1306874 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種聚醯亞胺聚合物及其製備方法， " 且特別是有關於一種用於製備覆銅積層板的聚醯亞胺聚合 物及其製備方法。 【先前技術】 ^ 軟性印刷電路板已經被廣泛地應用於如筆記型電腦、 ，行動電話、個人數位助理及數位相機等消費性電子產品， 隨著消費性電子產品逐漸走向輕薄短小的趨勢，軟性印刷 電路板也朝向使用更輕薄的無膠式聚醯亞胺覆銅層積板發 展。 以聚醯亞胺層與銅羯之間是否存在一層接著劑層為分 類，聚醯亞胺軟性印刷電路板可分為有膠與無膠式。一般 而言，聚醯亞胺聚合物對銅猪的接著性不佳，所以有膠式 之聚醯亞胺軟性印刷電路板會在聚醯亞胺模層與銅簿之間 • 以環氧樹脂或壓克力系樹脂作為接著劑層來將之接著固 定’而無膠式之聚醯亞胺軟性印刷電路板則是將聚酿亞胺 直接接著於銅箱表面，此聚醯亞胺聚合物必須選用適當的 單體組合來合成聚合物，或經過適當的改質才能用來作為 無膠式的覆銅積層板之聚醯亞胺聚合物材料。 : ㈣式的覆銅積層板主要係利用以聚醯亞胺之聚醯胺 * 豸前驅物’通常由芳香族四叛酸二野與芳香族二胺之單體 化學反應而製備，將聚酿胺酸前驅物塗佈於銅箱之表面，1306874 IX. Description of the Invention: [Technical Field] The present invention relates to a polyimine polymer and a preparation method thereof, and in particular to a polyimine for preparing a copper clad laminate Polymer and its preparation method. [Prior Art] ^ Flexible printed circuit boards have been widely used in consumer electronic products such as notebook computers, mobile phones, personal digital assistants and digital cameras. As consumer electronic products gradually become lighter and shorter, soft. Printed circuit boards are also being developed towards the use of thinner, thinner, non-gelled polyimide laminates. The presence of a layer of an adhesive layer between the polyimide layer and the copper beryllium can be classified into a glued and a gelless type. In general, polyimine polymers have poor adhesion to copper pigs, so a gelatinous polyimide flexible printed circuit board will be between the polyimide layer and the copper book. Or an acrylic resin as an adhesive layer to be subsequently fixed', and a non-gel type polyimide polyimide flexible printed circuit board is a polyimine polymer directly attached to the surface of the copper box. The polymer must be synthesized using a suitable combination of monomers, or suitably modified to be used as a polyimide-free polymer material for a non-gel type copper clad laminate. : The copper-clad laminate of type (4) is mainly prepared by chemical reaction of a polyamidoamine* ruthenium precursor of polyimine, which is usually a monomer of aromatic tetrazoic acid and an aromatic diamine. The amine acid precursor is coated on the surface of the copper box.
1306874 再進行加熱移除聚醯胺酸的溶劑，繼續加熱以高溫使聚酿 胺酸亞醯胺化在銅箔表面生成聚醯亞胺層，其特徵是聚酿 亞胺層與銅箔之間無須以接著劑層結合。 在軟性印刷電路板的生產過程中，覆鋼積層板或是已 經進行過蝕刻程序的軟性印刷電路板都必須是平坦的，因 為在製作過程中’軟性印刷電路板會經過許多設備的狹 縫’如果軟性印刷電路板捲曲了，就會造成軟性印刷電路 板無法順利通過設備狹縫，而使得整個製程中斷。 因此，習用之聚醯亞胺軟性印刷電路板常會在配方中 添加無機填充物，以拉近聚醯亞胺層與銅箔之間的熱膨脹 係數差異，避免捲曲現象的產生。然而，添加無機填充物 雖然改善了基材的平坦性，便於軟性印刷電路板的生產製 作’卻反而造成軟性印刷電路板在反復彎摺時，聚醯亞胺 層較易發生破裂（亦即抗撕裂程度較差）、耐彎折性降低、 以及軟性印刷電路板的透明度變差等問題，因而不利於光 電產業使用者光學對位製程之使用。 所以，如何改善聚醯亞胺軟性印刷電路板的抗撕裂 性、耐彎折性及透明性是熟習此項技藝者所欲解決的問題。 【發明内容】 本發明的目的就是在提供一種抗撕裂性佳的聚醯亞胺 聚合物，適用於製造聚醯亞胺覆銅積層板，尤其適用於製 造無膠式的覆銅積層板。其係將不含無機填充物之聚醯亞 胺聚合物直接塗覆於銅箔表面，形成抗撕裂性佳之覆銅積 1306874 層板。 本發明的另一目的是在提供一種耐彎折佳之聚酿亞胺 聚合物’適用於製造無膠式的覆銅積層板。將不含無機填 充物的聚醯亞胺聚合物直接塗覆於銅箔表面，形成耐彎折 • 佳之覆銅積層板。 本發明的又一目的是在提供一種透明性佳之聚醯亞胺 聚合物，適用於製造無膠式的覆銅積層板。將不含無機填 • 充物的聚醯亞胺聚合物直接塗覆於銅箔表面，形成透明性 ® 佳之覆銅積層板之介電層。 本發明的再一目的是在提供一種具有尺寸安定性的聚 醯亞胺聚合物，適用於製造聚醯亞胺覆銅積層板，尤其是 無膠式的聚酿亞胺覆銅積層板。其係藉由改變芳香族四敌 酸二酐或芳香族二胺之比例來製備聚醯胺酸溶液，再由此 聚醯胺酸溶液生產聚醯亞胺聚合物，所產生的聚醯亞胺聚 S物具有與銅箔相近之熱膨脹係數，使得聚醢亞胺覆銅積 層板有較佳的安定性，符合IPC-4204中所規範的尺寸安定 性。此外，聚醯亞胺層與銅荡之間不需要使用環氧樹脂或 壓克力系樹脂作為接著劑，所以不會有習用之軟性印刷電 路板在高溫製程中不耐高溫的問題。 本發明的又一目的是在提供一種製備聚醯亞胺聚合物 • #方法，尤其是關於-種製備可用於製備覆銅積層板之聚 ·. ，亞胺聚合物的方法。其係藉由改變芳香族四羧酸二酐及 方香族二胺之比例，得到與銅羯之熱膨服係數相近的聚酿 亞胺聚合物。在和具有無機填充物的聚酿亞胺聚合物比較 1306874 之下，其剥離強度（Peel Strength)相當。 、本發目❼係在提供一種製備覆鋼積層板的方 . 纟纟係由芳香族四叛酸二酐及芳香族二胺之單體化學反 冑而製備聚醯胺酸溶液’再將聚醯胺酸溶液塗佈於銅箔表 • ® ’進行加熱使㈣醜㈣胺化在鋼絲面生成聚醢亞 胺層’製得覆銅積層板。 藉由本發明的方法，可以得到具有良好的尺寸安定性 籲純佳的抗撕裂性、耐彎折性和透明性的聚醯亞胺覆銅積 膠 居妬。 【實施方式】 f發明的聚醯亞胺聚合物的製備係將芳香族四羧酸二 醉及芳香族二胺溶於極性㈣子溶射反應生成聚酿胺酸 溶液’聚醯胺时液經由加熱處心㈣㈣形成財熱性 聚醯亞胺聚合物，在不添加任何無機填充物的條件下，調 整聚酿胺酸溶液中各種芳香族四㈣二肝或各種芳香族二 胺的莫耳比例’使聚醯亞胺聚合物之熱膨脹係數介於約⑺ 至約30 ppm/°C之間。 在本發明的一實施例中，芳香族二胺係選用不同莫耳 比例混合的對苯二胺與二胺基二苯醚，而芳香族四羧酸二 酐係選用聯二苯四羧酸二酐。將溶劑N_甲基吡咯烷酮倒入 35t反應财，邊邊將對苯二胺與二絲二苯喊添加 到反應槽中，其中對苯二胺與二胺基二苯社莫耳比例為 約0.1至约1〇.〇,較佳為約10至約5 0。授拌12小時後， 8 1306874 再邊攪拌邊將聯二苯四羧酸二酐緩慢加入反應槽中，攪拌 隔夜得到聚醯胺酸溶液。將此聚醯胺酸溶液塗佈於銅箔表 面，經由加熱處理進行亞醯胺化以形成聚醯亞胺聚合物， 所述的聚醯亞胺聚合物會在㈣表面生成耐熱性的聚酿亞 胺層’即得到本發明之可用於軟性印刷電路板的覆銅積層 板。 根據本發明其他實施例，芳香族二胺較佳的係選自對 苯二胺、二胺基二苯醚、二苯胺甲烷及二胺基二苯酮，而 芳香族四羧酸二酐較佳的係選自聯二苯四羧酸二酐、均苯 四酸二軒及二苯鋼四羧酸二肝。 本發明之聚酿亞胺聚合物具有良好的耐熱性，其熱膨 脹係數約為15至約27 ppm/°C，由於接近銅箔的熱膨脹係 數18 PPm/°C，因此對於銅箔表面具有良好的接著效果，適 合用於生產無膠式覆銅積層板。 上述化合物係作為例示，並非用以限定本發明，熟習 此項技藝者可以依其需要選用適合的芳香族四羧酸二酐及 芳香族二胺種類，並選用適當的莫耳比例，只要能使所得 到的聚醢亞胺聚合物之熱膨脹係數介於約10至約ppm/ C之間’較佳的係介於約15至約27 ppm/°C之間。 綜上所述，本發明僅使用單一個二酐成分，且不需要 添加無機填充物，不但簡化了形成聚醯亞胺聚合物的反應 流程，還仍然可以達到IPC-4204中對於尺寸安定性及對於 剝離強度的要求。 此外’本發明的聚醯亞胺聚合物及覆銅積層板還具有 1306874 較佳的耐彎折性，參見下表i . 性的湔Μ鈷畢 總厚度（微米） 彎折次數（萬^ 試樣編號 1 2 3 4 31 31 43 43 背膠膜在内部背膠 5,000 5,000 3,610 3,240 2,530 2,050 1,500 1,050 、，士述耐彎折性測試係採用兩组不同厚度的試樣進行檢 測’其中，1和3為不添加無機填充物的覆銅積層板，2和 4為添加無機填充物的覆銅積層板。無論背膠膜位於内部或 外部’相同厚度的試樣中，不添加無機填充物的覆銅積層 板可承X的彎折次數都較習知（即有添加無機填充物）的為 多。 ‘ 本發明的聚醯亞胺聚合物及覆銅積層板還具有較佳的 抗撕裂性，參見下表2 : 表_ 2 :抗撕裂性的測讀蛙早 試樣編號 聚醯亞胺層的初始撕裂强度 厚度（微米） (克） 5 6 7 8 12.5 12.5 25 25 上 1100 720 2200 1500 述抗撕裂性測試係採用兩組不同厚度的試樣根據1306874 Further heating to remove the solvent of poly-proline, and continuing to heat to amidize the polyamidamine on the surface of the copper foil to form a polyimine layer, which is characterized by a layer between the polyimide layer and the copper foil. It is not necessary to bond with an adhesive layer. In the production of flexible printed circuit boards, the steel-clad laminate or the flexible printed circuit board that has been subjected to the etching process must be flat because the 'soft printed circuit board passes through the slits of many devices during the manufacturing process' If the flexible printed circuit board is curled, the flexible printed circuit board will not pass through the device slit, and the entire process will be interrupted. Therefore, the conventional polyimide printed circuit board often adds an inorganic filler to the formulation to narrow the difference in thermal expansion coefficient between the polyimide layer and the copper foil to avoid curling. However, the addition of the inorganic filler improves the flatness of the substrate and facilitates the production of the flexible printed circuit board. However, the polyimine layer is more susceptible to cracking (ie, resistance) when the flexible printed circuit board is repeatedly bent. The problem of poor tearing, reduced bending resistance, and poor transparency of flexible printed circuit boards are not conducive to the use of optical alignment processes by users in the optoelectronic industry. Therefore, how to improve the tear resistance, bending resistance and transparency of a polyimide printed circuit board is a problem that is well known to those skilled in the art. SUMMARY OF THE INVENTION An object of the present invention is to provide a polytheneimide polymer which is excellent in tear resistance and is suitable for use in the manufacture of a polyimide-copper-clad laminate, and is particularly suitable for the production of a non-glue copper-clad laminate. It directly coats the surface of the copper foil with a polyimide-free polymer containing no inorganic filler to form a copper-clad 1306874 laminate which is excellent in tear resistance. Another object of the present invention is to provide a binder-resistant copper-clad laminate which is excellent in bending resistance. The polyimide polymer without inorganic filler is directly applied to the surface of the copper foil to form a bend-resistant copper laminate. Still another object of the present invention is to provide a polyimine polymer which is excellent in transparency and which is suitable for producing a copper-free laminate without a gel. The polyimide polymer without inorganic filler is applied directly to the surface of the copper foil to form a dielectric layer of transparency ® good copper clad laminate. A further object of the present invention is to provide a dimensionally stable polyimine polymer suitable for use in the manufacture of polyimide-copper laminates, especially in the form of gelless polyacrylonitrile-clad laminates. The polyimine acid solution is prepared by changing the ratio of the aromatic tetracarboxylic acid dianhydride or the aromatic diamine, and the polyamidene polymer is produced from the polyamic acid solution, and the polyimine product is produced. The poly-S material has a thermal expansion coefficient similar to that of the copper foil, so that the polyimide-copper laminate has better stability and conforms to the dimensional stability specified in IPC-4204. In addition, there is no need to use an epoxy resin or an acrylic resin as an adhesive between the polyimide layer and the copper sway, so that there is no problem that the conventional flexible printed circuit board is not resistant to high temperatures in a high-temperature process. A further object of the present invention is to provide a process for preparing a polyimine polymer, a method, and more particularly to the preparation of a polyamine polymer which can be used to prepare a copper clad laminate. By changing the ratio of the aromatic tetracarboxylic dianhydride and the scented diamine, a polyanilin polymer having a thermal expansion coefficient similar to that of the copper ruthenium is obtained. The Peel Strength is comparable to that of the polyanilin polymer with an inorganic filler 1306874. The present invention is to provide a method for preparing a steel-clad laminate. The lanthanide is prepared by chemically reacting a monomer of aromatic tetra-retensive dianhydride and an aromatic diamine to prepare a poly-proline solution. The proline solution was applied to a copper foil sheet. • ® 'heated to make (iv) ugly (four) aminated to form a polyimide layer on the steel surface to produce a copper clad laminate. By the method of the present invention, it is possible to obtain a polyimide-based copper-clad laminate which has good dimensional stability and which is excellent in tear resistance, bending resistance and transparency. [Embodiment] The preparation of the polyimine polymer of the invention is carried out by dissolving the aromatic tetracarboxylic acid and the aromatic diamine in a polar (tetra) sub-solubilization reaction to form a poly-bristamine solution 'polyamine'. (4) (4) Forming a thermophilic polyimine polymer, adjusting the molar ratio of various aromatic tetrakis(II) di-hepatic or various aromatic diamines in the polyacrylic acid solution without adding any inorganic filler The polyamidene polymer has a coefficient of thermal expansion between about (7) and about 30 ppm/°C. In an embodiment of the present invention, the aromatic diamine is selected from the group consisting of p-phenylenediamine and diaminodiphenyl ether mixed in different molar ratios, and the aromatic tetracarboxylic dianhydride is selected from biphenyltetracarboxylic acid. anhydride. The solvent N-methylpyrrolidone is poured into a 35t reaction, and p-phenylenediamine and di-biphenylene are added to the reaction tank, wherein the ratio of p-phenylenediamine to diaminobiphenyl is about 0.1. To about 1 Torr., preferably from about 10 to about 50. After 12 hours of mixing, 8 1306874, biphenyltetracarboxylic dianhydride was slowly added to the reaction tank while stirring, and stirred overnight to obtain a polyamidonic acid solution. Applying the polyaminic acid solution to the surface of the copper foil, and performing mercaptomination by heat treatment to form a polyimine polymer, and the polyiminoimine polymer generates heat-resistant brewing on the surface of (4) The imine layer 'is obtained the copper clad laminate of the present invention which can be used for a flexible printed circuit board. According to other embodiments of the present invention, the aromatic diamine is preferably selected from the group consisting of p-phenylenediamine, diaminodiphenyl ether, diphenylamine methane, and diaminobenzophenone, and the aromatic tetracarboxylic dianhydride is preferred. The selection is selected from the group consisting of biphenyltetracarboxylic dianhydride, pyromellitic acid disulfide and diphenyl steel tetracarboxylic acid dihepatic. The polyanilin polymer of the present invention has good heat resistance, and has a thermal expansion coefficient of about 15 to about 27 ppm/° C., and has a thermal expansion coefficient of 18 PPm/° C. which is close to the copper foil, so that it has a good surface for the copper foil. The effect is then suitable for the production of glueless copper clad laminates. The above-mentioned compounds are exemplified and are not intended to limit the present invention. Those skilled in the art can select suitable aromatic tetracarboxylic dianhydrides and aromatic diamines according to their needs, and select appropriate molar ratios, as long as The resulting polyamidene polymer has a coefficient of thermal expansion between about 10 and about ppm/C. A preferred range is between about 15 and about 27 ppm/°C. In summary, the present invention uses only a single dianhydride component, and does not require the addition of an inorganic filler, which not only simplifies the reaction process for forming a polyimine polymer, but also achieves dimensional stability in IPC-4204. Requirements for peel strength. In addition, the polyimine polymer and copper-clad laminate of the present invention also have a preferable bending resistance of 1,306,874, see the following table i. S. bismuth cobalt total thickness (micron) bending times (10,000 ^ test Sample No. 1 2 3 4 31 31 43 43 The adhesive film is internally 5,000 5,000 3,610 3,240 2,530 2,050 1,500 1,050 , and the bending resistance test is carried out using two sets of samples of different thicknesses. 3 is a copper-clad laminate without adding an inorganic filler, and 2 and 4 are copper-clad laminates to which an inorganic filler is added. No filler of inorganic filler is added to the sample of the same thickness inside or outside the adhesive film. The number of bends of the copper laminate can be more than that of the conventional (that is, the addition of the inorganic filler). The polyimine polymer and the copper-clad laminate of the present invention also have better tear resistance. See Table 2 below: Table _ 2: Rear resistance test frog Early sample number Initial tear strength thickness of the polyimide layer (μm) 5 6 7 8 12.5 12.5 25 25 Upper 1100 720 2200 1500 The tear resistance test uses two sets of sample roots of different thicknesses.
1306874 敗魯㈣的2.4·16方法進行檢測，其中，巧 加無機填充物的覆銅積層板，6 # 為添加無機填充物的覆 銅積層板。在相同厚度的試樣中 、保1r不添加無機填充物的覆 銅積層板可承受的初始撕裂强产都 农蚀度都較習知（即有添加無機 填充物）的為大。 本發明的聚醯亞胺聚合物還具有較佳的透明性，參見 第la圖及帛lb圖。帛ia圖係顯示試樣編號8，係為習知 的聚醯亞胺聚合物透明度的測試結果，其在聚醯亞 物的製備過程中添加無機填充物。第⑶圖係顯示試樣㈣ 7,係為本發明的聚醢亞胺聚合物透明度的測試結果，其在 聚醯亞胺聚合物的製備過程中不添加無機填充物。相較之 下，本發明之不添加無機填充物所得到之聚醯亞胺聚合物 的透明性顯然較習知為佳。 因此’根據本發明的聚醯亞胺覆銅積層板具有良好的 尺寸安定性及較佳的抗撕裂性、耐彎折性和透明性。 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍内，當可作各種之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 為讓本發明之上述和其他目的、特徵、優點與實施例 能更明顯易懂，所附圖式之詳細說明如下··1306874 The method of 2.4.16 of the defeated Lu (4) was carried out, in which a copper-clad laminate with an inorganic filler was added, and 6 # was a copper-clad laminate with an inorganic filler. In the samples of the same thickness, the initial tear strength that can be withstood by the copper-clad laminate without the addition of the inorganic filler is greater than the conventional (i.e., with the addition of the inorganic filler). The polyiminoimine polymers of the present invention also have better transparency, see Figures la and 帛 lb. The 帛ia diagram shows sample No. 8, which is a test result of the transparency of a conventional polyimine polymer, which is added with an inorganic filler during the preparation of the polyfluorene. The figure (3) shows that the sample (4) 7 is the test result of the transparency of the polyimine polymer of the present invention, and no inorganic filler is added during the preparation of the polyimide pigment polymer. In contrast, the transparency of the polyimine polymer obtained by the present invention without the addition of the inorganic filler is clearly better than conventionally. Therefore, the polyimide film copper-clad laminate according to the present invention has good dimensional stability and better tear resistance, bending resistance and transparency. Although the present invention has been described above in terms of a preferred embodiment, it is not intended to limit the invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.
11 1306874 第1 a圖係顯示試樣編號8 ’係為習知的聚醢亞胺聚合 物透明度的測試結果，其在聚醯亞胺聚合物的製備過程中 添加無機填充物。 第1 b圖係顯示試樣編號7，係為本發明的聚酿亞胺聚 合物透明度的測試結果，其在聚醯亞胺聚合物的製備過程 中不添加無機填充物。11 1306874 Fig. 1a shows the sample number 8' as a test result of the transparency of a conventional polyimine polymer which is added with an inorganic filler during the preparation of the polyimide pigment polymer. Fig. 1b shows the sample No. 7, which is a test result of the transparency of the polyanilin polymer of the present invention, which does not contain an inorganic filler during the preparation of the polyimide pigment polymer.