TWI435893B - Precursor for polyimide and use thereof - Google Patents
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- TWI435893B TWI435893B TW096128743A TW96128743A TWI435893B TW I435893 B TWI435893 B TW I435893B TW 096128743 A TW096128743 A TW 096128743A TW 96128743 A TW96128743 A TW 96128743A TW I435893 B TWI435893 B TW I435893B
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- C—CHEMISTRY; METALLURGY
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- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/75—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Description
本發明係關於一種新穎聚醯亞胺之前驅物,本發明亦關於該新穎聚醯亞胺之前驅物於製備聚醯亞胺(polyimide,簡稱PI)之應用。The present invention relates to a novel polyimine precursor, and the invention also relates to the use of the novel polyimine precursor for the preparation of polyimide (PI).
聚醯亞胺由於具有優異的熱安定性及良好的機械、電氣及化學性質,一直是高性能高分子材料的首選。此外,由於半導體在特性上的要求越來越高,而傳統無機材料有其應用上的極限及缺點,聚醯亞胺的特性,在某些方面正可以彌補傳統材料的不足之處。因此,當杜邦公司之芳香族聚醯亞胺技術開發之後,即受到廣泛的注意,且發展出許多具多用途的聚醯亞胺。Polyimine has always been the first choice for high performance polymer materials due to its excellent thermal stability and good mechanical, electrical and chemical properties. In addition, due to the higher and higher requirements of semiconductors, and the limitations and disadvantages of traditional inorganic materials, the properties of polyimine can compensate for the shortcomings of traditional materials in some aspects. Therefore, when DuPont's aromatic polyimine technology was developed, it received extensive attention and developed many versatile polyimine.
在半導體工業上,聚醯亞胺被廣泛應用於鈍化膜、應力緩衝膜、α粒子遮蔽膜、乾式蝕刻防護罩、微機電和層間絕緣膜等方面,且正陸續開發出其他新用途。其中,以作為保護積體電路元件之塗膜的應用為大宗,因聚醯亞胺材料可通過積體電路元件可靠性之測試。惟,聚醯亞胺之應用不僅只於積體電路工業,其於電子構裝、漆包線、印刷電路板、感測元件、分離膜及結構材料上都相當重要,扮演著關鍵性材料的角色。In the semiconductor industry, polyimine is widely used in passivation films, stress buffer films, alpha particle masks, dry etching shields, microelectromechanics and interlayer insulating films, and other new applications are being developed. Among them, the application as a coating film for protecting integrated circuit components is bulky, and the polyimide material can be tested for reliability of integrated circuit components. However, the application of polyimine is not only in the integrated circuit industry, but also plays an important role in electronic construction, enameled wire, printed circuit boards, sensing components, separation membranes and structural materials.
一般係以二階段之聚合縮合反應方式以合成聚醯亞胺。其中,通常於第一階段將二胺單體溶於如N-甲基吡咯酮(NMP)、二甲基乙醯胺(DMAC)、二甲基甲醯胺(DMF)或二甲基亞碸(DMSO)之極性、非質子性溶劑中,再加入等莫耳二酸酐單體。其後,於低溫或常溫下進行縮合反應,形成聚醯亞胺前驅物(precursor),即,聚醯胺酸(poly(amic acid);簡稱為PAA)。Generally, a polystaged imine is synthesized by a two-stage polymerization condensation reaction. Among them, the diamine monomer is usually dissolved in a first stage such as N-methylpyrrolidone (NMP), dimethylacetamide (DMAC), dimethylformamide (DMF) or dimethyl azine. In a polar, aprotic solvent of (DMSO), an additional monic anhydride monomer is added. Thereafter, the condensation reaction is carried out at a low temperature or a normal temperature to form a polyimine precursor, that is, poly(amic acid; abbreviated as PAA).
接著,進行第二階段,藉由加熱方式的醯亞胺化(thermal imidization)或化學方式的醯亞胺化(chemical imidization),進行縮合脫水環化反應,將聚醯胺酸轉變為聚醯亞胺。Then, in the second stage, the condensed dehydration cyclization reaction is carried out by a thermal imidization or a chemical imidization method to convert the polylysine into a poly amine.
目前製備聚醯亞胺之反應流程可簡述如下:
於上述製備方法中,如第一階段所得之聚醯胺酸分子量未達一定標準(即,分子量過小),於醯亞胺化(imidization)後,無法得到具良好物性之聚醯亞胺膜。然,若第一階段所得聚醯胺酸之分子量過高,則其黏度便會太大,以致於操作性變差,易於塗佈時有流平性不良等缺點。舉例言之,於進行旋轉塗佈時,容易產生中凸與厚邊等不易流平現象。此外,過高之聚醯胺酸分子量,將於進行第二階段之醯亞胺化時,因分子間之交互作用以及分子鏈鍵長的縮短,產生極大內應力,致使所塗佈之基材彎曲變形。因此,為免除前述問題,文獻上業已廣泛探討第二階段醯亞胺化之升溫梯度曲線與內應力關係,並研究出各式降低內應力之方式。然而,前述流平性與內應力問題,究其原因,均來自第一階段所得聚醯胺酸分子量過高所致。換言之,若能妥善控制聚醯胺酸分子量,便可提供具優良物性之聚醯亞胺膜。In the above preparation method, if the molecular weight of the polyamic acid obtained in the first stage does not reach a certain standard (that is, the molecular weight is too small), after the imidization, a polyimide film having good physical properties cannot be obtained. However, if the molecular weight of the polyamic acid obtained in the first stage is too high, the viscosity thereof will be too large, so that the workability is deteriorated, and the flatness is poor when coating is easy. For example, when spin coating is performed, it is easy to cause unevenness such as convexity and thick edges. In addition, the molecular weight of the too high polyamine can cause a large internal stress due to the interaction between molecules and the shortening of the molecular chain bond length during the second stage of imidization, resulting in the coated substrate. Bending deformation. Therefore, in order to avoid the above problems, the relationship between the temperature gradient curve and the internal stress of the second stage ruthenium has been extensively discussed in the literature, and various ways of reducing the internal stress have been studied. However, the above-mentioned problems of leveling and internal stress are caused by the excessive molecular weight of the polylysine obtained in the first stage. In other words, if the molecular weight of the polyaminic acid can be properly controlled, a polyimide film having excellent physical properties can be provided.
此外,聚醯胺酸相當容易吸濕,進而使聚醯胺酸與水分子反應而降解,故不易保存。In addition, polylysine is relatively easy to absorb moisture, which in turn causes polylysine to react with water molecules to degrade, so it is difficult to store.
上述問題,多年來持續困擾著從事聚醯亞胺研究之人士,蓋材料特性與操作性之間往往存在衝突,無法兼得。本發明即針對前述問題所為之研發成果,藉由特殊之合成方式,可於兼顧操作性之情形下,提供具所欲物性之聚醯亞胺膜,符合業界之需求。The above problems have continued to plague people engaged in polyimine research for many years. There is often a conflict between the properties of the cover material and the operability, and it is impossible to have both. The present invention is directed to the research and development of the above problems, and the special synthetic method can provide the desired polyimide film with the desired properties, which meets the needs of the industry.
本發明之一目的在於提供一種新穎的聚醯亞胺之前驅物。It is an object of the present invention to provide a novel polyimine precursor.
本發明之另一目的在於提供一種包含上述前驅物之組合物。Another object of the present invention is to provide a composition comprising the above precursor.
本發明之又一目的在於提供一種製備聚醯亞胺之方法。It is still another object of the present invention to provide a process for preparing a polyimine.
本發明聚醯亞胺之前驅物係具下式(1)之結構之醯胺酸酯寡聚物:
根據本發明之一具體實施態樣,上述式(1)中之R係具1至14個碳原子之直鏈或支鏈烷基,其例如為具以下結構之直鏈或支鏈烷基:
前述具6至14個碳原子之芳基或芳烷基,較佳為選自由下列基團所構成群組:
上述乙烯系不飽和基,並無特殊限制,其實例包括(但不限於)乙烯基、丙烯基、甲基丙烯基、正丁烯基、異丁烯基、乙烯基苯基、丙烯基苯基、丙烯氧基甲基、丙烯氧基乙基、丙烯氧基丙基、丙烯氧基丁基、丙烯氧基戊基、丙烯氧基己基、甲基丙烯氧基甲基、甲基丙烯氧基乙基、甲基丙烯氧基丙基、甲基丙烯氧基丁基、甲基丙烯氧基戊基、及甲基丙烯氧基己基、以及如式(2)所示之基團
上述式(1)中之基團Rx
可各自獨立為H或任何具有可感光聚合之基團,該可感光聚合之基團較佳為含有如上文所定義之乙烯系不飽和基之基團。根據本發明,基團Rx
較佳各自獨立為H、甲基丙烯酸-2-羥基丙酯基、甲基丙烯酸乙酯基、丙烯酸乙酯基、丙烯基、甲基丙烯基、正丁烯基或異丁烯基,更佳各自獨立為H或甲基丙烯酸-2-羥基丙酯基:
本發明式(1)醯胺酸酯寡聚物所含之4價有機基團G,並無特殊限制,其例如為4價之芳香族基團或4價之脂肪族基團。前述芳香族基團可為單環或多環,較佳為選自由下列基團所構成群組:
根據本發明,上述4價脂肪族基可選自由下列基團所構成群組:
本發明式(1)醯胺酸酯寡聚物所含之2價有機基團P,並無特殊限制,其通常為芳香族基團,較佳各自獨立為
於一較佳具體實施態樣中,該2價有機基團P係
上述2價有機基團P,亦可為非芳香族基團,例如:
本案發明人發現,不同於先前技藝用以製備聚醯亞胺之聚醯胺酸前驅物,上述式(1)醯胺酸酯寡聚物由於酸基減少,故較不會吸濕,即使吸溼,亦較穩定,故可於室溫下保存備用,無需儲存於低溫(如:零下20℃)。The inventors of the present invention have found that, unlike the poly-proline precursors of the prior art for preparing polyimine, the above-mentioned phthalate oligomer of the formula (1) is less hygroscopic due to a decrease in acid groups, even if it is absorbed. Wet and stable, so it can be stored at room temperature and stored at low temperature (eg, minus 20 ° C).
本發明之醯胺酸酯寡聚物可藉本發明所屬技術領域中具有通常知識者所習知的聚合方法獲得,例如可藉由包含下列步驟之方法製得:(a)使一具下式(3)之二酸酐與具羥基之化合物(R-OH)反應,形成具下式(4)之化合物;以及
(c)視情況添加帶有可感光聚合基團(R*
)之單體,例如環氧丙烯酸酯(epoxy acrylate),進行反應,形成式(6)醯胺酸酯寡聚物,
於上述製備式(1)醯胺酸酯寡聚物之方法中,步驟(a)所使用之二酸酐,一般可為脂肪族或芳香族者,較佳為芳香族二酸酐,其實例包括(但不限於)均苯四酸二酐(PMDA)、4,4'-二酞酸二酐(BPDA)、4,4'-六氟亞異丙基二酞酸二酐(6FDA)、1-(三氟甲基)-2,3,5,6-苯四羧酸二酐(P3FDA)、二苯甲酮-四羧酸二酐(BTDA)、3,3',4,4'-二苯醚四羧酸二酐(ODPA)、1,4-雙(三氟甲基)-2,3,5,6-苯四羧酸二酐(P6FDA)、1-(3',4'-二羧基苯基)-1,3,3-三甲基茚滿-5,6-二羧酸二酐、1-(3',4'-二羧基苯基)-1,3,3-三甲基茚滿-6,7-二羧酸二酐、1-(3',4'-二羧基苯基)-3-甲基茚滿-5,6-二羧酸二酐、1-(3',4'-二羧基苯基)-3-甲基茚滿-6,7-二羧酸二酐、2,3,9,10-二萘嵌苯四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,6-二氯萘-1,4,5,8-四羧酸二酐、2,7-二氯萘-1,4,5,8-四羧酸二酐、2,3,6,7-四氯萘-2,4,5,8-四羧酸二酐、菲-1,8,9,10-四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、1,2',3,3'-二苯甲酮四羧酸二酐、3,3',4,4'-聯苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-聯苯四羧酸二酐、4,4'-亞異丙基二酞酸二酐、3,3'-亞異丙基二酞酸二酐、4,4'-氧基二酞酸二酐、4,4'-磺醯基二酞酸二酐、3,3'-氧基二酞酸二酐、4,4'-亞甲基二酞酸二酐、4,4'-硫基二酞酸二酐、4,4'-亞乙基二酞酸二酐、2,3,6,7-萘四羧酸二酐、1,2,4,5-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、苯-1,2,3,4-四羧酸二酐、吡啶-2,3,5,6-四羧酸二酐或其組合。In the above process for preparing the phthalate oligomer of the formula (1), the dianhydride used in the step (a) may be generally aliphatic or aromatic, preferably aromatic dianhydride, examples of which include But not limited to pyromellitic dianhydride (PMDA), 4,4'-diphthalic acid dianhydride (BPDA), 4,4'-hexafluoroisopropylidene dicarboxylic acid dianhydride (6FDA), 1- (trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P3FDA), benzophenone-tetracarboxylic dianhydride (BTDA), 3,3',4,4'-two Phenyl ether tetracarboxylic dianhydride (ODPA), 1,4-bis(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P6FDA), 1-(3',4'- Dicarboxyphenyl)-1,3,3-trimethylindan-5,6-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-1,3,3-tri Methyl indane-6,7-dicarboxylic dianhydride, 1-(3',4'-dicarboxyphenyl)-3-methylindan-5,6-dicarboxylic dianhydride, 1-( 3',4'-dicarboxyphenyl)-3-methylindan-6,7-dicarboxylic dianhydride, 2,3,9,10-perylene tetracarboxylic dianhydride, 1,4 ,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8- Tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene 2,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl Methyl ketone tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-isopropylidene dicarboxylic acid dianhydride, 3,3'-isopropylidene Dicapric acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 4,4'-sulfonyl dicarboxylic acid dianhydride, 3,3'-oxy dicarboxylic acid dianhydride, 4, 4' -methylene dicarboxylic acid dianhydride, 4,4'-thiodiphthalic acid dianhydride, 4,4'-ethylene dicarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid Anhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, pyridine- 2,3,5,6-tetracarboxylic dianhydride or a combination thereof.
較佳地,係於步驟(a)採用選自以下群組之芳香族二酸酐:均苯四酸二酐(PMDA)、4,4'-二酞酸二酐(BPDA)、4,4'-六氟亞異丙基二酞酸二酐(6FDA)、1-(三氟甲基)-2,3,5,6-苯四羧酸二酐(P3FDA)、1,4-雙(三氟甲基)-2,3,5,6-苯四羧酸二酐(P6FDA)、二苯甲酮-四羧酸二酐(BTDA)、3,3',4,4'-二苯醚四羧酸二酐(ODPA)及其混合物。於一具體實施態樣中,係採用均苯四酸二酐(PMDA)。Preferably, in step (a), an aromatic dianhydride selected from the group consisting of pyromellitic dianhydride (PMDA), 4,4'-diphthalic acid dianhydride (BPDA), 4, 4' is used. - hexafluoroisopropylidene dicarboxylic acid dianhydride (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P3FDA), 1,4-double (three Fluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P6FDA), benzophenone-tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyl ether Tetracarboxylic dianhydride (ODPA) and mixtures thereof. In one embodiment, pyromellitic dianhydride (PMDA) is employed.
可用於本發明方法以製備式(1)醯胺酸酯寡聚物之具羥基之化合物,可為醇類,例如一元醇、二元醇或多元醇,較佳為一元醇。可用於本發明之一元醇並無特殊的限制,其可為烷基醇、芳烷基醇或芳基醇。舉例言之(但不以此為限),該一元醇可為具1至14個碳原子之直鏈或支鏈烷基醇,例如具以下結構之直鏈或支鏈烷基醇:
可用於本發明方法中之具羥基之化合物亦可帶有可感光之基團,例如乙烯系不飽和基,較佳為具下式(7)者:
上述製備式(1)聚醯胺酸前驅物之方法中,步驟(b)所使用之二胺,並無特殊限制,通常使用芳香族二胺。可用於本發明方法之芳香族二胺,係熟悉此技術領域者所熟知。舉例言之(但不以此為限)可選自以下群組:4,4'-氧化二苯胺(ODA)、對苯二胺(pPDA)、間二甲基對二胺基聯苯(DMDB)、間二(三氟甲基)對二胺基聯苯(TFMB)、鄰二甲基對二胺基聯苯(oTLD)、4,4'-八氟聯苯胺(OFB)、四氟-對-苯二胺(TFPD)、2,2'-5,5'-四氯聯苯胺(TCB)、3,3'-二氯聯苯胺(DCB)、2,2'-雙(3-胺基苯基)六氟丙烷、2,2'-雙(4-胺基苯基)六氟丙烷、4,4'-氧基-雙[3-(三氟甲基)苯胺、3,5-二胺基三氟甲苯(3,5-diaminobenzotrifluoride)、四氟-1,4-伸苯二胺(tetrafluorophenylene diamine)、四氟-間-伸苯二胺、1,4-雙(4-胺基苯氧基)-2-第三丁基苯(BATB)、2,2'-二甲基-4,4'-雙(4-胺基苯氧基)聯苯(DBAPB)、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷(BAPPH)、2,2'-雙[4-(4-胺基苯氧基)苯基]原冰片烷(BAPN)、5-胺基-1-(4'-胺基苯基)-1,3,3-三甲基茚滿、6-胺基-1-(4'-胺基苯基)-1,3,3-三甲基茚滿、4,4'-亞甲基雙(鄰-氯苯胺)、3,3'-二氯二苯胺、3,3'-磺醯基二苯胺、4,4'-二胺基二苯甲酮、1,5-二胺基萘、雙(4-胺基苯基)二乙基矽烷、雙(4-胺基苯基)二苯基矽烷、雙(4-胺基苯基)乙基膦氧化物、N-(雙(4-胺基苯基))-N-甲基胺、N-(雙(4-胺基苯基))-N-苯基胺、4,4'-亞甲基雙(2-甲基苯胺)、4,4'-亞甲基雙(2-甲氧基苯胺)、5,5'-亞甲基雙(2-胺基苯酚)、4,4'-亞甲基雙(2-甲基苯胺)、4,4'-氧基雙(2-甲氧基苯胺)、4,4'-氧基雙(2-氯苯胺)、2,2'-雙(4-胺基苯酚)、5,5'-氧基雙(2-胺基苯酚)、4,4'-硫基雙(2-甲基苯胺)、4,4'-硫基雙(2-甲氧基苯胺)、4,4'-硫基雙(2-氯苯胺)、4,4'-磺醯基雙(2-甲基苯胺)、4,4'-磺醯基雙(2-乙氧基苯胺)、4,4'-磺醯基雙(2-氯苯胺)、5,5'-磺醯基雙(2-胺基苯酚)、3,3'-二甲基-4,4'-二胺基二苯甲酮、3,3'-二甲氧基-4,4'-二胺基二苯甲酮、3,3'-二氯-4,4'-二胺基二苯甲酮、4,4'-二胺基聯苯、間-苯二胺、4,4'-亞甲基二苯胺(MDA)、4,4'-硫基二苯胺、4,4'-磺醯基二苯胺、4,4'-亞異丙基二苯胺、3,3'-二甲氧基聯苯胺、3,3'-二羧基聯苯胺、2,4-甲苯基二胺、2,5-甲苯基二胺、2,6-甲苯基二胺、間-二甲苯基二胺、2,4-二胺基-5-氯甲苯、2,4-二胺基-6-氯甲苯、及其組合。較佳地,係採用4,4'-氧化二苯胺(ODA)、對苯二胺(pPDA)、間二甲基對二胺基聯苯(DMDB)、間二(三氟甲基)對二胺基聯苯(TFMB)、鄰二甲基對二胺基聯苯(oTLD)、4,4'-亞甲基二苯胺(MDA)或其混合物。In the above method for producing the poly (proline) precursor of the formula (1), the diamine used in the step (b) is not particularly limited, and an aromatic diamine is usually used. Aromatic diamines useful in the process of the invention are well known to those skilled in the art. For example, but not limited to, it may be selected from the group consisting of 4,4'-diphenylamine oxide (ODA), p-phenylenediamine (pPDA), m-dimethyl-p-diaminobiphenyl (DMDB). , bis(trifluoromethyl)-p-diaminobiphenyl (TFMB), o-dimethyl-p-diaminobiphenyl (oTLD), 4,4'-octafluorobenzidine (OFB), tetrafluoro- P-phenylenediamine (TFPD), 2,2'-5,5'-tetrachlorobenzidine (TCB), 3,3'-dichlorobenzidine (DCB), 2,2'-bis(3-amine Phenylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 4,4'-oxy-bis[3-(trifluoromethyl)aniline, 3,5- 3,5-diaminobenzotrifluoride, tetrafluorophenylene diamine, tetrafluoro-m-phenylenediamine, 1,4-bis(4-amino group Phenoxy)-2-tert-butylbenzene (BATB), 2,2'-dimethyl-4,4'-bis(4-aminophenoxy)biphenyl (DBAPB), 2,2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BAPPH), 2,2'-bis[4-(4-aminophenoxy)phenyl]bornane (BAPN) 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminobenzene )-1,3,3-trimethylindan, 4,4'-methylenebis(o-chloroaniline), 3,3'-dichlorodiphenylamine, 3,3'-sulfonyldiphenylamine , 4,4'-diaminobenzophenone, 1,5-diaminonaphthalene, bis(4-aminophenyl)diethyldecane, bis(4-aminophenyl)diphenylnonane , bis(4-aminophenyl)ethylphosphine oxide, N-(bis(4-aminophenyl))-N-methylamine, N-(bis(4-aminophenyl))- N-phenylamine, 4,4'-methylenebis(2-methylaniline), 4,4'-methylenebis(2-methoxyaniline), 5,5'-methylene double (2-Aminophenol), 4,4'-methylenebis(2-methylaniline), 4,4'-oxybis(2-methoxyaniline), 4,4'-oxyl double (2-chloroaniline), 2,2'-bis(4-aminophenol), 5,5'-oxybis(2-aminophenol), 4,4'-thiobis(2-methyl Aniline), 4,4'-thiobis(2-methoxyaniline), 4,4'-thiobis(2-chloroaniline), 4,4'-sulfonylbis(2-methylaniline) , 4,4'-sulfonyl bis(2-ethoxyaniline), 4,4'-sulfonyl bis(2-chloroaniline), 5,5'-sulfonyl bis(2-amino group) Phenol), 3,3'-dimethyl-4,4'-diamino Benzophenone, 3,3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 4, 4'-diaminobiphenyl, m-phenylenediamine, 4,4'-methylenediphenylamine (MDA), 4,4'-thiodiphenylamine, 4,4'-sulfonyldiphenylamine, 4,4'-isopropylidene diphenylamine, 3,3'-dimethoxybenzidine, 3,3'-dicarboxybenzidine, 2,4-tolyldiamine, 2,5-methylphenyl Amine, 2,6-tolyldiamine, m-xylylenediamine, 2,4-diamino-5-chlorotoluene, 2,4-diamino-6-chlorotoluene, and combinations thereof. Preferably, 4,4'-diphenylamine (ODA), p-phenylenediamine (pPDA), m-dimethyl-p-diaminobiphenyl (DMDB), m-bis(trifluoromethyl)-p-pair are used. Aminobiphenyl (TFMB), o-dimethyl-p-diaminobiphenyl (oTLD), 4,4'-methylenediphenylamine (MDA) or a mixture thereof.
較佳地,係於步驟(b)採用選自以下群組之二胺:、、、、、以及 Preferably, in step (b), a diamine selected from the group consisting of: , , , , , as well as
如前述,可視需要於步驟(c)中添加帶有可感光聚合基團之單體,使所得醯胺酸酯寡聚物帶有可感光聚合之基團。As described above, a monomer having a photopolymerizable group may be added in the step (c) as needed to impart a photopolymerizable group to the resulting phthalate oligomer.
具體言之,於未添加帶有可感光聚合基團之單體時,所得式(1)醯胺酸酯寡聚物中之Rx 為H;而於添加帶有可感光聚合基團之單體時,則所得之式(1)聚醯胺酸前驅物中之Rx 便為該可感光聚合之基團。若Rx 為可感光聚合基團,所得醯胺酸酯寡聚物於後續合成聚醯亞胺樹脂製程中,能產生分子與分子間的化學接合而形成交鏈(crosslinking)。Specifically, when a monomer having a photopolymerizable group is not added, R x in the obtained phthalate oligomer of the formula (1) is H; and a single sheet having a photopolymerizable group is added In the case of the body, the R x in the obtained polyamine precursor of the formula (1) is the photopolymerizable group. If R x is a photopolymerizable group, the resulting phthalate oligomer can undergo chemical bonding between molecules and molecules to form a crosslink in the subsequent synthesis of the polyimide resin.
本發明另提供一種用於製備聚醯亞胺之前驅物組合物,其係包含前述式(1)之醯胺酸酯寡聚物和溶劑。The present invention further provides a precursor composition for preparing a polyimine, which comprises the phthalate oligomer of the above formula (1) and a solvent.
於本發明組合物中,所使用之溶劑,較佳係為一極性的非質子性溶劑。舉例言之(但不以此為限),該非質子性溶劑可選自由以下所組成之群:N-甲基吡咯酮(NMP)、二甲基乙醯胺(DMAC)、二甲基甲醯胺(DMF)、二甲基亞碸(DMSO)、甲苯(toluene)、二甲苯(xylene)及其混合物。The solvent to be used in the composition of the present invention is preferably a polar aprotic solvent. By way of example (but not by way of limitation), the aprotic solvent may be selected from the group consisting of N-methylpyrrolidone (NMP), dimethylacetamide (DMAC), dimethylformamidine. Amine (DMF), dimethyl hydrazine (DMSO), toluene, xylene, and mixtures thereof.
於本發明前驅物組合物中,以整體組合物之總重量計,該醯胺酸酯寡聚物之含量為15%至70%,較佳為30%至60%;該溶劑之含量為20%至80%,較佳為45%至75%。In the precursor composition of the present invention, the content of the glutamate oligomer is 15% to 70%, preferably 30% to 60%, based on the total weight of the whole composition; the solvent content is 20 % to 80%, preferably 45% to 75%.
本發明組合物可視需要包含熟悉此項技術者已知之添加劑,例如光起始劑、矽烷偶合劑、整平劑、安定劑、催化劑及/或消泡劑等。The compositions of the present invention may optionally contain additives known to those skilled in the art, such as photoinitiators, decane coupling agents, leveling agents, stabilizers, catalysts and/or antifoaming agents, and the like.
當前述式(1)之醯胺酸酯寡聚物帶有可感光聚合之基團時,可視需要添加光起始劑。適用於本發明之光起始劑並無特殊限制,其可選自以下所組成之群:二苯甲酮(benzophenone),二苯乙醇酮(benzoin)、2-羥基-2-甲基-1-苯丙酮(2-hydroxy-2-methyl-1-phenyl-propan-1-one)、2,2-二甲氧基-1,2-二苯基乙-1-酮(2,2-dimethoxy-1,2-diphenylethan-1-one)、1-羥基環已基苯基酮(1-hydroxy cyclohexyl phenyl ketone)、2,4,6-三甲基苯甲醯基二苯基膦氧化物(2,4,6-trimethylbenzoyl diphenyl phosphine oxide)、N-苯基甘胺酸、9-苯基吖啶(9-phenylacridine)、苯甲基二甲基縮酮(benzyldimethylketal)、4,4'-雙(二乙基胺)二苯酮、2,4,5-三芳基咪唑二聚物(2,4,5-triarylimidazole dimers)及其混合物;較佳之光起始劑係二苯甲酮。具體而言,以本發明前驅物組合物之總重量計,所用光起始劑之含量為0.01至20重量%,較佳為0.1至5重量%。When the protonate oligomer of the above formula (1) has a photopolymerizable group, a photoinitiator may be added as needed. The photoinitiator suitable for use in the present invention is not particularly limited and may be selected from the group consisting of benzophenone, benzoin, 2-hydroxy-2-methyl-1. -2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one (2,2-dimethoxy -1,2-diphenylethan-1-one), 1-hydroxy cyclohexyl phenyl ketone, 2,4,6-trimethylbenzhydryldiphenylphosphine oxide 2,4,6-trimethylbenzoyl diphenyl phosphine oxide), N-phenylglycine, 9-phenylacridine, benzyldimethylketal, 4,4'-double (Diethylamine) benzophenone, 2,4,5-triarylimidazole dimers and mixtures thereof; preferred photoinitiators are benzophenones. Specifically, the photoinitiator is used in an amount of from 0.01 to 20% by weight, preferably from 0.1 to 5% by weight, based on the total weight of the precursor composition of the present invention.
常用的矽烷偶合劑選自(但不限於)由以下所組成之群:3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、2-胺丙基三甲氧基矽烷、2-胺丙基三乙氧烷基矽烷及其混合物。Commonly used decane coupling agents are selected from, but not limited to, the group consisting of 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxynonane, 2-Aminopropyltriethoxyalkyldecane and mixtures thereof.
本發明亦提供一種聚醯亞胺,其係藉由前述式(1)之聚醯胺酸前驅物聚合而得。舉例言之(但不以此為限),本發明之聚醯亞胺可藉以下流程圖所示聚合方法而製得:
傳統聚醯亞胺之合成方法,需先合成大分子量的聚醯胺酸當作前驅物,但由於分子量過高,黏度太大,以致於操作性變差,易於塗佈時產生流平性不良等缺點。此外,過高之聚醯胺酸分子量,當前驅物醯亞胺化時,因分子間之交互作用以及分子鏈鍵長的縮短,產生極大內應力,致使所塗佈之基材薄膜翹曲變形。另外,習知聚醯亞胺合成方法中,其聚合反應形成聚醯胺酸時的固含量,約介於10%至30%之間,所以經環化後體積收縮比(shrinkage ratio)大,需多次塗佈方可達到產品要求的厚度,增加製程複雜度。The synthesis method of the traditional polyimine needs to synthesize a large molecular weight poly-proline as a precursor, but because the molecular weight is too high, the viscosity is too large, so that the handleability is deteriorated, and the leveling property is easy to be formed during coating. And so on. In addition, the molecular weight of the poly-proline is too high, and the current interaction between the imines is caused by the interaction between the molecules and the shortening of the molecular chain bond length, resulting in a great internal stress, causing the coated substrate film to warp and deform. . In addition, in the conventional polyimine synthesis method, the solid content in the polymerization reaction to form poly-proline is about 10% to 30%, so the volume shrink ratio after cyclization is large, and more is needed. The secondary coating can achieve the required thickness of the product and increase the process complexity.
本發明之醯胺酸酯寡聚物,其特徵為同時具有酯基(-C(O)OR及羧基(-C(O)OH)之端基,處於介穩狀態(meta-stable status),因此在室溫下並不會與自身之胺基(-H2 N)產生反應,但由於聚醯胺酸前驅物分子量低,因此操控性佳,塗佈可達到平整效果。在最後固化(post cure)時,升溫至100℃以上,胺基可先將酯基及羧基端基還原成酸酐,然後再反應成醯胺酸酯寡聚物,之後所得寡聚物進一步聚合成更大的分子,進而縮合提供具優異熱性質、機械性質及拉伸性質之聚醯亞胺。相較於習知技術所使用之黏度較大的高分子聚醯胺酸,本發明係使用黏度較小之醯胺酸酯寡聚物作為前驅物,故於塗佈時,可呈現較高流平性與操作性。The phthalate oligomer of the present invention is characterized in that it has a terminal group of an ester group (-C(O)OR and a carboxyl group (-C(O)OH), and is in a meta-stable state. Therefore, it does not react with its own amine group (-H 2 N) at room temperature, but since the polyglycine precursor has a low molecular weight, it has good handleability, and the coating can achieve a leveling effect. In the case of cure, when the temperature is raised above 100 ° C, the amine group can first reduce the ester group and the carboxyl end group to an acid anhydride, and then react to form a phthalate oligomer, and then the obtained oligomer is further polymerized into a larger molecule. Further, the condensation provides a polyimine with excellent thermal, mechanical and tensile properties. Compared with the high molecular weight polyamic acid used in the prior art, the present invention uses a less viscous indoleamine. The acid ester oligomer serves as a precursor, so that it can exhibit high leveling property and workability at the time of coating.
本發明聚醯亞胺之另一特徵在於,由於所使用之前驅物組合物在進行醯亞胺化時,所含之醯胺酸酯寡聚物先進行分子內環化作用,再進行分子間的聚合與環化作用,可有效降低聚醯亞胺的殘存之內應力。與習知技術相較,藉由本發明之前驅物組合物所環化而得之聚醯亞胺,具有不翹曲的優點。Another feature of the polyimine of the present invention is that the phthalocyanate oligomer contained in the precursor composition is subjected to intramolecular cyclization prior to the imidization of the precursor composition, and then the intermolecular cyclization is carried out. The polymerization and cyclization can effectively reduce the residual internal stress of the polyimide. The polyimine obtained by cyclization of the precursor composition of the present invention has an advantage of not warping as compared with the prior art.
本發明之聚醯亞胺,由於其前驅物組合物具有高固含量(high solids content),含有較少溶劑,故可縮短軟烤時間與降低軟烤溫度,減少因大量溶劑揮發所造成之體積收縮現象,並具有乾燥成膜速度快和減少為達產品要求厚度所需的上膠次數等優點。The polyimine of the present invention has a high solids content and contains less solvent, thereby shortening the soft baking time and reducing the soft baking temperature, and reducing the volume caused by the evaporation of a large amount of solvent. Shrinkage, and has the advantages of fast drying film formation speed and reducing the number of sizing required to reach the required thickness of the product.
另一方面,以往製備聚醯亞胺所需的環化溫度通常高達300℃至350℃,然而本發明前驅物組合物於約200℃至250℃的溫度下即可進行環化反應,更可降低操作成本。On the other hand, the cyclization temperature required for the preparation of polyimine in the past is usually as high as 300 ° C to 350 ° C, however, the precursor composition of the present invention can be subjected to a cyclization reaction at a temperature of about 200 ° C to 250 ° C, and more preferably Reduce operating costs.
再者,於一般高分子聚合都會添加一些單體或短鏈寡聚體,使分子與分子間能形成交鏈(Crosslinking),然而,本發明前驅物因含有可感光聚合基團,進而於固化時可自身交聯,因此本發明前驅物組合物可以無需包含額外的不飽和單體或寡聚體,顯著降低製程複雜度與製程成本。Furthermore, some monomers or short-chain oligomers are added to the general polymer polymerization to form a crosslink between molecules and molecules. However, the precursor of the present invention contains a photopolymerizable group and is cured. When it is self-crosslinkable, the precursor composition of the present invention can be used to significantly reduce process complexity and process cost without the need to contain additional unsaturated monomers or oligomers.
以下實例將用來例舉本發明之實施態樣,以及闡釋本發明之技術特徵,並非用來限制本發明之保護範疇。任何熟悉此技術者可輕易完成之改變或均等性之安排均屬於本發明所主張之範圍,本發明之權利保護範圍應以所附之申請專利範圍為準。The following examples are intended to illustrate the embodiments of the invention, and to illustrate the technical features of the invention, and are not intended to limit the scope of the invention. Any changes or equivalents that can be easily made by those skilled in the art are intended to be within the scope of the invention. The scope of the invention should be determined by the scope of the appended claims.
以下實施例1至20係例示製備本發明用於形成聚醯亞胺之組合物之製作步驟與條件,比較例1則關於習知技術所製得之用於形成聚醯亞胺之組合物。The following Examples 1 to 20 illustrate the production steps and conditions for preparing the composition for forming a polyimine of the present invention, and Comparative Example 1 relates to a composition for forming a polyimide which is obtained by a conventional technique.
將21.81克(0.1莫耳)之均苯四酸二酐(pyromellitic dianhydride,下文簡稱為PMDA)溶於200克之N-甲基吡咯烷酮(N-methyl-2-pyrrolidone;下文簡稱為NMP)中,加熱所得混合物至50℃且反應攪拌兩個小時。慢慢滴入1.161克(0.01莫耳)之丙烯酸2-羥基乙酯(2-hydroxyethyl acrylate,下文簡稱為HEA),於50℃之固定溫度下反應攪拌兩個小時。其後,將20.024克(0.1莫耳)之4,4'-氧化二苯胺(4,4'-oxydianiline,下文簡稱為ODA)加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 g (0.1 mol) of pyromellitic dianhydride (hereinafter abbreviated as PMDA) was dissolved in 200 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and heated. The resulting mixture was brought to 50 ° C and the reaction was stirred for two hours. 1.161 g (0.01 mol) of 2-hydroxyethyl acrylate (hereinafter referred to as HEA) was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Thereafter, 20.024 g (0.1 mol) of 4,4'-oxydianiline (hereinafter referred to as ODA) was added to the solution, and after completely dissolved, it was further fixed at 50 ° C. The reaction was stirred for six hours.
將20.024克(0.1莫耳)之ODA溶於200克之NMP中,冰浴至0℃且反應攪拌一個小時,其後加入0.29克(0.002莫耳)之鄰苯二甲酐(phthalic anhydride),待反應攪拌一小時後,再慢慢加入21.59克(0.099莫耳)之PMDA,於50℃之固定溫度下反應攪拌十二個小時。20.024 g (0.1 mol) of ODA was dissolved in 200 g of NMP, ice-cooled to 0 ° C and the reaction was stirred for one hour, after which 0.29 g (0.002 mol) of phthalic anhydride was added. After the reaction was stirred for one hour, 21.59 g (0.099 mol) of PMDA was slowly added, and the reaction was stirred at a fixed temperature of 50 ° C for 12 hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入13.01克(0.01莫耳)之甲基丙烯酸2-羥基乙酯(2-hydroxyethyl methacrylate;下文簡稱為HEMA),於50℃之固定溫度下反應攪拌兩個小時。再將20.024克(0.1莫耳)之ODA加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 13.01 g (0.01 mol) of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Further, 20.024 g (0.1 mol) of ODA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入1.161克(0.01莫耳)之HEA,於50℃之固定溫度下反應攪拌兩個小時。再將10.814克(0.1莫耳)之對苯二胺(para-phenylenediamine,下文簡稱為pPDA)加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 10.814 g (0.1 mol) of para-phenylenediamine (hereinafter abbreviated as pPDA) was added to the solution, and after completely dissolved, the reaction was further stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入13.01克(0.01莫耳)之HEMA,於50℃之固定溫度下反應攪拌兩個小時。再將10.814克(0.1莫耳)之pPDA加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 10.814 g (0.1 mol) of pPDA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃下反應攪拌兩個小時。慢慢滴入1.161克(0.01莫耳)之HEA,於50℃之固定溫度下反應攪拌兩個小時。再將21.23克(0.1莫耳)之間二甲基對二胺基聯苯(2,2-dimethyl-4,4-diamino-biphenyl,下文簡稱為DMDB)加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP and heated to 50 ° C for 2 hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 21.23 g (0.1 mol) of dimethyl p-diamino-biphenyl (2,2-dimethyl-4,4-diamino-biphenyl, hereinafter referred to as DMDB) was added to the solution, after completely dissolved, The reaction was further stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入13.01克(0.01莫耳)之HEMA,於50℃之固定溫度下反應攪拌兩個小時。再將21.23克(0.1莫耳)之DMDB加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 21.23 g (0.1 mol) of DMDB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入1.161克(0.01莫耳)之HEA,於50℃之固定溫度下反應攪拌兩個小時。再將21.23克(0.1莫耳)之鄰二甲基對二胺基聯苯(o-Tolidine;下文簡稱為oTLD)加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. 21.23 g (0.1 mol) of o-tolidine (o-Tolidine; hereinafter referred to as oTLD) was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C. Six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入13.01克(0.01莫耳)之HEMA,於50℃之固定溫度下反應攪拌兩個小時。再將21.23克(0.1莫耳)之oTLD加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 21.23 g (0.1 mol) of oTLD was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入1.161克(0.01莫耳)之HEA,於50℃之固定溫度下反應攪拌兩個小時。再將32.02克(0.1莫耳)之間二(三氟甲基)對二胺基聯苯(2,2'-bis(trifluoromethyl)benzidine,下文簡稱為TFMB)加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 1.161 g (0.01 mol) of HEA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 32.02 g (0.1 mol) of bis(trifluoromethyl)-p-diaminobiphenyl (2,2'-bis(trifluoromethyl)benzidine, hereinafter referred to as TFMB) was added to the solution, after completely dissolved. The reaction was further stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入13.01克(0.01莫耳)之HEMA,於50℃之固定溫度下反應攪拌兩個小時。再將32.02克(0.1莫耳)之TFMB加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 13.01 g (0.01 mol) of HEMA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 32.02 g (0.1 mol) of TFMB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.32克(0.01莫耳)之甲醇,於50℃之固定溫度下反應攪拌兩個小時。再將20.024克(0.1莫耳)之ODA加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Further, 20.024 g (0.1 mol) of ODA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)之異丙醇,於50℃之固定溫度下反應攪拌兩個小時。再將20.024克(0.1莫耳)之ODA加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 20.024 g (0.1 mol) of ODA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.32克(0.01莫耳)之甲醇,於50℃之固定溫度下反應攪拌兩個小時。再將10.814克(0.1莫耳)之pPDA加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Further, 10.814 g (0.1 mol) of pPDA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)之異丙醇,於50℃之固定溫度下反應攪拌兩個小時。再將10.814克(0.1莫耳)之pPDA加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 10.814 g (0.1 mol) of pPDA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃下反應攪拌兩個小時。慢慢滴入10.32克(0.01莫耳)之甲醇,於50℃之固定溫度下反應攪拌兩個小時。再將21.23克(0.1莫耳)之DMDB加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP and heated to 50 ° C for 2 hours. 10.32 g (0.01 mol) of methanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 21.23 g (0.1 mol) of DMDB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)之異丙醇,於50℃之固定溫度下反應攪拌兩個小時。再將21.23克(0.1莫耳)之DMDB加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 21.23 g (0.1 mol) of DMDB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.32克(0.01莫耳)之甲醇,於50℃之固定溫度下反應攪拌兩個小時。再將21.23克(0.1莫耳)之oTLD加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Further, 21.23 g (0.1 mol) of oTLD was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)之異丙醇,於50℃之固定溫度下反應攪拌兩個小時。再將21.23克(0.1莫耳)之oTLD加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 21.23 g (0.1 mol) of oTLD was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.32克(0.01莫耳)之甲醇,於50℃之固定溫度下反應攪拌兩個小時。再將32.02克(0.1莫耳)之TFMB加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Further, 32.02 g (0.1 mol) of TFMB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
將21.81克(0.1莫耳)之PMDA溶於200克之NMP中,加熱至50℃且反應攪拌兩個小時。慢慢滴入0.601克(0.01莫耳)之異丙醇,於50℃之固定溫度下反應攪拌兩個小時。再將32.02克(0.1莫耳)之TFMB加至溶液中,待完全溶解後,再於50℃之固定溫度下反應攪拌六個小時。21.81 grams (0.1 mole) of PMDA was dissolved in 200 grams of NMP, heated to 50 ° C and stirred for two hours. 0.601 g (0.01 mol) of isopropanol was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 32.02 g (0.1 mol) of TFMB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours.
首先利用Waters Model:2010的HT-GPC儀器測量所得聚醯胺酸的分子量相關數據,如下表1所示:
由表1數據可知,本發明方法可提供具較低聚合物分散性之聚醯胺酸,亦即所製得聚醯胺酸之分子量範圍分布較窄、高低分子量差距較小,其品質較佳。It can be seen from the data in Table 1 that the method of the present invention can provide polylysine with lower polymer dispersibility, that is, the polyglycine produced has a narrow molecular weight range, a small difference in high molecular weight and low molecular weight, and the quality is better. .
取實施例1與比較例1所得組合物以旋轉塗佈之方式製作薄膜。再進一步以烘箱烘烤,而升溫曲線分為三段,分別為150℃/60 min,250℃/60 min及350℃/120 min,其升溫速度為2℃/min,之後,冷卻回溫。進行物性測試。The composition obtained in Example 1 and Comparative Example 1 was formed into a film by spin coating. Further drying in an oven, the heating curve is divided into three sections, respectively 150 ° C / 60 min, 250 ° C / 60 min and 350 ° C / 120 min, the heating rate is 2 ° C / min, and then cooled back to temperature. Conduct physical testing.
接著,利用萬能拉力機(宏達出產的高溫彎曲測定儀Model 9102)進行聚醯亞胺膜機械性質之測試。將所得聚醯亞胺膜裁切成12 cm×10 cm×0.25 mm之大小,架置於該萬能拉力機上,於溫度23℃下進行,速度設定為10 mm/min,分別對由實施例1組合物及比較例1組合物所得聚醯亞胺膜作拉力測試,以量測不同之抗張強度,結果如表2所示:
由表2結果顯示,本發明所提供之聚醯亞胺膜,可展現較為優異之拉伸強度與伸長率。The results of Table 2 show that the polyimide film provided by the present invention exhibits superior tensile strength and elongation.
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CN101807001B (en) * | 2010-03-17 | 2013-04-10 | 长兴化学工业股份有限公司 | Photosensitive resin composition and application thereof |
JP6076986B2 (en) * | 2011-09-20 | 2017-02-08 | ローディア オペレーションズ | Thermoplastic polyimide |
TWI535768B (en) | 2014-07-18 | 2016-06-01 | 長興材料工業股份有限公司 | Solvent-containing dry film and the use thereof |
CN106256846B (en) * | 2015-06-17 | 2019-04-16 | 长兴材料工业股份有限公司 | Polyimide precursor composition, use thereof, and polyimide prepared therefrom |
TWI598232B (en) | 2016-07-01 | 2017-09-11 | 長興材料工業股份有限公司 | Polyimide dry film and application thereof |
TWI621642B (en) * | 2016-11-30 | 2018-04-21 | 長興材料工業股份有限公司 | Precursor for polyimide and use thereof |
TWI650346B (en) * | 2016-11-30 | 2019-02-11 | 長興材料工業股份有限公司 | Polyimine precursor composition and application thereof |
TWI637980B (en) * | 2017-01-11 | 2018-10-11 | 長興材料工業股份有限公司 | Precursor for polyimide and use thereof |
TWI617441B (en) | 2017-03-31 | 2018-03-11 | 長興材料工業股份有限公司 | Method for preparing a patterned coverlay on a substrate |
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JP2643635B2 (en) * | 1991-03-18 | 1997-08-20 | 信越化学工業株式会社 | Photosensitive resin solution composition |
JPH06102667A (en) * | 1991-08-13 | 1994-04-15 | Toray Ind Inc | Photosensitive polyimide precursor composition and production there of |
JP3518080B2 (en) * | 1995-08-17 | 2004-04-12 | 東レ株式会社 | Method for producing polyimide precursor composition |
KR100548625B1 (en) * | 2003-03-24 | 2006-01-31 | 주식회사 엘지화학 | High heat resistant transparent polyimide precursor and photosensitive resin composition using same |
JP2005099353A (en) * | 2003-09-24 | 2005-04-14 | Hitachi Chemical Dupont Microsystems Ltd | Photosensitive resin composition, method for manufacturing pattern using the same, and electronic component |
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TW200906910A (en) | 2009-02-16 |
KR20090014123A (en) | 2009-02-06 |
KR101442841B1 (en) | 2014-09-23 |
JP5437604B2 (en) | 2014-03-12 |
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