狹、發明說明： 【發明所屬之技術領域】 ,本發明係有關於一種改質型聚醯亞胺的製造方法，特別是有關於— 種低吸水性聚醯亞胺材料的製造方法。 、 【先前技術】 聚醯亞胺係一般已知為具有優越耐熱性、耐化學性，以及多種優良 機械特性及電氣特性的材料，因此在諸如工程塑膠業、電子業、積2 電路相關產業、航空業等許多種行業中已被廣為使用，其用途包』有 高溫膠帶、電子構裝、漆包線、印刷電路板、感測元件、分離膜等。 聚醯亞胺在許多種的應用上也扮演著關鍵性材料的角色。 半導體產業傳統上常以無機材料為主要的應用材料，然而由於半導 體製程的要求愈來愈高，許多傳統的無機材料已無法滿足其需求，而 聚酸亞胺_其優綱耐触、耐化學性、機械強度及魏等特性， 恰可彌補傳統材料的不足，因此更顯現其重要性。 習知的聚醯亞胺製法是以雙胺及雙酐進行聚合縮合反應而製得聚 醯亞胺（PolyimideS: Thermally Stable Polymers，2nd edn，pienum，价你Narrow, description of the invention: [Technical field to which the invention belongs], the present invention relates to a method for producing a modified polyimide, and in particular, to a method for producing a low water-absorptive polyimide material. [Prior technology] Polyimide is generally known as a material with superior heat resistance, chemical resistance, and a variety of excellent mechanical and electrical properties. Therefore, it is widely used in industries such as engineering plastics, electronics, and IC circuit-related industries, It has been widely used in many industries such as the aviation industry, and its application packages include high-temperature tapes, electronic components, enameled wires, printed circuit boards, sensing elements, and separation films. Polyimide also plays a key role in many applications. The semiconductor industry has traditionally used inorganic materials as the main application materials. However, due to the increasing requirements of semiconductor manufacturing processes, many traditional inorganic materials have been unable to meet their needs. Polyimide _ its excellent contact resistance and chemical resistance The properties such as properties, mechanical strength, and Wei can just make up for the deficiencies of traditional materials, so their importance is even more obvious. The conventional polyimide method is a polyimide (PolyimideS: Thermally Stable Polymers, 2nd edn, pienum) which is obtained by polymerization and condensation reaction of bisamine and dianhydride.
York (1987)，pp· 1-95 ; J· P〇lym· sd· Al(1963)3135 ; J· Appl. Polym· Sci 11(1967)609)。此種製程-般可分成二個階段，纟第一階段為將雙胺及 雙酐單體充份溶於極性的非質子性溶劑内，例如N_methylpyrr〇Ud〇ne (NMP) ’以形成一種溶液，再在氮氣中將此溶液攪拌約一小時，使其 逐漸黏稠而形成聚醯胺酸，此為聚醯亞胺的前驅體。將此前驅體以適 當的方式加以熟化閉環處理即可轉變成聚醯亞胺。習知上用來處理此 前驅體以形成聚醯亞胺的方法是將此前驅體在35(rc的高溫下加熱一 小時，如此即可使聚醯胺酸熟化閉環而形成聚醯亞胺。 以習知方法製得的聚醯亞胺薄膜在常溫常壓下的吸水率約為 2.5%-4%，且水份的渗透擴散速率相當的快。會影響吸水率的原因除了 化學結構本身的因素外，其製程也是主要的因素之一。一般而言，若 200424234 ^對稱性高的賴來進行聚合反應，其所得的聚合高分子的結晶率較. 南’因此水分子料情雜不易發生，反之若是㈣亞舶殘存有溶 劑的話，則由於溶淋身的極性之故，將會易於與水分子產生氯鍵而 增加吸水率。 另外在聚醯胺酸的醯亞胺化過程中，若加熱速率太快，會導致聚醯 亞胺細喊纽洞，這魏涵存在亦會增加水分子社膜内的能 力。足些因素均會使得習用製法製得的聚醯亞胺材料的吸水性增大。 在降低聚醯亞胺吸水性的技術上，諸多文獻，如j· p〇lym· %，p〇iym·York (1987), pp. 1-95; J. Polly. Sd. Al (1963) 3135; J. Appl. Polym. Sci 11 (1967) 609). This process can generally be divided into two stages. The first stage is to dissolve the bisamine and dianhydride monomers in a polar aprotic solvent, such as N_methylpyrróUdone (NMP) 'to form a solution. Then, the solution was stirred in nitrogen for about an hour, which gradually made it viscous to form a polyamidic acid, which is a precursor of polyimide. The precursor can be converted into polyfluorene imine by aging and closed-loop treatment in an appropriate manner. The conventional method for treating the precursor to form a polyfluorene imine is to heat the precursor at a high temperature of 35 ° C for one hour, so that the polyamine can be cured and closed to form a polyfluorene. The polyimide film prepared by the conventional method has a water absorption of about 2.5% -4% under normal temperature and pressure, and the permeation and diffusion rate of water is quite fast. The reasons that affect the water absorption are in addition to the chemical structure itself. In addition to factors, its process is also one of the main factors. In general, if 200424234 ^ high symmetry Lailai polymerization reaction, the resulting polymer polymer has a higher crystallization rate. South 'Therefore, water molecule materials are not easy to occur On the other hand, if there is a solvent remaining in Xiabo, the polarity of the lyophilized body will easily generate chlorine bonds with water molecules and increase the water absorption rate. In addition, in the process of osmization of polyamic acid, if If the heating rate is too fast, it will cause polyimide to yell into new holes. The presence of Wei Han will also increase the capacity of the water molecule membrane. All these factors will make the polyimide material prepared by conventional methods absorb water. Increase in the reduction of polyimide In terms of water absorption technology, many documents, such as j · p〇lym ·%, p〇iym ·
Phys· Ed· 30: U23 (1992)、美國專利第5,338,826號及美國專利第 5，177，176號中均指出以含說的單體，如2,2，bis(3,4_dicarb似 hexaflu〇ropropane dianhydride (6FDA)及 〇χ_涵 曰反應了以製備低吸水性的聚醯亞胺，然而此種新單體的合成作章 是相當費時，«絲«以酬，以此财法並私於產業界的 需求。 另外，亦有在聚’胺膜上結合聚四氟乙稀樹脂（例如杜邦公司的Phys · Ed. 30: U23 (1992), U.S. Patent No. 5,338,826 and U.S. Patent No. 5,177,176 all indicate that monomers such as 2,2, bis (3,4-dicarb resemble hexafluropropane The dianhydride (6FDA) and 〇χ_ 涵 are reacted to prepare polyimide with low water absorption. However, the synthesis of this new monomer is quite time-consuming. Industry needs. In addition, there are also polytetrafluoroethylene resins (such as DuPont's
Kapton F樹脂）的製程，其做法為在聚醯亞胺膜上塗佈一層或二層的 鐵氟，樹脂（FEP®)，惟其對於降低聚輕胺吸水性的效果*多，^顯 =出若聚Si亞胺本身未經改質處理，其整體的吸水性仍然會是相當的 咼除此之外塗佈鐵氟龍的加工作業會增加生產成本，同時也會有 良率降低的問題。 響 因此產業界長久以來，一直需要有一種低成本而便捷的方法，以製 備低吸水性的聚酿亞胺。 【發明内容】 本發明之主要目的即是要提供一種製造低吸水性聚醯亞胺的方法。 以下將原則性地說明本發明的低吸水性聚醯亞胺製造方法，同時並 以數個範例來具體解說本發明的方法。 本發明的低吸水性聚醯亞胺製造方法是利用等化學當量的雙胺及 6 200424234 ... ..- , - · . 雙酐進行聚合反應而生成聚醯胺酸，此聚合反應是將上述二種單體溶1 於極性非質子性溶劑内進行的，其係為一種聚合縮合反應。適合應用 於本發明方法的雙胺單體包含有： (1) oxydianiline (ODA) (2) diaminodiphenylmethane (MDA) (3) diaminodiphenylaulfone (DDS) (4) phenylenediamine (PDA) (5) diaminobenzeophenone (DAB) 但並不僅限於此，其它具有類似特性的化合物亦可加以使用。而適 合使用在本發明方法的雙酐單體則包括有： (1) pyromellitic dianhydride (PMDA) ⑵ 3,3’,4,4’-benzophenone tetracarboxylic dianhydride (BTDA) ⑶ biphenyl tetracaiboxylic dianhydride (BPDA) (4) 4,4’~oxydiphthalic anhydride (ODPA) (5) 2,2,-bis(3,4dicaiboxyphenyl) hexafluorophiOpane dianhydride (6FDA) 但並不僅限於此，其它具有類似特性的化合物亦可加以使用。 另外，該極性非質子性溶劑則可以是： (1) N^NklimethylfomiamideODMF) ⑵ NJ^klimethylacetamide (DMAc) (3) N-methylpyrroMone (NMP) (4) Tetramethylurea (MTU) ⑶ Dimethylsulfoxide (DMSO) (6) Acetonitrile (7)cresol _或疋其中一者或多者自身所組成的共溶劑或是無它化操所 組成的共浴劑。 十取月々其在上述聚隨胺酸聚合過程中，另外加入具有有機溶 1 可Γ，四^乙、歸改質物粉末（以下簡稱“改質型聚四氟乙稀樹 月曰 ：、、、文貝J以在邊溶液内進行聚摻合反應，該改質型聚四氟 乙烯树脂的比例是約為〇. 001-5%重量百分比。 此改貝里水四氣乙稀樹脂，其結構如下圖所示： F η Δ ρ- y — =0.9-0.1 1-y 為主鏈包含四氟乙烯重覆單位之聚合物或其他基團（A)之聚合物， 此基團（A)有助於有機溶劑之溶解。 先奋液在氮氣下’麟約—小時後，即可得到黏稠狀改質過的聚醯 Μ义’經S&亞月女化即為改質成功聚酸亞胺。此黏稠狀聚醯胺酸的固有 黏度可高達1.2。 另-種改良方式是將上述的改質型聚四氟乙稀樹脂先溶於有機溶φ 片1如xylene或toluene或二者的共溶劑，再添加於聚合反應系統中。再 將此浴液加人雨述雙胺及雙gf溶於非質子性溶劑内所形成的溶液内， 然後再加以攪拌，亦可得到黏稠狀的聚醯胺酸。 依上法製得的聚醯胺酸可以利用刮刀法，將其塗佈於玻璃片上，然 後再利同350oC的高溫加以烘烤一小時，即可得到聚酸亞胺薄膜，其 ^度可為50μπι，或者是以其它合適的方式來加以乾燥之而製成粉末狀 聚醯亞胺或是纖維狀聚醯亞胺。就該刮刀法製得的聚醯亞胺薄膜而 :在以ASTM D570規範的標準來加以測試，此改質過的聚酿亞胺薄 膜的吸水性可低至1 · 17 %，和習知方法製得之未改質的聚醯亞胺薄膜的 8 200424234 t5r%的吸水性她下，本發明方法製得的聚酿亞胺薄膜的吸水性明. ’、—2^糾’本發明方法製得的魏亞胺膜相對於水的接觸 角而達1G4° ’且其表面自由能亦低至25 4 dyne/⑽，此等皆顯示出 ，明方法製出的雜亞胺難有極佳的疏水性。再者，本發明方 得的聚酿亞胺_在機械特性上，例如抗拉強度及延伸轉，均^ 由^知方法製得之未改質聚酿亞胺膜。表—中顯示出二種由本發^方 =得之改質減亞胺膜的範例與由龍方法製得之未改質聚酿亞胺 /專膜的特性的比較資料。 、，據本發明的另_實施例，其係在雜胺酸形成而未進行熟化閉環 或fe亞胺化作錢，將改質型聚四氟乙雜脂加人於該魏胺酸内， ^進Ϊ —2劇烈攪拌後脫泡，再將脫泡後的黏娜液塗佈於玻璃 ^二，同’皿加熱使其熟化閉環而形成聚醯亞胺薄膜。如此製得的聚 ^專膜巧吸水性為l 2l%’約高於本發明前一實施例之方法所製得 ^織亞胺_，但姆於習知方法製得之未改質_亞胺而言，則 性仍有㈣的改善。但是由此實施繼製得的韻亞胺膜麵 一 ^明顯的下降，其原因是在於聚醯胺酸及改質型聚四氟乙稀樹脂 3在混合時會產生相分離的現象，減少其改善效果，除此之外，其 &口後放置-段時間也會因相分離而產生分層的現象。 所述’本發明以聚摻合方式得到改質物不僅具滅的改質效 *欢且其加讀^也有所改善，實為—種簡單而具實祕的製程，而籲 於二方法，所雜之改f型聚砸胺，其優異的特性表現主要是來自 ^lvr貝^聚四氟乙烯樹脂改質聚醯亞胺的程度可達分子級的程度 olecular Scale) ’不會有相分離的情形，是以可在極小的比例下即 可得到顯著的改善。 【實施方式】Kapton F resin) process, the method is to coat one or two layers of iron fluoride, resin (FEP®) on the polyimide film, but its effect on reducing the light absorption of poly light amine is much, ^ show = out If the polySiimine itself is not modified, its overall water absorption will still be considerable. In addition, the processing operation of coating Teflon will increase the production cost and reduce the yield. Therefore, the industry has long needed a low-cost and convenient method to prepare polyimide with low water absorption. [Summary of the Invention] The main object of the present invention is to provide a method for manufacturing a low water-absorptive polyimide. Hereinafter, the method for producing a low water-absorptive polyfluorene imine of the present invention will be explained in principle, and the method of the present invention will be specifically explained with several examples. The manufacturing method of the low water-absorptive polyfluorene imide of the present invention is to use a polyamine of equal chemical equivalents and 6 200424234 ... ..-,-·. Dianhydride to polymerize to generate polyamino acid. This polymerization reaction is to The two monomers are dissolved in a polar aprotic solvent, which is a polymerization condensation reaction. Diamine monomers suitable for use in the method of the invention include: (1) oxydianiline (ODA) (2) diaminodiphenylmethane (MDA) (3) diaminodiphenylaulfone (DDS) (4) phenylenediamine (PDA) (5) diaminobenzeophenone (DAB) but It is not limited to this, and other compounds having similar characteristics may be used. The dianhydride monomers suitable for use in the method of the present invention include: (1) pyromellitic dianhydride (PMDA) ⑵ 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA) ⑶ biphenyl tetracaiboxylic dianhydride (BPDA) (4 ) 4,4 '~ oxydiphthalic anhydride (ODPA) (5) 2,2, -bis (3,4dicaiboxyphenyl) hexafluorophiOpane dianhydride (6FDA) But it is not limited to this, and other compounds with similar characteristics can also be used. In addition, the polar aprotic solvent can be: (1) N ^ NklimethylfomiamideODMF) ⑵ NJ ^ klimethylacetamide (DMAc) (3) N-methylpyrroMone (NMP) (4) Tetramethylurea (MTU) ⑶ Dimethylsulfoxide (DMSO) (6) Acetonitrile (7) cresol _ or a co-solvent composed of one or more of them or a co-bath composed of no other operations. In the above-mentioned polyacrylic acid polymerization process, Shizukuori added additional organic solvents that can be added to the polymer powder (hereinafter referred to as "modified polytetrafluoroethylene"): ,,,, Wenbei J performs a poly-blending reaction in the side solution, and the proportion of the modified polytetrafluoroethylene resin is about 0.001-5% by weight. This modified berry water tetragas ethylene resin has a structure As shown in the figure below: F η Δ ρ- y — = 0.9-0.1 1-y A polymer containing tetrafluoroethylene repeating units in the main chain or a polymer of other groups (A), this group (A) has It helps to dissolve organic solvents. After the Fenye solution is under nitrogen for about 1 hour, you can get a viscous and modified polymethylamine, which is successfully modified by S & Yueyue. The inherent viscosity of this viscous polyamino acid can be as high as 1.2. Another improvement method is to dissolve the modified polytetrafluoroethylene resin firstly in an organic solvent, such as xylene or toluene or a combination of the two. The solvent is then added to the polymerization reaction system. This bath is then added with bisamine and bisgf dissolved in an aprotic solvent. In the resulting solution, and then stirring, a viscous polyamic acid can also be obtained. The polyamino acid prepared according to the above method can be coated on a glass sheet by a doctor blade method, and then used at a high temperature of 350oC. After baking for one hour, a polyimide film can be obtained, the degree of which can be 50 μm, or it can be dried by other suitable methods to make a powdery polyimide or a fibrous polyimide. For the polyimide film prepared by the doctor blade method: When tested in accordance with the standard of ASTM D570, the water absorption of this modified polyimide film can be as low as 1.17%, and the conventional method The non-modified polyimide film has a water absorption of 8 200424234 t5r%. The polyimide film produced by the method of the present invention has a high water absorption. The contact angle of the obtained weimine film with respect to water is 1G4 ° ', and its surface free energy is also as low as 25 4 dyne / ⑽, all of which show that the heteroimine produced by the method is difficult to have excellent Hydrophobic. In addition, the polyimide obtained in the present invention has mechanical properties such as tensile resistance. Degree and extension, both of the unmodified polyimide film produced by the known method. Table-shows two examples of modified modified imine film obtained by the present formula = and the method of the dragon method The obtained comparative data of the properties of the unmodified polyimide / special film. According to another embodiment of the present invention, it is formed in the formation of heteroamino acids without undergoing ripening ring closure or feimine formation. Modified polytetrafluoroethylene grease was added to the glutamic acid, ^ into the Ϊ-2 after vigorous stirring, defoaming, and then the defoamed mucus solution was coated on glass ^ two, the same as the dish heating It matures and closes the ring to form a polyfluoreneimide film. The thus-obtained polyimide film has a water absorption of 121%, which is approximately higher than that obtained by the method of the previous embodiment of the present invention. As far as the unimproved _imine obtained by the conventional method is concerned, the performance is still improved. However, the surface of the melamine film produced by this implementation is significantly reduced, because the polyamic acid and the modified polytetrafluoroethylene resin 3 will cause phase separation when they are mixed, reducing their In addition to improving the effect, the & post-mouth placement-for a period of time will also cause the phenomenon of delamination due to phase separation. Said 'The modified product obtained by the poly-blend method of the present invention not only has the destructive effect of modification, but also improves the reading ^, which is actually a simple and secretive process, and calls for two methods, so F-type polyammonamine is modified, its excellent performance is mainly derived from ^ lvr shell ^ polytetrafluoroethylene resin modified polyimide to the extent of molecular level (olecular Scale) 'There will be no phase separation The situation is that significant improvements can be achieved at very small proportions. [Embodiment]
之將4對數個範例來更具體地說明本發明的低吸水性聚聽亞胺 方法’但是這些範例均僅是用來闡明本發明之方法的例子而 9 已，並非是用來對本發明的範圍加以限制。 範例一 將改質型聚讀乙騎脂丨公克溶於5Q公克的Kyi·中而形成一 ，容液，再將此溶液加人850公克的DMAC (N,N dimethyI織咖·則 >谷劑内’並添加47.85公克的雙胺單體〇xydianiline (〇da)及5215 公克的雙酐單體pyr〇melliticdianhydride (PMDA)，使上述二種單體完 全溶解於麟_。雜再錢氣内腳—小時，聚合成為聚_酸 的清漆（Varnish)。將上述的清漆利用刮刀塗佈於玻璃基材上，經由 350QC的高溫烘烤，而使醯胺酸閉環形成聚醯亞胺薄膜，其厚度為 50μπι。在此範例中，分別以重量百分比為〇1%、〇5%、1%等三^比 例的改λ用聚四氟乙烯樹脂來對聚醯亞胺加以改質，其改質而得的聚 酿亞胺膜的吸水性均在uim%的範圍内。其它相關的數據可參見 表一。 範例二 將1么克的5^四氟乙稀樹脂溶於9〇〇公克的極性溶劑dmac内，再 加入47.85公克的ODA單體及52.15公克的PMDA單體，再於氮氣内 攪拌一小時’使之聚合成聚醯胺酸清漆，其後以和範例一相同的方式 進行塗佈及熟化作業而得到聚醯亞胺薄膜。如此製得之聚醯亞膜薄膜 的吸水性為1.2%，約與範例一之聚醯亞胺薄膜相當。 範例三 將雙胺及雙酐單體溶於非質子性的極性溶劑（wDMAc)内，進行 ♦合反應而生成1，〇〇〇公克的聚醯胺酸清漆，其固含量可為10%，在此 例中其採用三種的混合比例o.lwt%、〇.5wt%、lwt% (見表一）。將聚 四氟乙烯樹脂1公克溶於50公克之xyiene中，形成一種溶液，再將此 溶液加入先前製備好的聚醯胺酸清漆内，進行劇烈攪拌一小時，並加 以脫泡，其後塗佈於玻璃上，並加以高溫熟化處理，即可得到聚酿亞 胺薄膜。所得之聚醯亞胺膜的特性可參見表一，其中分別列出三^混 200424234 。比例之聚醯亞胺的各項相關數據。 一以上的說明解釋本發明之低吸水性聚醯亞胺的製造方法，其令所揭 =⑽關說圖柄僅是側縣發明讀_容，以及此技術手 &所為之較佳的範例而已，並*因此而關本發明之㈣。本專利強 ，備㈣，胺高ί子過程中加入改質型聚四氟乙稀樹脂，此程序 ii=si亞胺化之麵加人，均在本發明範_。再者，舉凡是針 上”方法、比，材料等鱗效置換及變換 中 所逑之本發明申請糊範_欲加則轉 ，糸屬 【圖式簡單說明】4 pairs of examples will be used to more specifically describe the method of the present invention for the low-absorbent polyazimine method. However, these examples are only examples for illustrating the method of the present invention, 9 and are not intended to limit the scope of the present invention. Be restricted. Example 1: Modified polyreading Ethyl Acetate 丨 g was dissolved in 5Q g of Kyi · to form a solution, and the solution was added to 850 g of DMAC (N, N dimethyI weaving coffee. Add 47.85 grams of bisamine monomers Oxydianiline (〇da) and 5215 grams of dianhydride monomer pyromelliticdianhydride (PMDA), so that the above two monomers are completely dissolved in Lin. Feet-hours, polymerized into a polyacid varnish (varnish). The above varnish was coated on a glass substrate with a doctor blade and baked at a high temperature of 350QC, so that the amino acid was closed to form a polyimide film. The thickness is 50μπι. In this example, polytetrafluoroethylene resin is used to modify polyimide with three ^ ratios such as 0%, 05%, and 1% by weight, and the modification is performed. The water absorption of the obtained polyimide film was in the range of uim%. For other related data, please refer to Table 1. Example 2 One gram of 5 ^ tetrafluoroethylene resin was dissolved in 900 grams of polarity In solvent dmac, add 47.85 grams of ODA monomer and 52.15 grams of PMDA monomer, and stir under nitrogen. It was polymerized into a polyamic acid varnish in 1 hour, and then coated and cured in the same manner as in Example 1 to obtain a polyimide film. The water absorption of the poly (fluorene) film thus prepared was 1.2%. It is approximately equivalent to the polyfluorene imine film of Example 1. Example 3 The bisamine and dianhydride monomers are dissolved in an aprotic polar solvent (wDMAc), and a reaction is performed to generate 1,000 g of polymer. The acetic acid varnish can have a solid content of 10%. In this example, three mixing ratios of 0.1% by weight, 0.5% by weight, and 1% by weight (see Table 1) are used. One gram of polytetrafluoroethylene resin is dissolved. In 50 grams of xyiene, form a solution, and then add this solution to the previously prepared polyamic acid varnish, stir vigorously for one hour, defoam, and then coat it on glass and mature at high temperature. After processing, polyimide film can be obtained. The characteristics of the obtained polyimide film can be seen in Table 1, which lists the relevant data of the polyimide in the ratio of three. 200424234. More than one description Explain the manufacturing method of the low water-absorbent polyfluorene imide of the present invention , Its order revealed = Tongguan said that the handle is only the invention of the county side, and this technical hand & is a better example, and therefore related to the invention of this invention. This patent is strong, ready The modified polytetrafluoroethylene resin is added in the process of amine high, this procedure ii = si imidization is added in the scope of the present invention. Furthermore, the method of “pinning on the needle” Application of the present invention in the scale effect replacement and transformation of materials, etc.