TW201938686A - Composition for forming polyimide, polyimide and polyimide film - Google Patents
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本發明是有關於一種組成物，且特別是有關於一種用以形成聚醯亞胺的組成物、由所述組成物製得的聚醯亞胺及由所述聚醯亞胺所製得的聚醯亞胺膜。The present invention relates to a composition, and in particular to a composition for forming polyimide, a polyimide prepared from the composition, and a polyimide Polyimide film.
一般而言，聚醯亞胺（polyimide，PI）是由二胺（diamine）單體與二酸酐（dianhydride）單體經聚縮合反應（polycondensation reaction）所得到的高分子材料。目前，聚醯亞胺由於具有化學安定性、電氣性質和熱安定性等性質，因此已被廣泛地應用於各種產業，例如半導體工業、光電產業、航空材料、生醫材料、紡織產業、建築領域、汽車工業、通訊材料、機械工業或薄膜工業中，而成為生活中不可或缺的材料。為了更進一步提升聚醯亞胺的應用性，本領域之技術人員對新穎的聚醯亞胺的研究開展仍持續在發展中。Generally speaking, polyimide (PI) is a polymer material obtained by a polycondensation reaction of a diamine monomer and a dianhydride monomer. At present, polyimide has been widely used in various industries due to its chemical stability, electrical properties, and thermal stability, such as the semiconductor industry, optoelectronics industry, aviation materials, biomedical materials, textile industry, and construction. , Automotive industry, communication materials, machinery industry or film industry, and become indispensable materials in life. In order to further improve the applicability of polyfluorene imine, the research and development of the novel polyfluorene imine by those skilled in the art is still under development.
本發明提供一種用以形成聚醯亞胺的組成物，其可製得具有耐熱性及彈性的聚醯亞胺或聚醯亞胺膜。The invention provides a composition for forming polyimide, which can prepare a polyimide or a polyimide film having heat resistance and elasticity.
本發明的用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、二胺單體組分以及溶劑。二胺單體組分包括20莫耳份至65莫耳份的4,4'-二氨基二苯基醚（ODA；4,4'-diaminodiphenyl ether）、30莫耳份至70莫耳份的由式(I)所示的化合物以及1莫耳份至10莫耳份的三聚氰胺（melamine）：
式(I)，其中x與z的總和為1至20，且y為4至50。The composition for forming polyfluorene imide of the present invention includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent. The diamine monomer component includes 20 mol parts to 65 mol parts of 4,4'-diaminodiphenyl ether (ODA; 4,4'-diaminodiphenyl ether), and 30 mol parts to 70 mol parts. The compound represented by formula (I) and 1 to 10 mol parts of melamine:
Formula (I), wherein the sum of x and z is 1 to 20, and y is 4 to 50.
在本發明的一實施方式中，上述的四羧酸二酐單體組分包括含有芳香族的四羧酸二酐。In one embodiment of the present invention, the tetracarboxylic dianhydride monomer component includes an aromatic tetracarboxylic dianhydride.
在本發明的一實施方式中，上述的二胺單體組分包括25莫耳份至65莫耳份的4,4'-二氨基二苯基醚、30莫耳份至70莫耳份的由式(I)所示的化合物、及1莫耳份至10莫耳份的三聚氰胺。In one embodiment of the present invention, the above-mentioned diamine monomer component includes 25 to 65 mol of 4,4′-diaminodiphenyl ether, and 30 to 70 mol of A compound represented by formula (I), and 1 to 10 mol parts of melamine.
在本發明的一實施方式中，上述的四羧酸二酐單體組分為3,4,3',4'-二苯醚四甲酸二酐（ODPA；3,4,3',4'-oxydiphthalic anhydride）。In one embodiment of the present invention, the aforementioned tetracarboxylic dianhydride monomer component is 3,4,3 ', 4'-diphenyl ether tetracarboxylic dianhydride (ODPA; 3,4,3', 4 ' -oxydiphthalic anhydride).
在本發明的一實施方式中，上述的二胺單體組分包括20莫耳份至45莫耳份的4,4'-二氨基二苯基醚、50莫耳份至70莫耳份的由式(I)所示的化合物、及5莫耳份至10莫耳份的三聚氰胺。In one embodiment of the present invention, the diamine monomer component includes 20 to 45 mols of 4,4'-diaminodiphenyl ether, and 50 to 70 mols of A compound represented by formula (I), and 5 to 10 mol parts of melamine.
在本發明的一實施方式中，上述的四羧酸二酐單體組分為均苯四甲酸二酐（PMDA；pyromellitic dianhydride）。In one embodiment of the present invention, the tetracarboxylic dianhydride monomer component is pyromellitic dianhydride (PMDA).
在本發明的一實施方式中，上述的二胺單體組分包括25莫耳份至45莫耳份的4,4'-二氨基二苯基醚、50莫耳份至70莫耳份的由式(I)所示的化合物、及5莫耳份至10莫耳份的三聚氰胺。In one embodiment of the present invention, the diamine monomer component includes 25 to 45 mols of 4,4'-diaminodiphenyl ether, and 50 to 70 mols of A compound represented by formula (I), and 5 to 10 mol parts of melamine.
在本發明的一實施方式中，上述的四羧酸二酐單體組分為3,3',4,4'-聯苯四羧酸二酐（BPDA；3,3',4,4'-biphenyltetracarboxylic dianhydride）。In one embodiment of the present invention, the tetracarboxylic dianhydride monomer component is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA; 3,3', 4,4 ' -biphenyltetracarboxylic dianhydride).
在本發明的一實施方式中，上述的二胺單體組分更包括矽氧烷二胺。In one embodiment of the present invention, the diamine monomer component further includes siloxane diamine.
在本發明的一實施方式中，上述的矽氧烷二胺包括由式(II)所示的化合物：
式(II)，其中n為8至11。In one embodiment of the present invention, the above-mentioned siloxane diamine includes a compound represented by formula (II):
Formula (II), wherein n is 8 to 11.
在本發明的一實施方式中，上述的二胺單體組分包括35莫耳份至45莫耳份的4,4'-二氨基二苯基醚、40莫耳份至50莫耳份的由式(I)所示的化合物、5莫耳份至10莫耳份的三聚氰胺、及5莫耳份至10莫耳份的矽氧烷二胺。In one embodiment of the present invention, the diamine monomer component includes 35 to 45 mol of 4,4'-diaminodiphenyl ether, and 40 to 50 mol of A compound represented by formula (I), 5 mol parts to 10 mol parts of melamine, and 5 mol parts to 10 mol parts of siloxane diamine.
本發明的聚醯亞胺係由如前所述之用以形成聚醯亞胺的組成物所製得。The polyfluorene imide of the present invention is prepared from a composition for forming a polyfluorene imine as described above.
本發明的聚醯亞胺膜係由如前所述的聚醯亞胺所製得。The polyfluorene imide film of the present invention is prepared from the polyfluorine imine described above.
基於上述，本發明的用以形成聚醯亞胺的組成物透過包括四羧酸二酐單體組分、二胺單體組分以及溶劑，其中二胺單體組分包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺而可具有良好的成膜性。如此一來，透過本發明的用以形成聚醯亞胺的組成物可製得材料性質優異的聚醯亞胺膜。另外，透過本發明的用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、二胺單體組分以及溶劑，其中二胺單體組分包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺，藉此可製得具有耐熱性及彈性的聚醯亞胺或聚醯亞胺膜。除此之外，本發明的用以形成聚醯亞胺的組成物更可透過包括特定範圍內的矽氧烷二胺，以具有良好的成膜性，進而得以製成具有耐熱性及彈性的聚醯亞胺膜。Based on the above, the composition for forming a polyfluorene imide of the present invention includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent, wherein the diamine monomer component includes a content in a specific range, respectively. 4,4'-diaminodiphenyl ether in the compound, a compound represented by the formula (I), and melamine can have good film-forming properties. In this way, through the composition for forming polyimide of the present invention, a polyimide film having excellent material properties can be obtained. In addition, the composition for forming a polyfluorene imide through the present invention includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent, wherein the content of the diamine monomer component is within a specific range, respectively. 4,4'-diaminodiphenyl ether, a compound represented by formula (I), and melamine, whereby a polyimide or polyimide film having heat resistance and elasticity can be obtained. In addition, the composition for forming polyfluorene imide of the present invention can pass through the siloxane diamine in a specific range to have a good film-forming property, and then be made into a heat-resistant and elastic material. Polyimide film.
為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施方式作詳細說明如下。In order to make the above features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail below.
在本文中，由「一數值至另一數值」表示的範圍，是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此，某一特定數值範圍的記載，涵蓋該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍，如同在說明書中明文寫出該任意數值和該較小數值範圍一樣。In this article, a range represented by "one value to another value" is a summary representation that avoids enumerating all the values in the range one by one in the specification. Therefore, the record of a specific numerical range covers any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value were explicitly written in the description. Same scope.
本發明的一實施方式提出一種用以形成聚醯亞胺的組成物，其包括四羧酸二酐單體組分、二胺單體組分以及溶劑。在本實施方式中，二胺單體組分的總莫耳百分比與四羧酸二酐單體組分的總莫耳百分比的比例為1：0.95至1：1.05。An embodiment of the present invention provides a composition for forming polyfluorene imide, which includes a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent. In this embodiment, the ratio of the total mole ratio of the diamine monomer component to the total mole ratio of the tetracarboxylic dianhydride monomer component is 1: 0.95 to 1: 1.05.
在本實施方式中，二胺單體組分包括4,4'-二氨基二苯基醚（ODA；4,4'-diaminodiphenyl ether）、由式(I)所示的化合物以及三聚氰胺（melamine）：
式(I)，其中x與z的總和為1至20，y為4至50。也就是說，在本實施方式中，二胺單體組分包括三種二胺單體。另外，由式(I)所示的化合物的胺氫當量（amine hydrogen equivalent weight）介於250至270之間，其數目平均分子量大約為1000。In this embodiment, the diamine monomer component includes 4,4'-diaminodiphenyl ether (ODA; 4,4'-diaminodiphenyl ether), a compound represented by formula (I), and melamine :
Formula (I), wherein the sum of x and z is 1 to 20, and y is 4 to 50. That is, in this embodiment, the diamine monomer component includes three kinds of diamine monomers. In addition, the amine hydrogen equivalent weight of the compound represented by the formula (I) is between 250 and 270, and its number average molecular weight is about 1,000.
另外，在本實施方式中，二胺單體組分包括20莫耳份至65莫耳份的4,4'-二氨基二苯基醚、30莫耳份至70莫耳份的由式(I)所示的化合物、及1莫耳份至10莫耳份的三聚氰胺。若4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺中的至少一者的莫耳份未落在前述範圍內，則用以形成聚醯亞胺的組成物不具成膜性。In addition, in this embodiment, the diamine monomer component includes 20 to 65 mol of 4,4'-diaminodiphenyl ether, and 30 to 70 mol of the formula ( I) A compound represented by mol and 1 to 10 mol parts of melamine. If the mole fraction of at least one of 4,4'-diaminodiphenyl ether, a compound represented by formula (I), and melamine does not fall within the foregoing range, a composition for forming polyimide The material is not film-forming.
在本實施方式中，四羧酸二酐單體組分包括含有芳香族的四羧酸二酐。具體而言，含有芳香族的四羧酸二酐的實例包括但不限於：3,4,3',4'-二苯醚四甲酸二酐（ODPA；3,4,3',4'-oxydiphthalic anhydride）、均苯四甲酸二酐（PMDA；pyromellitic dianhydride）、3,3',4,4'-聯苯四羧酸二酐（BPDA；3,3',4,4'-biphenyltetracarboxylic dianhydride）、2,2',3,3'-聯苯四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,2-雙（2,3-二羧基苯基）六氟丙烷二酐、2,2-雙（3,4-二羧基苯基）六氟丙烷二酐（6FDA)、雙（2,3-二羧基苯基）甲烷二酐、雙（3,4-二羧基苯基）甲烷二酐、3,3',4,4'-二苯基碸四羧酸二酐（DSDA；3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride）、2,2-雙[4-(3,4-二羧基苯氧基）苯基]丙烷二酸酐（BPADA；2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane）、雙（2,3-二羧基苯基）碸二酐、雙（3,4-二羧基苯基）碸二酐或乙二醇雙偏苯三酸二酐（TMEG；ethylene glycol bis(4-trimellitate anhydride)），且優選為3,3',4,4'-聯苯四羧酸二酐、3,4,3',4'-二苯醚四甲酸二酐、均苯四酸二酐或2,2-雙（3,4-二羧基苯基）六氟丙烷二酐（6FDA)。In the present embodiment, the tetracarboxylic dianhydride monomer component includes an aromatic tetracarboxylic dianhydride. Specifically, examples of aromatic tetracarboxylic dianhydrides include, but are not limited to, 3,4,3 ', 4'-diphenyl ether tetracarboxylic dianhydride (ODPA; 3,4,3', 4'- oxydiphthalic anhydride), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA; 3,3', 4,4'-biphenyltetracarboxylic dianhydride) , 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-di Benzophenone tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylate Acid dianhydride (DSDA; 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride), 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride (BPADA; 2 , 2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane), bis (2,3-dicarboxyphenyl) fluorene dianhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride or ethyl Diethylene glycol bistrimellitic dianhydride (TMEG; ethylene glycol bis (4-tri mellitate anhydride)), and preferably 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-diphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride Or 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA).
另一方面，在本實施方式中，四羧酸二酐單體組分包括一種四羧酸二酐單體。舉例而言，在一實施方式中，四羧酸二酐單體組分為3,4,3',4'-二苯醚四甲酸二酐（ODPA），而此時，二胺單體組分包括25莫耳份至65莫耳份的4,4'-二氨基二苯基醚、30莫耳份至70莫耳份的由式(I)所示的化合物、及1莫耳份至10莫耳份的三聚氰胺，並且用以形成聚醯亞胺的組成物具有良好的成膜性。舉另一例而言，在一實施方式中，四羧酸二酐單體組分為均苯四甲酸二酐（PMDA），而此時，二胺單體組分包括20莫耳份至45莫耳份的4,4'-二氨基二苯基醚、50莫耳份至70莫耳份的由式(I)所示的化合物、及5莫耳份至10莫耳份的三聚氰胺，並且用以形成聚醯亞胺的組成物具有良好的成膜性。舉又一例而言，在一實施方式中，四羧酸二酐單體組分為3,3',4,4'-聯苯四羧酸二酐（BPDA），而此時，二胺單體組分包括25莫耳份至45莫耳份的4,4'-二氨基二苯基醚、50莫耳份至70莫耳份的由式(I)所示的化合物、及5莫耳份至10莫耳份的三聚氰胺，並且用以形成聚醯亞胺的組成物具有良好的成膜性。On the other hand, in this embodiment, the tetracarboxylic dianhydride monomer component includes a tetracarboxylic dianhydride monomer. For example, in one embodiment, the tetracarboxylic dianhydride monomer component is 3,4,3 ', 4'-diphenyl ether tetracarboxylic dianhydride (ODPA), and at this time, the diamine monomer group It includes 25 mol parts to 65 mol parts of 4,4'-diaminodiphenyl ether, 30 mol parts to 70 mol parts of the compound represented by formula (I), and 1 mol part to 10 mol parts of melamine, and the composition used to form polyimide has good film-forming properties. For another example, in one embodiment, the tetracarboxylic dianhydride monomer component is pyromellitic dianhydride (PMDA), and at this time, the diamine monomer component includes 20 mol parts to 45 mol parts. 4,4'-diaminodiphenyl ether, 50 to 70 mol parts of the compound represented by formula (I), and 5 to 10 mol parts of melamine, and The polyimide-forming composition has good film-forming properties. For another example, in one embodiment, the tetracarboxylic dianhydride monomer component is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), and at this time, the diamine monomer The body composition includes 25 to 45 mol parts of 4,4'-diaminodiphenyl ether, 50 to 70 mol parts of the compound represented by formula (I), and 5 mol parts. From 10 to 10 moles of melamine, and the composition used to form polyimide has good film-forming properties.
另外，就提升聚醯亞胺的彈性的觀點而言，二胺單體組分可更包括矽氧烷二胺。具體而言，矽氧烷二胺的實例包括（但不限於）：由以下式(II)所示的化合物，
式(II)，其中n為8至11。在一實施方式中，二胺單體組分包括35莫耳份至45莫耳份的4,4'-二氨基二苯基醚、40莫耳份至50莫耳份的由式(I)所示的化合物、5莫耳份至10莫耳份的三聚氰胺、及5莫耳份至10莫耳份的矽氧烷二胺。In addition, from the viewpoint of improving the elasticity of the polyimide, the diamine monomer component may further include a siloxane diamine. Specifically, examples of the siloxane diamine include (but are not limited to): a compound represented by the following formula (II),
Formula (II), wherein n is 8 to 11. In one embodiment, the diamine monomer component includes 35 to 45 moles of 4,4'-diaminodiphenyl ether, and 40 to 50 moles of formula (I) The compound shown, 5 to 10 mols of melamine, and 5 to 10 mols of siloxane diamine.
在本實施方式中，溶劑並無特別限制，只要能夠溶解四羧酸二酐單體組分及二胺單體組分即可。具體而言，溶劑的實例包括但不限於：N,N-二甲基乙醯胺（N,N-dimethylacetamide；DMAc）、N,N-二甲基甲醯胺（N,N-dimethylformamide；DMF）、N,N'-二乙基乙醯胺、N-甲基-2-吡咯啶酮（N-methyl-2-pyrrolidone；NMP）、γ-丁內酯、六甲基磷酸三醯胺等醯胺系溶劑；四甲基脲、N,N-二甲基乙基脲等脲系溶劑；二甲基亞碸、二苯基碸、四甲基碸等亞碸或碸系溶劑；氯仿、二氯甲烷等鹵化烷基系溶劑；苯、甲苯等芳香族烴系溶劑；苯酚、甲酚等酚系溶劑；或四氫呋喃、1,3-二氧戊烷、二甲醚、二***、對甲酚甲醚等醚系溶劑。上述溶劑可單獨使用或組合多種來使用。為提高四羧酸二酐單體組分及二胺單體組分的溶解性及反應性，溶劑較佳為DMAc、DMF、NMP等醯胺系溶劑。In this embodiment, the solvent is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride monomer component and the diamine monomer component. Specifically, examples of the solvent include, but are not limited to, N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF) ), N, N'-diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, trimethylamine hexamethyl phosphate, etc. Amidine-based solvents; urea-based solvents such as tetramethylurea, N, N-dimethylethylurea; fluorene-based or fluorene-based solvents such as dimethylfluorene, diphenylfluorene, and tetramethylfluorene; chloroform, Halogenated alkyl solvents such as dichloromethane; aromatic hydrocarbon solvents such as benzene and toluene; phenol solvents such as phenol and cresol; or tetrahydrofuran, 1,3-dioxolane, dimethyl ether, diethyl ether, and p-methyl Ether solvents such as phenol methyl ether. These solvents can be used alone or in combination. In order to improve the solubility and reactivity of the tetracarboxylic dianhydride monomer component and the diamine monomer component, the solvent is preferably an amine-based solvent such as DMAc, DMF, or NMP.
值得說明的是，如上所述，在本實施方式中，透過包括四羧酸二酐單體組分、二胺單體組分以及溶劑，其中二胺單體組分包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物以及三聚氰胺，藉此用以形成聚醯亞胺的組成物可具有良好的成膜性。It is worth noting that, as described above, in this embodiment, through including a tetracarboxylic dianhydride monomer component, a diamine monomer component, and a solvent, the content of the diamine monomer component is within a specific range, respectively. 4,4'-diaminodiphenyl ether, a compound represented by the formula (I), and melamine, whereby the composition for forming a polyimide can have good film-forming properties.
本發明的另一實施方式提供一種聚醯亞胺，由任一種前述實施方式中的用以形成聚醯亞胺的組成物所製得。用以形成聚醯亞胺的組成物中的二胺單體組分、四羧酸二酐單體組分及溶劑的相關描述已於前述實施方式中進行詳盡地說明，故於此不再贅述。Another embodiment of the present invention provides a polyfluorene imine, which is prepared from the composition for forming a polyfluorene imine in any one of the foregoing embodiments. Relevant descriptions of the diamine monomer component, the tetracarboxylic dianhydride monomer component, and the solvent in the composition for forming polyimide have been described in detail in the foregoing embodiment, and will not be repeated here. .
詳細而言，在本實施方式中，聚醯亞胺是由二胺單體組分與四羧酸二酐單體組分於溶劑中進行縮合聚合反應來製備。在一實施方式中，聚醯亞胺可使用三種二胺單體與一種四羧酸二酐單體來進行製備。在另一實施方式中，聚醯亞胺可使用四種二胺單體與一種四羧酸二酐單體來進行製備。須說明的是，由於二胺單體及四羧酸二酐單體將反應產生聚醯亞胺，因此二胺單體中的氨基的總莫耳數與四羧酸二酐單體中的酸酐基的總莫耳數的比例約為1：1。更詳細地說，所述比例可介於1：0.95至1：1.05之間。Specifically, in this embodiment, the polyfluorene imine is prepared by performing a condensation polymerization reaction of a diamine monomer component and a tetracarboxylic dianhydride monomer component in a solvent. In one embodiment, polyfluorene imine can be prepared using three diamine monomers and one tetracarboxylic dianhydride monomer. In another embodiment, polyfluorene imine can be prepared using four diamine monomers and one tetracarboxylic dianhydride monomer. It should be noted that, since the diamine monomer and the tetracarboxylic dianhydride monomer will react to produce polyimide, the total mole number of amino groups in the diamine monomer and the acid anhydride in the tetracarboxylic dianhydride monomer The ratio of the total moles of the base is approximately 1: 1. In more detail, the ratio may be between 1: 0.95 and 1: 1.05.
另外，在本實施方式中，聚醯亞胺例如是透過熱環化法或化學環化法來製備。熱環化法及化學環化法分別可利用所屬技術領域中具有通常知識者所周知的任何步驟來進行。舉例來說，透過熱環化法來製備聚醯亞胺包括以下步驟：使用以形成聚醯亞胺的組成物進行聚合反應以形成聚醯胺酸溶液後，加熱聚醯胺酸溶液以進行醯亞胺化反應（即脫水環化反應）來形成聚醯亞胺。詳細而言，用以形成聚醯亞胺的組成物的製備方法例如是在5o C至40o C的溫度範圍內，將二胺單體組分及四羧酸二酐單體組分於溶劑中混合均勻。混合的方法並無特別限制，只要能使二胺單體組分及四羧酸二酐單體組分於溶劑中混合均勻即可。在一實施方式中，在形成聚醯胺酸溶液的步驟中，反應溫度例如是介於5o C至40o C之間；反應時間例如是介於3小時至12小時之間。在一實施方式中，進行醯亞胺化反應的條件例如是在100o C、150o C及220o C的溫度環境下分別反應1至2小時。In this embodiment, the polyfluorene imine is prepared by, for example, a thermal cyclization method or a chemical cyclization method. The thermal cyclization method and the chemical cyclization method can be performed by using any steps known to those skilled in the art. For example, the preparation of polyimide by a thermal cyclization method includes the following steps: After using a composition to form a polyimide to perform a polymerization reaction to form a polyamidic acid solution, heating the polyamidic acid solution to perform polyimide Imination reaction (ie, dehydration cyclization reaction) to form polyfluorene imine. In detail, the preparation method of the composition for forming polyfluorene imide is, for example, in a temperature range of 5 o C to 40 o C, a diamine monomer component and a tetracarboxylic dianhydride monomer component are mixed in Mix well in solvent. The method of mixing is not particularly limited, as long as the diamine monomer component and the tetracarboxylic dianhydride monomer component can be mixed uniformly in a solvent. In one embodiment, the step of forming polyamide acid solution, the reaction temperature is between, for example, between 5 o C to 40 o C; the reaction time is, for example, between 3-12 hours. In one embodiment, the conditional acyl imidization reaction are, for example, 1-2 hours at ambient temperature 100 o C, 150 o C and 220 o C in.
舉另一例來說，透過化學環化法來製備聚醯亞胺包括以下步驟：使用以形成聚醯亞胺的組成物進行聚合反應以形成聚醯胺酸溶液後，將脫水劑與醯亞胺化劑加入聚醯胺酸溶液中以進行醯亞胺化反應（即脫水環化反應）來形成聚醯亞胺。詳細而言，用以形成聚醯亞胺的組成物的製備方法例如是在5o C至40o C的溫度範圍內，將二胺單體組分及四羧酸二酐單體組分於溶劑中混合均勻。混合的方法並無特別限制，只要能使二胺單體組分及四羧酸二酐單體組分於溶劑中混合均勻即可。在一實施方式中，在形成聚醯胺酸溶液的步驟中，反應溫度例如是介於5o C至40o C之間；反應時間例如是介於3小時至12小時之間。在一實施方式中，進行醯亞胺化反應的條件例如是在120o C的溫度環境下反應2小時至5小時，較佳為3小時。在一實施方式中，脫水劑的實例包括但不限於：乙酸酐、丙酸酐、正丁酸酐、苯甲酸酐或三氟乙酸酐；醯亞胺化劑的實例包括但不限於：吡啶、甲基吡啶、喹啉或異喹啉。在一實施方式中，相對於聚醯胺酸的醯胺基，脫水劑的添加量例如是0.5至10.0倍莫耳當量，而醯亞胺化劑的添加量例如是為0.5至5.0倍莫耳當量。For another example, preparing a polyimide by a chemical cyclization method includes the following steps: After using a composition to form a polyimide to perform a polymerization reaction to form a polyamidic acid solution, the dehydrating agent and the iminoimide are formed. A chemical agent is added to the polyfluorinated acid solution to carry out the fluorinated imidization reaction (that is, the dehydration cyclization reaction) to form the polyfluorinated imine. In detail, the preparation method of the composition for forming polyfluorene imide is, for example, in a temperature range of 5 o C to 40 o C, a diamine monomer component and a tetracarboxylic dianhydride monomer component are mixed in Mix well in solvent. The method of mixing is not particularly limited, as long as the diamine monomer component and the tetracarboxylic dianhydride monomer component can be mixed uniformly in a solvent. In one embodiment, the step of forming polyamide acid solution, the reaction temperature is between, for example, between 5 o C to 40 o C; the reaction time is, for example, between 3-12 hours. In one embodiment, the conditional acyl imidization reaction at a temperature, for example, 120 o C environment for 2 hours to 5 hours, preferably 3 hours. In an embodiment, examples of the dehydrating agent include, but are not limited to, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, or trifluoroacetic anhydride; examples of the fluorinating agent include, but are not limited to, pyridine, methyl Pyridine, quinoline or isoquinoline. In one embodiment, the added amount of the dehydrating agent is, for example, 0.5 to 10.0 times the molar equivalent, and the added amount of the fluorinated imidating agent is, for example, 0.5 to 5.0 times the molar amount relative to the fluorenyl group of the polyamic acid. equivalent.
值得說明的是，如上所述，在本實施方式中，由於用以形成聚醯亞胺的組成物透過包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺的二胺單體組分以及溶劑而可具有良好的成膜性，因此由用以形成聚醯亞胺的組成物所製得的聚醯亞胺可形成具有優異材料性質的薄膜。It is worth noting that, as described above, in the present embodiment, since the composition for forming polyfluorene imide penetrates through the tetracarboxylic dianhydride monomer component and includes 4,4 ′ in each of the specific ranges, -Diaminodiphenyl ether, a compound represented by the formula (I), a diamine monomer component of melamine, and a solvent can have good film-forming properties. Therefore, the composition is used to form a polyimide The prepared polyimide can form a thin film with excellent material properties.
另一方面，透過用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺的二胺單體組分以及溶劑，藉此聚醯亞胺不但具有優異的成膜性，且所形成的薄膜更具有耐熱性及彈性。如此一來，本發明的聚醯亞胺在各種產業上的應用性及商業價值大幅提升。On the other hand, the composition used to form the polyfluorene imide includes a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a content in a specific range, by formula (I ) And the diamine monomer component of melamine and the solvent, whereby the polyfluorene imide not only has excellent film-forming properties, but also the formed film has heat resistance and elasticity. In this way, the applicability and commercial value of the polyfluorene imine of the present invention in various industries have been greatly improved.
另外，在不損及本發明之聚醯亞胺的本質效果的範圍內，聚醯亞胺可依需求而與添加劑摻混，以進一步增加聚醯亞胺的應用性及商業價值。所述添加劑例如包括導電材料、阻燃劑、著色劑、填充劑或其組合物。舉例來說，為了賦予聚醯亞胺導電性以符合產業上針對導電性的需求，聚醯亞胺可與導電材料摻混，其中導電材料例如包括石墨烯、奈米碳管、奈米銀、奈米銀線或導電高分子；摻混的方法例如包括直接使聚醯亞胺與導電材料混合、或者使用以形成聚醯亞胺的組成物更包括導電材料。In addition, as long as the essential effect of the polyimide of the present invention is not impaired, the polyimide can be blended with additives as required to further increase the applicability and commercial value of the polyimide. The additives include, for example, a conductive material, a flame retardant, a colorant, a filler, or a combination thereof. For example, in order to impart conductivity to polyimide to meet the needs of the industry for conductivity, polyimide can be blended with conductive materials, including conductive materials such as graphene, nano carbon tubes, nano silver, Nanosilver wire or conductive polymer; blending methods include, for example, directly mixing polyimide with a conductive material, or a composition used to form polyimide further includes a conductive material.
另外，如前文所述，雖然用以形成聚醯亞胺的組成物可具有良好的成膜性而使得由其製得的聚醯亞胺可形成薄膜，但本發明的聚醯亞胺也可以粉體或溶液等的形態存在。In addition, as described above, although the composition used to form polyimide can have good film-forming properties so that the polyimide prepared from it can form a thin film, the polyimide of the present invention can also It exists in the form of powder or solution.
本發明的另一實施方式提供一種聚醯亞胺膜，由任一種前述實施方式中的聚醯亞胺所製得。聚醯亞胺的相關描述已於前述實施方式中進行詳盡地說明，故於此不再贅述。在本實施方式中，聚醯亞胺膜的厚度依應用用途而有所不同，一般來說，厚度約在15 μm至200 μm之間，較佳則為15 μm至100 μm之間。Another embodiment of the present invention provides a polyfluorene imine film, which is prepared from the polyfluorene imine in any one of the foregoing embodiments. The related description of polyimide has been described in detail in the foregoing embodiments, so it will not be repeated here. In this embodiment, the thickness of the polyimide film varies depending on the application. Generally, the thickness is between 15 μm and 200 μm, and preferably between 15 μm and 100 μm.
另外，在本實施方式中，聚醯亞胺膜可透過所屬技術領域中具有通常知識者所周知的任何方法來製備。舉例來說，在一實施方式中，可透過使聚醯亞胺進行溶液澆鑄法來形成聚醯亞胺膜。舉另一例來說，在一實施方式中，參照前文關於聚醯亞胺的製備方法，聚醯亞胺膜的製備方法可包括在形成聚醯胺酸溶液之後，透過塗佈製程將聚醯胺酸溶液塗佈至一基材上，並接著使其進行醯亞胺化反應。詳細而言，塗佈製程可利用所屬技術領域中具有通常知識者所周知的任何塗佈法來進行，例如刮刀塗佈法、旋轉塗佈法、氣動刮刀塗佈法、狹縫式塗佈法、擠壓式塗佈法或滾筒塗佈法；根據實際上的應用，基材可以是任何適合的基材，例如織物、銅箔、玻璃、鐵氟龍或塑膠等基材。In addition, in this embodiment, the polyfluoreneimide film can be produced by any method known to those skilled in the art. For example, in one embodiment, the polyimide film can be formed by subjecting the polyimide to a solution casting method. For another example, in one embodiment, referring to the method for preparing polyimide, the method for preparing a polyimide film may include, after forming a polyamic acid solution, applying the polyamine through a coating process. The acid solution is applied to a substrate and then subjected to a sulfonimidization reaction. In detail, the coating process can be performed using any coating method known to those skilled in the art, such as a doctor blade coating method, a spin coating method, a pneumatic blade coating method, and a slit coating method. , Extrusion coating method or roller coating method; according to the actual application, the substrate can be any suitable substrate, such as fabric, copper foil, glass, Teflon or plastic.
值得說明的是，如前文所述，在本實施方式中，透過用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺的二胺單體組分以及溶劑，藉此聚醯亞胺膜可具有優異的耐熱性及彈性。如此一來，本發明的聚醯亞胺膜在各種產業上的應用性及商業價值大幅提升。It is worth noting that, as described above, in this embodiment, the composition used to form the polyimide includes a tetracarboxylic dianhydride monomer component and includes 4,4 ′ in a specific range. -A diaminodiphenyl ether, a compound represented by the formula (I), a diamine monomer component of melamine, and a solvent, whereby a polyimide film can have excellent heat resistance and elasticity. In this way, the applicability and commercial value of the polyfluorene imide film of the present invention in various industries have been greatly improved.
另外，如前文所述，在不損及本發明之聚醯亞胺的本質效果的範圍內，為了符合導電性的需求，本發明的聚醯亞胺可與導電材料摻混，進而所形成的聚醯亞胺膜可具有導電性。在一實施方式中，具導電性的聚醯亞胺膜例如可透過在聚醯亞胺與導電材料混合後接著進行溶液澆鑄法來形成。在另一實施方式中，具導電性的聚醯亞胺膜例如可透過以下步驟來形成：使導電材料加入聚醯胺酸溶液中並均勻混合後，透過塗佈製程將混合溶液塗佈至一基材上，並接著使其進行醯亞胺化反應。值得一提的是，具導電性的聚醯亞胺膜由於同時具有優異膜質、耐熱性及彈性，可應用於例如是智慧織物（例如心跳帶、體感智慧手套）、拉伸式顯示裝置、體表電子貼片系統或電子皮膚等智慧型穿戴元件。In addition, as described above, in a range that does not impair the essential effects of the polyimide of the present invention, in order to meet the requirements for conductivity, the polyimide of the present invention may be blended with a conductive material to form a The polyfluorene film may have conductivity. In one embodiment, the polyimide film having conductivity can be formed by, for example, mixing a polyimide with a conductive material and then performing a solution casting method. In another embodiment, a polyimide film having conductivity can be formed, for example, by the following steps: After adding a conductive material to a polyamic acid solution and uniformly mixing it, the mixed solution is applied to a substrate through a coating process. On the substrate, and then allowed to undergo a fluorene imidization reaction. It is worth mentioning that the polyimide film with conductivity has excellent film quality, heat resistance and elasticity, and can be applied to smart fabrics (such as heartbeat belts, somatosensory smart gloves), stretch display devices, Smart wearable components such as body surface electronic patch system or electronic skin.
下文將參照實施例1-25，更具體地描述本發明的特徵。雖然描述了以下實施例1-25，但是在不逾越本發明範疇之情況下，可適當地改變所用材料、其量及比率、處理細節以及處理流程等等。因此，不應由下文所述的實施例對本發明作出限制性地解釋。尤其是，由於二胺單體及四羧酸二酐單體將反應產生聚醯亞胺，且二胺單體組分中的氨基的總莫耳數與四羧酸二酐單體組分中的酸酐基的總莫耳數的比例約為1：1，因此可得知四羧酸二酐單體的莫耳份應為二胺單體組分中的氨基的總莫耳份經平衡計算後的結果，且該比例可介於0.95：1至1.05：1之間。Hereinafter, features of the present invention will be described more specifically with reference to Examples 1-25. Although the following Examples 1 to 25 are described, the materials used, their amounts and ratios, processing details, processing flow, and the like can be appropriately changed without going beyond the scope of the present invention. Therefore, the present invention should not be interpreted restrictively by the examples described below. In particular, the diamine monomer and the tetracarboxylic dianhydride monomer will react to produce polyimide, and the total mole number of amino groups in the diamine monomer component is the same as that in the tetracarboxylic dianhydride monomer component. The ratio of the total moles of the acid anhydride groups is about 1: 1, so it can be known that the moles of the tetracarboxylic dianhydride monomer should be the total moles of the amino groups in the diamine monomer component. After the results, and the ratio can be between 0.95: 1 and 1.05: 1.
製備實施例1-25的聚醯亞胺膜所使用之主要材料的資訊如下所示。Information on the main materials used to prepare the polyfluorene imine films of Examples 1-25 is shown below.
二胺單體組分：
4,4'-二氨基二苯基醚（以下簡稱ODA）：購自西格瑪奧瑞奇公司（Sigma-Aldrich）；
由式(I)所示的化合物：產品名為RT-1000，購自亨斯曼公司（Huntsman Ltd.）；
三聚氰胺：購自西格瑪奧瑞奇公司；
矽氧烷二胺：購自科學高分子產品公司（Scientific Polymer Products, Inc.）。Diamine monomer component:
4,4'-diaminodiphenyl ether (hereinafter referred to as ODA): purchased from Sigma-Aldrich;
Compound represented by formula (I): product name is RT-1000, purchased from Huntsman Ltd .;
Melamine: purchased from Sigma-Aldrich;
Siloxane diamine: purchased from Scientific Polymer Products, Inc.
四羧酸二酐單體組分：
3,4,3',4'-二苯醚四甲酸二酐（以下簡稱ODPA）：購自西格瑪奧瑞奇公司；
均苯四甲酸二酐（以下簡稱PMDA）：購自西格瑪奧瑞奇公司；
3,3',4,4'-聯苯四羧酸二酐（以下簡稱BPDA）：購自西格瑪奧瑞奇公司。Tetracarboxylic dianhydride monomer component:
3,4,3 ', 4'-Diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA): purchased from Sigma-Aldrich;
Pyromellitic dianhydride (hereinafter referred to as PMDA): purchased from Sigma-Origin;
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA): purchased from Sigma-Aldrich.
脫水劑：
乙酸酐：購自西格瑪奧瑞奇公司。Dehydrating agent:
Acetic anhydride: purchased from Sigma-Aldrich.
醯亞胺化劑：
吡啶：購自西格瑪奧瑞奇公司。醯 Imination agent:
Pyridine: purchased from Sigma-Aldrich.
導電材料：
石墨烯：從財團法人紡織產業合研究所（TTRI）獲得。
實施例 1 Conductive material:
Graphene: Obtained from the Textile Industry Research Institute (TTRI).
Example 1
首先，將高純度氮氣通入150 mL的三頸瓶中，以維持瓶內乾燥。接著，在室溫下，將49莫耳份的ODA、50莫耳份的RT-1000、1莫耳份的三聚氰胺以及25 mL的DMAc（作為溶劑）加入三頸瓶中，並混合均勻。之後，在室溫下，將100.5莫耳份的ODPA加入前述混合溶液中，並持續於氮氣下反應12小時，以形成固含量為35%的聚醯胺酸溶液。接著，將20 mL的乙酸酐與10 mL的吡啶加入聚醯胺酸溶液中，並在120o
C下進行醯亞胺化反應3小時。待反應結束後，將所得混合溶液冷卻至室溫。接著，將所得混合溶液緩慢倒入攪拌中的大量的甲醇中後，透過過濾以取得固體部分。之後，將所得固體以甲醇進行沖洗，並在120°C下乾燥2小時，以得到實施例1的聚醯亞胺。接著，將實施例1的聚醯亞胺溶解於適量的DMAc中，以形成聚醯亞胺溶液。之後，將聚醯亞胺溶液澆鑄在玻璃板上，並在80o
C下烘烤3小時，以製得實施例1的聚醯亞胺膜。
實施例 2-14 First, high-purity nitrogen was passed into a 150 mL three-necked bottle to keep the bottle dry. Next, at room temperature, 49 mol parts of ODA, 50 mol parts of RT-1000, 1 mol part of melamine, and 25 mL of DMAc (as a solvent) were added to the three-necked flask and mixed well. Thereafter, at room temperature, 100.5 mol parts of ODPA was added to the aforementioned mixed solution, and the reaction was continued under nitrogen for 12 hours to form a polyamine solution having a solid content of 35%. Next, 20 mL of acetic anhydride and 10 mL of pyridine were added to the polyamine solution, ando
The amidine imidization reaction was performed at C for 3 hours. After the reaction is completed, the resulting mixed solution is cooled to room temperature. Next, the obtained mixed solution was slowly poured into a large amount of methanol under stirring, and then filtered to obtain a solid portion. Thereafter, the obtained solid was washed with methanol and dried at 120 ° C. for 2 hours to obtain the polyfluorene imine of Example 1. Next, the polyfluorene imine of Example 1 was dissolved in an appropriate amount of DMAc to form a polyfluorene imine solution. After that, the polyimide solution was cast on a glass plate ando
Bake at C for 3 hours to obtain the polyfluorene imine film of Example 1.
Examples 2-14
按照與實施例1相似的製備程序，以及按照表1所示出的成分及其莫耳份來製備實施例2-14的聚醯亞胺膜。
實施例 15 The polyimide films of Examples 2-14 were prepared according to a similar production procedure as in Example 1, and according to the ingredients shown in Table 1 and their mole fractions.
Examples 15
按照與實施例1相似的製備程序，以及按照表1所示出的成分及其添加比例來製備實施例15的聚醯亞胺膜，然其差異主要在於以下步驟：在製得實施例15的聚醯亞胺之後，使實施例15的聚醯亞胺與5 wt%的石墨烯一同溶解於15 mL的NMP中後才澆鑄於玻璃板上。
實施例 16-19 The polyimide film of Example 15 was prepared according to a preparation procedure similar to that of Example 1, and the ingredients and their addition ratios shown in Table 1 were used. However, the difference mainly lies in the following steps: After polyimide, the polyimide of Example 15 was dissolved together with 5 wt% of graphene in 15 mL of NMP before being cast on a glass plate.
Examples 16-19
按照與實施例15相似的製備程序，以及按照表1所示出的成分及其添加比例來製備實施例16-19的聚醯亞胺膜。
實施例 20 The polyimide films of Examples 16-19 were prepared according to a preparation procedure similar to that of Example 15, and according to the ingredients shown in Table 1 and their addition ratios.
Example 20
按照與實施例1相似的製備程序，以及按照表1所示出的成分及其添加比例來製備實施例20的聚醯亞胺膜，然其差異主要在於以下步驟：在實施例20中，將ODA、RT-1000、三聚氰胺以及矽氧烷二胺一起加入DMAc中；而在實施例1中，並未使用矽氧烷二胺。
實施例 21-22 The polyimide film of Example 20 was prepared according to a preparation procedure similar to that of Example 1 and the ingredients and their addition ratios shown in Table 1, but the difference mainly lies in the following steps: In Example 20, ODA, RT-1000, melamine, and siloxane diamine were added to the DMAc together; in Example 1, no siloxane diamine was used.
Examples 21-22
按照與實施例20相似的製備程序，以及按照表1所示出的成分及其添加比例來製備實施例21-22的聚醯亞胺膜。
實施例 23 The polyimide films of Examples 21-22 were prepared according to a preparation procedure similar to that of Example 20, and according to the ingredients shown in Table 1 and their addition ratios.
Example 23
按照與實施例20相似的製備程序，以及按照表1所示出的成分及其添加比例來製備實施例23的聚醯亞胺膜，然其差異主要在於以下步驟：在製得實施例23的聚醯亞胺之後，使實施例23的聚醯亞胺與16.7 wt%的石墨烯一同溶解於15 mL的NMP中後才澆鑄於玻璃板上。另外，實施例23的聚醯亞胺膜的厚度為100 μm。
實施例 24-25 The polyimide film of Example 23 was prepared according to a preparation procedure similar to that of Example 20, and the ingredients shown in Table 1 and their addition ratios. However, the difference mainly lies in the following steps: After polyimide, the polyimide of Example 23 was dissolved in 15 mL of NMP together with 16.7% wt of graphene, and then cast on a glass plate. The thickness of the polyimide film of Example 23 was 100 μm.
Examples 24-25
按照與實施例23相似的製備程序，以及按照表1所示出的成分及其添加比例來製備實施例24-25的聚醯亞胺膜，其中實施例24的聚醯亞胺膜的厚度為25 μm，實施例25的聚醯亞胺膜的厚度為100 μm。
表1
表1(續)
a：以所使用的二胺單體組分的莫耳份透過計算而得；b：以聚醯亞胺的總重量為100%計
表1(續)
a：以所使用的二胺單體組分的莫耳份透過計算而得；b：以聚醯亞胺的總重量為100%計The polyimide films of Examples 24-25 were prepared according to a preparation procedure similar to that of Example 23, and according to the components and their addition ratios shown in Table 1, where the thickness of the polyimide film of Example 24 was The thickness of the polyimide film of Example 25 was 100 μm.
Table 1
a: Calculated based on the mole fraction of the diamine monomer component used; b: Table 1 based on the total weight of polyimide as 100% (continued)
a: Calculated based on the mole fraction of the diamine monomer component used; b: calculated based on the total weight of polyimide as 100%
之後，分別對實施例1-25的聚醯亞胺膜進行成膜性的評價，分別對實施例1-6、9-14、20、22的聚醯亞胺膜進行5%熱重損失溫度（Td5%
）、10%熱重損失溫度（Td10%
）的量測，分別對實施例1-6、9-14的聚醯亞胺膜進行800°C的殘餘重量比率（Rw800
）的量測，分別對實施例3、10、12、20-22的聚醯亞胺膜進行玻璃轉移溫度（glass transition temperature；Tg
）的量測，分別對實施例3、10、12、20-21的聚醯亞胺膜進行抗拉強度（tensile strength）、以及斷裂伸長率（elongation）的量測，分別對實施例10、20的聚醯亞胺膜進行儲存模數（storage modulus）的量測，以及分別對實施例15-19、23-25的聚醯亞胺膜進行表面電阻率的量測。前述各項量測項目的說明如下，且評價或量測結果顯示於表2中。
〈成膜性的評價〉 Then, the polyimide films of Examples 1-25 were evaluated for film-forming properties, and the polyimide films of Examples 1-6, 9-14, 20, and 22 were subjected to 5% thermal weight loss temperatures. (T d5% ) and 10% thermogravimetric loss temperature (T d10% ), the residual weight ratios of 800 ° C (R w800 ) for the polyimide films of Examples 1-6 and 9-14, respectively For measurement, the glass transition temperature (T g ) of the polyimide films of Examples 3, 10, 12, and 20-22 was measured, respectively, for Examples 3, 10, 12, 20 -21 Polyurethane film was measured for tensile strength and elongation. The storage modulus of the polyfluoride film of Examples 10 and 20 was measured. Measurement and measurement of the surface resistivity of the polyfluorene imine films of Examples 15-19 and 23-25, respectively. The foregoing measurement items are described below, and the evaluation or measurement results are shown in Table 2.
<Evaluation of Film Formability>
分別對實施例1-25的聚醯亞胺膜進行肉眼觀察及光學顯微鏡觀察，並根據實際情形分為完整、破損及無法成型三個態樣。
〈 Td5% 、 Td10% 以及 Rw800 的量測 〉 The polyimide films of Examples 1-25 were visually observed and observed with an optical microscope, and were divided into three states of completeness, damage, and inability to form according to the actual situation.
< Measurement of T d5% , T d10% and R w800 >
使用熱重量分析法（TGA）分別量測實施例1-6、9-14、20、22的聚醯亞胺的Td5% 、Td10% ，以及使用熱重量分析法（TGA）分別量測實施例1-6、9-14的聚醯亞胺的Rw800 。熱重量分析條件是在氮氣氣氛下（氣流速率為60 cm3 /min），以等速加熱（加熱速率為10°C/min）樣品並記錄材料的重量變化，且量測儀器為熱重分析儀（型號Q50，由TA Instruments公司製造）。The T d5% and T d10% of the polyimide of Examples 1-6, 9-14, 20, and 22 were measured using thermogravimetric analysis (TGA), and were separately measured using thermogravimetric analysis (TGA). R w800 of the polyfluorene imine of Examples 1-6, 9-14 . The thermogravimetric analysis conditions are that the sample is heated at a constant rate (heating rate is 10 ° C / min) in a nitrogen atmosphere (air flow rate is 60 cm 3 / min) and the weight change of the material is recorded, and the measurement instrument is thermogravimetric analysis Instrument (model Q50, manufactured by TA Instruments).
Td5%
是指重量損失達5重量%的溫度，其中Td5%
越高代表樣品的耐熱性越佳。Td10%
是指重量損失達10重量%的溫度，其中Td10%
越高代表樣品的耐熱性越佳。Rw800
是指加熱溫度達800°C時的材料殘餘重量比率。
〈 Tg 的量測 〉 Td5%
Is the temperature at which the weight loss reaches 5% by weight, where Td5%
A higher value indicates better heat resistance of the sample. Td10%
The temperature at which the weight loss reaches 10% by weight, where Td10%
A higher value indicates better heat resistance of the sample. Rw800
Residual weight ratio when the heating temperature reaches 800 ° C.
< T g Measurement 〉
使用示差掃描熱分析法（DSC）分別量測實施例3、10、12、20、22的聚醯亞胺膜的Tg
，其分析條件是以等速加熱（加熱速率為10°C/min）樣品並記錄材料的熱焓變化，其中量測儀器為示差掃描熱分析儀（型號：Q10，由TA Instruments公司製造）。
〈抗拉強度以及斷裂伸長率的量測〉 Differential scanning thermal analysis (DSC) was used to measure the T of the polyimide films of Examples 3, 10, 12, 20, and 22, respectively.g
The analysis condition is to heat the sample at a constant rate (heating rate is 10 ° C / min) and record the enthalpy change of the material. The measuring instrument is a differential scanning thermal analyzer (model: Q10, manufactured by TA Instruments).
<Measurement of tensile strength and elongation at break>
使用萬能材料試驗機（型號：HT-8336-S，由鋐達設備公司（HUNG TA Instruments）製造）分別量測實施例3、10、12、20-21的聚醯亞胺膜的抗拉強度及斷裂伸長率，其中樣品為啞鈴形試片，且拉伸速率為3 mm/min。
〈儲存模數的量測〉 Using a universal material testing machine (model: HT-8336-S, manufactured by HUNG TA Instruments) to measure the tensile strength of the polyimide films of Examples 3, 10, 12, 20-21, respectively And elongation at break, where the sample is a dumbbell-shaped test piece and the tensile rate is 3 mm / min.
<Measurement of storage modulus>
使用動態機械分析法（DMA）量測實施例10、20的聚醯亞胺膜的儲存模數。儲存模數分析條件是以等速加熱（加熱速率為5°C/min，頻率：1 Hz）樣品並記錄材料的儲存模數的變化，其中量測儀器為動態機械分析儀（型號：Q800，由TA Instruments公司製造）。
〈表面電阻率的量測〉 The storage modulus of the polyimide films of Examples 10 and 20 was measured using dynamic mechanical analysis (DMA). The storage modulus analysis condition is to heat the sample at a constant speed (heating rate is 5 ° C / min, frequency: 1 Hz) and record the change of the storage modulus of the material. The measuring instrument is a dynamic mechanical analyzer (model: Q800, (Manufactured by TA Instruments).
<Measurement of surface resistivity>
使用四點探針法分別量測實施例15-19、23-25的聚醯亞胺膜的表面電阻率，其中量測儀器為四點探針低阻抗率計（MITSUBISHI CHEMICAL公司製造，型號：LORESTA-GP MCP-T600）。使用FTTS-FA-009所規範的等級標準來評估具導電性的標準；其中，當表面電阻率大於1×1012
Ω/cm2
，則代表絕緣材料；當表面電阻率介於1×105
Ω/cm2
與1×1012
Ω/cm2
之間，則代表靜電消散材料；當表面電阻率小於1×104
Ω/cm2
，則代表導電材料，表面電阻率越低則導電性越優異。
表2
表2(續)
表2(續)
Table 2
Table 2 (continued)
Table 2 (continued)
由上述表2可知，實施例1-14的聚醯亞胺膜在成膜性的評價上均具有良好表現。此表示，透過本發明的用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺的二胺單體組分以及溶劑，藉此用以形成聚醯亞胺的組成物可具有良好的成膜性，並由其得以製得材料性質優異的聚醯亞胺膜。As can be seen from Table 2 above, the polyfluorene imine films of Examples 1 to 14 all performed well in the evaluation of the film-forming properties. This indicates that the composition for forming polyfluorene imide through the present invention includes a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a content in a specific range, The compound shown in (I) and the diamine monomer component of melamine and the solvent, whereby the composition for forming a polyimide can have good film-forming properties, and a polymer having excellent material properties can be obtained from the composition.醯 imine film.
另外，由上述表2可知，實施例20-22的聚醯亞胺膜在成膜性的評價上均具有良好表現。此表示，透過使本發明的用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺的二胺單體組分以及溶劑，即使二胺單體組分更包括矽氧烷二胺，用以形成聚醯亞胺的組成物仍可具有良好的成膜性，並由其得以製得材料性質優異的聚醯亞胺膜。In addition, it can be seen from the above Table 2 that the polyfluorene imine films of Examples 20 to 22 all performed well in the evaluation of the film-forming properties. This means that by making the composition for forming a polyimide of the present invention include a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a content within a specific range, from The compound represented by formula (I) and the diamine monomer component and solvent of melamine, even if the diamine monomer component further includes siloxane diamine, the composition for forming polyfluorene imine can still have good properties. Film-forming properties, and a polyimide film having excellent material properties can be obtained from the film.
另外，由上述表2可知，實施例15-19的聚醯亞胺膜不但在成膜性的評價上均具有良好表現，還均具有導電性。此表示，透過使本發明的用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺的二胺單體組分以及溶劑，不僅可製得材料性質優異的聚醯亞胺膜，更可以在不損及本質效果的情況下，透過將聚醯亞胺與添加劑摻混來賦予聚醯亞胺膜具有額外的特性，例如導電性，進而增加聚醯亞胺膜的應用性及商業價值。In addition, it can be seen from the above Table 2 that the polyfluorene imine films of Examples 15 to 19 not only performed well in the evaluation of film-forming properties, but also all had conductivity. This means that by making the composition for forming a polyimide of the present invention include a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a content within a specific range, from The compound represented by the formula (I) and the diamine monomer component of melamine and the solvent can not only obtain a polyimide film with excellent material properties, but also can pass through the polyimide without compromising the essential effects. Blending imines with additives to impart polyimide films with additional properties, such as electrical conductivity, thereby increasing the applicability and commercial value of polyimide films.
另外，由上述表2可知，實施例23-25的聚醯亞胺膜不但在成膜性的評價上均具有良好表現，還均具有導電性。此表示，透過使本發明的用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺的二胺單體組分以及溶劑，即使二胺單體組分更包括矽氧烷二胺，仍然不僅可製得材料性質優異的聚醯亞胺膜，更可以在不損及本質效果的情況下，透過將聚醯亞胺與添加劑摻混來賦予聚醯亞胺膜具有額外的特性，例如導電性，進而增加聚醯亞胺膜的應用性及商業價值。In addition, as can be seen from Table 2 above, the polyfluorene imine films of Examples 23 to 25 not only performed well in the evaluation of film-forming properties, but also all had conductivity. This means that by making the composition for forming a polyimide of the present invention include a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a content within a specific range, from The compound of formula (I) and the diamine monomer component and solvent of melamine, even if the diamine monomer component further includes siloxane diamine, can not only obtain a polyfluorene imine film with excellent material properties, In addition, without impairing the essential effect, polyimide film can be added with additives to impart additional properties to the polyimide film, such as electrical conductivity, thereby increasing the applicability and commerciality of the polyimide film. value.
另外，由上述表2中關於Td5% 、Td10% 、Rw800 、Tg 、抗拉強度以及斷裂伸長率等方面的結果可知，透過本發明的用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物及三聚氰胺的二胺單體組分以及溶劑，藉此聚醯亞胺膜可具有耐熱性及彈性。In addition, from the results in Table 2 above regarding T d5% , T d10% , Rw800 , Tg , tensile strength, and elongation at break, etc., it can be seen that the composition for forming polyimide according to the present invention includes Tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a specific range, a diamine monomer component of a compound represented by formula (I) and melamine, and a solvent Therefore, the polyimide film can have heat resistance and elasticity.
另外，由上述表2可知，實施例20-21的聚醯亞胺膜在抗拉強度以及斷裂伸長上均具有良好表現。此表示，透過本發明的用以形成聚醯亞胺的組成物包括四羧酸二酐單體組分、包括含量分別在特定範圍內的4,4'-二氨基二苯基醚、由式(I)所示的化合物、三聚氰胺以及矽氧烷二胺的二胺單體組分以及溶劑，藉此所製得的聚醯亞胺膜可具有延性或彈性。In addition, it can be seen from the above Table 2 that the polyfluorene imine films of Examples 20-21 have good performances in both tensile strength and elongation at break. This indicates that the composition for forming polyfluorene imide through the present invention includes a tetracarboxylic dianhydride monomer component, including 4,4'-diaminodiphenyl ether in a content in a specific range, The compound shown in (I), the diamine monomer component of melamine and the siloxane diamine, and the solvent, and the polyimide film thus obtained may have ductility or elasticity.
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed as above in the embodiments, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouches without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.
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