TW474956B - Organic-soluble aromatic polyimides, organic solution and diamine for preparation thereof - Google Patents

Abstract

The present invention provides a formulation and preparation method of a kind of tractable polyimides that are organic-soluble with controllable solubility and can afford films with excellent mechanical properties and good thermal stability. The polyimides were prepared from an aromatic diamine having (tert)-butyl group, i.e., 1,2-bis(4-aminophenoxy)-4-(tert)-butyl-benzene, or its mixture with other diamines, and a mixture of dianhydrides that containing s-BPDA, DSDA, ODPA, 6FDA or other diether-dianhydrides.

Description

474956 五、發明説明（1 發明背景 經濟部智慧財產局員工消費合作社印製 芳香族* 5^胺是—種高耐熱性並有機能性之高性能 南分子材料，被應用於耐熱材料包括絕緣膜塗料、黏著 劑、氣體分細、電子及光電材料而甚受重視。但大部份 之芳香族輯亞胺卻因難溶及不祕紐直接加工 ，必須 使用不安定之前驅體加:η，使其應用大受限制。因此可溶 性可加工性之聚醯亞胺㈣成為熱門研究開發項目。由於 ΡΙ是由H胺合成’因此研究方法亦著重於這兩種單 體之分子設計或特性發現。 根據文獻檢索，大部份可溶性ρι之專利以二胺之特性 發現為主，一酐較少，這可能是因二胺種類較多、較易製 備之故。目前被報告可用於製備可溶性ρι之二胺大略可分 為二類·其一是使用非芳香族之聚矽氧烧二胺 (polysiloxane diamine)，其特點是可增加對半導體之附著 力，但其他特性如膜強度或耐熱性會變差。其二是含間位 胺基’如 3,3 _一胺基二苯礙（3,3’-diaminodiphenylsulfone) 或 1，3-雙(3-胺基本乳）苯[l，3-bis(3_aminophenoxy)benzene] 之類，用此等二胺有較佳的可溶性但亦有反應性較差、聚 合度不高之缺點。第三類是較剛直末端為對位胺之二胺， 但這類所合成之PI多呈不溶性，除非分子内同時含有多異 丙基、六氟異丙基、多_基或礙基之較柔軟大分子二胺才 具有Π可溶性。 發明要 4 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 、-=口 經濟部智慧財產局員工消費合作社印製 474956 A7 B7 五、發明説明（2 ) 本發明首先使用在其中間笨環含有特丁基之鄰位苯環 之三苯二醚二胺來製備有機溶劑可溶性PI，並具有良好的 膜機械性質和耐熱性。我們同時亦發明以此與一般難溶性 PI之合成單體配合共聚合，可得廣範圍、並可調整不同溶 解性之可溶性PI之製備方法。由於可溶性可加工性之PI 是目前期待之PI特性，而本發明選用之特別二胺[1，2·雙(4-胺基苯氧)-4-特丁基苯]，為一新穎之化合物。 本發明亦提供了 一種以本發明前述之可溶性PI聚合物 溶解於一種有機溶劑的溶液，該有機溶劑係選自沁曱基-2_fl比洛烧酮（A^methyl-2-pyrrolidone;以下簡稱 NMP)， 二甲基乙醯胺(MA^-dimethylacetamide;以下簡稱 DMAc) ’ 二甲基甲醢胺（dimethylformamide;以下簡稱DMF)，二甲亞 石風（dimethylsulfoxide;以下簡稱 DMSO)，m-曱紛（w-cresol)，°比°定(pyridine;以下簡稱Py)，氯化曱烧及氣化乙 烷所組成的族群。 發明之詳細說明 由於大部份芳香族聚醯亞胺(PI)皆難溶性，必須由前驅 體聚醯胺酸(polyamic acid，以下簡稱PAA)加以成形（膜） 後高溫烘烤而成，因此不適於不耐高溫基質，而且PAA不 安定、易劣化故甚為不便。少數由可溶性PI所形成的有機 溶液於加工後只要蒸發溶劑不必經高溫處理即可成膜，但 這類材料並不多，少數含三氟曱基、含矽氧烷(siloxan)鏈 或含非對位及多置換基芳香環之PI有此性質。但從未有人 _^_5_. _ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ~ (請先閲讀背面之注意事項再填寫本頁)474956 V. Description of the invention (1 Background of the invention Aromatic * 5 ^ amine printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a kind of high-performance and high-performance South molecular material, which is used in heat-resistant materials including insulating films Coatings, adhesives, gas separation, electronic and optoelectronic materials are highly valued. However, most of the aromatic imines are directly processed due to insoluble and insecure bonds, and must be used before the unstable precursor plus: η, Its application is greatly limited. So soluble and processable polyimide has become a popular research and development project. Since PI is synthesized from H amine, the research method also focuses on the molecular design or characteristic discovery of these two monomers. According to the literature search, most of the patents for soluble ρl are based on the discovery of the characteristics of diamines, and less monoanhydrides. This may be because there are more types of diamines and it is easier to prepare. It is currently reported that they can be used to prepare soluble ρl. Diamines can be roughly divided into two types. One is the use of non-aromatic polysiloxane diamines. Its characteristics are to increase the adhesion to semiconductors, but other characteristics Membrane strength or heat resistance will be worsened. The second is that it contains meta-amino groups such as 3,3'-diaminodiphenylsulfone or 1,3-bis (3-amine base milk). Benzene [1,3-bis (3_aminophenoxy) benzene] and the like, these diamines have better solubility but also have the disadvantages of poor reactivity and low degree of polymerization. The third type is para-amines with more rigid ends. Diamines, but most of these synthesized PIs are insoluble, unless the softer macromolecular diamines containing polyisopropyl, hexafluoroisopropyl, poly- or hindering groups are also soluble in the molecule. To 4 paper sizes applicable to China National Standard (CNS) A4 specifications (210X297 mm) (Please read the notes on the back before filling out this page),-= Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy 474956 A7 B7 5 2. Description of the invention (2) The present invention first uses triphenyl diether diamine containing an ortho benzene ring in the middle of its stupid ring to prepare an organic solvent-soluble PI, and has good film mechanical properties and heat resistance. We At the same time, it is also invented to cooperate with synthetic monomers of generally poorly soluble PI. By polymerization, a wide range can be obtained, and the method for preparing soluble PI with different solubility can be adjusted. Since the soluble processability PI is the currently expected PI characteristic, the special diamine [1,2, bis (4 -Aminophenoxy) -4-tert-butylbenzene], is a novel compound. The present invention also provides a solution in which the aforementioned soluble PI polymer of the present invention is dissolved in an organic solvent, the organic solvent is selected from the group consisting of Pyridinyl-2_fl-pyrrolidone (A ^ methyl-2-pyrrolidone; hereinafter referred to as NMP), dimethyl acetamide (MA ^ -dimethylacetamide; hereinafter referred to as DMAc) 'dimethylformamide (dimethylformamide; below DMF), dimethylsulfoxide (DMSO), m-cresol, pyridine (Py), dysprosium chloride and gasified ethane Ethnic group. Detailed description of the invention Since most aromatic polyimide (PI) is poorly soluble, it must be formed (film) from the precursor polyamic acid (PAA) and then baked at high temperature. It is not suitable for substrates that are not resistant to high temperatures, and PAA is unstable and easily deteriorated, which is very inconvenient. A small number of organic solutions formed from soluble PI can be formed into films as long as the solvent does not need to be subjected to high temperature treatment after processing. However, there are not many such materials. A few contain trifluorofluorenyl groups, siloxan chains or non- Para and multi-substituent aromatic ring PI have this property. But no one has _ ^ _ 5_. _ This paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) ~ (Please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 A7 —----— B7 五、發明説明~〜~~ 報告過本發明之構想，即由一特殊二胺與大部份會合成出 難溶性PI之單體共聚縮合而獲得可溶性PI。本發明選用 之特殊二胺，具特丁基之鄰位性芳香族二醚二胺(II),它是 一種新穎化合物尚未被發現與多種二酐所合成之PI具有 甚佳之有機溶劑易溶性。 本發明係製備一系列有機溶劑可溶性、並可任意調整 溶解性大小之芳香族聚醯亞胺⑴高分子材料。由於大部份 之芳香族聚醯亞胺(PI)皆難溶性，只有極少數特妹結構之 Π具有溶解性。我們發現把可溶性PI之合成單體與多數 只能合成難溶性ΡΙ之單體共聚縮合可改善ΡΙ之溶解性， 進而可合成有機溶劑可溶性PI，或可任意調整溶解性之大 小〇 由實驗發現含單特丁基之二醚二胺，即1，2雙(4-胺基 苯氧)-4-特丁基苯(Π)，與多數芳香族二酐之合成可生成可 溶性PI。這些二酐包括市售之聯苯二酐（以下簡稱k BPDA) ’ 二苯石風二gf(diphenylsulfonetetracarboxylic dianhydride，以下簡稱 DSDA)，二苯醚二酐(4,4’-oxydiphthalic anhydride,以下簡稱 ODPA)，六氟丙烷二苯 石風二 gf [2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride，以下簡稱6FDA]及一些由二紛合成之二_二 酐，如：1，4-雙(3,4-二羧酸苯氧)-2-特丁基苯二酐（1,4-bis(3,4-dicarboxyphenoxy)-2-ferfbutylbenzene dianhydride,以下簡稱 ί-BBDA)、1，2-雙(3,4-二羧酸苯氧） 苯二酐[1,2_bis(3,4-dicarboxyphenoxy)benzene __ ___6 ___ 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐] ~ ~ (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 —----— B7 V. Description of the invention ~~~~ The concept of the present invention has been reported, that is, a special diamine and most of them will synthesize insoluble PI. The monomer is copolymerized and condensed to obtain a soluble PI. The special diamine used in the present invention is tertiary butyl ortho-aromatic diether diamine (II), which is a novel compound that has not yet been found to have excellent solubility in organic solvents with PI synthesized from various dianhydrides. The present invention is to prepare a series of aromatic polyfluorene imide polymer materials which are soluble in organic solvents and whose solubility can be arbitrarily adjusted. Since most of the aromatic polyimide (PI) is poorly soluble, only a few of the special structures have solubility. We have found that the copolymerization of soluble PI synthetic monomers with most monomers that can only synthesize poorly soluble PI can improve the solubility of PI, so that organic solvent soluble PI can be synthesized, or the solubility can be arbitrarily adjusted. The synthesis of mono-tert-butyl diether diamine, namely 1,2 bis (4-aminophenoxy) -4-tert-butylbenzene (Π), with most aromatic dianhydrides can generate soluble PI. These dianhydrides include commercially available biphenyl dianhydride (hereinafter referred to as k BPDA) 'diphenylsulfonetetracarboxylic dianhydride (hereinafter referred to as DSDA), diphenyl ether dianhydride (4,4'-oxydiphthalic anhydride, hereinafter referred to as ODPA ), Hexafluoropropane diphenyl stone wind di gf [2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, hereinafter referred to as 6FDA], and some di-dianhydrides synthesized by dimers, such as: 1,4- Bis (3,4-dicarboxylic acid phenoxy) -2-tert-butyl phthalic anhydride (1,4-bis (3,4-dicarboxyphenoxy) -2-ferfbutylbenzene dianhydride, hereinafter referred to as ί-BBDA), 1, 2 -Bis (3,4-dicarboxylic phenoxy) phthalic anhydride [1,2_bis (3,4-dicarboxyphenoxy) benzene __ ___6 ___ This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X297 mm) ~ ~ (Please read the notes on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 474956 A7 ______B7 五、發明説明（4 ) dianhydride]、2,3-雙(3,4-二羧酸苯氧）萘二酐[2,3-bis(3,4_dicarboxyphenoxy)naphthalene dianhydride]、 2,2’-雙(3,4_二羧酸苯氧)聯苯二酸[2,24丨5(3,4-dicarboxyphenoxy)biphenyl dianhydride]、2,2-雙[4-(3,4-二羧酸苯氧)苯]六氟丙烷(2,2七13[4-(3,4-dicarboxyphenoxy) phenyl]hexafluoropropane dianhydride，以下簡稱 6FDEDA)、1,1-雙[4_(3,4_二羧酸苯 氧）苯]環己烷{1,1-1^[4-(3,4- dicarboxyphenoxy)phenyl]cyclohexane dianhydride} 等。由於此特定二胺(II)與這些二酐所合成PI為有機溶劑 可溶性，因此由這些二酐與常見之二種會形成不可溶PI 的二酐例如苯二 (pyromellitic dianhydride，以下簡稱 PMDA)及BTDA按某些比例配合與Π反應，結果發現可 廣範圍製備可溶性PI，並可改善合成PI之各種物性如機 械性質、附著性、耐熱性等。 H2N ^)-NH2Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 474956 A7 ______B7 V. Description of Invention (4) dianhydride], 2,3-bis (3,4-dicarboxylic acid phenoxy) naphthalenedihydride [2,3-bis (3 , 4_dicarboxyphenoxy) naphthalene dianhydride], 2,2'-bis (3,4-dicarboxyphenoxy) biphenyl dicarboxylic acid [2,24 丨 5 (3,4-dicarboxyphenoxy) biphenyl dianhydride], 2,2-bis [4- (3,4-dicarboxylic acid phenoxy) benzene] hexafluoropropane (2,2 seven 13 [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, hereinafter referred to as 6FDEDA), 1,1-bis [4_ (3,4_Dicarboxylic acid phenoxy) benzene] cyclohexane {1,1-1 ^ [4- (3,4-dicarboxyphenoxy) phenyl] cyclohexane dianhydride} and the like. Since the PI synthesized by this specific diamine (II) and these dianhydrides is soluble in organic solvents, dianhydrides such as pyromellitic dianhydride (hereinafter referred to as PMDA) which form insoluble PI from these dianhydrides and two common dianhydrides and BTDA reacts with Π in certain proportions. As a result, it was found that soluble PI can be prepared in a wide range, and various physical properties such as mechanical properties, adhesion, heat resistance, etc. of synthetic PI can be improved. H2N ^)-NH2

II 在二胺部份，除全用特定二胺II可製備可溶性π外， 各種不同結構之二胺與II混合使用亦發現同樣可改變成 改善合成PI之溶解性與物性。因此我們提供一系列可溶性 PI之組成、其化學通式如（I) 7 本紙張尺度適用中國國家¢ ( CNS ) 規格（210父297公楚^ (請先閲讀背面之注意事項再填寫本頁)II In the diamine section, in addition to the use of specific diamine II to prepare soluble π, the use of diamines of various structures with II can also be changed to improve the solubility and physical properties of synthetic PI. Therefore, we provide a series of soluble PI compositions with chemical formulas such as (I) 7 This paper size is applicable to Chinese National ¢ (CNS) specifications (210 father 297 public Chu ^ (Please read the precautions on the back before filling this page)

474956 A7 B7 五、發明説明（5474956 A7 B7 V. Description of the invention (5

9 〇 ·Ν、/Αγι ν Γί 〇 Ο I -Αΐ2- I式中Aq成分來自二針或一軒混合物，但必須含有可產生 可溶性PI之二酐（ArO並可配合其他二酐(Ah成分）以調節 溶解性大小。 故 Aq 為 Ar3 或 Ar4，且 Ar3 : Ar4(重量）=1〇〇 : 〇〜5 : 95，其中 Ar3 ： , ^0~°~〇C, cf3^〇t0^°tDC, ^〇r0y〇C?9 〇 · Ν, / Αγι ν Γί 〇〇 I -Αΐ2- I in the formula Aq comes from the two needles or Yixuan mixture, but must contain soluble dianhydride (ArO and can be combined with other dianhydride (Ah component) To adjust the solubility. So Aq is Ar3 or Ar4, and Ar3: Ar4 (weight) = 100: 〇 ~ 5: 95, where Ar3:, ^ 0 ~ ° ~ 〇C, cf3 ^ 〇t0 ^ ° tDC , ^ 〇r0y〇C?

經濟部智慧財產局員工消費合作社印製 普Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

____8 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁〕____8 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

π/ 發明説明（ 一胺。Μ仍可隨意配合其他二胺(Ar5成分)使用。 故為\ = 一^_ 或〜且π / Description of the invention (Monoamine. M can still be used with other diamines (Ar5 component) at will. Therefore, it is \ = 一 ^ _ or ~ and

PP

Ar「Ar5(重量卜1〇〇: 〇〜5 : %，其中^為一般已知之 二胺成分如下式： z - 0, S，CH2, CO, S02, C(Me)2, C(CF3)2, CW，X-C6H4-X， x-C10H8-X，X-c6RiR2R3R4〇c 或 其中及 Y = 〇, S，CH2, CO, S02, C(Me)2, C(CF3)2, CWR2，直 鏈，或 c6h10; 其中1^，112，113，114=1^鹵素，1^，€卩3,或(：(1^)3, 其中Me為曱基。Ar "Ar5 (weight: 100: 0 to 5:%, where ^ is a generally known diamine composition as follows: z-0, S, CH2, CO, S02, C (Me) 2, C (CF3) 2, CW, X-C6H4-X, x-C10H8-X, X-c6RiR2R3R4〇c or among them Y = 〇, S, CH2, CO, S02, C (Me) 2, C (CF3) 2, CWR2, Linear, or c6h10; where 1 ^, 112, 113, 114 = 1 ^ halogen, 1 ^, € 3, or (: (1 ^) 3, where Me is a fluorenyl group.

Ar5亦可為聚石夕氧烧二院(p〇iySii〇xane diamine)以增加 半導體之附著性。 聚合物PI之製備方法仍以二酐與二胺之二段法反應為 主’即先在適當溶劑中加成聚合反應成聚醯胺酸後，以熱 烤法或化學處理法（醋酸酐/吡啶）生成PI。亦可直接在高沸 點溶劑如m-cresol等直接加熱聚縮合而成PI。其反應式如 下： 9 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁)Ar5 can also be a polysilicon oxidized secondary courtyard (p0yySioxane diamine) to increase the adhesion of the semiconductor. The preparation method of polymer PI is still based on the two-stage reaction of dianhydride and diamine. That is, it is firstly polymerized in an appropriate solvent to form polyamic acid, and then heated or chemically treated (acetic anhydride / Pyridine) to form PI. It can also be directly heated and polycondensed in a high boiling point solvent such as m-cresol to form PI. The reaction formula is as follows: 9 This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

經濟部智慧財產局員工消費合作社印製 474956 A7 B7 五、發明説明（ 0An C^c° Μ 乂ο οPrinted by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 474956 A7 B7 V. Description of the invention (0An C ^ c ° Μ 乂 ο ο

0 IIA0 IIA

Η2Ν—Αγ2一ΝΗ2 II solvent (DMAcorNMP)Η2Ν—Αγ2 一 ΝΗ2 II solvent (DMAcorNMP)

O OH H II II I I ' C——Ar\—C—N—At2~N' -HOOc/ \c〇OHO OH H II II I I 'C——Ar \ —C—N—At2 ~ N' -HOOc / \ c〇OH

(a) 250 °C (b) A〇2〇 / Py 或 o o II II c ci 々l、〆。+ H2N—Ar2—袖2(a) 250 ° C (b) A〇2〇 / Py or o o II II c ci 々1, 〆. + H2N—Ar2—Sleeve 2

〇 O 太Λ ^N\ /N—Ar2- M ^ O o I C IIo〇 O Λ ^ N \ / N—Ar2- M ^ O o I C IIo

OO

II 200 °C w-cresol (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 10 實例1 4-特丁基 1，2 苯二醇（4_tertbutyM，2_benzenedi〇1) 166 克(0.1 mol)溶於100 mL的DMF，加入無水k2c〇3 21克 (〇·15 mol)及p-硝基氣化苯32.3克於15〇〜16〇。〇下授拌加 熱8小時，冷卻加入120 mL曱醇，過濾析出固體充分曱 醇洗後再水洗，乾燥後以冰醋酸再結晶得二硝基化合物 38.4 克(Yield 94%，mp 148_149°C) ’ 此二硝基化合物 37 克 懸浮於200 mL的乙醇中，加入0.12克之pd/c (1〇%)在8〇 °C下滴加16 mL之聯胺(Η2ΝΝΗ2·Η2〇)繼續加熱至不再溢 出A氣，趁熱過遽；冷卻種晶母得無色針狀結晶雙(4_ 胺基苯氧)-4-特丁基苯(II) 24.3 克(Yield 94%，mp 132-133 °C)。 本紙張尺度適财關家縣（CNS ) ( 2lQx297公 474956 A7 ___B7_ 五、發明説明（8 ) 元素分析 C22H2402N2Calcd: C，75.83%; H，6.94%; N，8.04%II 200 ° C w-cresol (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 10 Example 1 4-tertbutyM, 2_benzenedi〇1 166 g (0.1 mol) dissolved in 100 mL of DMF, 21 g (0.15 mol) of anhydrous k2co3 and 32.3 g of p-nitrogasified benzene were added to 150 ~ 160. 〇 Stir and heat for 8 hours, cool and add 120 mL of methanol, filter out the solids and wash with alcohol. After drying, recrystallize with glacial acetic acid to obtain 38.4 g of dinitro compound (Yield 94%, mp 148_149 ° C). '37 g of this dinitro compound was suspended in 200 mL of ethanol, 0.12 g of pd / c (10%) was added, and 16 mL of hydrazine (Η2ΝΝΗ2 · Η2〇) was added dropwise at 80 ° C and heating was continued until A gas was leaked again, and the heat was passed over; the seed crystal mother was cooled to obtain colorless needle-like crystals of bis (4-aminophenoxy) -4-tert-butylbenzene (II) 24.3 g (Yield 94%, mp 132-133 ° C ). This paper is suitable for Guancai County (CNS) (2lQx297 474956 A7 ___B7_ V. Description of the invention (8) Elemental analysis C22H2402N2Calcd: C, 75.83%; H, 6.94%; N, 8.04%

Found: C, 75.81%; Η, 6.95%; Ν, 7.87% 實例2 取二胺II [1，2-雙(4-胺基苯氧)-4-丁基苯]2 mmol溶於 10 mL的DM Ac中，分二次加聯苯四羧酸二酐O-BPD A)(IIIa) 2 mmol，於常溫攪拌1小時，測其固有黏度為1·2 dl/g (DMAc，30°C )，把生成之聚醯胺酸(PAA)(I’a)延展在平板玻 璃上，於80°C，30分内除去大部份溶劑，然後自l〇〇°C至 250°C每隔30°C，10分鐘之速度熱烤後冷卻，在水中脫膜。 其膜之機械性質是斷裂強度104 MPa，斷裂伸長率10%及 起始模數2.55 GPa。Ia之玻璃轉移點（&)在240°C，10%重 量損失溫度(Td)在575°C。Ia可溶於NMP及m-甲酚中，但 在 DMAc 中微溶，其riinh 為 0.94 dl/g (NMP 中，30。(：，〇·5 g/dl)，其反應結構式如下 I 舞— (請先閱讀背面之注意事項再填寫本頁) 、νά 經濟部智慧財產局員工消費合作社印製 11 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） 474956 A7 B7 五、發明説明（9 H2NHQ-0 〇-hQ)-nh2 ο ΟFound: C, 75.81%; tritium, 6.95%; Ν, 7.87% Example 2 Take diamine II [1,2-bis (4-aminophenoxy) -4-butylbenzene] 2 mmol dissolved in 10 mL of In DM Ac, add 2 mmol of biphenyltetracarboxylic dianhydride O-BPD A) (IIIa) in two portions, and stir at room temperature for 1 hour, and measure its intrinsic viscosity to be 1.2 dl / g (DMAc, 30 ° C) , The resulting poly (amino acid) (PAA) (I'a) was stretched on a flat glass, and most of the solvent was removed within 30 minutes at 80 ° C, and then every 30 minutes from 100 ° C to 250 ° C ° C, heat for 10 minutes, then cool and remove the film in water. The mechanical properties of the film are a breaking strength of 104 MPa, an elongation at break of 10%, and an initial modulus of 2.55 GPa. The glass transition point (&) of Ia was at 240 ° C, and the 10% weight loss temperature (Td) was at 575 ° C. Ia is soluble in NMP and m-cresol, but slightly soluble in DMAc. Its riinh is 0.94 dl / g (in NMP, 30. (:, 0.5 g / dl). The reaction structure is as follows: — (Please read the precautions on the back before filling this page), νά Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 11 This paper size applies to the Chinese National Standard (CNS) Α4 size (210 X 297 mm) 474956 A7 B7 5 Description of the invention (9 H2NHQ-0 〇-hQ) -nh2 ο Ο

IIII

Ilia -m-Ilia -m-

HO Ο DMAcHO Ο DMAc

HOOCHOOC

COOH n I，aCOOH n I, a

O I 舞— (請先閲讀背面之注意事項再填寫本頁)O I 舞 — (Please read the notes on the back before filling out this page)

250 °C > 检〇 wo~0~n〇〇t^n o o n la250 ° C > Check 〇 wo ~ 0 ~ n〇〇t ^ n o o n la

、1T 經濟部智慧財產局員工消費合作社印製 實例3 取量與反應物和實例2相同，但溶劑改用10 mL之m-曱酚，先在60°C攪拌30分後，移至加熱之矽油浴上，自 100°C在30分内升溫至200°C，並在200°C下繼續攪拌2 小時，冷卻倒入曱醇中析出絲狀物，曱醇浸洗乾燥，定量 收率，其固有黏度r|inh= 1.04 dl/g(NMP 中，30°C，〇·5 g/dl)， 可溶於NMP及m-甲盼。 實例4、 1T Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Example 3 The volume is the same as that of the reactant and Example 2, but the solvent is changed to 10 mL of m-pyrophenol. After being stirred at 60 ° C for 30 minutes, it is moved to the heated place. On a silicone oil bath, the temperature was raised from 100 ° C to 200 ° C within 30 minutes, and stirring was continued at 200 ° C for 2 hours, and the mixture was cooled and poured into methanol to precipitate filaments. The alcohol was dipped and dried to obtain a quantitative yield. Its inherent viscosity r | inh = 1.04 dl / g (30 ° C in NMP, 0.5 g / dl), which is soluble in NMP and m-methan. Example 4

合成方法與實例2相同，但更改各種芳香族二酐如 DSDA (IIIb)，ODPA (IIIC)，6FDA (IIId)，BTDA (IIIe)，PMDA 12 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 474956 A7 B7 五、發明說明（ (Hlf)及二驗二針如 ί-BBDA (Illg)專代替 s_BPDA (IIIa) ’ 所 得聚合物PI-IH之化學結構’溶解性和機械性質如不表1 與表2。表1 lbThe synthesis method is the same as that in Example 2, but various aromatic dianhydrides such as DSDA (IIIb), ODPA (IIIC), 6FDA (IIId), BTDA (IIIe), and PMDA 12 are modified. This paper standard applies to China National Standard (CNS) A4 specifications ( 210X 297 mm) 474956 A7 B7 V. Description of the invention ((Hlf) and second test such as ί-BBDA (Illg) instead of s_BPDA (IIIa) 'Chemical structure of the polymer PI-IH' solubility and mechanical properties As shown in Tables 1 and 2. Table 1 lb

Ic 衿>。 IdIe产广:;娜》 If ( )合心Ic 衿 >. IdIe: Cantonese; If () Hexin

溶解性* PJ Q Q Q 1 AA) PAA膜PI膜： NMP DMAc DMF DMSO W-甲盼 THF 1.38 韌 韌 + + + + + + — 1.00 韌 韌 + + + + + + 1.20 韌 韌 + + + + + + 1.38 韌 韌 _ 一 一 一 一 — — — — 1.60 韌 (請先閱讀背面之注意事項再填寫本頁) ο ο ♦Solubility * PJ QQQ 1 AA) PAA film PI film: NMP DMAc DMF DMSO W-Methan THF 1.38 toughness + + + + + — 1.00 toughness + + + + + 1.20 toughness + + + + + + 1.38 toughness _ one by one — — — — 1.60 toughness (please read the precautions on the back before filling this page) ο ο ♦

u v Pu v P

[a -( 經濟部智慧財產局員工消費合作社印製 韌 + + + — + + 動 + H— Η— 一 + —*溶解性是在0.5 wt%樣品濃度條件下而得，+ :表示在 室溫下於24小時內可溶解；-:表示在室溫下不可溶解；+-表示在室溫下部份溶解表2 PI~斷裂強度(MPa) 斷裂伸長率（％) 起始模數（GPa) 10 2^55 6 2.17 11 2.52 8 1.96 9 2.06 b- 1.20 韌 韌 104 97 109 94 103 13 本紙張尺度適用中國國豕標準（CNS)A4規格（210 X 297公爱） 474956 A7 B7 五、發明説明（11 ) 實例5、以聯苯二酐(心BPDA)之PI為例 與各種二醚二胺合成PI比較其溶解性。使用之二胺包 括①M-雙(4-胺基苯氧）苯，②l，3-雙(4-胺基笨氧）苯，③n 雙(4-胺基苯氧）苯，④1，4-雙(4·胺基苯氧)-2-丁基苯，⑤2,2_ 雙(4-胺基苯氧苯）丙烷，而合成操作如實例2之程序，結 果合成PI之化學結構、固有黏度(PAA)及溶解性如下： 表3 溶解性* PI 〇 〇 ηίηΗ(ΡΑΑ) NMP DM Ac 1.87 -.H- —ϋ mu —^n ϋϋ —ϋ 1^1 1^1 —II n W (請先閲讀背面之注意事項再填寫本頁)[a-(Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs + + + — + + + + + H — 一 — +1 — — * Solubility is obtained under the condition of 0.5 wt% sample concentration, +: indicates in the room It can be dissolved within 24 hours at temperature;-: means insoluble at room temperature; +-means partially dissolved at room temperature. Table 2 PI ~ breaking strength (MPa) breaking elongation (%) initial modulus (GPa ) 10 2 ^ 55 6 2.17 11 2.52 8 1.96 9 2.06 b- 1.20 Toughness 104 97 109 94 103 13 This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 474956 A7 B7 V. Invention Explanation (11) Example 5. Taking PI of biphenyl dianhydride (Heart BPDA) as an example and comparing its solubility with various diether diamines to synthesize PI. The diamines used include ①M-bis (4-aminophenoxy) benzene , ②l, 3-bis (4-aminophenoxy) benzene, ③n bis (4-aminophenoxy) benzene, ④1,4-bis (4-aminophenoxy) -2-butylbenzene, ⑤2, 2_ Bis (4-aminophenoxybenzene) propane, and the synthetic operation is the same as the procedure of Example 2. As a result, the chemical structure, intrinsic viscosity (PAA) and solubility of the synthesized PI are as follows: Table 3 Solubility * PI 〇〇ηίηΗ (ΡΑΑ ) NMP DM Ac 1.87- .H- —ϋ mu — ^ n ϋϋ —ϋ 1 ^ 1 1 ^ 1 —II n W (Please read the notes on the back before filling this page)

o A ② - 十 1 · 3 2 9 〇 ③ - 一 1.68 ④o A ②-ten 1 · 3 2 9 〇 ③-one 1.68 ④

1.20 經濟部智慧財產局員工消費合作社印製 ® 於^+^香《：0"〇：:十1 ·31 i Ο Ο / η Ia L20 Ρ> Ο 〇 |η *溶解性定義同表1 + + - 實例6、可溶性Co-PI之合成（一種二胺與二種二酐共聚合 之一） 以原不（難）溶性之BTDA(IIIe)系進行共聚合改質：取 14 線_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 474956 A7 B7 五、發明説明（12 ) 二胺[1，2-雙(4-胺基笨氧)_心丁基苯](π) 2 mrn〇le溶於10 mL的DMAc中，加入BTDA(IIIe)l mmole攪拌20分鐘後 再加入hBPDA(Ina) 1 mmole，繼續攪拌約20分後反應液 黏度增加（甚至攪拌困難），繼續攪拌1小時後加入2 mL之 縮合劑（AhO/Py = 2/1體積），置於80〜10〇ι之甘油浴中 授摔1小時後，倒入甲醇中析出絲狀固體，浸泡一晚，過 慮乾燥’再於空氣流中烘熱25〇0C 2〇分，得目的共聚醯 亞胺IVa，測其固有黏度、有機溶劑溶解性，結果如下表。 以同樣操作但更換後段添加之二酐，包括DSDA (IIIb) ’ ODPA (111。)及6FDA (IIId)，所得化學組成和性質測 定如下： (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製1.20 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs® Yu ^ + ^ 香 《： 0 " 〇 :: ten 1 · 31 i Ο Ο / η Ia L20 Ρ > 〇 〇 | η * Solution definition is the same as Table 1 + + -Example 6. Synthesis of soluble Co-PI (copolymerization of one diamine and two dianhydrides) Copolymerization modification with the original (difficult) soluble BTDA (IIIe) system: Take 14 threads_ This paper size Applicable to China National Standard (CNS) A4 (210 X 297 mm) 474956 A7 B7 V. Description of the invention (12) Diamine [1,2-bis (4-aminobenzyloxy) _cardiobutylbenzene] (π ) 2 mrnole was dissolved in 10 mL of DMAc, BTDA (IIIe) 1 mmole was added and stirred for 20 minutes, and then hBPDA (Ina) 1 mmole was added. After stirring for about 20 minutes, the viscosity of the reaction solution increased (even difficult to stir), and continued After stirring for 1 hour, add 2 mL of condensing agent (AhO / Py = 2/1 volume), place in a glycerol bath of 80 ~ 100m for 1 hour, pour into methanol to precipitate a filamentous solid, and soak for one night After being dried for 2 years, it was heated at 2500C for 20 minutes in the air stream to obtain the objective copolymerized imine IVa. The intrinsic viscosity and the solubility of organic solvents were measured. The results are shown in the table below. Do the same operation but replace the dianhydride added after the replacement, including DSDA (IIIb) 'ODPA (111.) and 6FDA (IIId). The chemical composition and properties obtained are as follows: (Please read the precautions on the back before filling this page) Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperative

本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 、1· 474956 A7 B7 五、發明説明（ 13 表4 溶解性:This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm), 1.474956 A7 B7 V. Description of the invention (13 Table 4 Solubility:

Co-PI IVa IVb IV.Co-PI IVa IVb IV.

B riinh (PAA) riinh (PI) NMP DMAc DMF DMSO w-甲酚B riinh (PAA) riinh (PI) NMP DMAc DMF DMSO w-cresol

LW-OC L 1.06 45LW-OC L 1.06 45

1.60 IV^ ^OrfcCC ^80 0.74 1.34 1.32 1.66 + + + + + + + 一 + + 一 + + 1.38 經濟部中央標準局員工消費合作社印裝 *溶解性定義同表1 **B可見於表4之前的產物化學結構式中 表4中特別可注意者為IVa，其原來之Homo-PI (表1 中之Ia，Ie)皆對DMAc難溶及不溶性，但其共聚合物卻呈 易溶性。表4所合成的系列應屬交替型共聚合物 (Alternating Co-PI)。 實例7、可溶性Co-PI之合成（一種二胺與二種二酐共聚合 之二） 以原不溶性Π且膜具碎裂性之PMDA系進行共聚合改 質：取二胺I [1，2-雙(4-胺基苯氧)_4_丁基苯]3 mm〇le ^於12 mL的DMAc中，加入卜BPDA 2 mmole攪拌2〇分後， 再加入PMDA 1 mmole，繼續於常溫下攪拌i小時成黏稠 狀黏液之聚醯胺酸(PAA)，取一部份測其黏度，其餘在平 板玻璃上以調厚度之玻棒推延成膜，於8〇〇c蒸除大部严心 • · 一—— - _16 本紙張纽適用中國國家榡準（CNS )八视^ ( 21〇><297公楚 Φ1 (請先閱讀背面之注意事項再填寫本頁)1.60 IV ^ ^ OrfcCC ^ 80 0.74 1.34 1.32 1.66 + + + + + + + + one + + one + + 1.38 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs * The definition of solubility is the same as Table 1 ** B can be seen before Table 4 In the chemical structural formula of the product, especially noteable in Table 4 is IVa. The original Homo-PI (Ia, Ie in Table 1) are hardly soluble and insoluble to DMAc, but their copolymers are easily soluble. The series synthesized in Table 4 should be Alternating Co-PI. Example 7. Synthesis of soluble Co-PI (copolymerization of one diamine and two dianhydrides) (II) Copolymerization and modification with the original insoluble Π and membrane fragmentation PMDA system: Take diamine I [1,2 -Bis (4-aminophenoxy) _4-butylbenzene] 3 mm ^ ^ in 12 mL of DMAc, add BPDA 2 mmole and stir for 20 minutes, then add PMDA 1 mmole, and continue stirring at normal temperature After 1 hour, PAA is formed into a viscous mucus. Take a part to measure its viscosity, and the rest is rolled into a film on a flat glass with a thickness-adjustable glass rod. Most of the distillate is distilled off at 800 ° C. · I——-_16 This paper is applicable to China National Standards Standards (CNS) Eight Views ^ (21〇 > &297; 297 Gongchu Φ1 (Please read the notes on the back before filling this page)

、1T 474956 A7 B7 五、發明説明（ 劑使膜固化後’在空氣流的南溫供箱内由1 〇〇°c逐漸升溫 至250°C(1.5°C/min之速度）在250°c停留30分鐘成Co-Pi Va。冷卻，經在水中脫膜後測其物性，以同樣操作只更換 先添加之二酐，包括DSDA，ODPA及6FDA，合成c〇-；pi vb, V。及vd，其合成物之化學結構式及其測得之固有黏 度、溶解性和機械性質如表5。 311 + 2 9 9 9 〇+ <cx> II IIο ο IIIf、 1T 474956 A7 B7 V. Description of the invention (After the film is cured by the agent, the temperature is gradually increased from 1000 ° C to 250 ° C (1.5 ° C / min speed) in the temperature of the south temperature of the air flow box at 250 ° c Leave it for 30 minutes to become Co-Pi Va. Cool, measure its physical properties after removing the film in water, and replace only the dianhydride added first, including DSDA, ODPA and 6FDA, in the same operation, to synthesize co-; pi vb, V. and vd, the chemical structural formula of the compound and its measured intrinsic viscosity, solubility and mechanical properties are shown in Table 5. 311 + 2 9 9 9 〇 + < cx > II IIο ο IIIf

Ο II ο ο mb~eοΟ II ο ο mb ~ eο

Va〜d 表5 〇 〇 II Μ,c、 ο ο 溶解性*Va ~ d Table 5 〇 〇 II Μ, c, ο ο Solubility *

Co-PICo-PI

η：ηΗ (PAA) riinh(PI) ΝΜΡ DMAc DMF DMSO 訂 線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製η: ηΗ (PAA) riinh (PI) NMMP DMAc DMF DMSO Ordering (Please read the precautions on the back before filling this page) Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

Va Vb ：0t〇c 1.20 1.25 0.82 0.80 Vc 1.40 1.07 Vd cf3 0.95 0.78 If *溶解性定義同表1 1.60 可見於表5之前的產物化學結構式中 17 + + + + 本紙伕尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 474956 A7 B7 五、發明説明（15 機械性質：Va Vb: 0t〇c 1.20 1.25 0.82 0.80 Vc 1.40 1.07 Vd cf3 0.95 0.78 If * Solubility definition is the same as in Table 1 1.60 It can be seen in the chemical structure formula of the product before Table 5 17 + + + + This paper's scale is applicable to Chinese national standards ( CNS) A4 specification (210X297 mm) 474956 A7 B7 V. Description of the invention (15 Mechanical properties:

Va 92 10 2.00 Vb 88 6 2.00 Vc 106 9 2.00 Vd 85 6 2.07 表5中亦發現如Va原成分，表丨中之込，If皆難溶於 DMAc ’但其共聚合物卻呈易溶性。表5所合成的系列應屬 團聯父替共聚合物（Block-Alternating Co_PI)。 實例8、可溶性Co-PI之合成（一種二酐與二種二胺） 取二胺，1,3-雙（4-胺苯氧）苯[l，3-bis(4-aminophenoxy)benzene，以下簡稱（TPE-R)] 1 mmole 及二 胺 II [1，2-bis(4-aminophenoxy)-4-ie，i-butylbenzene] 1 mmole 溶於 10 mL 的 DMAc 中，分二次加入 DSDA 2 mmole 攪拌1· 5小時後以實例5之方式合成Co-PI是一種雜亂排 列，其化學組成及物性如下： (請先閲讀背面之注意事項再填寫本頁)Va 92 10 2.00 Vb 88 6 2.00 Vc 106 9 2.00 Vd 85 6 2.07 It is also found in Table 5 that the original components of Va, such as those in Table 丨, If are difficult to dissolve in DMAc ′, but their copolymers are easily soluble. The series synthesized in Table 5 should belong to the Block-Alternating Co_PI. Example 8. Synthesis of soluble Co-PI (one dianhydride and two diamines) Take diamine, 1,3-bis (4-aminophenoxy) benzene [1,3-bis (4-aminophenoxy) benzene, the following (TPE-R)] 1 mmole and diamine II [1,2-bis (4-aminophenoxy) -4-ie, i-butylbenzene] 1 mmole was dissolved in 10 mL of DMAc, and DSDA 2 mmole was added in two portions. After stirring for 1.5 hours, the synthesis of Co-PI in the manner of Example 5 is a messy arrangement. Its chemical composition and physical properties are as follows: (Please read the precautions on the back before filling this page)

經濟部中央標準局貝工消費合作社印製Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

VI οVI ο

此 Co-PI VI 之Tjinh = 0.96 dl/g (DMAc，30°C)，可溶於 NMP，DMAc，DMF，甲齡。 此與 TPE-R 之 Homo-PI 18 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 474956 A7 B7 五、發明説明（This Co-PI VI has Tjinh = 0.96 dl / g (DMAc, 30 ° C), and is soluble in NMP, DMAc, DMF, and age. This is the same as TPE-R Homo-PI 18. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 474956 A7 B7. 5. Description of the invention (

S°2-f^VC\ II 0 比較，此VII不溶於NMP，DMAc及DMF。 實例9、可溶性Co-PI之合成（由二種二胺與二種二酐合成） 取二胺II，2 mmol溶於15 mL的DMAc中，加入二酐 6FDA 1 mmol攪拌20分鐘後，加入4,4’-氧二苯胺(4,4’_ oxydianiline，以下簡稱4,4，-ODA) 1 mmol攪拌溶解後再加 入二酐PMDA 1 mmol與二酐6FDA 1 mmol繼續授拌1 hr 成黏稠液。依照實例2之熱烤法製成Co-PI VIII ·· cf3S ° 2-f ^ VC \ II 0 By comparison, this VII is insoluble in NMP, DMAc and DMF. Example 9. Synthesis of soluble Co-PI (synthesis from two diamines and two dianhydrides) Take diamine II, 2 mmol dissolved in 15 mL of DMAc, add dianhydride 6FDA 1 mmol and stir for 20 minutes, then add 4 1,4'-oxydianiline (4,4'_oxydianiline, hereinafter referred to as 4,4, -ODA) 1 mmol, stir and dissolve, then add dianhydride PMDA 1 mmol and dianhydride 6FDA 1 mmol and continue to mix for 1 hr to form a viscous liquid . Co-PI VIII made according to the hot roasting method of Example 2 cf3

CF3 •丨 VIII 其Co-PI VIII之固有黏度〇·97 dl/g，可溶於DMAc，NMP 及DMF。機械性質是抗張強度88 MPa’斷裂伸長率7%， 起始模數2.06 GPa。比較於Kapton成分 經濟部中央標準局員工消費合作社印製 \ 〇 9 & cf II 0 / 它是不溶於有機溶劑 19 (請先閲讀背面之注意事項再填寫本頁)CF3 • 丨 VIII The intrinsic viscosity of Co-PI VIII is 0.97 dl / g, which is soluble in DMAc, NMP and DMF. The mechanical properties are a tensile strength of 88 MPa 'and an elongation at break of 7%, and an initial modulus of 2.06 GPa. Compared with Kapton ingredients Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economy \ 〇 9 & cf II 0 / It is insoluble in organic solvents 19 (Please read the precautions on the back before filling this page)

本紙張尺度適用中國囷家榡準（CNS ) A4規格（210X297公釐）This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

474956 公告本 申請專利範圍 Α8 Β8 C8 D8 1. 一種有機溶劑可溶性的聚醯亞胺，其具有下式（r) 的單元： Ο 0 II II /C、 A •Ν、，Αγ3、/N—Ar2- C II ο II ο (Γ) 其中Ar2為 Ar3為 ('"BPDA) 5474956 Announcing the scope of this application patent A8 B8 C8 D8 1. An organic solvent-soluble polyfluorene imine having units of the following formula (r): 〇 0 II / C, A • N ,, Aγ3, / N-Ar2 -C II ο II ο (Γ) where Ar2 is Ar3 is ('" BPDA) 5 (DSDA)， 贫 〇|(〇DPA)，^^(6FDA)’(DSDA), lean 〇 | (〇DPA), ^^ (6FDA) ’ 〇BBDA) (請先閲讀背面之注意事項再填寫本頁)〇BBDA) (Please read the notes on the back before filling in this page) (6FDEDA)，(6FDEDA), 經濟部中央標隼局員工消費合作社印製 2.如申請專利範圍第1項的聚醯亞胺，其進一步具有 下式(Γ’）的單元，並且(Γ)與(Γ’）單元係無序排列·· 20 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） 申請專利範圍 A8 B8 C8 D8 其中Ah的定義同式(Γ)，及Ar4為欢 〇 0 .C Λ _N Ar、/Ν—Αγ2- π ^ Ο Ο(I，，） (PMDA)或Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 2. If the polyimide of item 1 of the scope of patent application, it further has a unit of the following formula (Γ '), and the units (Γ) and (Γ') are not Ordering arrangement ·· 20 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) Patent application scope A8 B8 C8 D8 where Ah has the same definition as (Γ), and Ar4 is Huan 0 0 .C Λ _N Ar, / Ν—Αγ2- π ^ Ο Ο (I ,,) (PMDA) or (BTDA) 經濟部中央標隼局員工消費合作社印製 3 ι •如申請專利範圍第1項的聚醯亞胺，其進一步具有 下式(Ι ’’）的單元，並且(Γ)與(Γ，，）單元係無序排列·· 0 〇人AΆ、γΝ—Ar5 II II ο ο (I，，，） 其中的定義同式(Γ)，及八1*5為 其中 Ζ = 〇, S，CH2, CO, S02, C(Me)2, C(CF3)2, CWR2, x-c6h4-x，x-c1gh8-x，x-qrWW-x，x-c6h4-y- Gh-x或聚石夕氧烧主鏈； 其中 x = o, s，cr!r2及 Y = 〇, S，CH2, CO, S02, C(Me)2, C(CF3)2, CW， 直鏈，或c6h1(); 其中 R1，R2, R3, R4 = H，鹵素，Me，CF3，或 C(Me)3, 其中Me為甲基。 4·如申請專利範圍第3項的聚醯亞胺，其進一步具有 21 本紙張尺度適用中國國家榡準（CNS ) Α4%Κ 2ι〇χ297公羡） (請先閲讀背面之注意事項再填寫本頁)(BTDA) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 3 ι • If the polyimide of item 1 of the patent application scope, it further has a unit of the following formula (I), and (Γ) and (Γ ,,) Units are disorderly arranged ... 0 〇 person AΆ, γN-Ar5 II II ο ο (I ,,,) where the definition is the same as the formula (Γ), and eight 1 * 5 is where Z = 〇, S, CH2, CO, S02, C (Me) 2, C (CF3) 2, CWR2, x-c6h4-x, x-c1gh8-x, x-qrWW-x, x-c6h4-y-Gh-x or polystone Oxygen burning main chain; where x = o, s, cr! R2 and Y = 〇, S, CH2, CO, S02, C (Me) 2, C (CF3) 2, CW, straight chain, or c6h1 () Where R1, R2, R3, R4 = H, halogen, Me, CF3, or C (Me) 3, where Me is methyl. 4. If the polyimide of item 3 of the patent application scope, it further has 21 paper standards applicable to China National Standards (CNS) Α4% Κ 2ι〇χ297 public envy) (Please read the precautions on the back before filling in this page) 474956 A8 B8 C8 D8 六、申請專利範圍 下式（Γ，)及(Γ’’’）的單元，且(Γ)、（Γ，）、（Γ’’)及(Γ’’’）單元 可為無序排列，交替排列或團聯排列： 0 0 II II /CNa /C, •N、/Ar^ /N—Αγ2~ C II Ο C II Ο (I，，） N OHC./CHO /4\ > OMC\ /cno // N ATS 其中Ar2的定義同式(Γ)，Ar5的定義同式(Γ’’） 及 Ar4 為 (BTDA) 5.如申請專利範圍第1項至第4項任一項所述之有機 溶劑可溶性的聚醯亞胺，Ar*2是由具下式的1，2-雙(4-胺基 苯氧)-4-特 丁基苯[1，2_Bis(4-aminophenoxy)-4-ieri-butylbenzene]所提供： h2n-h〇>~o o-<Q>-nh2 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標隼局員工消費合作社印製 6.如申請專利範圍第1項之有機溶劑可溶性的聚醯亞 胺，其中 μ為 j〇n〇l^-BPDA)或 3〇ts〇2i0C (DSDA)。 7.如申請專利範圍第1項之有機溶劑可溶性的聚醯亞 cf3 ，其中 Ar3 為 (ODPA)或 胺 (6FDA) 8.如申請專利範圍第1項之有機溶劑可溶性的聚醯亞 22 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 申請專利範圍 A8 B8 C8 D8 胺’其中 Ar3 為 (_a)。 如申凊專利範圍第1項之有機溶劑可溶性的聚醯亞 胺’其中、為 CH3 或 ^〇γο_Ό~^<〇>~〇~〇]^ (DEDA) (6FDEDA) 巾μ專利範圍第1項之有機溶劑可溶性的聚醯 亞妝，其中Ar3為474956 A8 B8 C8 D8 6. The units of the formula (Γ,) and (Γ '' ') below the scope of the patent application, and (Γ), (Γ,), (Γ' ') and (Γ' '') units can be It is a disorderly arrangement, alternating arrangement or group arrangement: 0 0 II II / CNa / C, • N, / Ar ^ / N—Αγ2 ~ C II 〇 C II Ο (I ,,) N OHC./CHO / 4 \ > OMC \ / cno // N ATS where the definition of Ar2 is the same as the formula (Γ), the definition of Ar5 is the same as the formula (Γ '') and Ar4 is (BTDA) 5. If the scope of patent application is 1st to 4th The organic solvent-soluble polyfluorene imine according to any one of Ar * 2 is composed of 1,2-bis (4-aminophenoxy) -4-tert-butylbenzene [1,2-Bis (4 -aminophenoxy) -4-ieri-butylbenzene] Provided: h2n-h〇 > ~ o o- < Q > -nh2 (Please read the notes on the back before filling out this page) Employees of the Central Bureau of Standards, Ministry of Economic Affairs Printed by a cooperative 6. The organic solvent-soluble polyfluorene imine, such as in item 1 of the scope of patent application, where μ is jonol ^ -BPDA) or 30ts〇2i0C (DSDA). 7. For example, the organic solvent-soluble polyfluorene cf3 of the scope of the patent application, where Ar3 is (ODPA) or amine (6FDA) 8. As for the organic solvent-soluble polyfluoridea of the scope of patent application, 22 papers The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The scope of patent application is A8 B8 C8 D8 Amine 'where Ar3 is (_a). For example, the organic solvent-soluble polyimide of item 1 of the patent application range is CH3 or ^ 〇γο_Ό ~ ^ < 〇 > ~ 〇 ~ 〇] ^ (DEDA) (6FDEDA). 1 item of organic solvent-soluble polyisocyanate, wherein Ar3 is 〇^°〇 ^ ° (請先閲讀背面之注意事項再填寫本頁) 或处。(Please read the notes on the back before filling out this page) 亞胺，專利#&圍第2項之有機㈣可溶性的聚醯 亞胺其中Ar3:Ar4(重量）叫〇〇:〇〜5:95。 、1T 線·- 經濟部中央標準局員工消費合作社印裝 12·如申請專利範圍第3項 亞胺，λ 有機洛劑可溶性的聚 亞胺，其中Ar2 ·· Ar5(重量）=1〇〇 醯 13·如申請專利範圍第4項之 亞胺，1中·Δ 1Λ 有機4劑可溶性的聚醯 兄W 八 tp Ar3· Ar4(重量）=1〇〇:〇〜量）=100:0 〜5: 95。 · 5 及 Ar2·· Ar5(重Imine, Patent # & 2 of the organic fluorene soluble polyfluorene imine wherein Ar3: Ar4 (weight) is called 0: 0 ~ 5:95. Line 1T ·· Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 12 · If the scope of the patent application is the third imine, lambda soluble polyimide, of which Ar2 ·· Ar5 (weight) = 100% 13. As for the imine in item 4 of the scope of the application for patent, 1 medium. Δ 1 Λ organic 4 agent soluble polyisocyanate W eight tp Ar3 · Ar4 (weight) = 100: 0 ~ amount) = 100: 0 ~ 5 : 95. 5 and Ar2Ar5 (heavy • ·- II I • I- I -- 474956 A8 B8 C8 D8 六、申請專利範圍 14. 一種聚醯亞胺的有機溶液，包含一有機溶劑及溶 解於該有機溶劑的具有下列式（Γ)單元的聚醯亞胺，該有機 溶劑選自W曱基-2·吡咯烷酮，MTV-二曱基乙醯胺，二甲基 曱醯胺，二甲亞颯曱盼（m_cresol)，0比0定，氯化曱烧及 氯化乙烷所組成的族群： 0 0 II II 人、A -N Αγ3 N—Ar2-C C II II o o (請先閱讀背面之注意事項再填寫本頁) -Or (Γ) 經濟部中央標準局員工消費合作社印製 其中Ar2為 〇 P• ·-II I • I- I-474956 A8 B8 C8 D8 6. Scope of patent application 14. An organic solution of polyimide comprising an organic solvent and a unit having the following formula (Γ) dissolved in the organic solvent Polyimide, the organic solvent is selected from the group consisting of fluorenyl-2 · pyrrolidone, MTV-difluorenylacetamide, dimethylfluorenamine, m-cresol, 0 to 0, Tritium chloride and ethane chloride groups: 0 0 II II people, A -N Αγ3 N—Ar2-C C II II oo (Please read the precautions on the back before filling this page) -Or (Γ ) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs where Ar2 is 0 P (DSDA)， (6FDA)，(DSDA), (6FDA), 本紙張尺度適用中國國家標準（CNS ) A4说格（210 X 297公釐） 474956 申請專利範圍This paper size applies Chinese National Standard (CNS) A4 standard (210 X 297 mm) 474956 Patent application scope °T〇C 或'〇分, 0 0 II A .Λ ^ νΝ C II C II 0 II 0 (I，，） 其中Ar*2的定義同式(1，）， 及 Ar4 為 (pMDA)或° T〇C or '〇 分, 0 0 II A .Λ ^ νΝ C II C II 0 II 0 (I ,,) where Ar * 2 has the same definition as (1,), and Ar4 is (pMDA) or (BTDA) 16·如申請專利範圍第14項的有機溶液，其進一步具 有下式(Γ”)的單元，並且(1，)與(Γ，，)單元係無序排列： 0 II 經濟部中央標隼局員工消費合作社印製 γ^γΝ- 〇 6 (Γ，，） 其中Αι*3的定義同式(Γ)，及Ar5為 ~0^ΖΌ~ 其中 ζ = 〇, s，CH2, C0, S02, c(Me)2, C(CF3)2, CVR2, x-C6H4-X，x_ci()H8-X，X-qWW-X，X-C6H4-Y- C6iVX或聚矽氧烷主鏈； 6氏張尺度適用 (請先閲讀背面之注意事項再填寫本頁)(BTDA) 16. The organic solution according to item 14 of the scope of patent application, which further has units of the following formula (Γ "), and the (1,) and (Γ ,,) units are arranged disorderly: 0 II Central of the Ministry of Economic Affairs Printed by the Bureau of Consumers' Cooperatives of Standards Bureau γ ^ γN- 〇6 (Γ ,,) where Aι * 3 has the same definition as (Γ), and Ar5 is ~ 0 ^ ZΌ ~ where ζ = 〇, s, CH2, C0, S02, c (Me) 2, C (CF3) 2, CVR2, x-C6H4-X, x_ci () H8-X, X-qWW-X, X-C6H4-Y-C6iVX or polysiloxane main chain; 6's scale is applicable (please read the precautions on the back before filling this page) 申請專利範圍 A8 B8 C8 D8 其中 X^C^S’CRiR2 及 Y = 〇, S，CH2, CO, S02, C(Me)2, C(CF3)2, CWR2, 直鏈，或C6H1(); 其中 R1，R2, R3, R4 =： H，_ 素，Me，CF3，或 C(Me)3, 其中Me為曱基。 17·如申請專利範圍第14項的有機溶液，其進一步具 有下式（I )及(I’’’’）的單元，且(Γ)、（Γ，）、（I，，，)及(I，，，，）單 7L可為無序排列，交替排列或團聯排列： 〇 〇 Η 〇 δ Ν—Αγ2_ (I，，） Ν—Ar^ (I，，，，） (請先閎讀背面之注意事項再填寫本頁} 經濟部中央標準局員工消費合作社印製 其中At*2的定義同式(Γ)，Αγ5的定義同式(Γ，，） 及仏為 ^C(pmda)5|0X〇C (btda)。 18.如申請專利範圍第14項至第17項任一項所述之 有機溶液，Ah是由具下式的1，2-雙(4-胺基苯氧)-4_特丁基 本[1,2 Bis(4-aminophenoxy)-4々eri-butylbenzene]所提供·H2N -〇^^〇~^^«蘭2 19·如申請專利範圍第14項的有機溶液，其中為 ㈣PDA)或^_s〇2^^ (dsda) 〇 26 本紙伕尺度適用中國國家梯準（CNS ) A4規格（21OX297公釐）Application for patent scope A8 B8 C8 D8 where X ^ C ^ S'CRiR2 and Y = 〇, S, CH2, CO, S02, C (Me) 2, C (CF3) 2, CWR2, straight chain, or C6H1 (); Where R1, R2, R3, R4 =: H, _ prime, Me, CF3, or C (Me) 3, where Me is a fluorenyl group. 17. The organic solution according to item 14 of the scope of patent application, which further has units of the following formulae (I) and (I '' ''), and (Γ), (Γ,), (I ,,,) and ( I ,,,,) single 7L can be disordered, alternating or grouped: 〇〇Η 〇δ Ν—Αγ2_ (I ,,) Ν-Ar ^ (I ,,,,) (Please read first Note on the back, please fill out this page again} Printed by the Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, where the definition of At * 2 is the same formula (Γ), the definition of Αγ5 is the same formula (Γ ,,) and 仏 C (pmda) 5 0X〇C (btda) 18. According to the organic solution described in any one of the 14th to the 17th of the scope of patent application, Ah is composed of 1,2-bis (4-aminophenoxy) with the following formula -4_Provided by [1,2 Bis (4-aminophenoxy) -4々eri-butylbenzene] · H2N -〇 ^^ 〇 ~ ^^ «2 2 · The organic solution such as the 14th in the scope of patent application , Of which ㈣PDA) or ^ _s〇2 ^^ (dsda) 〇26 The standard of this paper is applicable to China National Standard (CNS) A4 (21OX297mm) 474956 A8 B8 C8 D8 六、申請專利範圍 20.如申請專利範圍第14項的有機溶液，其中Ai*3為C V (6FDA) CF3l 21. 如申請專利範圍第14項的有機溶液，其中Af3為 ^0-〇多^〇^0[^ (，-BBDA)。 22. 如申請專利範圍第14項的有機溶液，其中Ar3為474956 A8 B8 C8 D8 6. Application scope of patent 20. If the scope of application of the scope of the patent No. 14 organic solution, where Ai * 3 is CV (6FDA) CF3l 21. If the scope of the scope of application of the patent No. 14 of the organic solution, where Af3 is ^ More than 0-〇 ^^^ 0 [^ (, -BBDA). 22. For the organic solution in the scope of application for item 14, wherein Ar3 is (6FDEDA) 23.如申請專利範圍第14項的有機溶液，其中Ar3為(6FDEDA) 23. The organic solution according to item 14 of the application, wherein Ar3 is (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製(Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs οο °-〇c 24. 如申請專利範圍第15項的有機溶液，其中Ar3 Ar4(重量）=100 : 0 〜5 : 95。 25. 如申請專利範圍第16項的有機溶液，其中Ar2 八1*5(重量）=100:0〜5:95。 27 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 474956 A8 B8 C8 D8 六、申請專利範圍 26. 如申請專利範圍第17項的有機溶液，其中Ar3 : Ar4(重量）=100 : 0 〜5 : 95 及 Ar2 ·· Ar5(重量）=100 ·· 5 : 95 ° 27. —種具下式的1，2-雙(4-胺基苯氧)-4_特丁基苯 [l,2-Bis(4-aminophenoxy)-4-ieri-butylbenzene] ^ h2nh〇^o o-^Q^-nh2 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 28 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）° -〇c 24. The organic solution according to item 15 of the scope of patent application, wherein Ar3 Ar4 (weight) = 100: 0 to 5:95. 25. For example, the organic solution under the scope of application for patent No. 16, wherein Ar2 is 8 * 5 (weight) = 100: 0 ~ 5: 95. 27 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 474956 A8 B8 C8 D8 6. Application for patent scope 26. For the organic solution of item 17 in the scope of patent application, where Ar3: Ar4 (weight) = 100 : 0 to 5: 95 and Ar2 · · Ar5 (weight) = 100 · · 5: 95 ° 27. — 1,2-bis (4-aminophenoxy) -4_tert-butylbenzene with the following formula [l, 2-Bis (4-aminophenoxy) -4-ieri-butylbenzene] ^ h2nh〇 ^ o o- ^ Q ^ -nh2 (Please read the precautions on the back before filling this page) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative 28 This paper size applies to China National Standard (CNS) A4 (210X297 mm)