can add mica powder to improve the characteristics of polyimide laminates. The same results and trends were shown when silicon dioxide was added in Examples 7 and 8. Table 4 Example 5 Example 6 P-PDA Molar% 7 5 7 5 75
第20頁 1220901 五、發明說明（17) P-PDA(克） 7. 6 7. 6 7. 6 0DA(克） 4. 7 4. 7 4. 7 雲母（％) 0 10 20 剝離強 度（kgf/cm) 1 . 1 1 . 5 1 . 7 尺寸安 定性（％ ) -0.09 -0.07 -0· 03 姓刻後 外觀 平坦 平坦 平 坦 表三 例四 例七 例八 p-PDA莫耳％ 75 75 75 P-PDA (克） 7. 6 7.62 7.62 0DA (克） 4. 7 4. 7 4. 7 二氧化矽（％ ) 0 10 20 剝離強度（k g f / c m ) 1 . 2 1 . 5 1 . 6 尺寸安定性（％ ) -0.09 -0.07 -0.05 1虫刻後外觀 平坦 平坦 平坦 p-PDA 對苯二胺；ODA:二胺基二苯醚 p-PDA :對苯二胺；0DA :二胺基二苯醚Page 20 1220901 V. Description of the invention (17) P-PDA (g) 7. 6 7. 6 7. 6 0DA (g) 4. 7 4. 7 4. 7 Mica (%) 0 10 20 Peel strength (kgf / cm) 1. 1 1. 5 1. 7 Dimensional stability (%) -0.09 -0.07 -0 · 03 Appearance flat and flat after the last name Table 3 cases 4 cases 7 cases 8 p-PDA Moire% 75 75 75 P-PDA (g) 7. 6 7.62 7.62 0DA (g) 4. 7 4. 7 4. 7 Silicon dioxide (%) 0 10 20 Peel strength (kgf / cm) 1. 2 1.. 5 1.6 Size Stability (%) -0.09 -0.07 -0.05 1 Appearance is flat after flattening p-PDA p-phenylenediamine; ODA: diaminodiphenyl ether p-PDA: p-phenylenediamine; 0DA: diaminodiamine Phenyl ether
第頁 1220901 圖式簡單說明 益Page 1220901 Simple illustration of diagrams
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