TW201231504A - Polyimide composite, polyamide solution, method for manufacturing polyimide composite and film comprising polyimide composite - Google Patents

Abstract

A polyimide composite and method for manufacturing the same are provided in the disclosure, wherein the colorless transparency, mechanical properties and heat-tolerance owned by polyimides of specific structures are not harmed; on the other hand, fluorescence of a specific wavelength is emitted by ultraviolet irradiation, and the intensity of the fluorescence is high. The polyimide composite of the disclosure is obtained through the following steps: by adding 0.001 to 4 parts by weight of an europium (Eu) compound based on 100 parts by weight of the polyamide solution (S1) to obtain a polyamide solution (S2), and then by imidizing a polyamide contained in the polyamide solution (S2) and eliminating the solvent (C) to obtain the polyimide composite. The polyamide in the polyamide solution (S1) is obtained with an alicyclic diamine compound (A) and an aromatic tetracarboxylic dianhydride (B). The polyamide solution (S1) is obtained by a specific polyamide and the solvent (C) dissolving the same.

Description

201231504 六、發明說明： 【發明所屬之技術領域】 本發明是有關於—種聚醯亞胺複合體及聚醯亞胺複合 體的製造方法。 詳細而言，是有關於無色透明、藉由照射紫外線而瞬 間發出特定波長的螢光、且螢光強度高的含有銪（Eu)化 合物的聚醯亞胺複合體、及其製造方法。 【先前技術】 聚醯亞胺除了其優異的耐熱性外，還在機械特性、電 氣特性等方面優異，因此先前以來在各種領域中廣泛用作 成形材料、複合材料、電氣電子材料。 先前’聚醯亞胺通常為藉由使二胺與四幾酸二針於溶 劑中反應而生成聚龜胺酸’並將聚酿胺酸進行脫水閉環等 方法而獲得。 該些聚醢亞胺之中，由芳香族四竣酸二酐與芳香族二 胺而得的聚醯亞胺大多耐熱性及機械特性優異。然而，該 些聚醯亞胺會變成呈現紅褐色〜黃色的樹脂，光學特性存 在問題。並且亦有如下例子，藉由使二胺與四羧酸二酐兩 者或任一者形成為脂環式結構，或者導入較蓬鬆、且分極 率較低的氟基或三氣甲基等，而獲得具有無色透明性的聚 酿亞胺’但無法賦予聚酿亞胺所具有的耐熱性或機械特性。 /另一方面，螢光材料通常可分為三大類：量子點、有 機系色素及稀土類錯合物。量子點具有較寬的吸收帶、優 異的發光特性、長期穩定性，但具有斯托克斯位移（Stokes 201231504 馨tt的缺點。此處，就螢光材料而言，通常激發波 曰、螢t長存在錄’將此波長差稱為斯托克斯位移。 : 機系色素具有較高的吸光係數與量子產率、良好 人ί工性ΐ特徵’但難有光穩定性。另—方面，稀土類錯 σ具有量子產率較高，但吸光係數較低的特徵。 曰 ^且，5亥些螢光材料為低分子量化合物時，與成為母 5的樹脂混合時，會殘留有低分子縣材料凝聚而浮滅 a(qUench)的問題、或來自樹脂的溢出（bleed out)等問 題。 就稀土類陽離子而言，有在由紫外至紅外範圍發出寬 ，的波長區域的螢光的稀土類陽離子。該些稀土類陽離子 疋基於不易叉到配位子場（ligand field)等外界的影響的f 軌道電子的躍遷（ff躍遷），因此為發光帶的波長寬度與有 機螢光體等相比非常窄，且原理上色純度較高的有用的榮 光種。並且，由於對於熱或光的穩定性亦優異，因此一直 應用於電視接收機的顯示器等。 例如含有銪（Eu)的金屬錯合物等複合體藉由紫外光 激發而會發出紅色螢光。 專利文獻1中揭示，包含透明聚醯亞胺的螢光材料， 上述透明聚醯亞胺以含有二苯基醚等的四羧酸二酐、與主 鏈具有脂環式結構的二胺等作為原料。此聚醯亞胺將發光 波長（emission wavelength)進行短波長化而發出藍色〜紫 色區域的螢光’聚醯亞胺自身會藉由紫外線照射而發光。 專利文獻2中揭示，在聚合物的主鏈或側鏈具有羰基 201231504 的聚合物中含有稀土類开去 g 素離子而成的光記憶材料。由於 疋者眼於光S己憶效果的韻^日日 ϋ Ο· 發明，因此為了發揮光記憶性，而 添加大篁的稀土類元夸雜2 θ 離子。因此，無法獲得輯亞胺所 具有的優異的機械特性戎雷友 ^次電虱特性。並且，為了提高發光 ^而必舰饤長時_紫外線照射，而無法獲得高速 響應性。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開遍5·,393號公報 [專利文獻2]日本專利特開薦屬79號公報 【發明内容】 ^發明是提供-種㈣亞胺複合體及其製造方法，其 :損及特定結構的聚__具有的無色透明性、機械 *生及耐熱性，並且藉由卿料線而發出特 光，且螢光強度高。 蛩 ，發明者等人為了解決上述課題而銳意研究結 現，藉由將特定結構的聚酿亞胺與銪（Eu)化合物複合化， 而可解決上述課題，從而完成了本發明。即， 、本發明的聚醯亞胺複合體的特徵在於：其是相對於由 通式（1)所示的聚醯胺酸、與溶解此聚醯胺酸的溶劑、 而得的聚酿胺酸溶液（S1)觸重量份，而添加銪（） 0.001重量份〜4重量份，而獲得聚醯胺酸 、2) ’上述聚醯胺酸由脂環式二胺化合物（A)與芳 四竣Ssc —gf (B)而得，藉由此聚醯胺酸溶液（幻）所含 6 201231504 的聚醯胺酸的醯亞胺化及除去溶劑（c)而獲得：201231504 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a polyimine complex and a polyimide composition. More specifically, it is a polyimine complex containing an europium (Eu) compound which is colorless and transparent, emits fluorescence of a specific wavelength instantaneously by irradiation of ultraviolet rays, and has high fluorescence intensity, and a method for producing the same. [Prior Art] Polyimine is excellent in mechanical properties, electrical properties, and the like in addition to its excellent heat resistance, and thus has been widely used as a molding material, a composite material, and an electric and electronic material in various fields. The former 'polyimine is usually obtained by a method in which a diamine and a tetra-acid are reacted in a solvent to form a polymyric acid, and the poly-aracine is subjected to dehydration ring closure. Among these polyimines, polyimines obtained from aromatic tetraphthalic dianhydrides and aromatic diamines are often excellent in heat resistance and mechanical properties. However, these polyimines become resins which exhibit a reddish brown to yellow color, and optical properties are problematic. Further, there are also examples in which a dicyclic structure is formed by either or both of a diamine and a tetracarboxylic dianhydride, or a fluffy, low-polarity fluorine group or a trimethyl group is introduced. However, the polyanilin having colorless transparency is obtained, but the heat resistance or mechanical properties possessed by the polystyrene cannot be imparted. On the other hand, fluorescent materials can be generally divided into three categories: quantum dots, organic pigments, and rare earth complexes. Quantum dots have a wide absorption band, excellent luminescence properties, and long-term stability, but have Stokes shifts (Stokes 201231504 Xin tt's shortcomings. Here, in the case of fluorescent materials, usually excited waves, fluorescent t The long-lived record 'this wavelength difference is called the Stokes shift. : The machine pigment has a high absorption coefficient and quantum yield, good humanity characteristics 但 but difficult to have light stability. Another aspect, The rare earth type error σ has a high quantum yield, but the absorption coefficient is low. ,^ and, when some of the fluorescent materials are low molecular weight compounds, when mixed with the resin which becomes the mother 5, low molecular counties remain. A problem in which a material agglomerates and a(qUench) is floated, or a problem arises from a resin bleed out. In the case of a rare earth cation, there are fluorescent rare earths emitting a wide wavelength region from the ultraviolet to the infrared range. The cations are based on the transition of the f orbital electrons (ff transition) which is not easily affected by external influences such as a ligand field, and thus the wavelength width of the light-emitting band is compared with that of an organic phosphor or the like. very much And the principle is to color a useful glory with high purity. Moreover, since it is excellent in stability to heat or light, it has been applied to displays of television receivers, etc. For example, metal complexes containing europium (Eu), etc. The composite emits red fluorescence by excitation by ultraviolet light. Patent Document 1 discloses a fluorescent material containing a transparent polyimine, which is a tetracarboxylic dianhydride containing diphenyl ether or the like. And a diamine having an alicyclic structure with a main chain as a raw material. The polyimine emits a blue-to-purple region in which the emission wavelength is shortened to emit a short wavelength. Light is emitted by ultraviolet light irradiation. Patent Document 2 discloses that an optical memory material containing a rare earth-based gluconic acid ion in a polymer having a carbonyl group 201231504 in a main chain or a side chain of a polymer is disclosed in the light S. The rhyme of the effect of the memory is invented. Therefore, in order to exhibit optical memory, the rare earth element added with the large yttrium is mixed with the 2 θ ion. Therefore, the excellent mechanical properties of the imine are not obtained.戎 友 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线 紫外线[Patent Document 2] Japanese Patent Laid-Open Publication No. 79-A SUMMARY OF THE INVENTION [Invention] Provided is a (tetra) imine complex and a method for producing the same, which comprises a poly-_ having a specific structure It is colorless and transparent, mechanically and heat-resistant, and emits special light by a clearing line, and has high fluorescence intensity. 蛩 Inventors and others have studied the realization in order to solve the above problems by using a specific structure. The present invention can be accomplished by combining the polyimine and the europium (Eu) compound to solve the above problems. In other words, the polyimine complex of the present invention is characterized in that it is a polyamine derived from a polylysine represented by the formula (1) and a solvent in which the polylysine is dissolved. The acid solution (S1) is in parts by weight, and 0.001 parts by weight to 4 parts by weight of bismuth () is added to obtain poly-proline, 2) 'the above poly-amino acid is composed of the alicyclic diamine compound (A) and the aromatic four.竣Ssc —gf (B), obtained by the ruthenium imidization of the polyamine acid of 6 201231504 and the removal of the solvent (c) by the polyacetic acid solution (magic):

Η Ο Ο Η I II II I X一N-C' yC-N HO-C VC-〇H II II O 0Η Ο Ο Η I II II I X-N-C' yC-N HO-C VC-〇H II II O 0

(1) (式（1 )中’ X表示碳數4〜15的二價脂環族基，γ 表示碳數6〜27的四價芳香族基）。 並且’上述聚醯亞胺複合體所含的聚醯亞胺較佳為包 含下述通式（2)所示的結構單元：(1) (wherein X represents a divalent alicyclic group having a carbon number of 4 to 15 and γ represents a tetravalent aromatic group having a carbon number of 6 to 27). Further, the polyimine contained in the above polyimine complex preferably contains a structural unit represented by the following formula (2):

(2) 式（2)中，X為選自由(2) In the formula (2), X is selected from

所組成群組中的至少1種脂環族基； Y為選自由 201231504:At least one alicyclic group in the group consisting of; Y is selected from 201231504:

)〇r°^°i〇C 所組成群組中的至少1種芳香族基。 上述聚醯亞胺複合體所含的聚醯亞胺亦較佳為包含下 述通式（3)所示的結構單元：At least one aromatic group in the group consisting of 〇r°^°i〇C. The polyimine contained in the above polyimine complex is also preferably a structural unit represented by the following formula (3):

(3) 〇 上述聚醯亞胺複合體所含的聚醯亞胺亦較佳為包含下 述通式（4)所示的結構單元：(3) The polyimine contained in the above polyimine complex is also preferably a structural unit represented by the following formula (4):

上述聚醯亞胺複合體所含的聚醯亞胺亦較佳為包含下 述通式（5)所示的結構單元： 8 201231504The polyimine contained in the above polyimine complex is also preferably a structural unit represented by the following formula (5): 8 201231504

上述聚醯亞胺複合體所含的聚醯亞胺亦較佳為包含下 述通式（6)所示的結構單元：The polyimine contained in the above polyimine complex is also preferably a structural unit represented by the following formula (6):

(6) (式中，m與η表示各括弧内所示的重複結構單元的 重複數，m的平均值與η的平均值之比（m : η)為i : 9 〜9 : 1 )。 上述銪（Eu)化合物較佳為選自氣化销、确酸銷及乙 酸銪中的至少1種。 本發明的聚醯亞胺複合體通常藉由照射波長25〇⑽ 〜400 nm的紫外線’而較佳為發出波長5〇〇啦〜謂伽 的螢光。 本發明的膜的特徵在於：其包含本發明的聚醯亞胺複 此聚酿亞胺複合體難為全光騎料為8〇%以上 合體。 本發明的聚醯亞胺複合體的製造方法的特徵 含以下的步驟1〜步驟3: 、 201231504 (步驟1)獲得由通式（丨）所示的聚醯胺酸、與溶解 此聚酿胺酸的溶劑（c)而得的聚醯胺酸溶液（S1)的步 驟’上述聚酿胺酸為由脂環式二胺化合物（A)與芳香族 四羧酸二酐（B)而得：(6) (wherein m and η represent the number of repetitions of the repeating structural unit shown in each parenthesis, and the ratio of the average value of m to the average value of η (m : η) is i : 9 〜 9 : 1 ). The above ruthenium (Eu) compound is preferably at least one selected from the group consisting of a gasification pin, a succinic acid pin, and ruthenium acetate. The polyimine complex of the present invention is usually irradiated with ultraviolet light having a wavelength of from 25 Å to 10 nm, and preferably emitted at a wavelength of from 5 Å to deg. The film of the present invention is characterized in that it comprises a polyamidene complex of the present invention which is difficult to be a full light riding material of 8 % by weight or more. The method for producing a polyimine complex of the present invention is characterized by the following steps 1 to 3: , 201231504 (step 1), obtaining a polylysine represented by the formula (丨), and dissolving the polyamine Step of the polyamic acid solution (S1) obtained from the acid solvent (c) The above polyamic acid is obtained from the alicyclic diamine compound (A) and the aromatic tetracarboxylic dianhydride (B):

(式（1 )中’ X表示碳數4〜15的二價脂環族基，Y 表示碳數6〜27的四價芳香族基）； (步驟2)相對於此聚醯胺酸1〇〇重量份，而添加銪 (Eu)化合物0.001重量份〜4重量份，而獲得聚醯胺酸 溶液（S2)的步驟；及 (步驟3)藉由此聚醯胺酸溶液（S2)所含的聚醯胺 酸的醯亞胺化及除去溶劑（C)而獲得聚醯亞胺複合體的 步驟。 本發明的聚醯胺酸溶液（S2)的特徵在於：其是在下 述通式（1)所示的聚醯胺酸、以及(In the formula (1), 'X represents a divalent alicyclic group having 4 to 15 carbon atoms, and Y represents a tetravalent aromatic group having 6 to 27 carbon atoms; (Step 2) 1 相对 relative to the polyglycine 〇 by weight, adding 0.001 parts by weight of the Eu (Eu) compound to 4 parts by weight to obtain a solution of the polyaminic acid solution (S2); and (Step 3) by the polyamic acid solution (S2) The step of obtaining a polyimine complex by hydrazylation of polyamic acid and removal of solvent (C). The polyaminic acid solution (S2) of the present invention is characterized in that it is a polylysine represented by the following formula (1), and

15的二價脂環族基，γ (式（1)中，X表示碳數4-表示碳數6〜27的四價芳香族基） 201231504 其是於溶解此聚醯胺酸的溶劑（c)中，相對於此聚 醯胺酸100重量份，而添加銪（Eu)化合物0.001重量份 〜4重量份而獲得。 上述溶劑（C)較佳為非質子性醯胺系溶劑。 [發明的效果] 藉由本發明而得的聚醯亞胺複合體不會損及聚醯亞胺 單獨本來所具有的光學特性（無色透明性）、機械物性及耐 熱性’另一方面，藉由照射紫外線而瞬間發出特定波長的 螢光。並且’由於螢光強度非常高，因此可高效率地發出 螢光。因此’此聚醯亞胺複合體適合於波長轉換用材料、 顯示器等顯示用材料、螢光塗料用等螢光材料、安全油墨 (security ink)用等安全印刷（security printing)用材料、 照明用材料、太陽光發電用材料、放射線感測器用材料、 農業用膜等。 【實施方式】 對本發明的聚醯亞胺複合體及其製造方法進行說明。 <聚醯胺酸溶液（S1) > (聚醯胺酸） 本發明中’製作聚醯亞胺複合體時，可利用包含作為 聚醯亞胺的前驅體的聚醯胺酸的溶液（S1)、即聚醜胺酸 凊漆（varnish)(亦稱為聚醯亞胺前驅體清漆）。在溶解聚 胺酸的溶劑的存在下，聚醯胺酸為由脂環式二胺化人物 (A)與芳香族四叛酸二針（B)的反應而獲得，並具有下 述通式（1)所示的半脂環式的重複結構： 201231504 ~Τ X \J~T^ LJlia divalent alicyclic group of 15 , γ (wherein X represents a tetravalent aromatic group having a carbon number of 4 to 27 and a carbon number of 6 to 27 in the formula (1)) 201231504 which is a solvent for dissolving the polylysine (c In the above, the ruthenium (Eu) compound is added in an amount of 0.001 part by weight to 4 parts by weight based on 100 parts by weight of the polyamic acid. The solvent (C) is preferably an aprotic amide-based solvent. [Effect of the Invention] The polyimine composite obtained by the present invention does not impair the optical properties (colorless transparency), mechanical properties, and heat resistance inherent in the polyimide polyimide alone. The ultraviolet light is irradiated to emit a specific wavelength of fluorescence instantaneously. And because the fluorescence intensity is very high, it can emit fluorescence efficiently. Therefore, the polyimine complex is suitable for materials for wavelength conversion, materials for display such as displays, fluorescent materials for fluorescent coatings, materials for security printing such as security inks, and lighting materials. Materials, materials for photovoltaic power generation, materials for radiation sensors, agricultural films, and the like. [Embodiment] The polyimine complex of the present invention and a method for producing the same will be described. <Polyuric acid solution (S1) > (polyproline) In the present invention, when a polyimine complex is produced, a solution containing polyglycine as a precursor of polyimine can be used ( S1), namely varnish (also known as polyimine precursor varnish). In the presence of a solvent for dissolving polyamine, polylysine is obtained by the reaction of an alicyclic diamined person (A) with an aromatic tetra-neuric acid two-needle (B), and has the following formula ( 1) The semi-alicyclic repeat structure shown: 201231504 ~Τ X \J~T^ LJli

•頂脂環務丞 表示碳數6〜27的四價芳香族基） 聚酿胺I洛液（S1)中的聚醯胺酸的濃度只要可製个 聚醯亞胺複合體，則並無特別限制，較佳為相對於聚醯用 酸100重量份，溶劑為100重量份〜10000重量份，更个 為200重量份〜5000重量份。 ’ 本發明的《亞胺由脂環式二胺化合物⑷與芳； 族四竣酸二酐（B)構成，因此在作為前驅體的聚酿細 雜m㈣__基UafbGxylgK)up)的緩酸g (carboxylate)陰離子與金屬陽離子可形成離子鍵。因此 地將銪（Eu)化合物進行複合，不會損及機械射 及财熱性，雖然為無色透明，但例如藉由照射2〇〇nm〜40 1。^^’，而/常可瞬間發出5〇〇細〜_細的聋 光發光，而V以雷了促使因錄㈤）的卿遷所引起的璧 光發光，而可以π電子牵絲挪 搶刪）效果而高效率地&體(—0經由光學天線（〇—: 位的有機分子部位且有芳能量轉移，於可與近配 靜。m th 有方香知性時，可具有非常高的螢光 光Γ ㈣聚私職合射高效率地發出勞 201231504 (二價脂環式二胺化合物（A)) 式（1)的重複結構t的X源自二價脂環式二胺化合 ，（A)。二胺化合物（A)只要可製造聚醯胺酸、聚醯亞 胺，則並無特別限定，例如可列舉： 裱丁烷二胺類、環己烷二胺類（包括反义屯環己基 胺）、二(胺基甲基)環己烷類（1，4_雙(胺基甲基)環己烷等雙 (胺基甲基)環己炫類）、二胺基雙環庚炫類、二胺基甲基雙 環庚烷類（包括降冰片烷二胺等降冰片烷二胺類）、二胺基 氧基雙環庚烷類、二胺基曱基氧基雙環庚烷類（包括氧雜 降冰片烷二胺等氧雜降冰片烷二胺類）、異佛爾鲖二胺等異 佛爾酮二胺類、二胺基三環癸烷類、二胺基甲基三環癸烷 類、雙(4-胺基環己基）甲烷等雙(胺基環己基）甲烷類/( 4,2 亞曱基雙(環己基胺)等亞甲基雙(環己基胺)類）、雙(胺基環 己基)異亞丙基類等。 較佳的脂環式二.胺化合物（A)就可獲得性、光學物 性良好性、及熱穩定性且力學穩定性的理由而言，可列 包含反-1，4-環己基胺的環己烷二胺類、包含込屯雙(胺^曱 基)環己烧的二(胺基甲基)環己烧類、二胺基曱基雙譬庚产 類（包括降冰片烷二胺等降冰片烷二胺類）、氧雜降=片= 二胺、異佛爾酮二胺、4,4，-亞曱基雙(環己基胺)等。若對: 二胺基曱基雙環庚烷類（包括降冰片烷二胺類）進行更詳 細地說明，則可列舉：（2S，5S)-二胺基曱基-雙環[2·2丨]庚 燒、（28,511)-二胺基甲基·雙環[2·2.η庚烷、（28,6办二胺基 甲基-雙環[2.2.1]庚烷、及(2S，6S)_二胺基曱基·雙環[2 2& 13 201231504 • * V» · t 庚烧。另外，此二胺基曱基雙環庚烧具有異構物，可單獨 使用1種異構物，亦可使用異構物的混合物。 並且，該些二胺化合物（A)可單獨使用，或亦可將2 種以上加以混合而使用。 (四價芳香族四缓酸二酐（B)) 式⑴的重複結構中的γ源自四價芳香族四紐二 。酸二針（B)只要可製造聚醯胺酸、聚酿亞胺， 則並無特別限定，例如可列舉： 均苯四甲酸二酐等均苯四甲酸二針類、3,3，，4,4,-聯苯 四曱酸二酐等聯苯四曱酸二酐類、二苯曱_四曱酸二酐 類、雙(3,4_二絲苯基)醚二料雙(二絲苯基)鱗二針 類、雙（羧基苯基）酯二酐類、2,2_雙（3,4_二羧基苯 基)_U，1，3,3,3-六氟丙烧二酐等雙(二緩基苯基)六氟丙统 二酐類等。 其中，較佳的酸二針（B)是可經由光學天線效果高 效率地轉财齡子的綠魏量、並具有高吸光係數的 π電子系的施體，因此可列舉：均苯四曱酸二酐類、聯苯 四曱1st一酐類、雙（二叛基笨基）趟二肝類等，更具體為 1，2,4,5-均笨四曱酸二軒、3,3，，4,4，_聯苯四曱酸二肝/雙(3,4'_ 一幾·基苯基)喊二針。 並且，該些酸二肝（Β)可單獨使用，或將2種以上 加以混合而使用。 (溶劑） 本發明的聚醯胺酸溶液（S1)的製作時所❹的溶劑 201231504 只要可溶解所形成的聚醯胺酸，則並無特別限定，例如可 列舉： 苯盼、鄰氣苯盼、間氣苯盼、對氯苯紛、鄰曱盼、間 曱酚、對曱酚、2,3-二曱苯酚、2,4-二曱苯酚、2,5-二曱苯 酚、2,6-二曱苯酚、3,4-二曱苯酚、3,5-二曱苯酚等苯酚系 溶劑； N，N-二曱基甲醯胺、Ν,Ν-二曱基乙醯胺、N，N-二乙基 乙醯胺、N-曱基乙醯胺、N-曱基-2-吡咯啶酮、1,3-二曱基 -2-咪唑啉酮、N-甲基己内醯胺、六曱基磷醯三胺等非質子 性或等效的醯胺系溶劑； 1,2-二曱氧基乙烷、雙(2-曱氧基乙基)醚、1，2-雙(2-曱 氧基乙氧基）乙烷、四氫呋喃、雙[2-(2-曱氧基乙氧基）乙基] 酸、1,4-二°惡烧等醚系溶劑； 0比σ定、嗤淋、異喧琳、α_曱基u比咬、β_曱基u比σ定、γ-曱基吡啶、異佛爾酮、哌啶、2,4-二曱基吡啶、2,6_二曱基 吡啶、三甲基胺、三乙基胺、三丙基胺、三丁基胺系溶劑； 及 二曱基亞砜、二曱基砜、二苯基醚、環丁砜、二苯基 砜、四曱基脲、苯曱醚、水、苯、曱苯、鄰二曱苯、間二 曱苯、對二曱苯、氣苯、鄰二氯苯、間二氯苯、對二氯苯、 溴苯、鄰二溴笨、間二溴苯、對溴苯、鄰氣曱苯、間氣曱 苯、對氯曱苯、鄰溴曱苯、間溴曱苯、對溴曱苯、丙酮、 曱基乙基酮、甲基異丁基酮、環戊酮、環己酮、γ-丁内酯、 曱醇、乙醇、丙醇、異丙醇、丁醇、異丁醇、戊烷、己烷、 15 201231504• Top alicyclic oxime means a tetravalent aromatic group having a carbon number of 6 to 27) The concentration of polylysine in the polystyrene I Lo solution (S1) is not required to be a polyamidene complex. Particularly, it is preferably 100 parts by weight to 10,000 parts by weight, and more preferably 200 parts by weight to 5,000 parts by weight, based on 100 parts by weight of the acid for polyfluorene. 'The imine of the present invention is composed of an alicyclic diamine compound (4) and an aromatic; tetradecanoic acid dianhydride (B), and thus is a retarded acid in the poly(m)(4)-based UfbGxylgK)up) as a precursor. The carboxylate anion forms a ionic bond with the metal cation. Therefore, the Eu (Eu) compound is compounded without damaging the mechanical and financial properties, and although it is colorless and transparent, it is irradiated by, for example, 2 〇〇 nm to 40 1 . ^^', and / often can instantly send 5 〇〇 fine ~ _ fine twilight luminescence, and V to thunder to promote the light of the record (5)) moved by the Qing dynasty, and can be π electronic wire Delete the effect and efficiently & body (-0 via the optical antenna (〇-: position of the organic molecular part and there is aromatic energy transfer, can be used with the near static. m th has a square sensibility, can have very high Fluorescent light Γ (4) Poly private work and high-efficiency labor 201231504 (divalent alicyclic diamine compound (A)) The repeat structure t of formula (1) is derived from divalent alicyclic diamine compound (A) The diamine compound (A) is not particularly limited as long as it can produce polyglycolic acid or polyimine, and examples thereof include anthracene diamines and cyclohexane diamines (including Cyclohexylamine), bis(aminomethyl)cyclohexane (bis(aminomethyl)cyclohexyl) such as 1,4-bis(aminomethyl)cyclohexane, diamine Bicycloheptane, diaminomethylbicycloheptane (including norbornane diamine such as norbornane diamine), diaminooxybicycloheptane, diaminomercaptooxybicycloheptane class( Including oxabornane diamines such as oxabornane diamines, isophorone diamines such as isophorol diamine, diaminotricyclodecanes, and diaminomethyltricyclos. Bis(aminocyclohexyl)methanes such as decanes and bis(4-aminocyclohexyl)methane/(methylene bis(cyclohexylamine) such as 4,2-fluorenylene bis(cyclohexylamine) A bis(aminocyclohexyl)isopropylidene group or the like. A preferred alicyclic diamine compound (A) is used for the reasons of availability, optical property, thermal stability and mechanical stability. And may include a cyclohexanediamine containing trans-1,4-cyclohexylamine, a bis(aminomethyl)cyclohexane group containing a bis(amine) group, and a diamine group.曱基双譬庚(including norbornane diamines such as norbornane diamine), oxalate = tablets = diamine, isophorone diamine, 4,4,-arylene di(cyclo) Hexylamine), etc.. For the more detailed description of diaminomercaptobicycloheptanes (including norbornanediamines), (2S,5S)-diaminoindenyl-bicyclo[ 2·2丨]heptane, (28,511)-diaminomethyl·bicyclo[2·2.ηg Alkane, (28,6, diaminomethyl-bicyclo[2.2.1]heptane, and (2S,6S)-diaminodecyl-bicyclo[2 2& 13 201231504 • * V» · t In addition, the diaminomercaptobicycloheptane has an isomer, and one isomer may be used alone, and a mixture of isomers may also be used. Further, the diamine compound (A) may be used alone, or Two or more kinds may be used in combination. (Quaternary aromatic tetrabasic acid dianhydride (B)) The γ in the repeating structure of the formula (1) is derived from tetravalent aromatic tetranuclear acid. The acid two needles (B) are as long as The polyamic acid or the polyamidiamine can be produced, and is not particularly limited. For example, pyromellitic acid dianhydride or the like, pyromellitic acid, two needles, 3,3,4,4,-biphenyltetrazide Biphenyltetracarboxylic dianhydrides such as phthalic acid dianhydride, diphenyl hydrazine _ tetradecanoic dianhydride, bis(3,4-diphenyl) ether di-bis(diphenyl) squaring needle , bis(carboxyphenyl)ester dianhydride, 2,2-bis(3,4-dicarboxyphenyl)_U, 1,3,3,3-hexafluoropropane dianhydride, etc. Base) hexafluoropropane dianhydride and the like. Among them, the preferred acid two-needle (B) is a π-electron-based donor body which can efficiently transfer the amount of green sage of the stagnation age and has a high light absorption coefficient via the optical antenna effect. Acid dianhydrides, biphenyl tetraterpene 1st-anhydrides, bis (two rebellious stupid) sputum livers, etc., more specifically 1,2,4,5-all stupid tetradecanoic acid dix, 3,3 ,, 4,4,_Biphenyl tetradecanoic acid / double (3,4'_ a few phenyl) shouted two needles. Further, these acid di-hepatic acids may be used singly or in combination of two or more. (Solvent) The solvent 201231504 which is produced in the production of the polyaminic acid solution (S1) of the present invention is not particularly limited as long as it can dissolve the formed polyamic acid, and examples thereof include benzophenone and phthalate. , Benzene Benzene, p-Chlorobenzoquinone, o-p., m-nonylphenol, p-nonylphenol, 2,3-dioxanol, 2,4-diphenylphenol, 2,5-diphenylphenol, 2,6 a phenolic solvent such as dinonylphenol, 3,4-dinonylphenol or 3,5-diphenylphenol; N,N-dimercaptomethylamine, hydrazine, fluorenyl-dimercaptoacetamide, N,N - diethyl acetamide, N-mercaptoacetamide, N-mercapto-2-pyrrolidone, 1,3-dimercapto-2-imidazolidinone, N-methyl caprolactam, Aprotic or equivalent amide-based solvent such as hexamethylenephosphonium triamine; 1,2-dimethoxy ethane, bis(2-decyloxyethyl)ether, 1,2-double (2 - anthracene ethoxy) ethane, tetrahydrofuran, bis[2-(2-decyloxyethoxy)ethyl] acid, 1,4-dioxalate, etc., ether solvent;嗤, 喧, α α 曱 u 比 、, β 曱 u u u 、 β, γ-mercaptopyridine, isophorone, piperidine, 2,4-dimercaptopyridine, 2,6 _Dimercaptopyridine, three Methylamine, triethylamine, tripropylamine, tributylamine solvent; and dimercaptosulfoxide, dimercaptosulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetradecyl urea, Benzoate, water, benzene, toluene, o-diphenyl, m-nonylbenzene, p-terpene, benzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromo Stupid, m-bromobenzene, p-bromobenzene, o-benzene, m-benzene, p-chlorophenyl, o-bromobenzene, m-bromobenzene, p-bromo-p-benzene, acetone, mercapto ethyl ketone, Isobutyl ketone, cyclopentanone, cyclohexanone, γ-butyrolactone, decyl alcohol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane, 15 201231504

• A V 戾烷、環己烷 t * 一肌、軋坏、四氣化碳、氟苯、乙酸 甲酉曰、乙酸乙酯、乙酸丁酯、甲酸甲酯、甲酸乙酯等复他 溶劑。 、 該些溶劑可單獨使用或將2種以上加以混合而使用。 土ί述'谷劑中，較佳為非質子性或等效的醢胺系溶劑， =^ Ν，Ν·二甲基甲醮胺、聯二甲基乙醢胺、Ν，Ν_二乙 ==、泳甲基乙醯胺、队甲基_2_吡_、 基= 坐琳，、Ν_甲基己内酿胺、六甲細三胺。 (聚醯胺酸溶液（S1)的掣作） 聚酿=胺，;溶f的聚酿胺酸溶液⑶)(亦稱為 可製造聚_酸，則並無特別限: 在是 獲得。 質子性醯胺系溶劑中進行聚合而 内的方法制對原料添加至聚合反應系 劑的同時添加二胺化合物（牛A)與酸二肝⑻及溶 ⑻(的)方t將一版化合物（Α)與溶劑混合後添加酸二酐 (Α)的方法字《肝⑻與溶劑混合後添加二胺化合物 (d)在將酸二酐⑻與溶劑、二胺化合物U)與 201231504 溶劑分別浪合後’各自進行混合並添加的方法等。並且， 在進行此聚合反應中的溫度控制時，可進行冷卻或加熱操 作0 在製造聚醯胺酸或聚醯亞胺時，為了調節所生成的聚 醯胺酸或聚醯亞胺的分子量，通常進行調節二胺化合物 (A)與酸一Sf (B)之量比（qUantity rati〇)o 本發明的製造方法中，在製造聚醯胺酸時，所有二胺 化合物（A)與所有酸二酐（B)之莫耳比（所有二胺化合 物⑷/所有酸二酐（B))，通常為0.9〜1.1的範圍。另 外’將寡聚物成分聚合時’二胺化合物⑷與酸二酐⑻ 之莫耳比為任意’可為0·^Λ的範圍，亦可不為〇9〜 1.1的範圍。 例如 右賴有二胺化合物（Α)與所有酸二酐⑻ :莫耳比設為0.9〜U ’則在Ν,Ν_二甲基乙醯胺(dmAc) (ηΓ 度為❹以仏坑下測定的對數黏度通常為 ϋ.1 dL/g〜3.0dL/g的範圍的聚醯胺酸。 ，由本發明而得㈣㈣胺複合體所含㈣酿 ^其聚醯麟可料分子末端封端。在將分子末端封端 不且mi如先前以來所知曉般，藉由與胺及二親軒 /、有反應性的基進行封端。 端體^ 1㈣想為，㈣亞胺及聚__分子末 知藉由二羧酸酐、或單胺化合物進行封端。 于禾 將聚醯胺酸或聚醯亞胺的分子末 下2種。即，在二胺化合物過量而將末蠕藉由二羧 17 201231504 端時，相對於二胺化合物丨莫耳，四m 莫耳以上且小於^莫耳，二賊料^^以為^ 广於0.3莫耳。在四幾酸二肝⑻過量而將末端藉 化合物封端時，相對於四幾酸二酐⑻j莫耳， =狀9莫耳以上且小㈣莫耳，單胺化合物—為〇二 莫耳以上且小於0.3莫耳。 勺υ.υυΐ 聚物^在Τϋϊ酸或聚醯亞胺為共聚物時’構成此共 =2種以上的重複單元的定序性或規則性可加以限制 ,制。並且’共聚物的種類可為無規(ra—、 =(alternative)及嵌段（bl〇ck)的任一種。因此 2用-胺化合物⑷及酸二酐（B)而包含3種以上 或2 = 添加方法可為一次性 <聚醯胺酸溶液（S2) > 本發明的聚醯胺酸溶液（S2) 溶液⑻中添加鎖㈣在上述聚酿胺酸 定，:====發揮本發明的效果，則並無限 硝酸銪、乙酸銪。該些銪化合-佳，化銪、 上的本包其他金屬化合=合=種以 醯胺酸溶液(s心將：合物添加至本發明的聚 下之效果，；5又各4 X侍的聚醯亞胺複合體會發揮如 下之效果，及，不會損及光學特性（無色透明）、機械物性 201231504 及耐熱性m ii由騎紫外線（例如波長25〇嫌 〜4〇Omn)而通常瞬間發出波長· nm〜_n 並且，榮光強度非常高。 一般認為，㈣促使_ (Eu)的ff躍遷所引起的發 光的激發能量，可11由與有機分子進行錯合仙（⑶mplex formation)’而經由光學天線效果獲得有機分子的光激發能 量。因此’具有高吸光係數的π電子系的施體例如藉由使 用芳香族化合物’而能量轉㈣效率變得非常高。因此， 可授予激發能量的最貼近的配位子較理想為芳香族系，並 且推測可由與料族四贿二肝（Β)具有某種較強相互 作用的該鎖化合物發出高效率的螢光。即，在聚醯亞胺中 單純地添加銪化合物，聚醯邱絲法期待本發明的效 果。並且制’由於基於此種特定結構的相互作用，所得 的聚醯亞胺複合體會具有本發明的物性。 上述情況例如亦可根據如下情形加以推測：由销化合 物、芳香族四賴二酐及芳香族二胺而得的祕亞胺複合 體，由於在雜亞胺的分子内、分子間形成被稱為電荷轉• A V decane, cyclohexane t * one muscle, crushed, four gasified carbon, fluorobenzene, acetic acid methyl hydrazine, ethyl acetate, butyl acetate, methyl formate, ethyl formate and other complex solvents. These solvents may be used singly or in combination of two or more. In the glutinous rice, it is preferably an aprotic or equivalent amide solvent, =^ Ν, Ν·dimethylformamide, dimethyl dimethyl acetamide, hydrazine, Ν_二乙==, swimming methyl acetamide, team methyl _2_pyridyl, base = sitting, Ν _ methyl caprolactam, hexamethylene triamine. (Polymerization of polyaminic acid solution (S1)) Polymerization = amine, poly-aracine solution (3) which dissolves f (also known as poly-acids), there is no special limitation: It is obtained. Protons A method in which a polymerization is carried out in a melamine-based solvent to add a diamine compound (bovine A) to an acid di-hepatic (8) and a soluble (8) square t to add a compound to the polymerization reaction agent. After adding the acid dianhydride (Α) with the solvent, the method of adding the diamine compound (d) after mixing the liver (8) with the solvent, and separately mixing the acid dianhydride (8) with the solvent and the diamine compound U) with the solvent of 201231504 A method of mixing and adding each. Further, when performing temperature control in the polymerization reaction, cooling or heating operation may be performed. 0 In order to adjust the molecular weight of the produced polyaminic acid or polyimine, in the production of polyamic acid or polyimine, Usually, the ratio of the diamine compound (A) to the acid-Sf (B) is adjusted (qUantity rati). In the production method of the present invention, all the diamine compounds (A) and all the acids are produced in the production of polyglycine. The molar ratio of the dianhydride (B) (all diamine compounds (4) / all acid dianhydrides (B)) is usually in the range of 0.9 to 1.1. Further, when the oligomer component is polymerized, the molar ratio of the diamine compound (4) to the acid dianhydride (8) is in any range of from 0 to Λ, and may not be in the range of from 〇9 to 1.1. For example, right lie has a diamine compound (Α) and all acid dianhydride (8): the molar ratio is set to 0.9~U 'in Ν, Ν dimethyl dimethyl acetamide (dmAc) (ηΓ degree is 仏 仏 under the pit The measured logarithmic viscosity is usually a polyamic acid in the range of d1 dL/g to 3.0 dL/g. According to the invention, the (iv) (iv) amine complex contains (iv) the end of the poly unicorn molecular end capping. The end of the molecule is not capped and mi is capped by a reactive group with an amine and amphipathic as previously known. End body ^ 1 (d) is thought to be (iv) imine and poly-_ molecule It is known that the terminal is blocked by a dicarboxylic acid anhydride or a monoamine compound. The molecular weight of the polyaminic acid or the polyamidimide is 2, that is, the excess of the diamine compound is used to decompose the dicarboxylic acid. 17 201231504 end, relative to the diamine compound 丨 Mo ear, four m Mo and above and less than Mo Mo, two thief material ^ ^ thought ^ is wider than 0.3 Mo. In the tetraacid acid liver (8) excess and the end borrowed When the compound is capped, it is more than 9 moles and less (four) moles than the tetrabasic acid dianhydride (8), and the monoamine compound is above the oxime and less than 0.3 mole. Υυΐ υυΐ υυΐ Τϋϊ Τϋϊ Τϋϊ Τϋϊ Τϋϊ Τϋϊ Τϋϊ Τϋϊ Τϋϊ Τϋϊ Τϋϊ 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或Any of a random (ra-, = (alternative) and block (bl〇ck). Therefore, 2-containing the amine compound (4) and the acid dianhydride (B) may contain three or more or 2 = the addition method may be a one-time <Polyuric acid solution (S2) > Addition of a lock (4) to the solution (8) of the polyaminic acid solution (S2) of the present invention is carried out in the above-mentioned polystyrene, and the effect of the present invention is exerted. Infinite bismuth nitrate, strontium acetate. These bismuth compounds are good, bismuth, and other metal compounds in the package are combined with lysine solution (the effect of adding the compound to the polymerization of the present invention, 5 and each of the 4 X-spot polyimine complexes will exert the following effects, and will not damage the optical properties (colorless and transparent), mechanical properties 201231504 and heat resistance m ii by riding ultraviolet rays (for example, wavelength 25 〇 ～ 4〇Omn) and usually emits a wavelength · nm~_n instantaneously, and the glory intensity is very high. It is generally believed that (4) _ (Eu) ff The excitation energy of the luminescence caused by the migration can obtain the photoexcitation energy of the organic molecule through the optical antenna effect by performing the mismatching with the organic molecule. Therefore, the π-electron donor having a high absorption coefficient For example, by using an aromatic compound, the energy conversion (four) efficiency becomes very high. Therefore, the closest ligand to which the excitation energy can be imparted is preferably an aromatic system, and it is presumed that it is possible to bury the liver with the family. The lock compound having a certain strong interaction emits highly efficient fluorescence. That is, the ruthenium compound is simply added to the polyimine, and the effect of the present invention is expected. And the resulting polyimine complex has the physical properties of the present invention due to the interaction based on such a specific structure. The above case can be estimated, for example, based on the following situation: a secret imine complex obtained from a pin compound, an aromatic tetra dianhydride, and an aromatic diamine is called a molecule in the molecule and is formed between molecules. Charge transfer

St (CT錯合物）的錯合物，因此變為無輻射躍遷， 榮光發光性明顯降低。 (聚醯胺酸溶液（S2)的製作） 聚醯胺酸溶液（S2)(亦稱為複合清漆）是在包含聚 醯胺酸及溶劑的«胺酸溶液（S1)中添域（Eu)化合 物，並將該些成分加以混合而製作。 銪化合物的添加量只要發揮出本發明的效果，則並無 19 201231504 t二較f為相對於上述聚酿胺酸則重量份而為麵 4重量份，更佳為Ml重量份〜3.5重量份，尤 重二LI量份〜3重量份。若銷化合物的添加量為請1 化人“t Γ卩便稀薄亦可獲得充分的螢光發光，若銪 複::為4重量份以下，則最終所得的聚醯亞胺 —σ 、力予強度較為充分，從而實用上無問題。並且， 添加量為上述範圍，則最終所得的聚醯亞胺 “ = 明性、高耐熱性、力學強度的任—種物性 涡足實用範圍，因此較佳。 =外’ H (Eu)化合物的添加方法並無特職制，例 °可直接添加，較佳為將銪（Eu)化合物細細粉碎 ^其私碎物。並且，亦可將鋪（Eu)化合物預先溶解或分 酸溶液（S1)反應的_後，添加 胺酸溶液（S1)中。 、’且’销（Eu)化合物的混合方法並無特別限制，例 ^可在空氣下、氮氣等惰性氣體下的基礎環境下，藉由通 常的混合機、攪拌機等公知的設備進行混合。 9 上述混合就抑制聚醯胺酸的醯亞胺化的觀點而今， 理想為在（TC〜5〇〇C左右進行，更佳為在1〇〇c〜4〇。&左右 進行，就作業上的優點而言，最佳為在室溫下進行。並且， 混合時間亦無特別限定，較佳為3 〇分鐘〜24小時的範圍，’ 更佳為在1小時〜20小時的範圍内攪拌。 已 並且，為了自所得的聚醯胺酸溶液（S2)除去雜 不溶成分等’可根據需要進行職。過_如可藉由具^ 20 201231504 λ v ( PTFE (四氟乙烯樹脂）製濾紙的加壓過據進行。 在以上述方式獲得的聚醯胺酸溶液（S2)中在不損 及本發_效果的範_，還可添加例如添加劑、填充劑 等。 添加劑例如可列舉：石墨、碳化♦(娜咖dum)、 二硫化!目、㈣樹脂科雜提昇劑，三氧化銻、魏環 (phosphazene)化合物、磷酸酯等阻燃性提昇劑，黏土、 ，母、高嶺土等電氣特性提昇劑，石棉、二氧化矽、石墨 等财電痕（tracking resistance)提昇劑，二氧化石夕、偏石^ 酸辦等賴性提昇劑，鐵粉、鋅粉、紹粉等導熱率提昇劑， 其他玻璃珠、玻璃球'玻璃纖維、滑石、矽藻土、氧化鋁、 水合氧化㉖、三氧化鈦、師中空球㈤聰Μ1〇 著色料及顏料等。 ； (聚醯胺酸複合體） 若在聚醯胺酸溶液（S2)所含的聚醯胺酸不進行 =Γ(^。件下Μ㈣’料製料賴酸複合體 、-人^種除去溶劑的方法例如可列舉：將不溶解聚酿胺酸 PAAC)的不良溶劑添加至聚醯胺酸溶液（幻） 酸複合體(PAAC)析出的再沉 ^ 減壓下使溶劑揮發而蒸鎌錢減壓乾燥法等。及在 <聚醯亞胺複合體> (聚醯亞胺） 本發明的無色透明的聚醯亞胺複合體所含的聚隨亞胺 201231504 具有下述通式（2)所示的半脂環式的重複結構。The complex of St (CT complex) thus becomes a non-radiative transition, and the luminosity of glory is significantly reduced. (Preparation of poly-proline solution (S2)) Poly-proline solution (S2) (also known as composite varnish) is added to the amino acid solution (S1) containing poly-proline and solvent. The compound is prepared by mixing the components. When the amount of the ruthenium compound added is such that the effect of the present invention is exerted, there is no 19 201231504 t 2 and f is 4 parts by weight, more preferably M1 parts by weight to 3.5 parts by weight, based on the weight part of the polyamic acid. , especially heavy two LI parts by weight ~ 3 parts by weight. If the amount of the compound to be added is "1", it is sufficient to obtain sufficient fluorescence, and if it is 4 parts by weight or less, the final polyimine-σ, force is given. The strength is sufficient, so that there is no problem in practical use. Further, when the amount added is in the above range, the finally obtained polyimine "= is a practical range of any physical property of high visibility, high heat resistance, and mechanical strength, and therefore is preferable. . The method of adding the outer 'H (Eu) compound has no special function, and the example can be directly added, and it is preferred to finely pulverize the Eu (Eu) compound. Further, the (Eu) compound may be preliminarily dissolved or reacted with the acid solution (S1) to be added to the amine acid solution (S1). The method of mixing the 'Eu' compound is not particularly limited. For example, it can be mixed by a known apparatus such as a usual mixer or a mixer under an air atmosphere or an inert gas such as nitrogen. 9 The above-mentioned mixing suppresses the ruthenium imidization of polyglycolic acid. It is preferably carried out at about (TC~5〇〇C, more preferably at 1〇〇c~4〇.& The above advantages are preferably carried out at room temperature, and the mixing time is also not particularly limited, and is preferably in the range of 3 Torr to 24 hours, and more preferably in the range of 1 hour to 20 hours. Further, in order to remove the impurity-insoluble component or the like from the obtained polyamic acid solution (S2), it can be carried out as needed. If it is a filter paper made of PTFE (tetrafluoroethylene resin) In the poly-proline solution (S2) obtained in the above manner, for example, an additive, a filler, or the like may be added without damaging the effect of the present invention. The additive may, for example, be graphite. , carbonization ♦ (naca dum), disulfide! Mesh, (four) resin lift enhancer, antimony trioxide, phosphazene compound, phosphate ester and other flame retardant enhancer, clay, mother, kaolin and other electrical properties Lifting agent, asbestos, cerium oxide, graphite and other financial traces (t Racking resistance, corrosive agent, sulphur dioxide, sapphire, acid, etc., thermal conductivity enhancer for iron powder, zinc powder, Shao powder, other glass beads, glass ball 'glass fiber, talc, algae Soil, alumina, hydrated oxidation 26, titanium dioxide, division hollow ball (5) Congxi 1 〇 coloring materials and pigments, etc.; (poly-proline complex) If the polyamine contained in poly-proline solution (S2) The acid is not carried out = Γ (^. Μ Μ 四 四 四 四 四 四 四 四 四 四 四 四 四 四 赖 赖 赖 赖 赖 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去 除去Re-sinking of solution (phantom) acid complex (PAAC), evaporation of solvent under reduced pressure, distillation, decompression drying, etc., and in <polyimine complex> (polyimine) The polyimine 201231504 contained in the colorless and transparent polyimine complex of the invention has a semi-alicyclic repeat structure represented by the following formula (2).

2 ____ (式（2)中，X表示碳數4〜15的二價脂環族基，Y 表示碳數6〜27的四價芳香族基）。 具有上述式（2)所示的重複結構的聚醯亞胺如上所 述，藉由二價脂環式二胺化合物（Α)與四價芳香族四羧 酸二酐（Β)的反應而形成。 並且，在本發明的聚醯亞胺為共聚物時，構成此共聚 物的2種以上重複單元的定序性或規則性可加以限制亦可 無限制，共聚物的種類可為無規、交替及嵌段的任一種。 因此，在併用二胺化合物（Α)及四羧酸二酐（Β)而包含 3種以上時，各自的添加順序為任意，該些原料的添加方 法亦可任意為一次性或分次的任一種。 本發明中，上述式（2)中的X及Υ就本發明的聚醯 亞胺複合體的無色透明性、高耐熱性、力學強度優異的理 由而言，較佳為具有以下結構單元。 上述式（2)中的X為選自由 22 2012315042 ____ (In the formula (2), X represents a divalent alicyclic group having 4 to 15 carbon atoms, and Y represents a tetravalent aromatic group having 6 to 27 carbon atoms). The polyimine having the repeating structure represented by the above formula (2) is formed by the reaction of a divalent alicyclic diamine compound (Α) with a tetravalent aromatic tetracarboxylic dianhydride (Β) as described above. . Further, when the polyimine of the present invention is a copolymer, the ordering or regularity of the two or more types of repeating units constituting the copolymer may be limited or unrestricted, and the type of the copolymer may be random or alternate. And any of the blocks. Therefore, when three or more kinds of diamine compounds (fluorene) and tetracarboxylic dianhydride are used in combination, the order of addition is arbitrary, and the method of adding these raw materials may be arbitrarily one-time or divided. One. In the present invention, X and oxime in the above formula (2) preferably have the following structural unit in view of the colorless transparency, high heat resistance and mechanical strength of the polyimine composite of the present invention. X in the above formula (2) is selected from 22 201231504

乂}ch2〈^ ,乂}ch2<^ ,

所組成群組中的至少1種脂環族基； 上述式（2)中的Y為選自由At least one alicyclic group in the group consisting of; Y in the above formula (2) is selected from

所組成群組中的至少1種芳香族基。 並且，本發明中，源自銪的螢光波長即便為同等程度， 就螢光強度變高的理由而言，尤其更佳為包含以下通式（3) 〜通式（11)的任一式的聚醯亞胺。 通式（3)中，二胺化合物[1]為降冰片烷二胺，化合 物[2]由1,2,4,5-均苯四曱酸二酐獲得。At least one aromatic group in the group consisting of. In the present invention, the fluorescence wavelength derived from ruthenium is equivalent to the same, and it is particularly preferable to include any one of the following general formulae (3) to (11). Polyimine. In the formula (3), the diamine compound [1] is norbornanediamine, and the compound [2] is obtained from 1,2,4,5-pyrenetetracarboxylic dianhydride.

(3) 通式（4)中，二胺化合物[1]為反-1,4-環己基二胺， 23 201231504 化合物[2]由3,3’,4,4’-聯苯四曱酸二酐獲得。(3) In the formula (4), the diamine compound [1] is trans-1,4-cyclohexyldiamine, 23 201231504, the compound [2] is composed of 3,3',4,4'-biphenyltetradecanoic acid. The dianhydride is obtained.

(4) 通式（5)中，二胺化合物[1]為1，4-雙(胺基甲基)環己 烷，化合物[2]由3,3’，4,4'-聯苯四曱酸二酐獲得。(4) In the formula (5), the diamine compound [1] is 1,4-bis(aminomethyl)cyclohexane, and the compound [2] is composed of 3,3',4,4'-biphenyltetra Obtained by phthalic acid dianhydride.

(5) 通式（6)中，二胺化合物[1]為反-1，4-環己基二胺及 降冰片烷二胺，化合物[2]由3,3’,4,4’-聯苯四甲酸二酐獲得。(5) In the formula (6), the diamine compound [1] is trans-1,4-cyclohexyldiamine and norbornanediamine, and the compound [2] is composed of 3,3',4,4'-linked. Obtained by pyromellitic dianhydride.

(式中，m與η表示各括弧内所示的重複結構單元的 重複數，m的平均值與η的平均值之比（m : η)為1 : 9 〜9 : 1。） 通式（7)中，二胺化合物[1]為4,4’-亞甲基雙(環己基 胺），化合物[2]由1，2,4,5-均苯四曱酸二酐獲得。 24 (7) 201231504(wherein, m and η represent the number of repetitions of the repeating structural unit shown in each parenthesis, and the ratio of the average value of m to the average value of η (m : η) is 1:9 to 9: 1.) In 7), the diamine compound [1] is 4,4'-methylenebis(cyclohexylamine), and the compound [2] is obtained from 1,2,4,5-pyrenetetracarboxylic dianhydride. 24 (7) 201231504

ο οο ο

ο ο 通式（8)中，二胺化合物[1]為降冰片烷二胺，化合 物[2]由雙(3,4-二羧基苯基)醚二酐獲得。ο ο In the formula (8), the diamine compound [1] is norbornanediamine, and the compound [2] is obtained from bis(3,4-dicarboxyphenyl)ether dianhydride.

(8) 通式（9)中，二胺化合物[1]為降冰片烷二胺，化合 物[2]由2,2-雙(3,4-二羧基苯基)-1，1，1,3,3,3-六氟丙烷二酐 獲得。(8) In the formula (9), the diamine compound [1] is norbornane diamine, and the compound [2] is composed of 2,2-bis(3,4-dicarboxyphenyl)-1,1,1. 3,3,3-hexafluoropropane dianhydride was obtained.

(9) 通式（10)中，二胺化合物[1]為降冰片烷二胺、及氧 雜降冰片烷二胺，化合物[2]由2,2-雙（3,4-二羧基苯 基)-1,1，1，3,3,3-六氟丙烷二酐獲得。 25 201231504(9) In the formula (10), the diamine compound [1] is norbornane diamine and oxabornane diamine, and the compound [2] is composed of 2,2-bis(3,4-dicarboxybenzene). Base-1,1,1,3,3,3-hexafluoropropane dianhydride. 25 201231504

(式中，m與η表示大括弧：[]内與小括弧：（） 内所示的重複結構單元的重複數，m : η之比為4 : 6〜9 : 1。） 通式（11)中，二胺化合物[1]為降冰片烷二胺、及異 佛爾酮二胺，化合物[2]由2,2-雙（3,4-二羧基苯 基)-1，1，1，3,3,3-六氟丙烷二酐獲得。(where m and η represent braces: [] and the parentheses: the number of repetitions of the repeating structural unit shown in (), the ratio of m: η is 4: 6 to 9: 1.) In the diamine compound [1] is norbornane diamine and isophorone diamine, and the compound [2] is composed of 2,2-bis(3,4-dicarboxyphenyl)-1,1,1 , 3,3,3-hexafluoropropane dianhydride was obtained.

(式中，m與η表示大括弧：[]内與小括弧：（） 内所示的重複結構單元的重複數，m : η之比為5 : 5〜9 : 1。） 並且，該些之中，就螢光強度、與力學強度等的平衡 的方面而言，特佳為包含通式（3)〜通式（6)所示的聚 醯亞胺。 (聚醯亞胺複合體） 本發明的聚醯亞胺複合體中，相對於上述式（2)所示 的聚醯亞胺的重複單元100當量，通常包含0.001當量〜 26 201231504 • &amp; V/ «/ 10當量的銪（Eu)。 並且，聚醯亞胺複合體為無色透明。此處，本發明中， 無色透明是指製作30 μιη厚的膜時的波長為4〇〇 nm以 上、較佳為400 nm〜800 rim的可見光線區域的波長的光 線透射率通常為8〇%〜1〇〇%、較佳為85〜1〇〇%。在光線 透射率小於上述範圍時，基本上於必需「無色透明」的構 件中無法將聚醯亞胺複合體作為材料而使用。 本發明的聚醯亞胺複合體例如藉由照射波長ho nm 〜400 nm的紫外線’而通常瞬間發出波長5〇〇 nm〜8〇〇 nm、較佳為55〇 nm〜7〇〇 nm的螢光。此螢光通常可識別 為紅色。另外，瞬間是指若照射紫外線則即刻發出螢光， 疋指對紫外線的響應快。而且，聚醯亞胺複合體的螢光強 度非常局。 此種效果推測是由於以下原因導致：藉由醯亞胺化及 去溶劑，而在聚醯胺酸溶液（S2)中形成的、作為此聚醯 胺酸側鏈的、以在芳香環上取代的羧基與銪（Eu)為基礎 的結構’以更加牢固的形態形成於聚醯亞胺複合體中。形 成此結構的詳細機制未必明確，但推測：為了醯亞胺化而 採用的反應條件是伴有熱脫水或化學性脫水的縮合反應， f此基於在芳香環上取代的此羧基與銪（Eu)的結構更加 牛固地开&gt;成於聚醯亞胺複合體中。因此，用以促使因销 (Eu)的ff躍遷所引起的發光的激發能量，為經由光學天 線效果而獲得來自具有此羧基的芳香族有機化合物的光激 發能量’本發明的聚醯亞胺複合體雖然為無色透明，但例 27 201231504 如會發揮出藉由照射250 nm〜400 nm的紫外線，而通常 瞬間發出500 nm〜800 nm的螢光的效果。 並且，本發明的聚醯亞胺複合體的耐熱性優異，具有 較佳為200°C以上、更佳為25(TC以上的玻璃轉移溫度 (Tg)〇 本發明中所得的聚醯亞胺複合體藉由以較佳範圍的添 加，將銪化合物複合化，而可保持優異的機械物性及尺寸 穩疋性。較佳為，與未添加銪化合物的聚醯亞胺單體相比， 將，線膨脹係數（CTE)的增減抑制在_5 ppm〜+ 5 ppm 的範圍，更佳為抑制在-3 ppm〜+ 3 ppm的範圍，且將拉 伸試驗中的拉伸伸長率的增減抑制在_1〇%〜+ 1〇%的範 圍，更佳為處於-5%〜+ 5%的範圍，從而可有效地賦予上 述無色透明性、高螢光性。 (聚醯亞胺複合體的製作） 本發明的聚醯亞胺複合體可藉由將上述聚醯胺酸溶液 (S2)所含的聚醯胺酸進行醯亞胺化，在此醯亞胺化的同 時或醯亞胺化後將溶劑除去而製造。並且，在即便於醯亞 胺化的同時進行溶劑的除去亦無法將溶劑充分除去時，可 在繼醯亞胺化之後再進行溶_除去。另外，亦可使用包 含上述聚軸_清漆储上述祕舰溶液（S2)，藉 由相同的操作製作聚醯亞胺複合體。 酿亞胺化可採用公知的方法，例如可列舉熱醯亞胺 化：化學醯亞胺化等 另外，可將多種該些醯亞胺化方法 加以組合而進㈣亞胺化。並且，鏡碰化通常藉由在 28 201231504 3〇〇C的溫度、較佳為200°C〜300。(：下4办 分鐘〜4小時而進行 上300C下，加熱30 反應所引起的醖亞胺環形成進二“成則::因脫水縮合 =聚酿亞胺複合體的著色方二ΐ較;且化二 化疋糟由乙崎等醯亞胺化 b予酿亞知 環境並無彳__，例如可在。=胺化時的氣體 境下進㈣亞胺化。 亂下、氮氣等惰性氣體環 例如可藉由進行加熱、並且根據 溶劑除去。 卿而要進仃减壓而進行 定，ΐίΐ!，件根據溶劑種類而不同，並無特別限 °C〜寶⑽溫度下加熱％分鐘〜4 ^夺來進仃。此時的加熱氣體環境並無特別限制，例如可 減壓:、空氣下、氮氣等惰性氣體環境下進行溶劑除去。 在藉由熱醯亞胺化進行醯亞胺化時，例如可在其力埶 的同時將溶劑除去。並且’在醯亞胺化反應期間無法^ 除去溶劑時，通常可在15代〜期。⑽溫度下進行再加二 而將溶劑除去。 ” 在藉由化學醯亞胺化進行醯亞胺化時，例如可藉由在 化學醯亞胺化後，通常在15〇〇C〜300〇C的溫度下加熱3〇 分鐘〜4小時而將溶劑除去。 … 藉由此種醯亞胺化而獲得本發明的聚醯亞胺複合體， 此聚醯亞胺複合體所含的聚醯亞胺包含上述式所示的 重複單元。 &lt;用途&gt; 29 201231504^ 本發明的聚醯亞胺複合體可廣泛用於必需無色透明 性、高耐熱性、高力學強度、高螢光性、波長轉換性、優 異的電氣特性等的構件或材料，例如高靈敏度感測器、光 通信、光子設備、電子設備、包括液晶顯示器或有機電致 發光（EL ’ electroluminescence)顯示器的平板顯示器、撓 性顯示器及發光顯示器、螢光塗料、安全用油墨、照明器 具、太陽光發電、放射線感測器及農業用膜等。 例如，藉由將本發明的聚醯亞胺複合體作為波長轉換 材料而覆蓋於太陽電池面板，亦可轉換紫外區域的能量， 並可獲得高效率的電池。並且，在發光二極體（LED , light emitting diode)的領域中，可由本發明的聚酿亞胺複合體 直接發出色純度優異的色彩。 並且，本發明的聚醯亞胺複合體例如可用於膜、包含 金屬積層板的硬性及撓性電路基材、反射材料等成形體= 積層體等。另外，製造該些成形體的條件可根據膜的^度、 成形體的形狀等進行適當設定。 &amp; (膜） 本發明的聚醯亞胺複合體例如可用作膜、具有至少i 層包含此聚醯亞胺複合體的層的金屬積層體等。膜為無色 透明’例如可用於波長轉換用膜、光學用材料、感光^樹 脂用覆蓋材料、顯示器及撓性顯示器等顯示材料構件、要 求透明的硬性及撓性電路基板、太陽電池等的 丁 示瘦膜、促 進光合成或促進作物培育等的農業用膜等。 本發明的膜並無特別限定，通常具有數)11111〜數百 201231504 的厚度。具有此種厚度的膜例如可藉由將聚醯胺酸溶液 (S2)、或包含聚醯胺酸複合體（pAAC)的塗佈材料以厚 度10 μιη〜1〇〇〇 μιη的方式進行塗佈，並進行醯亞胺化、 脫溶劑而製作。另外，上述塗佈材料的濃度、其他成分的 含量等可根據用途等進行適當設定。 [實例] 以下’藉由實例及比較例對本發明進行更詳細地說 明，但本發明並不受該些實例及比較例的任何限制。 &lt;試驗方法&gt; 貫例中共通的各種試驗的試驗方法如以下所示。 (1) 聚合物溶液的固有對數黏度 使用Ν，Ν-二曱基乙醯胺（DMAc)、j-甲基_2』比咯啶 _ (NMP)、1，3·二甲基_2+坐_ (DMI)中與合成時相 同的溶劑來溶解聚合物，以固體成分濃度為〇5 dL/g的方 式製備聚合物溶液，使用烏式黏度計（Ubbd〇hde type viscometer)於35°C下進行測定。 (2) 全光線透射率 使用具有積分球的斯伽試驗機（SugaTest In_ments) (股）公司製造的HZ-2(TM雙光束方式） ，以開口徑：Φ20 mm、光源：D65進行測定。 (3) 螢光光譜測定 使用日本分光（股）公司製造的FP-6600，以掃描速 度為5〇OOnm/min掃描激發光為22〇nm〜_nm的範圍， 並在250 nm〜800 nm的範圍獲得最大激發波長的螢光光 31 201231504 譜。此=的PMT電麗為55〇 v，藉由玫瑰紅B進行光譜修 正，測直所得的極大螢光波長的螢光強度。 (4) 玻璃轉移溫度（Tg)及熱線膨脹係數（CTE) 使用島津製作所（股）公司製造的TMA-50型，在空 氣流下，以升溫速度10〇c/分鐘、負載14 g/mm2進行測定。 另外，熱線膨脹係數在100°c〜2〇〇°c的範圍進行測量。 (5) 拉伸伸長率試驗 製作標線寬度5 mm的啞鈴型衝壓試驗片，使用島津 製作所（股）公司製造的EZ-S拉伸試驗機，測量以拉伸 速度30 mm/分鐘的條件拉伸至斷裂為止的應力及其伸長 率而獲得應力-應變曲線。測定是以10次的平均值的形式 求出。 &lt;原料及溶劑&gt; 以下的合成例、實例、參考例、及比較例中所使用的 試劑如以下所示。 (A) 銪化合物 •氣化銪六水合物（EuC13、東京化成工業製造） •硝酸銪六水合物（Eu(N03)3、高純專用化學品（strem Chemical)製造） •乙酸銪水合物（Eu(00CCH3)3、阿法埃莎（Alfa Aesar)製造） (B) 聚醯亞胺原料 (a)二胺化合物 NBDA :降冰片烷二胺（化合物1) 32 201231504 H-XDA: 1，4-雙(胺基曱基)環己烷（化合物2) tCHDA :反-1,4-環己基二胺（化合物3) ONDA :氧雜降冰片烷二胺（化合物4) IPDA :異佛爾酮二胺（化合物5) 11-]\40八：4,4|-亞曱基雙(環己基胺）（化合物6) ODA : 4,4'-二胺基二苯基醚[4,4’-二胺基二苯醚](化合 物7) APB : 1，3-雙(3-胺基苯氧基)苯（化合物8) mBP : 4,4’-雙(3-胺基苯氧基)聯苯（化合物9) (b)四羧酸二酐 PMDA :均苯四曱酸二酐（化合物10) BPDA:3,3’，4,4’-聯苯四甲酸二酐（化合物ll) 00卩人：雙(3,4-二羧基苯基)醚二酐（化合物12) 6尸0人：2,2-雙(3,4-二羧基苯基)-1，1，1，3,3,3-六氟丙烷二 針（化合物13 ). 11-?]^0八：1,2,4,5-環己烷四曱酸二酐（化合物14) 33 201231504 λ v i ^/±i. 化合物1 化合物2 化合物3(where m and η represent braces: [] and the parentheses: the number of repetitions of the repeating structural unit shown in (), the ratio of m: η is 5: 5 to 9: 1.) and, Among them, in terms of the balance between the fluorescence intensity and the mechanical strength, it is particularly preferable to contain the polyimine represented by the general formula (3) to the general formula (6). (Polyimine complex) The polyamidene complex of the present invention usually contains 0.001 equivalent to 26 201231504 • &amp; V with respect to 100 equivalents of the repeating unit of the polyimine represented by the above formula (2). / «/ 10 equivalents of 铕 (Eu). Further, the polyimine complex is colorless and transparent. Here, in the present invention, the colorless transparency means that the light transmittance of the wavelength of the visible light region having a wavelength of 4 Å or more, preferably 400 nm to 800 rim when the film having a thickness of 30 μm is produced is usually 8〇%. 〜1〇〇%, preferably 85~1〇〇%. When the light transmittance is less than the above range, it is basically impossible to use the polyimine composite as a material in a member which is required to be "colorless and transparent". The polyimine complex of the present invention usually emits a light having a wavelength of 5 〇〇 nm to 8 〇〇 nm, preferably 55 〇 nm to 7 〇〇 nm, for example, by irradiating ultraviolet rays having a wavelength of ho nm to 400 nm. Light. This fluorescent light is usually recognized as red. In addition, the instant means that if the ultraviolet light is irradiated, the fluorescent light is emitted immediately, and the finger refers to the ultraviolet light. Moreover, the fluorescence intensity of the polyimine complex is very low. This effect is presumed to be due to the following reasons: by the ruthenium imidization and solvent removal, the polyglycine solution (S2) is formed as a side chain of the polyglycine to be substituted on the aromatic ring. The carboxyl group and the europium (Eu)-based structure are formed in a more robust form in the polyimine complex. The detailed mechanism for forming this structure is not necessarily clear, but it is speculated that the reaction conditions employed for the ruthenium imidization are condensation reactions accompanied by thermal dehydration or chemical dehydration, f based on this carboxyl group and oxime substituted on the aromatic ring (Eu The structure is more sturdy to open into the polyimine complex. Therefore, the excitation energy for luminescence caused by the ff transition of the pin (Eu) is a photo-excitation energy of the aromatic organic compound having the carboxyl group obtained by the effect of the optical antenna. Although the body is colorless and transparent, Example 27 201231504 will exhibit the effect of emitting ultraviolet light of 500 nm to 800 nm in an instant by irradiating ultraviolet rays of 250 nm to 400 nm. Further, the polyimine composite of the present invention is excellent in heat resistance, and has a glass transition temperature (Tg) of preferably 200 ° C or more, more preferably 25 (TC or more), and a polyamidene complex obtained in the present invention. By combining the ruthenium compound with a preferred range of addition, excellent mechanical properties and dimensional stability can be maintained. Preferably, compared with the polyamidene monomer to which no ruthenium compound is added, The increase or decrease of the coefficient of linear expansion (CTE) is suppressed in the range of _5 ppm to + 5 ppm, more preferably in the range of -3 ppm to + 3 ppm, and the tensile elongation in the tensile test is increased or decreased. The inhibition is in the range of _1 〇 % to + 1 〇 %, and more preferably in the range of -5% to + 5%, so that the above-mentioned colorless transparency and high fluoribility can be effectively imparted. The polyimine complex of the present invention can be imidated by polyamidonic acid contained in the above polyamic acid solution (S2), at the same time as the imidization or after the imidization It is produced by removing the solvent, and when the solvent is removed even if the solvent is removed while the hydrazine is imidized, the solvent cannot be sufficiently removed. The solution can be removed after the imidization of the hydrazine. Alternatively, the polyamine imine complex can be produced by the same operation using the above-mentioned poly-axis varnish to store the above-mentioned secret ship solution (S2). A known method can be used for the amination, and examples thereof include thermal sulfiliation: chemical ruthenium imidation, and the like, and a plurality of these ruthenium imidization methods can be combined to carry out (iv) imidization. By the temperature of 3 201231504 3〇〇C, preferably 200 ° C ~ 300. (: 4 minutes to 4 hours to carry out the upper 300C, the reaction of heating 30 reaction caused by the quinone ring formed into two" Cheng:: Due to the dehydration condensation = the color of the poly-imine complex is better than that of the tannin; and the bismuth of the bismuth is obtained by the imidization of b. = azide in the gasification during amination. The inert gas ring such as nitrogen gas can be heated, and removed according to the solvent, for example, in order to be decompressed, and 件ίΐ! The type of solvent is different, there is no special limit °C ~ Bao (10) temperature heating under minutes ~ 4 ^ to come in The heating gas atmosphere at this time is not particularly limited, and for example, the solvent can be removed under reduced pressure: under air or under an inert gas atmosphere such as nitrogen. When the hydrazine imidization is carried out by thermal imidization, for example, The solvent is removed while the hydrazine is removed. And when the solvent cannot be removed during the hydrazine imidization reaction, it is usually carried out in the 15th generation period. The solvent is removed by adding two more at the temperature of (10). When the amination is carried out, the solvent can be removed by, for example, heating at a temperature of 15 ° C to 300 ° C for 3 minutes to 4 hours after the chemical hydrazine imidization. The polyimine complex of the present invention is obtained by imidization of a quinone, and the polyimine contained in the polyimine complex contains a repeating unit represented by the above formula. &lt;Use&gt; 29 201231504^ The polyimide composition of the present invention can be widely used for members or materials which are required to have colorless transparency, high heat resistance, high mechanical strength, high fluorescence, wavelength conversion property, excellent electrical characteristics, and the like. For example, high-sensitivity sensors, optical communications, photonic devices, electronic devices, flat panel displays including liquid crystal displays or organic electroluminescent (EL's electroluminescence) displays, flexible displays and illuminating displays, fluorescent paints, security inks, Lighting fixtures, solar power generation, radiation sensors, and agricultural membranes. For example, by coating the solar cell panel with the polyimine composite of the present invention as a wavelength converting material, energy in the ultraviolet region can be converted, and a highly efficient battery can be obtained. Further, in the field of a light emitting diode (LED), the color of the color purity can be directly emitted from the polyanilin composite of the present invention. Further, the polyimine composite of the present invention can be used, for example, as a film, a rigid and flexible circuit substrate including a metal laminate, a molded body such as a reflective material, a laminate or the like. Further, the conditions for producing the molded articles can be appropriately set depending on the degree of the film, the shape of the molded body, and the like. & Film (film) The polyimine complex of the present invention can be used, for example, as a film, a metal laminate having at least one layer containing the polyimine complex, and the like. The film is colorless and transparent, for example, it can be used for a film for wavelength conversion, a material for optics, a cover material for a photosensitive resin, a display material member such as a display or a flexible display, a rigid and flexible circuit board requiring transparency, and a solar cell. A thin film, an agricultural film that promotes light synthesis or promotes crop cultivation, and the like. The film of the present invention is not particularly limited, and usually has a thickness of from 11,111 to several hundreds of 201231504. The film having such a thickness can be applied, for example, by coating a polyphthalic acid solution (S2) or a coating material containing a polyamic acid complex (pAAC) to a thickness of 10 μm to 1 μm. And yttrium imidization and solvent removal. Further, the concentration of the coating material, the content of other components, and the like can be appropriately set depending on the use and the like. [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by the examples and comparative examples. &lt;Test method&gt; The test methods for various tests common to the examples are as follows. (1) The intrinsic logarithmic viscosity of the polymer solution is Ν,Ν-dimercaptoacetamide (DMAc), j-methyl _2 』pyridyl _ (NMP), 1,3·dimethyl_2+ The polymer was dissolved in the same solvent as in the synthesis (DMI), and the polymer solution was prepared at a solid concentration of 〇5 dL/g using a Ubd〇hde type viscometer at 35 °C. The measurement was carried out. (2) Total light transmittance The HZ-2 (TM dual beam method) manufactured by Suga Test Inss Co., Ltd., which has an integrating sphere, was measured with an opening diameter of Φ20 mm and a light source: D65. (3) Fluorescence spectroscopy was performed using FP-6600 manufactured by JASCO Corporation, and the scanning excitation light was in the range of 22 〇 nm to _nm at a scanning speed of 5,000 nm/min, and was in the range of 250 nm to 800 nm. The fluorescence light of the maximum excitation wavelength is obtained 31 201231504. The PMT of this = is 55 〇 v, and the fluorescence intensity of the obtained maximum fluorescence wavelength is measured by spectral correction by Rose Red B. (4) Glass transition temperature (Tg) and coefficient of thermal linear expansion (CTE) were measured using a TMA-50 model manufactured by Shimadzu Corporation, at a temperature increase rate of 10 〇c/min and a load of 14 g/mm2 under air flow. . Further, the coefficient of thermal linear expansion is measured in the range of 100 ° c to 2 ° ° c. (5) Tensile elongation test A dumbbell-shaped test piece with a line width of 5 mm was produced, and the EZ-S tensile tester manufactured by Shimadzu Corporation was used to measure the tensile speed at 30 mm/min. The stress-strain curve is obtained by extending the stress to the fracture and its elongation. The measurement was obtained in the form of an average of 10 times. &lt;Raw material and solvent&gt; The following reagents used in the synthesis examples, examples, reference examples, and comparative examples are as follows. (A) Bismuth compound • Gasified hydrazine hexahydrate (EuC13, manufactured by Tokyo Chemical Industry Co., Ltd.) • Cerium nitrate hexahydrate (Eu(N03)3, manufactured by Strem Chemical) • Barium acetate hydrate ( Eu(00CCH3)3, manufactured by Alfa Aesar) (B) Polyimine raw material (a) Diamine compound NBDA: norbornane diamine (compound 1) 32 201231504 H-XDA: 1,4 - bis(aminomercapto)cyclohexane (compound 2) tCHDA : trans-1,4-cyclohexyldiamine (compound 3) ONDA : oxanorbornane diamine (compound 4) IPDA : isophorone Diamine (Compound 5) 11-]\40 八: 4,4|-Amidino bis(cyclohexylamine) (Compound 6) ODA : 4,4'-Diaminodiphenyl ether [4,4' -diaminodiphenyl ether](Compound 7) APB : 1,3-bis(3-aminophenoxy)benzene (compound 8) mBP : 4,4'-bis(3-aminophenoxy) Biphenyl (Compound 9) (b) Tetracarboxylic dianhydride PMDA: Pyromellitic dianhydride (Compound 10) BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride (Compound ll) 00 Deaf: bis(3,4-dicarboxyphenyl)ether dianhydride (compound 12) 6 corpse 0 person: 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3, 3,3- Fluoropropane two-needle (compound 13). 11-?]^0 eight: 1,2,4,5-cyclohexanetetradecanoic acid dianhydride (compound 14) 33 201231504 λ vi ^/±i. Compound 1 Compound 2 Compound 3

化合物4 化合物6Compound 4 compound 6

化合物7 h2n 化合物5Compound 7 h2n compound 5

NHz 化合物9NHz compound 9

化合物1 0 化合物1 1 化合物1 2 0 0 0 0 〇 0 II Μ II II II IICompound 1 0 Compound 1 1 Compound 1 2 0 0 0 0 〇 0 II Μ II II II II

0 0 0 0 0 0 化合物1 3 化合物1 40 0 0 0 0 0 Compound 1 3 Compound 1 4

II II II II 〇 0 0 0 (C)溶劑 • Ν,Ν-二曱基乙醯胺（DMAc、和光純藥工業製造） • 1-曱基-2-吡咯啶酮（NMP、和光純藥工業製造） • 1，3-二甲基-2-咪唑啉酮（DMI、和光純藥工業製造） &lt;聚醯胺酸的聚合及聚醯亞胺膜的製作&gt; 34 201231504 -tl VTTJjJlf (合成例1) 在具有溫度計、轉機、氮氣導人管、滴液漏斗的1 L 的五口可分離燒瓶中，添加均苯四甲酸二酐（pMDA) 153 g (0.700冑耳）與作為有機溶劑# N，N_:f基乙酿胺 (DMAC) 420 在〇t的冰水浴中授拌而製成裝料狀液 體。歷時2小時緩慢滴加裝人至滴液漏斗内的降冰片烧二 胺（NBDA) 108 g (〇·莫耳）與N，N_二甲基乙酿胺 (DMAc) 188 g。滴加結束後，再於室溫下攪拌16小時， 而獲得聚_酸清漆。此㈣胺酸的时對數減為〇 69 dL/g。將結果示於表1。 使用刮刀將所得的聚醯胺酸溶液流延至玻璃基板上。 並將其移至無氧化烘箱（inert Gven)，在氮氣流中歷時2 小時自50°C升溫至270。(：，接著再於27(TC保持2小時而 獲得具有自持性的膜厚26 μιη的無色透明聚醯亞胺膜。將 此聚醯亞胺膜的諸物性（全光線透射率、最大激發波長、 最大螢光波長及其強度、玻璃轉移溫度、熱線膨脹係數、 及拉伸伸長率）的測定結果示於表2。 (合成例2) 在具有溫度計、攪拌機、氮氣導入管的丨L的五口可 分離燒瓶中，於室溫下添加1，4_雙（胺基甲基）環己烷 (H-XDA) 35.6g (0.250 莫耳）、3,3，，4,4，_聯苯四甲酸二酐 (BPDA) 73.5 g (〇.25〇莫耳）、及溶劑N，N_二甲基乙醯胺 (DMAc) 620 g，將反應容器於保持為1〇〇°c的油浴中浸 10分鐘。在約5分鐘時發生鹽析出，並迅速再溶解，確認 35 201231504 到4黏的狀態。自油浴取出後，再於室溫下授拌 而獲得聚醯胺酸清漆。所得的聚醯胺酸的固 小時， 1.22dL/g (35。(：、G.5g/dL)。將結果示於表丨。站度為 、無色透明聚醯亞胺膜的製作是以與合成例丨相 式來進行，將所得的膜的諸物性的測定結果示於表2。、 (合成例3) ' ° 將H-XDA變更為反·Μ·環己基二胺（tCHDA) 57 1 g (0·500莫耳）’除此以外，以與合成例2相同的方式，^ 作聚醯胺酸溶液及無色透明聚醯亞胺膜，將諸物性的 結果示於表1及表2。 “ (合成例4) 將NBDA變更為4,4，-亞曱基雙(環己基胺）（h_mda) 105 g，除此以外，以與合成例丨相同的方式，製作聚醯胺 酸溶液及無色透明聚醯亞胺膜，將諸物性的測定結果示於 表1及表2。 (合成例5及合成例6 ) 將PMDA分別變更為雙（3,4-二羧基苯基）醚二酐 (ODPA) 155 g、2,2-雙(3,4-二羧基苯基)-1，1，1，3,3,3-六氟 丙烷二酐（6FDA) 222 g，除此以外，以與合成例1相同 的方式’製作聚醯胺酸溶液及無色透明聚醯亞胺膜，將諸 物性的結果示於表1及表2。 (合成例7及合成例8 ) 將二胺成分單獨為NBDA的情形分別變更為氧雜降 冰片烷二胺（ONDA) 50 mol%與NBDA的共聚物、異佛 36 201231504 * V , 爾嗣二胺（IPDA ) 30 mol%與NBDA的共聚物，除此以外， 以與合成例1烟的方式，製作聚醯胺酸溶液及無色透明 聚醯亞胺膜’將諸物性的測定結果示於表丨及表2。 (合成例9) 在具有溫度計、攪拌機、氮氣導入管的300 mL的五 口可分離燒瓶中，添加反]，4環己基二胺（咖叫n々 、（(U00莫耳）、作為溶劑的N_甲基吡咯啶酮 並搜拌在製成的透明溶液中直接裝入粉狀的3,3，，4,4，_聯 Ϊ四甲酸二酐（BPDA) 25.9 g⑽綱莫耳），將反應容 益於保持為120t：的油浴中浸5分鐘。BPDA裝入後不久 發生鹽析出，然後迅速地再溶解並確認到增黏的狀態。自 油浴取出後，再於室溫下攪拌18小時，而獲得末端具有源 自tCHDA的胺基的寡醯胺酸清漆。 接著’在具有溫度計、攪拌機、氮氣導入管的200 mL 的五口可分離燒瓶中，添加降冰片烷二胺（NBDA) 6 19g (0.0402莫耳）與ι，3_二甲基_2_咪嗤琳酮（DMI) 64 5 g f攪拌。在製成的透明溶液中直接裝入粉狀的3,3，,4,4，_聯 ，四曱酸二酐（BPDA) 15.3 g (0.0522莫耳），將反應容 益於保持為120。(：的油浴中浸5分鐘。BPDA裝入後暫時 發生鹽析出，但很快再溶解並確認到均勻的透明溶液。在 此可分離燒瓶中安裝冷卻管與迪恩-斯達克（Dean-Stark ) 型濃縮器，在反應溶液中追加二甲苯15 g，在i8〇°C下一 邊攪拌4小時一邊進行脫水熱醯亞胺化反應。在二曱苯蒸 顧除去後’獲得末端具有源自BPDA的酸酐結構的寡醯亞 37 201231504 胺清漆。 將上述所得的寡醯胺酸清漆及寡醯亞胺清漆混合，添 加NMP稀釋並攪拌至15 wt%，而合成多嵌段狀聚醯胺酸 酿亞胺清漆。所得的此清漆的固有對數黏度為1.31 dL/g (35°C、0.5 g/dL)。將結果示於表卜 無色透明聚醯亞胺膜的製作是以與合成例1相同的方 式來進行’將所得的膜的諸物性的測定結果示於表2。 (合成例10、合成例12及合成例14) 將二胺成分的NBDA分別變更為：1，3-雙(3-胺基苯氧 基)苯（APB) 146g (0.500 莫耳）且溶劑 DMI602 g、4,4，· 二胺基二苯基醚[4,4，-二胺基二苯醚](〇DA) 100 g (0.500 莫耳）且溶劑NMP 494 g、4、4，-雙(3-胺基苯氧基)聯苯 (mBP) 184g(0.500莫耳）且溶劑DMI 690 g，並且將四 綾酸二酐成分的PMDA均變更為1,2,4,5-環己烷四甲酸二 軒（H-PMDA) 112 g ( 0.500莫耳），除此以外，以與合成 例1相同的方式，製作聚醯胺酸溶液及無色透明聚醯亞胺 獏，將諸物性的測定結果示於表1及表2。 (合成例11、合成例13及合成例15) 將合成例10、合成例12及合成例14中所得的各聚醯 胺酸清漆注入至具有冷卻管與迪恩_斯達克型濃縮器的燒 瓶中，添加作為共沸劑的20 wt%左右的二甲笨，於油浴 180°C中實施6小時的共沸脫水反應，最後將二甲苯蒸餾除 去而獲得聚醯亞胺清漆。將所得的聚醯亞胺的固有對數黏 度的結果示於表1。 38 201231504 並且，無色透明聚醯亞胺膜的製作是以與合成例1相 同的方式來進行，將所得的膜的諸物性的測定結果示於表 2 ° (合成例16及合成例17) 將二胺成分的H-XDA分別變更為ι，3-雙(3-胺基苯氧 基)苯（APB) 146 g (0.500莫耳）、4,4，-雙(3-胺基苯氧基) 聯笨（mBP) 166 g (0_450莫耳）且4,4，_二胺基二苯基醚 [4,4’_二胺基二苯抝（0DA) 1〇 〇 g (〇 〇5〇〇 莫耳），將四 致酸一酐成分的BPDA均變更為均苯四甲酸二針（pmda) l〇9g( 0.500莫耳），除此以外，以與合成例2相同的方式， 製作聚醯胺酸溶液及聚醯亞胺膜，將諸物性的測定結果示 於表1及表2。 (合成例18) 將二胺成分的H-XDA變更為反-i，4-環己基二胺 (tCHDA)57.1 g( 0.500莫耳），將四羧酸二酐成分的bpda 變更為1，2,4,5-環己烷四曱酸二酐（H-PMDA ) 112 g ( 0.500 莫耳），除此以外，以與合成例2相同的方式，製作聚醯胺 酸溶液及無色透明聚醯亞胺膜，將諸物性的測定結果示於 表1及表2。 ' (合成例19) 在具有溫度計、攪拌機、氮氣導入管的500 mL的五 口可分離燒瓶中’添加4,4，-二胺基二苯基醚[4,4，-二胺基二 苯趟](ODA) 35.6 g ( 0.Π8莫耳）與作為有機溶劑的ϋ 二甲基乙醯胺（DMAc) 267 g，於（TC的冰水浴中攪拌而 39 201231504 =成均勻溶液。於其中直接裝人粉狀的2,2雙(3 4二減 苯基)_1，1，1，3,3,3-六氟丙烧二針（6FDa) % 9 呂（〇 178 莫 耳）’於室溫下麟16小時’而獲得聚酿胺酸清漆。此聚 醯胺酸的S1有對數黏度為0.98 dL/g。將結果示於表i。聚 醯亞胺膜疋以與合成例1相同的方式進行製作，將諸物性 的測定結果不於表2。 (實例1、實例3、實例6〜實例U及實例13) 在上述合成例1〜合成例9中所得的聚合物溶液（聚 醯胺酸清漆或聚醯胺酸醯亞胺清漆）中，相對於所對應的 此聚醯胺酸或此聚醯胺酸醯亞胺的固體成分量1〇〇重量 份，以成為1.0重量份的方式添加氣化銪六水合物，使用 自轉-公轉混合機（或混練、混合脫泡裝置）（基恩斯 (KEYENCE )股份有限公司製造、製品名：Hybrid Mixer-500)授拌5分鐘，而獲得所對應的複合清漆。使用 到刀將此清漆流延至玻璃基板上，將其移至無氧化烘箱 中’在氮氣流中歷時2小時自50°C升溫至270°C，接著再 於270 C下保持2小時，而獲得具有自持性及無色透明性 的聚醯亞胺複合膜。 將此聚酿亞胺複合膜的諸物性（全光線透射率、最大 激發波長、最大螢光波長及其強度、玻璃轉移溫度、熱線 膨脹係數、及拉伸伸長率）的測定結果示於表3。 (實例2及實例12) 在上述合成例2及合成例9中所得的聚合物溶液（聚 醯胺酸清漆）中，相對於所對應的此聚醯胺酸的固體成分 201231504 量100重量份，以成為0.20重量份的方式變更為氣化銪六 水合物的添加量，除此以外，以與實例1相同的方式，製 作所對應的複合清漆及具有自持性及無色透明性的聚醯亞 胺複合膜。將諸物性的測定結果示於表3。 (實例4) 在上述合成例2中所得的聚合物溶液（聚醯胺酸清漆） 中，相對於此聚醯胺酸的固體成分量1〇〇重量份，以成為 1.0重量份的方式變更硝酸銪六水合物的添加量，除此以 外’以與實例3相同的方式，製作複合清漆及具有自持性 及無色透明性的聚醯亞胺複合膜。將諸物性的測定結果示 於表3 _。 (實例5) 在上述合成例2中所得的聚合物溶液（聚醯胺酸清漆） 中’相對於此聚醯胺酸的固體成分量1〇〇重量份，以成為 1.0重量份的方式變更乙酸銪水合物的添加量，除此以外， 以與實例3相同的方式，製作複合清漆及具有自持性及無 色透明性的聚醯亞胺複合膜。將諸物性的測定結果示於表 3。 (參考例1及參考例2) 在上述合成例2及合成例9中所得的聚合物溶液（聚 酿胺酸清漆或聚醯胺酸醯亞胺清漆）中，相對於所對應的 此聚醯胺酸或此聚醯胺酸醯亞胺的固體成分量^量 份’以成為5.G重量份的方式變更氣倾六水合物的添加 量，除此以外’以與實例i相同的方式，製作所對應的複 201231504 合清漆及具有自雜及無色透概的輯亞贿合膜。將 諸物性的測定結果示於表4。 (比較例1〜比較例9) 在上述合成例10〜合成例18巾所制聚合物溶液（聚 醯胺酸清漆或料亞胺清漆）巾，相對於所軸的此聚酿 胺酸或此聚醯亞胺的固體成分量100重量份’以成為10 重量份的方式變更氣化銪六水合物的添加量，除此以外， 以與實例1相_方式’製作所對應的複合清漆及聚醯亞 胺複合膜。將諸物性的測定結果示於表5。 (比較例10) 在上述合成例2中所得的無色透明聚醯亞胺膜上，旋 塗硝酸銪水合物的3%乙腈溶液，而製作經室溫乾燥的膜， 以與實例1相同的方式測定此膜的諸物性。將其結果示於 表5。 (比較例11) 將上述合成例2中所得的無色透明聚醯亞胺膜於确酸 銪水合物的3%乙腈溶液中浸潰6小時，而製作經室溫乾 燥後的膜，以與實例1相同的方式測定此膜的諸物性。將 其結果示於表5。 (比較例12) 在上述合成例19中所得的聚合物溶液（聚醯胺酸清 漆）中，相對於此聚醯胺酸的固體成分量1〇〇重量份，以 成為1.0重量份的方式變更硝酸銪六水合物的添加量，除 此以外，以與實例1相同的方式，製作所對應的複合清漆 42 201231504 ~Γ X V- 及具有自持性的聚醯亞胺複合膜。將諸物性的測定結果示 於表5。 表1 合成例 組成mi) (二胺化合物/四羧酸二酐） 聚合物的狀態 聚合物溶液的物性 固有對數黏度（dL/g) 1 NBDA/PMDA 聚醯胺酸 0.69 2 H-XDA/BPDA 聚醯胺酸 1.22 3 tCHDA/BPDA 聚醯胺酸 1.65 4 H-MDA/PMDA 聚醯胺酸 1.05 5 NBDA/ODPA 聚醯胺酸 0.53 6 NBDA/6FDA 聚醯胺酸 0.43 7 (NBDA5〇/ONDA5〇) /PMDA 聚醯胺酸 0.51 8 (nbda7〇/ipda3〇) /pmda 聚醯胺酸 0.53 9 (NBDA29/tCHDA 71 ) /BPDA 聚醖胺酸醯亞胺 1.31 10 APB/H-PMDA 聚醯胺酸 0.30 11 T 聚醯亞胺 0.25 12 ODA/H-PMDA 聚醯胺酸 0.34 13 T 聚醯亞胺 0.56 14 mBP/H-PMDA 聚醯胺酸 0.47 15 T 聚醯亞胺 0.49 16 APB/PMDA 聚醯胺酸 0.69 17 (mBP9〇/ODAi〇) /PMDA 聚醯胺酸 0.70 18 tCHDA/H-PMDA 聚醯胺酸 0.21 19 ODA/6FDA 聚醯胺酸 0.98 (註1)合成例7〜合成例9、合成例17中的組成的下標文字表示莫耳分率。 43 201231504II II II II 〇0 0 0 (C) Solvent • Ν,Ν-dimercaptoacetamide (DMAc, Wako Pure Chemical Industries, Ltd.) • 1-Mercapto-2-pyrrolidone (NMP, Wako Pure Chemical Industries) Manufactured by: 1,3-Dimethyl-2-imidazolidinone (DMI, manufactured by Wako Pure Chemical Industries, Ltd.) &lt;Polymerization of Polylysine and Preparation of Polyimine Film&gt; 34 201231504 -tl VTTJjJlf (Synthesis) Example 1) Addition of pyromellitic dianhydride (pMDA) 153 g (0.700 胄) to an organic solvent in a 1 L five-neck separable flask equipped with a thermometer, a transfer, a nitrogen gas guide, and a dropping funnel# N,N_:f-based ethylamine (DMAC) 420 was mixed in an ice water bath of 〇t to prepare a liquid. The norbornene diamine (NBDA) 108 g (〇·mol) and N,N-dimethylethenamine (DMAc) 188 g were slowly added dropwise to the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at room temperature for 16 hours to obtain a poly-acid varnish. The time logarithm of this (iv) aminic acid was reduced to 〇 69 dL/g. The results are shown in Table 1. The resulting polyaminic acid solution was cast onto a glass substrate using a doctor blade. It was transferred to an oxygen free oven (inert Gven) and heated from 50 ° C to 270 over 2 hours in a stream of nitrogen. (:, followed by 27 (TC held for 2 hours to obtain a colorless transparent polyimide film with a self-sustaining film thickness of 26 μη. The physical properties of this polyimide film (total light transmittance, maximum excitation wavelength) The measurement results of the maximum fluorescence wavelength and its intensity, the glass transition temperature, the coefficient of thermal expansion, and the tensile elongation are shown in Table 2. (Synthesis Example 2) Five of 丨L having a thermometer, a stirrer, and a nitrogen introduction tube In a separable separable flask, add 1,4-bis(aminomethyl)cyclohexane (H-XDA) 35.6 g (0.250 mol), 3,3,4,4,_biphenyl at room temperature. Tetracarboxylic acid dianhydride (BPDA) 73.5 g (〇.25〇mol), and solvent N,N-dimethylacetamide (DMAc) 620 g, the reaction vessel was kept in an oil bath at 1 °C Immersion for 10 minutes. Salt precipitation occurred at about 5 minutes and quickly dissolved again, confirming the state of 35 201231504 to 4. The oil was taken out from the oil bath and then mixed at room temperature to obtain a polyamic acid varnish. The solid hour of the poly-proline, 1.22dL / g (35. (:, G.5g / dL). The results are shown in the table. Station, colorless transparent polyimide film The measurement results of the physical properties of the obtained film are shown in Table 2. (Synthesis Example 3) ' ° Change H-XDA to anti-Μ·cyclohexyldiamine ( In the same manner as in Synthesis Example 2, a poly-proline solution and a colorless transparent polyimide film were used, and the results of the physical properties are shown in the table. 1 and Table 2. "(Synthesis Example 4) In the same manner as in the synthesis example, a polycondensation was carried out except that NBDA was changed to 4,4,-fluorenylene bis(cyclohexylamine) (h_mda) 105 g. The results of measuring the physical properties of the proline solution and the colorless transparent polyimide film are shown in Tables 1 and 2. (Synthesis Example 5 and Synthesis Example 6) The PMDA was changed to bis(3,4-dicarboxybenzene). Ether dianhydride (ODPA) 155 g, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) 222 g, In the same manner as in Synthesis Example 1, a polyamic acid solution and a colorless transparent polyimide film were produced, and the results of the physical properties are shown in Tables 1 and 2. (Synthesis Example 7 and Synthesis Example 8) The case where the diamine component is separately NBDA is changed separately. a copolymer of 50 mol% of oxabornane diamine (ONDA) and NBDA, a copolymer of isophora 36 201231504 * V , oxadiamine (IPDA) 30 mol% and NBDA, in addition to In the case of the method of the first embodiment, the polyamic acid solution and the colorless transparent polyimide film were prepared. The measurement results of the physical properties are shown in Table 2 and Table 2. (Synthesis Example 9) A thermometer, a stirrer, and a nitrogen introduction tube were used. In a 300 mL five-neck separable flask, add anti-, 4-cyclohexyldiamine (called n々, ((U00 Mo), N-methylpyrrolidone as a solvent and mix it in a transparent The solution was directly filled with powdered 3,3,4,4,_tetrabenzidine carboxylic acid dianhydride (BPDA) 25.9 g (10) Mohr), and the reaction was allowed to dip for 5 minutes in an oil bath maintained at 120 t: . Salt precipitation occurred shortly after the loading of the BPDA, and then quickly dissolved again to confirm the state of adhesion. After taking out from the oil bath, it was further stirred at room temperature for 18 hours to obtain an oligoaminan varnish having an amine group derived from tCHDA at the end. Then, in a 200 mL five-neck separable flask with a thermometer, a stirrer, and a nitrogen inlet tube, add norbornane diamine (NBDA) 6 19g (0.0402 mol) and ι, 3 dimethyl 2 _ Kelinone (DMI) 64 5 gf is stirred. The powdered 3,3,4,4,-, tetradecanoic acid dianhydride (BPDA) 15.3 g (0.0522 mol) was directly charged into the resulting clear solution, and the reaction was kept at 120. (: The oil bath was immersed for 5 minutes. After the BPDA was charged, salt precipitation occurred temporarily, but it quickly dissolved again and confirmed a uniform transparent solution. In this separable flask, a cooling tube was installed with Dean-Stark (Dean). -Stark) type concentrator, 15 g of xylene was added to the reaction solution, and dehydration and heat imidization reaction was carried out while stirring at i8 ° C for 4 hours. After the diphenylbenzene was removed, the end had a source. An acetal varnish of the anhydride structure of BPDA from 201231504. The oligophthalic acid varnish obtained above and the oligophthalimide varnish were mixed, diluted with NMP and stirred to 15 wt%, and the polyblock polyamine was synthesized. Acidic imine varnish. The inherent logarithmic viscosity of the obtained varnish is 1.31 dL/g (35 ° C, 0.5 g/dL). The results are shown in the table. The colorless transparent polyimide film is prepared and synthesized. In the same manner, the measurement results of the physical properties of the obtained film are shown in Table 2. (Synthesis Example 10, Synthesis Example 12, and Synthesis Example 14) The NBDA of the diamine component was changed to 1,3-double. (3-Aminophenoxy)benzene (APB) 146g (0.500 mole) and solvent DMI602 g, 4, 4, Diaminodiphenyl ether [4,4,-diaminodiphenyl ether] (〇DA) 100 g (0.500 mol) and solvent NMP 494 g, 4,4,-bis(3-aminophenoxyl) Biphenyl (mBP) 184 g (0.500 mol) and solvent DMI 690 g, and the PMDA of the tetradecanoic dianhydride component was changed to 1,2,4,5-cyclohexanetetracarboxylic acid di-xanthene (H- In the same manner as in Synthesis Example 1, a polyamic acid solution and a colorless transparent polyimine oxime were prepared in the same manner as in Synthesis Example 1, and the measurement results of the physical properties are shown in Table 1 and Table. (Synthesis Example 11, Synthesis Example 13 and Synthesis Example 15) Each of the polyamic acid varnishes obtained in Synthesis Example 10, Synthesis Example 12, and Synthesis Example 14 was injected into a cooling tube and Dean-Stark type concentrated. To the flask of the apparatus, about 20 wt% of dimethyl benzene was added as an azeotropic agent, and an azeotropic dehydration reaction was carried out for 6 hours in an oil bath at 180 ° C. Finally, xylene was distilled off to obtain a polyimide varnish. The results of the inherent logarithmic viscosity of the obtained polyimine are shown in Table 1. 38 201231504 Further, the production of the colorless transparent polyimide film was carried out in the same manner as in Synthesis Example 1, and the obtained The measurement results of the physical properties of the film are shown in Table 2 (Synthesis Example 16 and Synthesis Example 17). The H-XDA of the diamine component was changed to iota, 3-bis(3-aminophenoxy)benzene (APB). ) 146 g (0.500 mol), 4,4,-bis(3-aminophenoxy) phenyl (mBP) 166 g (0-450 mol) and 4,4,-diaminodiphenyl ether [ 4,4'-diaminodiphenyl hydrazine (0DA) 1〇〇g (〇〇5〇〇莫耳), the BPDA of the tetra-acid mono-anhydride component was changed to two needles of pyromellitic acid (pmda) A polyamic acid solution and a polyimide film were produced in the same manner as in Synthesis Example 2 except that 9 g (0.500 mol) was used. The measurement results of the physical properties are shown in Tables 1 and 2. (Synthesis Example 18) The H-XDA of the diamine component was changed to 5,71 g (0.500 mol) of trans-i,4-cyclohexyldiamine (tCHDA), and the bpda of the tetracarboxylic dianhydride component was changed to 1,2. A polyglycine solution and a colorless transparent polypeptone were prepared in the same manner as in Synthesis Example 2 except that 4,5-cyclohexanetetradecanoic acid dianhydride (H-PMDA) 112 g (0.500 mol) was used. The results of measuring the physical properties of the imine film are shown in Tables 1 and 2. '(Synthesis Example 19) Adding 4,4,-diaminodiphenyl ether [4,4,-diaminodiphenyl] in a 500 mL five-neck separable flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube趟](ODA) 35.6 g (0.Π8 mol) and 267 dimethyl dimethyl acetamide (DMAc) 267 g as an organic solvent, stirred in an ice bath of TC and 39 201231504 = homogeneous solution. Directly packed with powdered 2,2 bis (3 4 diphenyl)_1,1,1,3,3,3-hexafluoropropanone (6FDa) % 9 LV (〇178 莫耳)' The polyamic acid varnish was obtained at room temperature for 16 hours. The S1 of this polyamic acid had a logarithmic viscosity of 0.98 dL/g. The results are shown in Table i. The polyimine film was the same as in Synthesis Example 1. The production method was carried out, and the measurement results of the physical properties were not shown in Table 2. (Example 1, Example 3, Example 6 to Example U and Example 13) The polymer solution obtained in the above Synthesis Examples 1 to 9 (Polymerized) In the case of the amino acid varnish or the polyamidamine varnish, the amount of the solid component of the corresponding polyaminic acid or the polyamidimide is 1 part by weight to be 1.0 part by weight. Way to add The ruthenium hexahydrate is mixed with a rotation-revolution mixer (or a kneading/mixing defoaming device) (manufactured by KEYENCE Co., Ltd., product name: Hybrid Mixer-500) for 5 minutes to obtain a corresponding compound. Varnish. The varnish was cast onto a glass substrate using a knife and transferred to an oxidizing oven. 'The temperature was raised from 50 ° C to 270 ° C for 2 hours in a stream of nitrogen, followed by another 2 hours at 270 C. The polyimine composite film having self-sustaining property and colorless transparency is obtained. The physical properties of the polyimide-based composite film (total light transmittance, maximum excitation wavelength, maximum fluorescence wavelength and intensity, glass transition temperature, The measurement results of the coefficient of thermal linear expansion and the tensile elongation are shown in Table 3. (Example 2 and Example 12) In the polymer solution (polyamic acid varnish) obtained in the above Synthesis Example 2 and Synthesis Example 9, In the same manner as in Example 1, except that 100 parts by weight of the solid component of the polyglycolic acid was used in an amount of 0.20 part by weight, and the amount of the vaporized ruthenium hexahydrate added was changed to 0.20 part by weight. A corresponding composite varnish and a polyimide film having a self-sustaining property and a colorless transparency. The measurement results of the physical properties are shown in Table 3. (Example 4) The polymer solution obtained in the above Synthesis Example 2 (polyamide) In the same manner as in Example 3, the acid varnish was changed in an amount of 1 part by weight based on the solid content of the polyamic acid, and the amount of the cerium nitrate hexahydrate added was changed to 1.0 part by weight. A composite varnish and a polyimide film having a self-sustaining property and a colorless transparency were produced, and the measurement results of the physical properties are shown in Table 3 _. (Example 5) In the polymer solution (poly-proline varnish) obtained in the above Synthesis Example 2, acetic acid was changed in an amount of 1 part by weight based on the solid content of the polyamic acid, and 1.0 part by weight was changed. A composite varnish and a polyimide film having a self-sustaining property and a colorless transparency were produced in the same manner as in Example 3 except that the amount of the hydrazine hydrate was added. The measurement results of the physical properties are shown in Table 3. (Reference Example 1 and Reference Example 2) In the polymer solution (polyaluminate varnish or polyamidimide varnish) obtained in the above Synthesis Example 2 and Synthesis Example 9, the corresponding polyfluorene was In the same manner as in Example i, the amount of the solid content of the amine acid or the polyamidimide is changed to 5. G parts by weight, and the amount of the gas hexahydrate added is changed. The corresponding 201231504 varnish and the combination of self-mixed and colorless. The measurement results of the physical properties are shown in Table 4. (Comparative Example 1 to Comparative Example 9) The polymer solution (polyacrylic acid varnish or imide varnish) prepared in the above Synthesis Example 10 to Synthesis Example 18, relative to the axis of the polyacrylic acid or the like The composite varnish and polyfluorene which are produced in the same manner as in Example 1 except that the amount of the solid content of the polyimine is 100 parts by weight 'the amount of the vaporized hydrazine hexahydrate added is 10 parts by weight. Imine composite membrane. The measurement results of the physical properties are shown in Table 5. (Comparative Example 10) A 3% acetonitrile solution of cerium nitrate hydrate was spin-coated on the colorless transparent polyimide film obtained in the above Synthesis Example 2 to prepare a film which was dried at room temperature in the same manner as in Example 1. The physical properties of this film were measured. The results are shown in Table 5. (Comparative Example 11) The colorless transparent polyimine film obtained in the above Synthesis Example 2 was immersed in a 3% acetonitrile solution of ruthenium oxalate hydrate for 6 hours to prepare a film which was dried at room temperature, and an example thereof. The physical properties of this film were measured in the same manner. The results are shown in Table 5. (Comparative Example 12) The polymer solution (poly-proline varnish) obtained in the above-mentioned Synthesis Example 19 was changed so as to be 1.0 part by weight based on 1 part by weight of the solid content of the polyamic acid. In the same manner as in Example 1, except that the amount of the cerium nitrate hexahydrate added was changed, the corresponding composite varnish 42 201231504 ~ Γ X V- and a self-sustaining polyimine composite film were produced. The measurement results of the physical properties are shown in Table 5. Table 1 Synthesis Example Composition mi) (Diamine Compound / Tetracarboxylic Acid dianhydride) State of Polymer Properties of Intrinsic Logarithmic Viscosity of Polymer Solution (dL/g) 1 NBDA/PMDA Polyglycine 0.69 2 H-XDA/BPDA Polyglycolic acid 1.22 3 tCHDA/BPDA Polyglycine 1.65 4 H-MDA/PMDA Polyglycine 1.05 5 NBDA/ODPA Polyglycine 0.53 6 NBDA/6FDA Polyglycine 0.43 7 (NBDA5〇/ONDA5〇 /PMDA Polyglycolic acid 0.51 8 (nbda7〇/ipda3〇) /pmda Polyglycine 0.53 9 (NBDA29/tCHDA 71 ) /BPDA Polyphosphonium imide 1.31 10 APB/H-PMDA Polylysine 0.30 11 T Polyimine 0.25 12 ODA/H-PMDA Polyglycine 0.34 13 T Polyimine 0.56 14 mBP/H-PMDA Polyglycine 0.47 15 T Polyimine 0.49 16 APB/PMDA Polyfluorene Amino acid 0.69 17 (mBP9〇/ODAi〇) /PMDA Polyglycine 0.70 18 tCHDA/H-PMDA Polyglycine 0.21 19 ODA/6FDA Polyglycine 0.98 (Note 1) Synthesis Example 7 to Synthesis Example 9, The subscript text of the composition in Synthesis Example 17 indicates the molar fraction. 43 201231504

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LP 201231504 一如表3的實例所示，在聚醯亞胺的二胺化合物/四綾酸 二酐的成分分別為脂環族/芳香族時，所製作的複合膜具 無色透明性’且藉由激發光的照射而觀測到在波長6丨5 n m 表現極大發光值的源自銪化合物的螢光。根據此時的掃描 速度為5000 nm/min，可知此螢光發光具有高速響應性。田 並且，如表4的參考例所示可知，即便是與表3相同 的結構的聚醯亞胺’在由銪化合物的添加量相對於聚合物 100重量份而添加5重量份的清漆製作的複合膜時，與由 添加1重#份此銪化合物的清雜作的複合膜概 強度及臈物_有降低，但域具有無色剌性 應性螢級光。 迷響 另一方面，如表5的比較例所示，在聚醯亞胺的 =合物/四紐二_齡為料助旨_、或脂環族/脂 %知時’複合膜雜具有無色透明性，但即便照射激發光， 亦觀測不到源自銪化合物的$光（波長615nm左右）。並 且在聚醯亞賴二胺化合物/四紐二軒的成分為芳香族 /芳香族時，複合膜為黃色或棕色的有色性，較照射激發 光，源自添加劑的螢光強度（波長615nm左右）亦極小二 且由於複合翻身的有色性而目視確認不到螢光發光性。 特別是如比較m2所示，可明白即便是與專利文獻2相同 的組成’如本測定般掃描速度較快（5〇〇〇nm/min)時 表現不出勞光。 並且’使在合成例2中所得的無色透明聚酿亞胺膜上 旋塗硝酸銪水合物的3%乙腈溶液而得者、或在此溶液中 48 201231504LP 201231504 As shown in the example in Table 3, when the components of the polyamine compound/tetradecanoic dianhydride of the polyimine are alicyclic/aromatic, respectively, the composite film produced has colorless transparency' and Fluorescence derived from a ruthenium compound exhibiting a large luminescence value at a wavelength of 6 丨 5 nm was observed by irradiation of excitation light. According to the scanning speed at this time, it is 5000 nm/min, and it is understood that this fluorescent light has high-speed responsiveness. As shown in the reference examples of Table 4, even the polyimine of the same structure as in Table 3 was prepared by adding 5 parts by weight of varnish to 100 parts by weight of the polymer. In the case of the composite film, the composite film having a fineness of 1 part by weight of the ruthenium compound and the mash _ are reduced, but the domain has colorless fluorinated phosgene light. On the other hand, as shown in the comparative example of Table 5, in the case of polyimine, the compound/four-in-one is used as a material, or the alicyclic/lipid is known as a composite film. Colorless transparency, but even when the excitation light is irradiated, no light (about 615 nm wavelength) derived from the ruthenium compound is observed. In addition, when the component of the poly(arylene diamine compound/tetraxins) is aromatic/aromatic, the composite film is yellow or brown colored, and the fluorescence intensity derived from the additive is higher than the irradiation excitation light (wavelength of about 615 nm). ) It is also extremely small and the fluorescent luminescence is not visually recognized due to the color of the composite turn. In particular, as shown by the comparison of m2, it is understood that even if the composition of the same as in Patent Document 2 is faster than the measurement (5 〇〇〇 nm/min), it does not show a light. Further, a solution of 3% acetonitrile of ruthenium nitrate hydrate was spin-coated on the colorless transparent polyimide intermediate film obtained in Synthesis Example 2, or in this solution 48 201231504

I X V 浸潰6小時而得者在室溫下乾燥而得的膜中，即便照射激 發光，亦確認不到源自銪化合物的螢光強度（波長615 nm 左右）。藉此可知，為了在無色透明聚醯亞胺與麵化 間具有相互仙’而必須以聚醯亞胺前驅體 ς 漆的狀態進行複合化。 Κ職胺s曼清 【圖式簡單說明】 圖1表示對合成例2、實例2、實例3及參 得的膜照射紫外線時的螢光發光光譜。 所 【主要元件符號說明】 1 :實例3 2 :實例2 3:參考例1 4:合成例2 49In the film obtained by immersing I X V for 6 hours at room temperature, the fluorescence intensity (wavelength of about 615 nm) derived from the ruthenium compound was not observed even when the laser was irradiated. From this, it is understood that in order to have a mutual color between the colorless transparent polyimide and the surface, it is necessary to be composited in the state of the polyimide precursor lacquer. The sputum amine sman clear [Simplified description of the drawings] Fig. 1 shows the fluorescence luminescence spectrum when the films of Synthesis Example 2, Example 2, Example 3, and the obtained film were irradiated with ultraviolet rays. [Explanation of main component symbols] 1 : Example 3 2 : Example 2 3: Reference example 1 4: Synthesis example 2 49

Claims (1)

201231504 七、申請專利範圍： 1. 一種聚醯亞胺複合體，其是相對於由通式（1)所 示的聚醯胺酸與溶解上述聚醯胺酸的溶劑（C)而得的聚 醯胺酸溶液（S1) 100重量份，添加銪（Eu)化合物0.001 重量份〜4重量份，而獲得聚醯胺酸溶液（S2)，上述聚醯 胺酸由脂環式二胺化合物（A)與芳香族四羧酸二酐（B) 而得， 藉由上述聚醯胺酸溶液（S2)所含的聚醯胺酸的醯亞 胺化及除去上述溶劑（C)而獲得：201231504 VII. Patent Application Range: 1. A polyamidene complex which is a polymer obtained by dissolving polyacrylic acid represented by the general formula (1) and a solvent (C) which dissolves the above polyamic acid. 100 parts by weight of a proline acid solution (S1), 0.001 parts by weight to 4 parts by weight of a cerium (Eu) compound, to obtain a polyaminic acid solution (S2), which is obtained from an alicyclic diamine compound (A) And the aromatic tetracarboxylic dianhydride (B) obtained by the hydrazine imidization of the poly phthalic acid contained in the above polyamic acid solution (S2) and removal of the above solvent (C): (1) 一（式（1)中，X表示碳數4〜15的二價脂環族基，γ 表示碳數6〜27的四價芳香族基）。 2·如申請專利範圍第丨項所述之聚醯亞胺複合體，其 中十述聚醯亞胺複合體所含的聚醯亞胺包含下述通式（2) 所示的結構單元：(1) In the formula (1), X represents a divalent alicyclic group having 4 to 15 carbon atoms, and γ represents a tetravalent aromatic group having 6 to 27 carbon atoms. 2. The polyimine complex according to the invention of claim 1, wherein the polyimine contained in the polyamidene complex comprises a structural unit represented by the following formula (2): Ο 〇 II II C、，c、 A , c c II II ο ο 式（2)中，χ為選自由 50 201231504 ~τ χ ο -or, -cr, -tr:Ο 〇 II II C, c, A, c c II II ο ο In the formula (2), χ is selected from 50 201231504 ~τ χ ο -or, -cr, -tr: 所組成群組中的至少1種脂環族基， Y為選自由 )〇c，)aOc,)a?Oc ;amSa, ^-。普。-¾ , )〇~。州交。以 及。分。众 所組成群組中的至少1種芳香族基。 3.如申請專利範圍第1項所述之聚醯亞胺複合體，其 中上述聚醯亞胺複合體所含的聚醯亞胺包含下述通式（3) 所示的結構單元：At least one alicyclic group in the group consisting of Y is selected from the group consisting of 〇c,) aOc,) a?Oc; amSa, ^-. general. -3⁄4 , )〇~. State diplomatic relations. as well as. Minute. At least one aromatic group in the group. 3. The polyimine complex according to claim 1, wherein the polyimine contained in the polyimine complex comprises a structural unit represented by the following formula (3): 4.如申請專利範圍第1項所述之聚醯亞胺複合體，其 中上述聚醯亞胺複合體所含的聚醯亞胺包含下述通式（4) 所示的結構單元： 51 2012315044. The polyimine complex according to claim 1, wherein the polyimine contained in the polyimine complex comprises a structural unit represented by the following formula (4): 51 201231504 5.如申請專利範圍第1項所述之聚醯亞胺複合體，其 中上述聚醯亞胺複合體所含的聚醯亞胺包含下述通式f 所示的結構單元： ；5. The polyimine complex according to claim 1, wherein the polyimine contained in the polyamidene complex comprises a structural unit represented by the following formula f: 6.如申請專利範圍第丨項所述之聚醯亞胺複合體，其 中上述聚醯亞胺複合體所含的聚醯亞胺包含下述通式、 所示的結構單元：6. The polyimine complex according to claim 2, wherein the polyimine contained in the polyimine complex comprises a structural unit represented by the following formula: (式中，m與η表示各括弧内所示的重複結構單元的 重複數，m的平均值與η的平均值之比（m : η)為ι : 9 〜9 : 1)。 7·如申請專利範圍第1項至第6項中任一項所述之聚 醯亞胺複合體，其中上述銪（Eu)化合物為選自氣化銪、 石肖酸销及乙酸銪的至少1種。 52 201231504 • A V/ I 8. 如申請專利範圍第1項至第7項中任一項所述之聚 醯亞胺複合體，其藉由照射波長伽〜4⑻nm的紫外 線，而發出波長500 nm〜80〇 nm的螢光。 9. 如申請專利範圍第8項所述之聚醯亞胺複合體，其 全光線透射率為80%以上。 ίο. —種膜，其包含如申請專利範圍第丨項至第9項 中任一項所述之聚醯亞胺複合體。 、 11. 一種聚醯亞胺複合體的製造方法，其特 包含以下的步驟1〜步驟3: 、 (步驟1) S得由通式⑴所示的聚醯胺酸與溶解此 聚醯胺酸的溶劑（C)而得的聚醯胺酸溶液（S1)的步驟， 上述聚醯胺_脂環式二胺化合物（A)與芳香族四緩酸 二野（B )而得：(wherein, m and η represent the number of repetitions of the repeating structural unit shown in each parenthesis, and the ratio of the average value of m to the average value of η (m : η) is ι : 9 〜 9 : 1). The polyimine complex according to any one of claims 1 to 6, wherein the bismuth (Eu) compound is at least selected from the group consisting of gasification hydrazine, tartaric acid pin and cerium acetate. 1 species. 52 201231504 • AV/I 8. The polyimine complex according to any one of claims 1 to 7, which emits a wavelength of 500 nm by irradiating ultraviolet rays having a wavelength of ～4 (8) nm. 80 〇 nm fluorescence. 9. The polyimine composite according to claim 8, wherein the total light transmittance is 80% or more. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. 11. A method for producing a polyimine complex, which comprises the following steps 1 to 3: (Step 1) S is obtained by polylysine represented by the formula (1) and dissolved in the polyaminic acid The step of the polyamine acid solution (S1) obtained by the solvent (C), the polyamine-alicyclic diamine compound (A) and the aromatic tetrazoic acid (B) are obtained: (式（1)中，X表示碳數4〜15的二價脂環族基，γ 表示碳數6〜27的四價芳香族基）； 土 (步驟2)相對於上述聚醯胺酸1〇〇重量份，而添加 銪（Eu)化合物0.001重量份〜4重量份，而獲得变 酸溶液（S2)的步驟；以及 人 (步驟3)藉由上述聚醯胺酸溶液（S2)所含的聚醯 胺酸的醯亞胺化及除去上述溶劑（C)而獲得聚醯亞胺複 53 201231504 合體的步驟。 12. —種聚醯胺酸溶液（S2)，其是在下述通式（1) 所示的聚醯胺酸、(In the formula (1), X represents a divalent alicyclic group having 4 to 15 carbon atoms, γ represents a tetravalent aromatic group having 6 to 27 carbon atoms; and soil (step 2) is relative to the above polyglycolic acid 1 〇〇 by weight, adding 0.001 parts by weight of the Eu (Eu) compound to 4 parts by weight to obtain a solution for changing the acid solution (S2); and human (Step 3) by the above polyamic acid solution (S2) The ruthenium imidization of poly-proline and the removal of the above solvent (C) to obtain a polyimine complex 53 201231504 complex. 12. A polyaminic acid solution (S2) which is a polyaminic acid represented by the following formula (1), (式（1)中，X表示碳數4〜15的二價脂環族基，Y 表示碳數6〜27的四價芳香族基） 與溶解上述聚醯胺酸的溶劑（C)中， 相對於上述聚醯胺酸100重量份，添加銪（Eu)化合 物0.001重量份〜4重量份而得。 13.如申請專利範圍第12項所述之聚醯胺酸溶液 (S2)，其中上述溶劑（C)為非質子性醯胺系溶劑。 54(In the formula (1), X represents a divalent alicyclic group having 4 to 15 carbon atoms, Y represents a tetravalent aromatic group having 6 to 27 carbon atoms), and a solvent (C) in which the above polylysine is dissolved, The ruthenium (Eu) compound is added in an amount of 0.001 part by weight to 4 parts by weight based on 100 parts by weight of the polyamic acid. 13. The polyaminic acid solution (S2) according to claim 12, wherein the solvent (C) is an aprotic amide-based solvent. 54